TWI522493B - Metal surface treatment agent, surface treatment steel material and surface treatment method thereof, and coating steel material and manufacturing method thereof - Google Patents

Metal surface treatment agent, surface treatment steel material and surface treatment method thereof, and coating steel material and manufacturing method thereof Download PDF

Info

Publication number
TWI522493B
TWI522493B TW102127953A TW102127953A TWI522493B TW I522493 B TWI522493 B TW I522493B TW 102127953 A TW102127953 A TW 102127953A TW 102127953 A TW102127953 A TW 102127953A TW I522493 B TWI522493 B TW I522493B
Authority
TW
Taiwan
Prior art keywords
group
surface treatment
carbon atoms
treatment agent
metal surface
Prior art date
Application number
TW102127953A
Other languages
Chinese (zh)
Other versions
TW201422845A (en
Inventor
Munenao Hirokami
Original Assignee
Shinetsu Chemical Co
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 Shinetsu Chemical Co filed Critical Shinetsu Chemical Co
Publication of TW201422845A publication Critical patent/TW201422845A/en
Application granted granted Critical
Publication of TWI522493B publication Critical patent/TWI522493B/en

Links

Classifications

    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/50—Treatment of iron or alloys based thereon
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

Description

金屬表面處理劑、表面處理鋼材及其表面處理方法，及塗裝鋼材及其製造方法 Metal surface treatment agent, surface treated steel material and surface treatment method thereof, coated steel material and manufacturing method thereof

本發明係關於一種金屬表面處理劑、以該處理劑進行表面處理之表面處理鋼材及其表面處理方法、以及於其上具有上層被膜之塗裝鋼材及其製造方法；該金屬表面處理劑，較佳為作為冷軋鋼材、熱軋鋼材、不鏽鋼鋼材、以及電鍍鋅鋼材、熔融鍍鋅鋼材、鋅-鋁合金系鍍敷鋼材、鋅-鐵合金系鍍敷鋼材、鋅-鎂合金系鍍敷鋼材、鋅-鋁-鎂合金系鍍敷鋼材、鋁系鍍敷鋼材、鋁-矽合金系鍍敷鋼材、錫系鍍敷鋼材、鉛-錫合金系鍍敷鋼材、鉻系鍍敷鋼材、鎳系鍍敷鋼材等之塗裝鋼材用等。 The present invention relates to a metal surface treatment agent, a surface-treated steel material surface-treated with the treatment agent, a surface treatment method thereof, and a coated steel material having an upper layer film thereon and a method for producing the same; the metal surface treatment agent Jiawei is used as cold-rolled steel, hot-rolled steel, stainless steel, and electrogalvanized steel, hot-dip galvanized steel, zinc-aluminum alloy-plated steel, zinc-iron alloy-plated steel, and zinc-magnesium alloy-plated steel. Zinc-aluminum-magnesium alloy-based plated steel, aluminum-based plated steel, aluminum-bismuth alloy-based plated steel, tin-based plated steel, lead-tin alloy-based plated steel, chromium-based plated steel, and nickel-based plated It is used for coating steel materials such as steel.

以往，金屬之表面處理劑，係使用鉻酸鹽或磷酸鉻酸鹽等之鉻系表面處理劑，現今亦廣泛被使用。然而，隨著最近之環境限制的動向，由於鉻所具有之毒性、特別是致癌性，將來之使用有受到限制的可能性。因此，期盼開發一種不含鉻但具有與鉻酸鹽處理劑同等之密合性、耐蝕性的金屬表面處理劑。 Conventionally, a metal surface treatment agent is a chromium-based surface treatment agent such as chromate or phosphoric acid chromate, which is widely used today. However, with the recent trend of environmental restrictions, due to the toxicity of chromium, especially carcinogenicity, there is a possibility of limited use in the future. Therefore, it has been desired to develop a metal surface treatment agent which does not contain chromium but has the same adhesion and corrosion resistance as the chromate treatment agent.

於日本特開平11-29724號公報(專利文獻1)，提出一種於水溶性樹脂含有含硫羰基之化合物與磷酸離子、及水分散性氧化矽之無鉻之防鏽處理劑。然而，該系係注重於裸耐蝕性(一次防鏽性)的改善。處理被膜之加工性及與基材之密合性並不充分，且其之處理品之上塗密合性雖為良好，但並無法滿足塗裝後耐蝕性。 Japanese Laid-Open Patent Publication No. Hei 11-29724 (Patent Document 1) proposes a chrome-free rust-preventing agent containing a sulfur-containing carbonyl group-containing compound, a phosphate ion, and a water-dispersible cerium oxide in a water-soluble resin. However, this system focuses on the improvement of bare corrosion resistance (primary rust resistance). The processability of the film to be treated and the adhesion to the substrate are not sufficient, and the adhesion of the treated article is good, but the corrosion resistance after coating cannot be satisfied.

又，於日本特開平8-073775號公報(專利文獻2)，揭示一種含有2種以上之矽烷耦合劑之酸性表面處理劑，而該系，當於金屬表面處理劑處理後要求高之耐蝕性與加工性時耐蝕性不足。 Japanese Patent Publication No. 8-073775 (Patent Document 2) discloses an acidic surface treatment agent containing two or more kinds of decane coupling agents, which requires high corrosion resistance after being treated with a metal surface treatment agent. Insufficient corrosion resistance with processability.

於與該等有關聯之日本特開2001-316845號公報(專利文獻3)，揭示一種含有矽烷耦合劑、水分散性氧化矽、鋯或鈦離子作為必須成分之無鉻酸鹽金屬表面處理劑，雖耐蝕性與加工性已改善，但於對基材之塗布性、及與上層被膜之密合強度等之方面並不充分。 Japanese Laid-Open Patent Publication No. 2001-316845 (Patent Document 3) discloses a chromate-free metal surface treatment agent containing a decane coupling agent, water-dispersible cerium oxide, zirconium or titanium ions as essential components. Although the corrosion resistance and the workability are improved, the coating property to the substrate and the adhesion strength to the upper film are not sufficient.

於日本特開平10-60315號公報(專利文獻4)，揭示一種含有具有與水系乳膠反應之特定官能基的矽烷耦合劑的鋼構造物用表面處理劑，於該場合，所要求之耐蝕性係僅針對如濕潤實驗之比較溫和之試驗的裸耐蝕性(耐白鏽性)，與可承受如本發明之嚴苛之耐蝕試驗的金屬表面處理劑相比，耐蝕性不足。 Japanese Laid-Open Patent Publication No. Hei 10-60315 (Patent Document 4) discloses a surface treatment agent for a steel structure containing a decane coupling agent having a specific functional group reactive with an aqueous latex. In this case, the required corrosion resistance system is disclosed. Only for the bare corrosion resistance (white rust resistance) of the mild test such as the wet test, the corrosion resistance is insufficient as compared with the metal surface treatment agent which can withstand the severe corrosion test of the present invention.

於日本特開2000-297093號公報(專利文獻5)，記載著將含有咪唑基之有機矽化合物使用於金屬等之表面處理劑，作為用以改善鋁合金板等金屬材料與環氧樹脂等樹 脂之接著性(接著強度)者提出，但作為塗裝品之耐蝕性與深拉性等並非充分滿足者。 Japanese Laid-Open Patent Publication No. 2000-297093 (Patent Document 5) discloses that an organic ruthenium compound containing an imidazole group is used for a surface treatment agent such as a metal to improve a metal material such as an aluminum alloy sheet and a resin such as an epoxy resin. The adhesion (adhesion strength) of the grease is proposed, but the corrosion resistance and deep drawability of the coated article are not sufficiently satisfied.

於日本特開2007-297648號公報(專利文獻6)，揭示含有水系乳膠與3價過渡金屬離子與β-二酮2分子與水2分子已配位之化合物、矽烷耦合劑的防鏽用表面處理劑(化成處理液)，其特徵係，藉由3價過渡金屬離子因乾燥而成為難溶性化合物以展現防鏽性能、塗膜密合性能，但所要求之耐蝕性並非能承受如本發明之嚴苛之耐蝕試驗者，仍有許多改善的空間。 JP-A-2007-297648 (Patent Document 6) discloses a rust-preventing surface containing a compound containing a water-based latex and a trivalent transition metal ion and a β-diketone 2 molecule and a water molecule, and a decane coupling agent. a treatment agent (chemical conversion treatment liquid) characterized in that a trivalent transition metal ion becomes a poorly soluble compound by drying to exhibit rust prevention performance and coating film adhesion property, but the required corrosion resistance is not capable of withstanding the present invention. There are still many room for improvement in the harsh corrosion testers.

由於以上所述，期盼開發一種於薄膜能以更高次元實現塗裝後之加工性、密合性、耐蝕性等各種性能的金屬表面處理劑。 In view of the above, it is desired to develop a metal surface treatment agent which can achieve various properties such as processability, adhesion, and corrosion resistance after coating in a higher order.

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. Hei 8-073775

專利文獻3：日本特開2001-316845號公報 Patent Document 3: Japanese Laid-Open Patent Publication 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. Hei 10-60315

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

專利文獻6：日本特開2007-297648號公報 Patent Document 6: Japanese Laid-Open Patent Publication No. 2007-297648

本發明係有鑑於上述情事所完成者，其目的在於提供一種無鉻酸鹽金屬表面處理劑、以該處理劑進行表面處理之表面處理鋼材及其表面處理方法、以及於其上具有上層 被膜之塗裝鋼材及其製造方法；該金屬表面處理劑，最適於作為金屬、特別是金屬被膜鋼材用，不含有鉻，作為塗料等之塗敷的前處理，可賦予優異之加工性、密合性、耐蝕性。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a chromate-free metal surface treatment agent, a surface-treated steel material surface-treated with the treatment agent, a surface treatment method thereof, and an upper layer thereon A coated steel material and a method for producing the same; the metal surface treatment agent is most suitable for use as a metal, particularly a metal coated steel material, does not contain chromium, and is excellent in workability and density as a pretreatment for coating a coating material or the like. Synergy and corrosion resistance.

本發明為了達成上述目的，而提供下述之金屬表面處理劑、表面處理鋼材及其之表面處理方法、以及塗裝鋼材及其製造方法。 In order to achieve the above object, the present invention provides a metal surface treatment agent, a surface-treated steel material, a surface treatment method thereof, a coated steel material, and a method for producing the same.

[1]一種金屬表面處理劑，其特徵係含有：(A)以下述通式(1) (式中，R為水解性基，R’為碳數1~4之烷基，A為直鏈狀或分支鏈狀之碳數1~8之伸烷基，X為氧原子、硫原子、NR3基之任一者，R1、R2、R3分別獨立為氫原子、碳數1~20之烷基、碳數1~20之氟烷基、碳數6~10之芳基、碳數2~10之烯基、或下述通式(2)所示之取代基，m為1~3之整數。) [1] A metal surface treatment agent characterized by comprising: (A) the following general formula (1) (wherein R is a hydrolyzable group, R' is an alkyl group having 1 to 4 carbon atoms, A is a linear or branched chain alkyl group having 1 to 8 carbon atoms, and X is an oxygen atom or a sulfur atom; In any one of the NR 3 groups, R 1 , R 2 and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 10 carbon atoms. The alkenyl group having 2 to 10 carbon atoms or the substituent represented by the following formula (2), m is an integer of 1 to 3.)

(式中，R為水解性基，R’為碳數1~4之烷基，B為直鏈狀或分支鏈狀之碳數1~8之伸烷基，m為1~3之整數。) 所表示之有機矽化合物；(B)水及/或有機溶劑。 (wherein R is a hydrolyzable group, R' is an alkyl group having 1 to 4 carbon atoms, B is a linear or branched chain alkyl group having 1 to 8 carbon atoms, and m is an integer of 1 to 3. ) an organic hydrazine compound represented; (B) water and/or an organic solvent.

[2] 如[1]所記載之金屬表面處理劑，其中，上述有機矽化合物，係下述通式(3)。 [2] The metal surface treatment agent according to [1], wherein the organic hydrazine compound is represented by the following formula (3).

(式中，R為水解性基，R’為碳數1~4之烷基，A為直鏈狀或分支鏈狀之碳數1~8之伸烷基，R1~R3分別獨立為氫原子、碳數1~20之烷基、碳數1~20之氟烷基、碳數6~10之芳基、碳數2~10之烯基、或下述通式(4)所示之取代基，m為1~3之整數。) (wherein R is a hydrolyzable group, R' is an alkyl group having 1 to 4 carbon atoms, and A is a linear or branched chain alkyl group having 1 to 8 carbon atoms, and R 1 to R 3 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a formula represented by the following formula (4) The substituent, m is an integer from 1 to 3.)

(式中，R為水解性基，R’為碳數1~4之烷基，B為直鏈狀或分支鏈狀之碳數1~8之伸烷基，m為1~3之整數。) (wherein R is a hydrolyzable group, R' is an alkyl group having 1 to 4 carbon atoms, B is a linear or branched chain alkyl group having 1 to 8 carbon atoms, and m is an integer of 1 to 3. )

[3] 如[2]所記載之金屬表面處理劑，其中，上述有機矽化合物，係下述通式(5)。 [3] The metal surface treatment agent according to [2], wherein the organic hydrazine compound is represented by the following formula (5).

(式中，R為水解性基，R’為碳數1~4之烷基，R1為氫原子、碳數1~20之烷基、碳數1~20之氟烷基、碳數6~10之芳基、碳數2~10之烯基、或下述通式(6)所示之取代 基，m為1~3之整數。) (wherein R is a hydrolyzable group, R' is an alkyl group having 1 to 4 carbon atoms, R 1 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, and a carbon number of 6 An aryl group of ~10, an alkenyl group having 2 to 10 carbon atoms, or a substituent represented by the following formula (6), and m is an integer of 1 to 3.)

(式中，R為水解性基，R’為碳數1~4之烷基，m為1~3之整數。) (wherein R is a hydrolyzable group, R' is an alkyl group having 1 to 4 carbon atoms, and m is an integer of 1 to 3.)

[4] 如[1]至[3]中任一項所記載之金屬表面處理劑，其進一步含有下述通式(7)R4 xSi(OR5)4-x (7)(式中，R4為碳數1~20之非取代或取代之一價烴基，R5為碳數1~8之非取代或取代之一價烴基，x為0~3之整數。) [4] The metal surface treatment agent according to any one of [1] to [3] further comprising the following formula (7) R 4 x Si(OR 5 ) 4-x (7) (wherein R 4 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 5 is an unsubstituted or substituted one-valent hydrocarbon group having 1 to 8 carbon atoms, and x is an integer of 0 to 3.

所表示之烷氧矽烷或其之部分水解縮合物。 The alkoxysilane or a partially hydrolyzed condensate thereof.

[5] 如[1]至[4]中任一項所記載之金屬表面處理劑，其進一步含有有機酞酸酯。 [5] The metal surface treatment agent according to any one of [1] to [4] further comprising an organic phthalic acid ester.

[6] 如[1]至[5]中任一項所記載之金屬表面處理劑，其進一步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] further comprising water-dispersible cerium oxide or organic solvent-dispersible cerium oxide.

[7] 如[1]至[6]中任一項所記載之金屬表面處理劑，其進一步含有選自Fe、Zr、Ti、V、W、Mo、Al、Sn、Nb、Hf、Y、Ho、Bi、La、Ce及Zn之群中之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] further comprising a member selected from the group consisting of Fe, Zr, Ti, V, W, Mo, Al, Sn, Nb, Hf, Y, A compound of one or more metals selected from the group consisting of Ho, Bi, La, Ce, and Zn.

[8] 如[1]至[7]中任一項所記載之金屬表面處理劑，其進一步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 further contains a sulfur-containing carbonyl group-containing compound.

[9] 如[1]至[8]中任一項所記載之金屬表面處理劑，其進一步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] further comprising a water-soluble resin or a water-dispersible resin.

[10]如[1]至[9]中任一項所記載之金屬表面處理劑，其進一步含有磷酸離子。 [10] The metal surface treatment agent according to any one of [1] to [9] further comprising a phosphate ion.

[11]一種鋼材之表面處理方法，其特徵係將鋼材之表面以[1]至[10]中任一項所記載之金屬表面處理劑進行表面處理。 [11] A surface treatment method for a steel material, characterized in that the surface of the steel material is surface-treated with the metal surface treatment agent according to any one of [1] to [10].

[12]如[11]所記載之表面處理方法，其中，鋼材係金屬被覆鋼材。 [12] The surface treatment method according to [11], wherein the steel material is a metal coated steel material.

[13]一種表面處理鋼材，其係以[11]或[12]所記載之表面處理方法所得。 [13] A surface-treated steel material obtained by the surface treatment method described in [11] or [12].

[14]一種塗裝鋼材之製造方法，其特徵係，以[1]至[10]中任一項所記載之金屬表面處理劑處理鋼材之後，再設置上層被膜層。 [14] A method of producing a coated steel material, which is characterized in that after the steel material is treated with the metal surface treatment agent according to any one of [1] to [10], an upper coating layer is further provided.

[15]一種塗裝鋼材，其係以[14]所記載之塗裝鋼材之製造方法所得。 [15] A coated steel material obtained by the method for producing a coated steel material according to [14].

本發明之金屬表面處理劑，當以具有硫醯胺之矽烷耦合劑作為必須成分，而含有被處理鋼材、及其他金屬(離子)成分時，藉由其與該矽烷耦合劑之硫醯胺基配位鍵結而形成難溶性之錯合物，而展現良好的防鏽性能，藉由水解性矽烷基，與鋼材及視需要設置於上層之有機、無機樹脂被膜層之加工密合性優異，因此接著強度增高，其結果，能以高次元展現所得塗裝鋼材之防鏽耐蝕性。 When the metal surface treatment agent of the present invention contains a decane coupling agent having thioguanamine as an essential component and contains a steel material to be treated and other metal (ion) components, the thiol amine group with the decane coupling agent Coordination bond to form a poorly soluble complex, and exhibits good rust-preventing properties, and is excellent in processing adhesion to a steel and, if necessary, an organic or inorganic resin coating layer provided on the upper layer by a hydrolyzable alkylene group. Therefore, the strength is increased, and as a result, the rust and corrosion resistance of the obtained coated steel material can be exhibited in a high dimension.

以下，具體說明本發明。 Hereinafter, the present invention will be specifically described.

本發明之金屬表面處理劑，係以具有硫醯胺基之有機矽化合物(矽烷耦合劑)作為必須成分，將其溶解於水、有機溶劑、或水與有機溶劑之混合溶劑所成者。 The metal surface treatment agent of the present invention is obtained by dissolving an organic ruthenium compound having a sulfonamide group (an olefin coupling agent) as an essential component in water, an organic solvent, or a mixed solvent of water and an organic solvent.

[有機矽化合物] [Organic bismuth compound]

本發明所使用之有機矽化合物係以下述通式(1)所表示。 The organic hydrazine compound used in the present invention is represented by the following formula (1).

(式中，R為水解性基，R’為碳數1~4之烷基，A為直鏈狀或分支鏈狀之碳數1~8之伸烷基，X為氧原子、硫原子、NR3基之任一者，R1、R2、R3分別獨立為氫原子、碳數1~20，較佳為1~8之烷基、碳數1~20，較佳為1~8之氟烷基、碳數6~10之芳基、碳數2~10之烯基、或下述通式(2)所示之取代基，m為1~3之整數)。 (wherein R is a hydrolyzable group, R' is an alkyl group having 1 to 4 carbon atoms, A is a linear or branched chain alkyl group having 1 to 8 carbon atoms, and X is an oxygen atom or a sulfur atom; In any one of the NR 3 groups, R 1 , R 2 and R 3 are each independently a hydrogen atom, a carbon number of 1 to 20, preferably an alkyl group of 1 to 8, a carbon number of 1 to 20, preferably 1 to 8. The fluoroalkyl group, the aryl group having 6 to 10 carbon atoms, the alkenyl group having 2 to 10 carbon atoms, or the substituent represented by the following formula (2), m is an integer of 1 to 3).

(式中，R為水解性基，R’為碳數1~4之烷基，B為直鏈狀或分支鏈狀之碳數1~8之伸烷基，m為1~3之整數)。 (wherein R is a hydrolyzable group, R' is an alkyl group having 1 to 4 carbon atoms, and B is a linear or branched chain alkyl group having 1 to 8 carbon atoms, and m is an integer of 1 to 3) .

較佳為，以下述通式(3)所表示。 Preferably, it is represented by the following general formula (3).

(式中，R為水解性基，R’為碳數1~4之烷基，A為直鏈狀或分支鏈狀之碳數1~8之伸烷基，R1~R3分別獨立為氫原子、碳數1~20，較佳為1~8之烷基、碳數1~20，較佳為1~8之氟烷基、碳數6~10之芳基、碳數2~10之烯基、或下述通式(4)所示之取代基，m為1~3之整數)。 (wherein R is a hydrolyzable group, R' is an alkyl group having 1 to 4 carbon atoms, and A is a linear or branched chain alkyl group having 1 to 8 carbon atoms, and R 1 to R 3 are each independently Hydrogen atom, carbon number 1 to 20, preferably 1 to 8 alkyl group, carbon number 1 to 20, preferably 1 to 8 fluoroalkyl group, carbon number 6 to 10 aryl group, carbon number 2 to 10 The alkenyl group or a substituent represented by the following formula (4), m is an integer of 1 to 3).

(式中，R為水解性基，R’為碳數1~4之烷基，B為直鏈狀或分支鏈狀之碳數1~8之伸烷基，m為1~3之整數)。 (wherein R is a hydrolyzable group, R' is an alkyl group having 1 to 4 carbon atoms, and B is a linear or branched chain alkyl group having 1 to 8 carbon atoms, and m is an integer of 1 to 3) .

更佳為，以下述通式(5)所表示。 More preferably, it is represented by the following general formula (5).

(式中，R為水解性基，R’為碳數1~4之烷基，R1為氫原子、碳數1~20之烷基、碳數1~20之氟烷基、碳數6~10之芳基、碳數2~10之烯基、或下述通式(6)所示之取代基，m為1~3之整數)。 (wherein R is a hydrolyzable group, R' is an alkyl group having 1 to 4 carbon atoms, R 1 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, and a carbon number of 6 An aryl group of ~10, an alkenyl group having 2 to 10 carbon atoms, or a substituent represented by the following formula (6), m is an integer of 1 to 3).

(式中，R為水解性基，R’為碳數1~4之烷基，m為1~3之整數)。 (wherein R is a hydrolyzable group, R' is an alkyl group having 1 to 4 carbon atoms, and m is an integer of 1 to 3).

此處，上述式中之R之水解性基，可舉例如氯、溴等鹵素原子、甲氧基、乙氧基等碳數1~4之烷氧基，以烷氧基為佳、甲氧基更佳。R’可舉例如甲基、乙基、丙基等烷基，而以甲基為佳。A為直鏈狀者，可舉例如伸甲基、伸乙基、伸丙基等，分支鏈狀者可舉例如甲基丙烯基、異丙烯基等，以碳數1~3之直鏈狀之伸烷基為佳、伸丙基為特佳。B為直鏈狀者，可舉例如伸甲基、伸乙基、伸丙基等，分支鏈狀者可舉例如甲基丙烯基、異丙烯基等，以碳數1~3之直鏈狀之伸烷基為佳、伸丙基為特佳。X可舉例如氧原子、硫原子、氮原子，其中以氮原子為佳。若X為氮原子，則成為硫脲型而與金屬的配位力增高，耐蝕性亦增高。R1、R2、R3可舉例如氫原子、甲基、乙基、丙基、異丙基、丁基、異丁基等烷基、該等之基之氫原子之一部分或全部以氟原子取代之氟烷基、苯基、甲苯基等之芳基、乙烯基、丁烯基、戊烯基等之烯基。m為1~3之整數，較佳為2或3、特佳為3。 Here, the hydrolyzable group of R in the above formula may, for example, be a halogen atom such as chlorine or bromine, an alkoxy group having 1 to 4 carbon atoms such as a methoxy group or an ethoxy group, and an alkoxy group as a preferred methoxy group. The base is better. R' may, for example, be an alkyl group such as a methyl group, an ethyl group or a propyl group, and a methyl group is preferred. A is a linear one, and examples thereof include a methyl group, an ethyl group, and a propyl group. Examples of the branched chain include a methacryl group, an isopropenyl group, and the like, and a linear chain of 1 to 3 carbon atoms. The alkyl group is preferred and the propyl group is particularly preferred. B is a linear one, and examples thereof include a methyl group, an ethyl group, and a propyl group. Examples of the branched chain include a methacryl group, an isopropenyl group, and the like, and a linear chain of 1 to 3 carbon atoms. The alkyl group is preferred and the propyl group is particularly preferred. X may, for example, be an oxygen atom, a sulfur atom or a nitrogen atom, and among them, a nitrogen atom is preferred. When X is a nitrogen atom, it becomes a thiourea type, and the coordinating force with a metal is increased, and corrosion resistance is also high. R 1 , R 2 and R 3 may, for example, be an alkyl group such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or an isobutyl group, or a part or all of the hydrogen atom of the group may be fluorine. An aryl group substituted with an atom, a aryl group such as a phenyl group or a tolyl group, or an alkenyl group such as a vinyl group, a butenyl group or a pentenyl group. m is an integer of 1 to 3, preferably 2 or 3, and particularly preferably 3.

有機矽化合物之具體結構，可舉例如下述者，但並不限於該等例示者。 The specific structure of the organic hydrazine compound may, for example, be as follows, but is not limited to the exemplified ones.

上述有機矽化合物，例如，為具有胺基及水解性基之 矽烷化合物與異硫氰酸烷基酯反應所得者，或者，於具有異硫氰酸酯基及水解性基之矽烷化合物於觸媒下使氨水、1級胺、或2級胺反應所得者。 The above organic hydrazine compound, for example, has an amine group and a hydrolyzable group The obtained decane compound is reacted with an alkyl isothiocyanate, or the decane compound having an isothiocyanate group and a hydrolyzable group is reacted with ammonia water, a primary amine or a secondary amine under a catalyst.

上述有機矽化合物(矽烷耦合劑)，可與金屬(離子)形成如下述式(15)或(16)之安定的配位鍵。 The above organic hydrazine compound (decane coupling agent) can form a stable coordination bond with a metal (ion) as shown in the following formula (15) or (16).

(式中，X表示氧原子、硫原子、或氮原子，M表示金屬(離子)。R1、R2係如上述。) (wherein X represents an oxygen atom, a sulfur atom or a nitrogen atom, and M represents a metal (ion). R 1 and R 2 are as described above.)

本發明之金屬表面處理劑之剩餘部分，可舉例如水、溶解上述有機矽化合物之有機溶劑、或水與該有機溶劑之混合溶劑，該有機溶劑，可舉例如甲醇、乙醇等醇系溶劑、甲醯胺、N,N-二甲基甲醯胺、吡咯酮、N-甲基吡咯酮等之醯胺系溶劑、丙酮、甲乙酮、甲基異丁基酮等酮系溶劑、戊烷、己烷、庚烷等飽和烴系溶劑、苯、甲苯、二甲苯等芳香族烴系溶劑等，該等之中，以甲醇或乙醇為特佳，但不限於此處所列舉之例。 The remainder of the metal surface treatment agent of the present invention may, for example, be water, an organic solvent in which the organic hydrazine compound is dissolved, or a mixed solvent of water and the organic solvent, and the organic solvent may, for example, be an alcohol solvent such as methanol or ethanol. a guanamine solvent such as guanamine, N,N-dimethylformamide, pyrrolidone or N-methylpyrrolidone, a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone, pentane or hexane A saturated hydrocarbon solvent such as heptane, an aromatic hydrocarbon solvent such as benzene, toluene or xylene, etc., among which methanol or ethanol is particularly preferred, but is not limited to the examples listed herein.

又，上述式(1)~(6)之有機矽化合物，於本發明之金屬表面處理劑中，以0.01~200g/L、特別是0.05~100g/L之濃度含有為佳，含量若過少則本發明之效果不 充分，若過多則塗料之液安定性會降低。 Further, the organic ruthenium compound of the above formulae (1) to (6) is preferably contained in the metal surface treatment agent of the present invention at a concentration of 0.01 to 200 g/L, particularly 0.05 to 100 g/L, and if the content is too small, The effect of the invention is not Sufficient, if too much, the liquid stability of the coating will decrease.

本發明之金屬表面處理劑，較佳為，進一步含有上述式(1)~(6)所示之有機矽化合物以外的有機矽化合物。有機矽化合物，只要為上述式(1)~(6)所示之有機矽化合物以外之具有水解性矽烷基的化合物即可，並無特別限定，而較佳為下述通式(7)所表示之具有水解性矽烷基之有機矽化合物或其之部分水解縮合物。 The metal surface treatment agent of the present invention preferably further contains an organic ruthenium compound other than the organic ruthenium compound represented by the above formulas (1) to (6). The organic hydrazine compound is not particularly limited as long as it is a compound having a hydrolyzable decyl group other than the organic hydrazine compound represented by the above formulas (1) to (6), and is preferably a compound of the following formula (7). An organic hydrazine compound having a hydrolyzable decyl group or a partially hydrolyzed condensate thereof.

R4 xSi(OR5)4-x (7)(式中，R4為碳數1~20、特別是1~15之非取代(較佳為甲基、乙基、丙基、乙烯基、苯基)或取代(較佳為含有環氧基、(甲基)丙烯醯氧基、巰基、胺基、胺基醇基胺基、烷基胺基、異氰酸酯基、聚醚基、鹵素取代烷基、全氟烷基、全氟具醚基者)之一價烴基，R5為碳數1~8、特別是1~6之非取代或取代之一價烴基，較佳為甲基、乙基。x為0~3之整數，特別以0~2為佳。) R 4 x Si(OR 5 ) 4-x (7) (wherein R 4 is an unsubstituted carbon number of 1 to 20, particularly 1 to 15 (preferably methyl, ethyl, propyl, vinyl) , phenyl) or substituted (preferably containing an epoxy group, (meth) propylene fluorenyloxy group, fluorenyl group, amine group, amino alcohol group amine group, alkyl amine group, isocyanate group, polyether group, halogen substitution a monovalent hydrocarbon group of an alkyl group, a perfluoroalkyl group or a perfluoroether group; and R 5 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 6, preferably a methyl group. Ethyl.x is an integer from 0 to 3, especially 0 to 2. ()

具體而言，可舉例如四甲氧矽烷、四乙氧矽烷、甲基三甲氧矽烷、甲基三乙氧矽烷、二甲基二甲氧矽烷、二甲基二乙氧矽烷、三甲基甲氧矽烷、三甲基乙氧矽烷、苯基三甲氧矽烷、苯基三乙氧矽烷、苯基甲基二甲氧矽烷、苯基甲基二乙氧矽烷、苯基二甲基甲氧矽烷、苯基二甲基乙氧矽烷、二苯基二甲氧矽烷、二苯基二乙氧矽烷、乙烯基三甲氧矽烷、乙烯基三乙氧矽烷、乙烯基甲基二甲氧矽烷、乙烯基甲基二乙氧矽烷、γ-環氧丙氧基丙基三甲氧矽烷、γ-環氧丙氧基丙基三乙氧矽烷、γ-環氧丙氧基丙 基甲基二甲氧矽烷、γ-環氧丙氧基丙基甲基二乙氧矽烷、γ-(甲基)丙烯醯氧基丙基三甲氧矽烷、γ-(甲基)丙烯醯氧基丙基三乙氧矽烷、γ-(甲基)丙烯醯氧基丙基甲基二甲氧矽烷、γ-(甲基)丙烯醯氧基丙基甲基二乙氧矽烷、3-巰基丙基三甲氧矽烷、3-巰基丙基三乙氧矽烷、3-巰基丙基甲基二甲氧矽烷、3-巰基丙基甲基二乙氧矽烷、3-胺基丙基三甲氧矽烷、3-胺基丙基三乙氧矽烷、3-胺基丙基甲基二甲氧矽烷、3-胺基丙基甲基二乙氧矽烷、N-胺基乙基-γ-胺基丙基三甲氧矽烷、N-胺基乙基-γ-胺基丙基三乙氧矽烷、N-胺基乙基-γ-胺基丙基甲基二甲氧矽烷、N-胺基乙基-γ-胺基丙基甲基二乙氧矽烷、γ-異氰酸酯基丙基三甲氧矽烷、γ-異氰酸酯基丙基三乙氧矽烷、γ-異氰酸酯基丙基甲基二甲氧矽烷、γ-異氰酸酯基丙基甲基二乙氧矽烷、3-氯丙基三甲氧矽烷、3-氯丙基三乙氧矽烷、3-氯丙基甲基二甲氧矽烷、3-氯丙基甲基二乙氧矽烷、2-(3,4-乙氧基環己基)乙基三甲氧矽烷、2-(3,4-乙氧基環己基)乙基三乙氧矽烷、2-(3,4-乙氧基環己基)乙基甲基二甲氧矽烷、2-(3,4-乙氧基環己基)乙基甲基二乙氧矽烷等。 Specific examples thereof include tetramethoxy decane, tetraethoxy decane, methyltrimethoxy decane, methyl triethoxy decane, dimethyl dimethoxy decane, dimethyl diethoxy decane, and trimethyl methacrylate. Oxane, trimethylethoxyoxane, phenyltrimethoxydecane, phenyltriethoxydecane, phenylmethyldimethoxydecane, phenylmethyldiethoxydecane, phenyldimethylmethoxypropane, Phenyl dimethyl ethoxy decane, diphenyl dimethoxy decane, diphenyl diethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, vinyl methyl dimethoxy decane, vinyl Diethoxy oxane, γ-glycidoxypropyltrimethoxy decane, γ-glycidoxypropyl triethoxy decane, γ-glycidoxypropyl Methyl dimethoxy decane, γ-glycidoxypropyl methyl diethoxy decane, γ-(methyl) propylene methoxy propyl trimethoxy decane, γ-(methyl) propylene decyloxy Propyltriethoxy decane, γ-(meth)acryloxypropylmethyldimethoxydecane, γ-(meth)acryloxypropylmethyldiethoxy decane, 3-mercaptopropyl Trimethoxy decane, 3-mercaptopropyltriethoxy decane, 3-mercaptopropylmethyldimethoxy decane, 3-mercaptopropylmethyldiethoxy decane, 3-aminopropyltrimethoxy decane, 3- Aminopropyltriethoxyoxane, 3-aminopropylmethyldimethoxydecane, 3-aminopropylmethyldiethoxyoxane, N-Aminoethyl-gamma-aminopropyltrimethoxy Decane, N-aminoethyl-γ-aminopropyltriethoxyoxane, N-aminoethyl-γ-aminopropylmethyldimethoxydecane, N-aminoethyl-γ-amine Propyl methyl diethoxy decane, γ-isocyanate propyl trimethoxy decane, γ-isocyanate propyl triethoxy decane, γ-isocyanate propyl methyl dimethoxy decane, γ-isocyanate propyl Methyl diethoxy decane, 3-chloropropyl trimethoxy decane, 3-chloropropyl triethoxy Decane, 3-chloropropylmethyldimethoxydecane, 3-chloropropylmethyldiethoxydecane, 2-(3,4-ethoxycyclohexyl)ethyltrimethoxydecane, 2-(3, 4-ethoxycyclohexyl)ethyltriethoxydecane, 2-(3,4-ethoxycyclohexyl)ethylmethyldimethoxydecane, 2-(3,4-ethoxycyclohexyl) Ethyl methyl diethoxy decane, and the like.

當配合上述之有機矽化合物時，較佳為，於金屬表面處理劑中以0.05~100g/L之濃度含有，特佳為以0.5~60g/L之濃度含有。當含量未滿0.05g/L時耐蝕性會有不足的情形，若超過100g/L則耐蝕性飽和、生產性會降低。 When the above organic ruthenium compound is blended, it is preferably contained in a concentration of 0.05 to 100 g/L in the metal surface treatment agent, and particularly preferably in a concentration of 0.5 to 60 g/L. When the content is less than 0.05 g/L, the corrosion resistance may be insufficient. When the content exceeds 100 g/L, the corrosion resistance is saturated and the productivity is lowered.

本發明之金屬表面處理劑，較佳為，進一步含有有機 鈦酸酯類。該有機鈦酸酯類，可使用市售者，構造等並無特別限定，有機鈦酸酯類之具體例，可舉例如鈦酸四乙酯、酞酸四異丙酯、鈦酸四正丁酯、鈦酸丁酯二聚物、鈦酸四(2-乙基己基)酯、及該等之聚合物，可使用鈦酸鈦乙醯酯、聚乙酸鈦乙醯酯、甘胺酸鈦鋅酯、乳酸鈦、乳酸鈦乙酯、三乙醇胺鈦等之鈦螯合物，該等可單獨使用1種、或併用2種以上。 The metal surface treatment agent of the present invention preferably further comprises an organic Titanate. The organic titanate can be used, and the structure and the like are not particularly limited. Specific examples of the organic titanate include tetraethyl titanate, tetraisopropyl citrate, and tetra-n-butyl titanate. An ester, a butyl titanate dimer, a tetrakis(2-ethylhexyl) titanate, and the like, and a titanate titanate, a titanyl acetate, a titanium zinc glycinate, or a zinc silicate can be used. A titanium chelate compound such as an ester, a titanium lactate, a titanium lactate or a titanium triethanolamine may be used alone or in combination of two or more.

當配合上述有機鈦酸酯類時，較佳為，於金屬表面處理劑中以0.05~100g/L的濃度含有、特佳為以0.5~60g/L的濃度含有。當含量未滿0.05g/L時耐蝕性會有不足的情形，若超過100g/L則耐蝕性飽和、相反地會使金屬表面處理劑之浴安定性降低。 When the organic titanate is blended, it is preferably contained in a metal surface treatment agent at a concentration of 0.05 to 100 g/L, particularly preferably at a concentration of 0.5 to 60 g/L. When the content is less than 0.05 g/L, the corrosion resistance may be insufficient. When the content exceeds 100 g/L, the corrosion resistance is saturated, and conversely, the bath stability of the metal surface treatment agent is lowered.

本發明之金屬表面處理劑，較佳為進一步含有水分散性或有機溶劑分散性氧化矽。該水分散性或有機溶劑分散性氧化矽，並無特別限定，較佳為，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。球狀氧化矽，可舉例如「SnowTexN」、「SnowTexUP」(皆為日產化學工業股份有限公司製)等膠質氧化矽、「Aerosil」(日本Aerosil股份有限公司製)等發煙氧化矽，鏈狀氧化矽，可舉例如「SnowTexPS」(日產化學工業股份有限公司製)等矽膠，而鋁修飾氧化矽，可舉例如「AdeliteAT-20A」(股份有限公司ADEKA製)等之市售之矽膠。 The metal surface treatment agent of the present invention preferably further contains water-dispersible or organic solvent-dispersible cerium oxide. The water-dispersible or organic solvent-dispersible cerium oxide is not particularly limited, and is preferably a spherical cerium oxide, a chain cerium oxide or an aluminum-modified cerium oxide having a small amount of impurities such as sodium. For the spherical cerium oxide, for example, "SnowTexN" or "SnowTexUP" (all manufactured by Nissan Chemical Industries Co., Ltd.), such as cerium oxide, "Aerosil" (made by Nippon Aerosil Co., Ltd.), etc., chain-like The cerium oxide may, for example, be a silicone rubber such as "SnowTexPS" (manufactured by Nissan Chemical Industry Co., Ltd.), and the aluminum-modified cerium oxide may, for example, be a commercially available silicone rubber such as "Adelite AT-20A" (manufactured by ADEKA Co., Ltd.).

又，有機溶劑，可例示如甲醇、乙醇、異丙醇等醇、 丙二醇單甲醚、四氫呋喃等醚化合物。 Further, the organic solvent may, for example, be an alcohol such as methanol, ethanol or isopropanol. An ether compound such as propylene glycol monomethyl ether or tetrahydrofuran.

當配合上述水分散性或有機溶劑分散性氧化矽時，較佳為，於金屬表面處理劑中以固體成分計以0.05~100g/L、特別是0.5~60g/L的濃度含有。當水或有機溶劑分散性之氧化矽的含量未滿0.05g/L時，耐蝕性會有不足的情形，若超過100g/L則未見耐蝕性提升效果、相反地會使金屬表面處理劑之浴安定性降低。 When the water-dispersible or organic solvent-dispersible cerium oxide is blended, it is preferably contained in a metal surface treatment agent at a concentration of 0.05 to 100 g/L, particularly 0.5 to 60 g/L, based on the solid content. When the content of cerium oxide dispersed in water or an organic solvent is less than 0.05 g/L, the corrosion resistance may be insufficient. If it exceeds 100 g/L, the corrosion-improving effect is not observed, and conversely, the metal surface treatment agent is Bath stability is reduced.

本發明之金屬表面處理劑，較佳為，進一步含有選自Fe、Zr、Ti、V、W、Mo、Al、Sn、Nb、Hf、Y、Ho、Bi、La、Ce及Zn之群中之任1種以上之金屬的化合物。具體而言，可舉例如，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、氟酸或其之鹽、含氧酸鹽、有機酸鹽等。更具體而言，鋯(Zr)化合物之例，可舉例如碳酸鋯銨、氟鋯酸、氟鋯酸銨、氟鋯酸鉀、氟鋯酸鈉、乙醯丙酮鋯、丁氧基鋯1-丁醇溶液、正丙氧基鋯等。又，鈦(Ti)化合物之例，可舉例如氟鈦酸、氟鈦酸銨、草酸鈦鉀、異丙氧基鈦、鈦酸異丙酯、乙氧基鈦、鈦-2-乙基-1-己酸鹽、鈦酸四異丙酯、鈦酸四-正丁酯、氟鈦酸鉀、氟鈦酸鈉等。又，釩(V)化合物之例，可舉例如五氧化釩(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)、氧三氯化釩VOCl3、三氯化釩VCl3、六氟釩酸(III)或其之鹽(鉀 鹽、銨鹽等)、偏釩酸(V)或其之鹽(鈉鹽、銨鹽等)、乙醯丙酮釩(IV)VO(OC(=CH2)CH2COCH3)2、乙醯丙酮釩(III)V(OC(=CH2)CH2COCH3)3、磷釩鉬酸H15-X[PV12-XMoO40]‧nH20(6<X<12，n<30)等。又，鎢(W)化合物之例，可舉例如氧化鎢(IV)、氧化鎢(V)、氧化鎢(VI)、氟化鎢(IV)、氟化鎢(VI)、鎢酸(VI)H2WO4或其之鹽(銨鹽、鈉鹽等)、偏鎢酸(VI)H6[H2W12O40]或其之鹽(銨鹽、鈉鹽等)、仲鎢酸(VI)H10[H10W12O46]或其之鹽(銨鹽、鈉鹽等)等。又，鉬(Mo)化合物之例，可舉例如磷釩鉬酸H15-X[PV12-XMoO40]‧nH20(6<X<12，n<30)、氧化鉬、鉬酸H2MoO40、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、鉬磷酸鈉Na3[PO4Mo12O36]‧nH2O等)等。又，鋁(Al)化合物之例，可舉例如硝酸鋁、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。又，錫(Sn)化合物之例，可舉例如氧化錫(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)3SnF6等。又，鈮(Nb)化合物之例，可舉例如五氧化鈮(Nb2O5)、鈮酸鈉(NaNbO3)、氟化鈮(NbF5)、六氟鈮酸銨(NH4)NbF6等。又，鉿(Hf)化合物、釔(Y)化合物、鈦(Ho)化合物、鉍(Bi)化合物、鑭(La)化合物之例，可舉例如氧化鉿、六氟鉿氫酸、氧化釔、乙醯丙酮釔、氧化鈥、氧 化鉍、氧化鑭等。又，鈰(Ce)化合物之例，可舉例如氧化鈰、乙酸鈰Ce(CH3CO2)3、硝酸鈰(III)或(IV)、硝酸鈰銨、硫酸鈰、氯化鈰等。又，鋅(Zn)化合物之例，可舉例如氧化鋅、氫氧化鋅、乙酸鋅、硝酸鋅、硫酸鋅、氯化鋅、鋅酸鈉等。上述化合物，可單獨使用1種、或併用2種以上。 The metal surface treatment agent of the present invention preferably further contains a group selected from the group consisting of Fe, Zr, Ti, V, W, Mo, Al, Sn, Nb, Hf, Y, Ho, Bi, La, Ce, and Zn. A compound of one or more kinds of metals. Specific examples thereof include a metal carbonate, an oxide, a hydroxide, a nitrate, a sulfate, a phosphate, a fluoride, a hydrofluoric acid or a salt thereof, an oxyacid salt, an organic acid salt, and the like. More specifically, examples of the zirconium (Zr) compound include, for example, ammonium zirconium carbonate, fluorozirconic acid, ammonium fluorozirconate, potassium fluorozirconate, sodium fluorozirconate, zirconium acetonate, zirconium butoxide 1- Butanol solution, n-propoxy zirconium, and the like. Further, examples of the titanium (Ti) compound include, for example, fluorotitanic acid, ammonium fluorotitanate, potassium oxalate, titanium isopropoxide, isopropyl titanate, titanium ethoxide, titanium-2-ethyl- 1-hexanoic acid salt, tetraisopropyl titanate, tetra-n-butyl titanate, potassium fluorotitanate, sodium fluorotitanate, and the like. Further, examples of the vanadium (V) compound include vanadium pentoxide (V), vanadium (III) oxide, vanadium (IV) oxide, vanadium (II) hydroxide, vanadium (III) hydroxide, and vanadium sulfate. (II), vanadium sulfate (III), vanadyl sulfate (IV), vanadium fluoride (III), vanadium fluoride (IV), vanadium fluoride (V), vanadium trichloride oxide VOCl 3, vanadium trichloride VCl 3 , hexafluorovanadic acid (III) or a salt thereof (potassium salt, ammonium salt, etc.), metavanadic acid (V) or a salt thereof (sodium salt, ammonium salt, etc.), acetonitrile acetone vanadium (IV) VO (OC(=CH 2 )CH 2 COCH 3 ) 2 , Ethyl acetonide vanadium (III) V (OC(=CH 2 )CH 2 COCH 3 ) 3 , Phosphovanadomolybdic acid H 15-X [PV 12-X MoO 40 ]‧nH 20 (6<X<12, n<30), etc. Further, examples of the tungsten (W) compound include tungsten (IV) oxide, tungsten (V) oxide, tungsten (VI) oxide, tungsten (IV) fluoride, tungsten (VI) fluoride, and tungstic acid (VI). H 2 WO 4 or a salt thereof (ammonium salt, sodium salt, etc.), metatungstic acid (VI) H 6 [H 2 W 12 O 40 ] or a salt thereof (ammonium salt, sodium salt, etc.), paratungstic acid ( VI) H 10 [H 10 W 12 O 46 ] or a salt thereof (ammonium salt, sodium salt, etc.) or the like. Further, examples of the molybdenum (Mo) compound include, for example, phosphorus vanadium molybdate H 15-X [PV 12-X MoO 40 ]‧nH 20 (6<X<12, n<30), molybdenum oxide, molybdic acid H 2 MoO 40 , ammonium molybdate, ammonium paramolybdate, sodium molybdate, molybdenum phosphate compounds (for example, ammonium molybdate (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. Further, examples of the aluminum (Al) compound include aluminum nitrate, aluminum sulfate, potassium aluminum sulfate, aluminum sulfate aluminum, aluminum ammonium sulfate, aluminum phosphate, aluminum carbonate, aluminum oxide, and aluminum hydroxide. Further, examples of the tin (Sn) compound include tin (IV) oxide, sodium stannate Na 2 SnO 3 , tin (II) chloride, tin (IV) chloride, tin (II) nitrate, and tin nitrate ( IV), ammonium hexafluorostannate (NH 4 ) 3 SnF 6 and the like. Further, examples of the ruthenium (Nb) compound include ruthenium pentoxide (Nb 2 O 5 ), sodium citrate (NaNbO 3 ), cesium fluoride (NbF 5 ), and ammonium hexafluoroantimonate (NH 4 ) NbF 6 . Wait. Further, examples of the ruthenium (Hf) compound, the ruthenium (Y) compound, the titanium (Ho) compound, the bismuth (Bi) compound, and the lanthanum (La) compound include ruthenium oxide, hexafluorohydrogen acid, ruthenium oxide, and B.醯 acetone oxime, cerium oxide, cerium oxide, cerium oxide, and the like. Further, examples of the cerium (Ce) compound include cerium oxide, cerium acetate Ce(CH 3 CO 2 ) 3 , cerium (III) nitrate or (IV), cerium ammonium nitrate, cerium sulfate, cerium chloride, and the like. Further, examples of the zinc (Zn) compound include zinc oxide, zinc hydroxide, zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, and sodium zincate. These compounds may be used alone or in combination of two or more.

當配合上述化合物時，於金屬表面處理劑中，金屬離子之量，較佳為分別以0.01~50g/L、特別是0.05~5g/L的濃度含有。若上述化合物之含量分別未滿0.01g/L，則耐蝕性會有不足的情形，若超過50g/L則未見加工密合性的提升效果、相反地會使浴安定性降低。 When the above compound is blended, the amount of the metal ion in the metal surface treatment agent is preferably contained in a concentration of 0.01 to 50 g/L, particularly 0.05 to 5 g/L. When the content of the above compound is less than 0.01 g/L, the corrosion resistance may be insufficient. When the content exceeds 50 g/L, the effect of improving the process adhesion is not observed, and conversely, the bath stability is lowered.

本發明之金屬表面處理劑，以進一步含有含硫羰基之化合物為佳。含硫羰基之化合物，可例示如硫脲、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、2,2-三甲苯基硫脲、硫乙醯胺、二甲基二硫代胺基甲酸鈉、二硫化四甲基秋藍姆、二硫化四丁基秋藍姆、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、乙烯硫脲、二硫化二甲基黃原酸酯、二硫草醯胺、聚二硫代胺基甲酸或其之鹽等之至少含有1個硫羰基之化合物。上述化合物，可單獨使用1種、或併用2種以上。 The metal surface treatment agent of the present invention preferably further contains a sulfur-containing carbonyl group-containing compound. The thiocarbonyl-containing compound may, for example, be thiourea, dimethylthiourea, 1,3-dimethylthiourea, dipropylthiourea, dibutylthiourea, 1,3-diphenyl-2- Thiourea, 2,2-trimethylthiourea, thioacetamide, sodium dimethyldithiocarbamate, tetramethyl thiuram disulfide, tetrabutyl thiuram disulfide, N-ethyl -N-phenyldithiocarbamic acid zinc, zinc dimethyldithiocarbamate, pentamidine pentamethyldithiocarbamate, zinc diethyldithiocarbamate, two Sodium ethyldithiocarbamate, zinc isopropyl xanthate, ethylene thiourea, dimethylxanthogen disulfide, dithiosalazine, polydithiocarbamic acid or a salt thereof A compound containing at least one thiocarbonyl group. These compounds may be used alone or in combination of two or more.

當配合上述含硫羰基之化合物時，於本發明之金屬表面處理劑中，較佳為以0.01~100g/L、特別是0.1~10g/L 的濃度含有。若上述化合物之含量未滿0.01g/L，則耐蝕性會有不足的情形，若超過100g/L則耐蝕性飽和、會不經濟。 When the above sulfur-containing carbonyl group-containing compound is blended, it is preferably 0.01 to 100 g/L, particularly 0.1 to 10 g/L, in the metal surface treatment agent of the present invention. The concentration contains. When the content of the above compound is less than 0.01 g/L, the corrosion resistance may be insufficient, and if it exceeds 100 g/L, the corrosion resistance is saturated and it is uneconomical.

本發明之金屬表面處理劑，較佳以進一步含有水溶性或水分散性樹脂。水溶性或水分散性樹脂，可舉例如丙烯酸樹脂、環氧系樹脂、胺基甲酸酯系樹脂、乙烯丙烯酸共聚物、苯酚系樹脂、聚酯系樹脂、聚烯烴樹脂、醇酸樹脂、聚碳酸酯系樹脂等。該等之樹脂，可單獨使用、可併用2種以上、亦可共聚合使用。具體而言，例如，水溶性丙烯酸樹脂，可為以丙烯酸及/或甲基丙烯酸為主成分之共聚物，可例示如丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯等，亦可使用該等之衍生物、或與其他丙烯酸系單體之共聚物。特別是，共聚物中之丙烯酸及/或甲基丙烯酸單體之比例，以70質量%以上為佳。 The metal surface treatment agent of the present invention preferably further contains a water-soluble or water-dispersible resin. Examples of the water-soluble or water-dispersible resin include an acrylic resin, an epoxy resin, a urethane resin, an ethylene acrylic acid copolymer, a phenol resin, a polyester resin, a polyolefin resin, an alkyd resin, and a poly A carbonate resin or the like. These resins may be used singly or in combination of two or more kinds thereof, or may be used in a copolymerization. Specifically, for example, the water-soluble acrylic resin may be a copolymer mainly composed of acrylic acid and/or methacrylic acid, and examples thereof include methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. Alternatively, such derivatives or copolymers with other acrylic monomers may be used. In particular, the ratio of the acrylic acid and/or the methacrylic monomer in the copolymer is preferably 70% by mass or more.

又，於使用樹脂時，為了提升其之造膜性、以更均勻地形成平滑的塗膜，亦可使用有機溶劑。再者，亦可使用界面活性劑、整平劑、濕潤性提升劑、消泡劑。 Moreover, when using a resin, in order to improve the film-forming property, and to form a smooth coating film more uniformly, an organic solvent can also be used. Further, a surfactant, a leveling agent, a wettability enhancer, or an antifoaming agent can also be used.

水溶性或水分散性樹脂之分子量，以凝膠滲透層析儀所得之聚苯乙烯換算之重量平均分子量，較佳為1萬以上。更佳為30萬~200萬。當未滿1萬時，會有無法充分發揮本發明之效果、特別是塗膜之深拉性提升效果的情形。又，若超過200萬則黏度增高，而使操作作業之效率降低。 The molecular weight of the water-soluble or water-dispersible resin is preferably 10,000 or more in terms of polystyrene-equivalent weight average molecular weight obtained by a gel permeation chromatography. More preferably 300,000 to 2 million. When it is less than 10,000, the effect of the present invention, particularly the effect of improving the deep drawability of the coating film, may not be sufficiently exhibited. Moreover, if it exceeds 2 million, the viscosity will increase, and the efficiency of an operation operation will fall.

當配合上述水溶性或水分散性樹脂時，於金屬表面處 理劑中，較佳為以0.1~100g/L、特別是5~80g/L的濃度含有。若樹脂之濃度未滿0.1g/L，則彎曲密合性與深拉性之提升效果會有不足的情形，若超過100g/L則彎曲密合性與深拉性之提升效果飽和、會不經濟。 When blended with the above water-soluble or water-dispersible resin, at the surface of the metal The agent is preferably contained in a concentration of 0.1 to 100 g/L, particularly 5 to 80 g/L. If the concentration of the resin is less than 0.1 g/L, the effect of improving the bending adhesion and the deep drawing property may be insufficient. If it exceeds 100 g/L, the effect of improving the bending adhesion and the deep drawing property may be saturated. economic.

本發明之金屬表面處理劑，亦進一步含有磷酸離子為佳。藉由添加磷酸離子，可進一步提升耐蝕性。該磷酸離子之添加，可藉由添加於水中能形成磷酸離子的化合物來進行。如此之化合物，可舉例如磷酸、Na3PO4、Na2HPO4、NaH2PO4等之磷酸鹽類、縮合磷酸、聚磷酸、偏磷酸、二磷酸等之縮合之磷酸或該等之鹽類等。可單獨使用1種、或併用2種以上。 The metal surface treatment agent of the present invention further preferably contains a phosphate ion. Corrosion resistance can be further improved by adding phosphate ions. The addition of the phosphate ion can be carried out by adding a compound capable of forming a phosphate ion in water. Examples of such a compound include phosphoric acid such as phosphoric acid, Na 3 PO 4 , Na 2 HPO 4 or NaH 2 PO 4 , condensed phosphoric acid, polyphosphoric acid, metaphosphoric acid, diphosphoric acid or the like, or such salts. Classes, etc. These may be used alone or in combination of two or more.

添加上述磷酸離子時之添加量，於金屬表面處理劑中，較佳為0.01~100g/L之濃度、更佳為0.1~10g/L的濃度。若添加量未滿0.01g/L，則耐蝕性之改善效果會有不足的情形，若超過100g/L則對鍍鋅系鋼材會產生過剩之蝕刻而引起性能降低，當含有其他成分之水性樹脂時會產生凝膠化的情形。 The amount of the phosphate ion added is preferably from 0.01 to 100 g/L, more preferably from 0.1 to 10 g/L, in the metal surface treatment agent. When the amount of addition is less than 0.01 g/L, the effect of improving the corrosion resistance may be insufficient. When the amount is more than 100 g/L, the galvanized steel material may be excessively etched to cause a decrease in performance, and when the water-containing resin containing other components is contained, Gelation occurs.

又，本發明之金屬表面處理劑，亦可進一步配合作為金屬表面處理劑之周知之添加劑。例如，可例示如單寧酸或其之鹽、植酸或其之鹽等。 Further, the metal surface treatment agent of the present invention may further be blended with a well-known additive as a metal surface treatment agent. For example, a tannic acid or a salt thereof, phytic acid or a salt thereof can be exemplified.

本發明之金屬表面處理劑，可作為冷軋鋼材、熱軋鋼材、不鏽鋼鋼材、以及電鍍鋅鋼材、熔融鍍鋅鋼材、鋅-鋁合金系鍍敷鋼材、鋅-鐵合金系鍍敷鋼材、鋅-鎂合金系鍍敷鋼材、鋅-鋁-鎂合金系鍍敷鋼材、鋁系鍍敷鋼 材、鋁-矽合金系鍍敷鋼材、錫系鍍敷鋼材、鉛-錫合金系鍍敷鋼材、鉻系鍍敷鋼材、鎳系鍍敷鋼材等之金屬鋼材之表面處理劑使用，特別是金屬被敷鋼材(鍍敷鋼材)的效果顯著。 The metal surface treatment agent of the present invention can be used as cold rolled steel, hot rolled steel, stainless steel, and electrogalvanized steel, hot-dip galvanized steel, zinc-aluminum alloy plated steel, zinc-iron alloy plated steel, zinc- Magnesium alloy plated steel, zinc-aluminum-magnesium alloy plated steel, aluminum plated steel Use of surface treatment agents for metal materials such as steel, aluminum-bismuth alloy-plated steel, tin-based plated steel, lead-tin alloy-plated steel, chromium-based plated steel, and nickel-based plated steel, especially metal The effect of the applied steel (plated steel) is remarkable.

該表面處理劑之使用方法、亦即表面處理方法，可為將上述金屬表面處理劑塗布於被塗布物，於塗布後使被塗布物乾燥的方法，亦可為事先加熱被塗布物，之後塗布上述本發明之金屬表面處理劑，利用餘熱使其乾燥的方法。 The method of using the surface treatment agent, that is, the surface treatment method, may be a method in which the metal surface treatment agent is applied to the object to be coated, and the object to be coated is dried after coating, or the object to be coated may be heated in advance, and then coated. The metal surface treatment agent of the present invention described above is dried by using residual heat.

上述乾燥條件於任何情形下，可為室溫~250℃下2秒~1小時、較佳為40~180℃下5秒~20分鐘。若超過250℃則密合性或耐蝕性等之性能會有產生劣化的可能性。 The above drying conditions may be from 2 seconds to 1 hour at room temperature to 250 ° C, preferably from 5 seconds to 20 minutes at 40 to 180 ° C in any case. When it exceeds 250 ° C, the properties such as adhesion or corrosion resistance may be deteriorated.

上述表面處理方法中，上述本發明之金屬表面處理劑之塗布量，較佳為，乾燥後之被膜質量為0.1mg/m2以上。當被膜質量未滿0.1mg/m2時，防鏽性不足。另一方面，附著量若過多則作為塗裝用前處理劑不經濟，更佳為0.5~500mg/m2、又更佳為1~250mg/m2。 The surface treatment method, the coating of the present invention the amount of metal surface treatment agent of, preferably, film mass after drying was 0.1mg / m 2 or more. When the film quality is less than 0.1 mg/m 2 , the rust prevention property is insufficient. On the other hand, if the amount of adhesion is too large, it is uneconomical as a pretreatment agent for coating, more preferably 0.5 to 500 mg/m 2 , still more preferably 1 to 250 mg/m 2 .

上述表面處理方法中，金屬表面處理劑之塗布方法並無特別限定，可藉由一般所使用之輥塗法、淋浴塗裝法、噴霧、浸漬、刷毛塗布法等來進行塗布。又，處理對象之鋼材，較佳為，上述之金屬鋼材、特別是各種鍍敷鋼材之處理。 In the surface treatment method, the coating method of the metal surface treatment agent is not particularly limited, and the coating can be carried out by a roll coating method, a shower coating method, a spray, a dipping, a brush coating method, or the like which are generally used. Further, the steel material to be processed is preferably a metal steel material, in particular, a variety of plated steel materials.

本發明之塗裝鋼材之製造方法，係以上述金屬表面處理劑對上述金屬鋼材進行表面處理、並進行乾燥，接著塗布上層被膜層之方法。上述被膜層，可舉例如，藉由視需 要於無鉻酸鹽底漆塗布乾燥後、再塗布面塗之塗裝系統所得者，或者，具有耐指紋性或潤滑性等機能之機能塗裝等。上述製造方法，不限於預覆鋼材，亦可適用於後塗漆鋼材，本發明中所謂塗裝鋼材係包含該等。又，本發明中所謂之鋼材係包含鋼板的概念。 The method for producing a coated steel material according to the present invention is a method in which the metal steel material is surface-treated with the metal surface treatment agent, dried, and then the upper layer coating layer is applied. The above-mentioned film layer can be exemplified, for example, by It is required to apply the coating system after coating and drying without the chromate primer, or to apply the function such as fingerprint resistance or lubricity. The above-described production method is not limited to the pre-coated steel material, and may be applied to the post-painted steel material. The coated steel material in the present invention includes these. Moreover, the steel material in the present invention includes the concept of a steel sheet.

本發明可使用之上述無鉻酸鹽底漆，於底漆之配合中未使用鉻酸鹽系防鏽顏料的底漆皆可使用。如此之底漆，較佳為，使用釩酸系防鏽顏料與磷酸系防鏽顏料之底漆(V/P顏料底漆)或使用矽酸鈣系防鏽顏料之底漆。 The above-mentioned chromate-free primer which can be used in the present invention can be used as a primer which does not use a chromate-based anti-rust pigment in the blending of the primer. As such a primer, a primer of a vanadium-based rust preventive pigment and a phosphate-based rust preventive pigment (V/P pigment primer) or a primer using a calcium citrate-based rust preventive pigment is preferably used.

上述底漆之塗布膜厚，以乾燥膜厚計以1~20μm為佳。當未滿1μm時耐蝕性會不足，若超過20μm，則加工密合性會降低。 The coating film thickness of the above primer is preferably 1 to 20 μm in terms of dry film thickness. When the thickness is less than 1 μm, the corrosion resistance is insufficient, and if it exceeds 20 μm, the processing adhesion is lowered.

上述無鉻酸鹽底漆之鍍敷乾燥條件，例如，可為金屬表面溫度為150~250℃、時間為10秒鐘~5分鐘。 The plating drying condition of the above chromate-free primer may be, for example, a metal surface temperature of 150 to 250 ° C and a time of 10 seconds to 5 minutes.

上述面塗並無特別限定，一般之塗裝用面塗皆可使用。又，機能塗裝並無特別限定，現今鉻酸鹽系前處理被膜之上所實施之塗布等，皆可使用。上述無鉻酸鹽底漆及面塗或機能塗裝之塗布方法並無特別限定，可利用一般所使用之輥塗、淋浴塗布、空氣噴霧、無空氣噴霧、浸漬等。 The top coat is not particularly limited, and a general top coat for painting can be used. Further, the functional coating is not particularly limited, and any coating or the like applied on the chromate pretreatment film can be used. The coating method of the above-mentioned chromate-free primer and top coating or functional coating is not particularly limited, and roll coating, shower coating, air spraying, airless spraying, dipping, and the like which are generally used can be used.

[實施例] [Examples]

以下，舉合成例、實施例及比較例以更詳細地說明本發明，但本發明並不限於該等實施例。又，以下之例中份 係表示質量份，Me表示甲基、Et表示乙基、Ph表示苯基、IR表示紅外光分析法的簡稱。 Hereinafter, the present invention will be described in more detail by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the Examples. Also, the following example It means a mass part, Me represents a methyl group, Et represents an ethyl group, Ph represents a phenyl group, and IR represents an abbreviation of infrared light analysis method.

[合成例1：有機矽化合物(8)(下述式(8)之製造法)] [Synthesis Example 1: Organic hydrazine compound (8) (manufacturing method of the following formula (8))]

於具備攪拌機、回流冷卻器、滴下漏斗及溫度計之1L分離式燒瓶裝填3-胺基丙基三甲氧矽烷(信越化學工業股份有限公司製，KBM-903)358.6g(2mol)，將異硫氰酸甲酯146.2g(2mol)滴下至其中，於室溫下攪拌1小時。之後，藉IR測定確認來自原料之異硫氰酸酯之吸收峰完全消失後，反應結束。所得之生成物為褐色液體，藉由凝膠滲透層析(GPC)分析，可知反應生成物為單一之生成物。 A 1-L separation flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer was charged with 3-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.), 358.6 g (2 mol), and isothiocyanate. 146.2 g (2 mol) of methyl ester was added dropwise thereto, and the mixture was stirred at room temperature for 1 hour. Thereafter, it was confirmed by IR measurement that the absorption peak of the isothiocyanate from the raw material completely disappeared, and the reaction was completed. The obtained product was a brown liquid, and it was found by gel permeation chromatography (GPC) that the reaction product was a single product.

[合成例2：有機矽化合物(9)(下述式(9)之製造法)] [Synthesis Example 2: Organic oxime compound (9) (manufacturing method of the following formula (9))]

於具備攪拌機、回流冷卻器、滴下漏斗及溫度計之1L分離式燒瓶裝填3-胺基丙基三甲氧矽烷(信越化學工業股份有限公司製，KBM-903)358.6g(2mol)，將異硫氰酸乙酯174.3g(2mol)滴下至其中，於室溫下攪拌1小時。之後，藉IR測定確認來自原料之異硫氰酸酯之吸收峰完全消失後，反應結束。所得之生成物為褐色液體，藉 由凝膠滲透層析(GPC)分析，可知反應生成物為單一之生成物。 A 1-L separation flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer was charged with 3-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.), 358.6 g (2 mol), and isothiocyanate. 174.3 g (2 mol) of ethyl acetate was added dropwise thereto, and the mixture was stirred at room temperature for 1 hour. Thereafter, it was confirmed by IR measurement that the absorption peak of the isothiocyanate from the raw material completely disappeared, and the reaction was completed. The resulting product is a brown liquid, borrowed Analysis by gel permeation chromatography (GPC) revealed that the reaction product was a single product.

[合成例3：有機矽化合物(10)(下述式(10)之製造法)] [Synthesis Example 3: Organic hydrazine compound (10) (method of the following formula (10))]

於具備攪拌機、回流冷卻器、滴下漏斗及溫度計之1L分離式燒瓶裝填3-胺基丙基三甲氧矽烷(信越化學工業股份有限公司製，KBM-903)358.6g(2mol)，將異硫氰酸苯酯270.4g(2mol)滴下至其中，於室溫下攪拌1小時。之後，藉IR測定確認來自原料之異硫氰酸酯之吸收峰完全消失後，反應結束。所得之生成物為褐色液體，藉由凝膠滲透層析(GPC)分析，可知反應生成物為單一之生成物。 A 1-L separation flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer was charged with 3-aminopropyltrimethoxysilane (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.), 358.6 g (2 mol), and isothiocyanate. 270.4 g (2 mol) of phenyl ester was added dropwise thereto, and the mixture was stirred at room temperature for 1 hour. Thereafter, it was confirmed by IR measurement that the absorption peak of the isothiocyanate from the raw material completely disappeared, and the reaction was completed. The obtained product was a brown liquid, and it was found by gel permeation chromatography (GPC) that the reaction product was a single product.

[合成例4：有機矽化合物(13)(下述式(13)之製造法)] [Synthesis Example 4: Organic hydrazine compound (13) (method of the following formula (13))]

於具備攪拌機、回流冷卻器、滴下漏斗及溫度計之1L分離式燒瓶裝填3-異硫氰酸酯丙基三甲氧矽烷221.4g(1mol)、己烷500g、二(2-乙基己烷)酸錫1g，加熱至60℃。將氨水吹入其中，藉IR測定確認來自原料之異 硫氰酸酯之吸收峰完全消失後，停止吹入。之後，除去溶劑所得之生成物為黃色液體，藉由凝膠滲透層析(GPC)分析，可知反應生成物為單一之生成物。 In a 1 L separation flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 221.4 g (1 mol) of 3-isothiocyanate propyl trimethoxide, 500 g of hexane, and bis(2-ethylhexane) acid were charged. Tin 1g, heated to 60 ° C. Ammonia water is blown into it, and the difference from the raw materials is confirmed by IR measurement. After the absorption peak of the thiocyanate completely disappeared, the blowing was stopped. Thereafter, the product obtained by removing the solvent was a yellow liquid, and it was found by gel permeation chromatography (GPC) that the reaction product was a single product.

[實施例1] [Example 1]

於甲醇990g、水10g之混合溶劑添加作為不揮發成分之合成例1所得之有機矽化合物(8)10g，藉由於室溫下攪拌5分鐘，製得金屬表面處理劑。將所得之金屬表面處理劑脫脂乾燥後，以使乾燥膜厚為10μm的方式以棒塗布器No.20塗布於市售之熔融鍍鋅鋼板(日本testpanel公司製；70×150×0.4mm)，以金屬表面溫度105℃乾燥10分鐘。之後，以使乾燥膜厚為5μm的方式以棒塗布器No.16塗布含有V/P顏料之無鉻酸鹽底漆，以金屬表面溫度215℃乾燥5分鐘。再以使乾燥膜厚為15μm的方式以棒塗布器No.36塗布作為面塗之Flekicoat1060(聚酯系上塗塗料；日本塗料公司製)，以金屬表面溫度230℃使其乾燥製得試驗板。依據下述之評價方法評價所得試驗板之彎曲密合性、深拉性、耐蝕性，將其之結果記載於表1。 10 g of the organic ruthenium compound (8) obtained in Synthesis Example 1 as a nonvolatile component was added to a mixed solvent of 990 g of methanol and 10 g of water, and a metal surface treatment agent was prepared by stirring at room temperature for 5 minutes. The obtained metal surface treatment agent was degreased and dried, and then applied to a commercially available hot-dip galvanized steel sheet (manufactured by Japan Testpanel Co., Ltd.; 70×150×0.4 mm) by a bar coater No. 20 so as to have a dry film thickness of 10 μm. It was dried at a metal surface temperature of 105 ° C for 10 minutes. Thereafter, a chromium-free primer containing V/P pigment was applied to the bar coater No. 16 so that the dry film thickness was 5 μm, and dried at a metal surface temperature of 215 ° C for 5 minutes. Further, Flekicoat 1060 (polyester-based top coat; manufactured by Nippon Paint Co., Ltd.) which was topcoated was applied by a bar coater No. 36 so as to have a dry film thickness of 15 μm, and dried at a metal surface temperature of 230 ° C to obtain a test plate. The bending adhesion, deep drawability, and corrosion resistance of the obtained test plate were evaluated according to the following evaluation methods, and the results thereof are shown in Table 1.

[實施例2~4] [Examples 2 to 4]

於實施例1中，將合成例1所得之化合物改變成合成例2~4所得之化合物(9)、(10)、(13)，除此之 外，與實施例1同樣地調製金屬表面處理劑。使用該等金屬表面處理劑，與實施例1同樣地製作試驗板，進行該等之評價。將所得之結果記載於表1。 In Example 1, the compound obtained in Synthesis Example 1 was changed to the compounds (9), (10), and (13) obtained in Synthesis Examples 2 to 4, except Further, a metal surface treatment agent was prepared in the same manner as in Example 1. Using these metal surface treatment agents, a test plate was produced in the same manner as in Example 1, and the evaluation was performed. The results obtained are shown in Table 1.

[實施例5~12] [Examples 5 to 12]

於實施例1中，分別以表1所記載之方式配合矽烷化合物之種類與濃度、有機鈦酸酯、水分散性氧化矽、鋯離子、含硫羰基之化合物、水溶性樹脂及磷酸離子之濃度，除此之外，與實施例1同樣地調製金屬表面處理劑。使用該等金屬表面處理劑，與實施例1同樣地製作試驗板，進行該等之評價。將所得之結果記載於表1。 In Example 1, the type and concentration of the decane compound, the organic titanate, the water-dispersible cerium oxide, the zirconium ion, the sulfur-containing carbonyl compound, the water-soluble resin, and the phosphate ion concentration were blended in the manner described in Table 1. A metal surface treatment agent was prepared in the same manner as in Example 1 except for the above. Using these metal surface treatment agents, a test plate was produced in the same manner as in Example 1, and the evaluation was performed. The results obtained are shown in Table 1.

[比較例1、2] [Comparative Examples 1, 2]

於實施例1中，不使用合成例所得之化合物，分別以表1所記載之方式配合矽烷化合物之種類與濃度、有機鈦酸酯、水分散性氧化矽、鋯離子、含硫羰基之化合物、水溶性樹脂及磷酸離子之濃度，除此之外，與實施例1同樣地調製金屬表面處理劑。使用該等金屬表面處理劑，與實施例1同樣地製作試驗板，進行該等之評價。將所得之結果記載於表1。 In the first embodiment, the compound obtained in the synthesis example was not used, and the type and concentration of the decane compound, the organic titanate, the water-dispersible cerium oxide, the zirconium ion, the sulfur-containing carbonyl compound, and the like were mixed in the manner described in Table 1. A metal surface treatment agent was prepared in the same manner as in Example 1 except that the concentration of the water-soluble resin and the phosphate ion was changed. Using these metal surface treatment agents, a test plate was produced in the same manner as in Example 1, and the evaluation was performed. The results obtained are shown in Table 1.

[比較例3] [Comparative Example 3]

於實施例1中，取代金屬表面處理劑，使用將市售之塗布型鉻酸鹽處理劑(含樹脂型)以使鉻附著量為20 mg/m2的方式塗布、乾燥者、及含有鉻之底漆(含鉻酸鍶顏料之底漆)，除此之外，與實施例1同樣地製作及評價試驗板，將所得之結果記載於表1。 In Example 1, in place of the metal surface treatment agent, a commercially available coating type chromate treatment agent (including a resin type) was applied so as to have a chromium adhesion amount of 20 mg/m 2 , dried, and containing chromium. A test plate was produced and evaluated in the same manner as in Example 1 except that the primer (the primer containing the strontium chromate pigment) was used, and the results obtained are shown in Table 1.

又，下述表1中，矽烷化合物、有機鈦酸酯、水分散性氧化矽、形成鋯離子之化合物、含硫羰基之化合物、水溶性樹脂、形成磷酸離子之化合物，係使用以下之市售品。 Further, in the following Table 1, a decane compound, an organic titanate, a water-dispersible cerium oxide, a compound which forms a zirconium ion, a compound containing a thiocarbonyl group, a water-soluble resin, and a compound which forms a phosphate ion are commercially available as follows. Product.

[矽烷化合物] [decane compound]

A：KBM-903(γ-胺基丙基三甲氧矽烷；信越化學工業股份有限公司製) A: KBM-903 (γ-aminopropyltrimethoxy decane; manufactured by Shin-Etsu Chemical Co., Ltd.)

B：KBM-403(γ-環氧丙氧基丙基三甲氧矽烷；信越化學工業股份有限公司製) B: KBM-403 (γ-glycidoxypropyltrimethoxy decane; manufactured by Shin-Etsu Chemical Co., Ltd.)

[有機鈦酸酯] [Organic titanate]

四異丙氧基鈦 Titanium isopropoxide

[水分散性氧化矽] [Water-dispersible cerium oxide]

甲醇矽溶膠(日產化學工業股份有限公司製) Methanol sol (produced by Nissan Chemical Industry Co., Ltd.)

[形成鋯離子之化合物] [Formation of zirconium ion]

JirukozoruAC-7(碳酸鋯銨；第一稀元素化學工業股份有限公司製) Jirukozoru AC-7 (ammonium zirconium carbonate; manufactured by First Rare Element Chemical Industry Co., Ltd.)

[含硫羰基之化合物] [sulfur-containing carbonyl compound]

硫脲 Thiourea

[水溶性樹脂] [Water-soluble resin]

聚丙烯酸(重量平均分子量100萬) Polyacrylic acid (weight average molecular weight 1 million)

[形成磷酸離子之化合物] [Compound forming a phosphate ion]

磷酸 Phosphate

[評價方法] [Evaluation method]

上述實施例1~12及比較例1~3中之彎曲密合性、伸拉性、耐蝕性之評價，係根據以下之方法、評價基準進行。 The evaluation of the bending adhesion, the stretchability, and the corrosion resistance in the above Examples 1 to 12 and Comparative Examples 1 to 3 was carried out based on the following methods and evaluation criteria.

(1)彎曲密合性 (1) Bending adhesion

於20℃之環境下，使用錐形心軸試驗機將試驗板以2mm 之間隔器夾持，進行180°彎曲加工，將彎曲加工部進行3次膠帶剝離，以20倍放大鏡觀察剝離程度，以下述之基準進行評價。 Using a conical spindle tester to 2 mm the test plate at 20 ° C The spacer was sandwiched, subjected to 180° bending, and the bent portion was peeled off three times, and the degree of peeling was observed with a magnifying glass of 20 times, and evaluated according to the following criteria.

A：無裂痕 A: no cracks

B：於加工部前面有裂痕 B: There is a crack in front of the processing department.

C：剝離面積未滿加工部之20% C: The peeling area is less than 20% of the processing part

D：剝離面積為加工部之20%以上~未滿80% D: The peeling area is more than 20% of the processing part ~ 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 processing department

(2)深拉性 (2) deep drawing

於20℃之環境下，以拉深比：2.3、皺褶抑制壓：2t、衝孔R：5mm、凸緣R：5mm、無塗油之條件下進行置入有方格切痕之試驗板的圓筒拉深試驗。之後，由圓筒側壁部之方格切痕部測定塗膜的剝離寬度，以下述之基準進行評價。 In the environment of 20 ° C, the test plate with the square cut is placed under the conditions of drawing ratio: 2.3, wrinkle suppression pressure: 2t, punching R: 5mm, flange R: 5mm, and no oiling. The cylinder draw test. Thereafter, the peeling width of the coating film was measured from the square cut portion of the cylindrical side wall portion, and evaluated based on the following criteria.

A：剝離寬度未滿1mm A: The peel width is less than 1mm

B：剝離寬度為1mm以上~未滿2mm B: peeling width is 1mm or more ~ less than 2mm

C：剝離寬度為2mm以上~未滿3mm C: peeling width is 2mm or more ~ less than 3mm

D：剝離寬度為3mm以上~未滿5mm D: peeling width is 3mm or more ~ less than 5mm

E：剝離寬度為5mm以上 E: peeling width is 5mm or more

(3)耐蝕性 (3) Corrosion resistance

(切割部) (cutting department)

對試驗板置入達鍍鋅層之方格切痕，根據JIS Z 2371進行鹽水噴霧試驗500小時後，測定方格切痕部(切割部)單側之膨脹寬度，以下述之基準進行評價。 A square cut of the galvanized layer was placed on the test plate, and after 500 hours of salt spray test according to JIS Z 2371, the expansion width on one side of the square cut portion (cut portion) was measured and evaluated on the basis of the following criteria.

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

B：膨脹寬度超過0mm~未滿1mm B: Expansion width exceeds 0mm~ less than 1mm

C：膨脹寬度為1mm以上~未滿3mm C: expansion width is 1mm or more ~ less than 3mm

D：膨脹寬度為3mm以上~未滿5mm D: expansion width is 3mm or more ~ less than 5mm

E：膨脹寬度為5mm以上 E: expansion width is 5mm or more

(端面) (end face)

對試驗板根據JIS Z 2371進行鹽水噴霧試驗500小時後，與切割部以同樣基準評價由上毛邊端面的膨脹寬度。 After the test plate was subjected to a salt spray test for 500 hours in accordance with JIS Z 2371, the expansion width of the upper burr end face was evaluated on the same basis as the cut portion.

以上之實施例及比較例之結果，係使用本發明之金屬表面處理劑所形成之被膜可提供良好之防鏽性能及基材密合性的實證。 As a result of the above examples and comparative examples, the film formed by using the metal surface treating agent of the present invention can provide good rust prevention performance and substrate adhesion.

又，目前為止係以實施形態說明本發明，但本發明並不限定於此處所示之實施形態，亦可於其他實施形態、追加、改變、刪除等之所屬技術領域者可想到的範圍內進行變更，任一形態中只要可達成本發明之作用效果，亦包含於本發明範圍中。 Further, the present invention has been described in terms of embodiments, but the present invention is not limited to the embodiments shown herein, and may be within the scope of those skilled in the art, such as other embodiments, additions, changes, deletions, and the like. It is also within the scope of the present invention to carry out the change in any form as long as it can achieve the effect of the invention.

Claims (15)

一種金屬表面處理劑，其特徵係含有：(A)以下述通式(1) (式中，R為水解性基，R’為碳數1~4之烷基，A為直鏈狀或分支鏈狀之碳數1~8之伸烷基，X為氧原子、硫原子、NR3基之任一者，R1、R2、R3分別獨立為氫原子、碳數1~20之烷基、碳數1~20之氟烷基、碳數6~10之芳基、碳數2~10之烯基、或下述通式(2)所示之取代基，m為1~3之整數) (式中，R為水解性基，R’為碳數1~4之烷基，B為直鏈狀或分支鏈狀之碳數1~8之伸烷基，m為1~3之整數)所表示之有機矽化合物；(B)水及/或有機溶劑。 A metal surface treatment agent characterized by: (A) having the following general formula (1) (wherein R is a hydrolyzable group, R' is an alkyl group having 1 to 4 carbon atoms, A is a linear or branched chain alkyl group having 1 to 8 carbon atoms, and X is an oxygen atom or a sulfur atom; In any one of the NR 3 groups, R 1 , R 2 and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 10 carbon atoms. The alkenyl group having 2 to 10 carbon atoms or the substituent represented by the following formula (2), m is an integer of 1 to 3) (wherein R is a hydrolyzable group, R' is an alkyl group having 1 to 4 carbon atoms, and B is a linear or branched chain alkyl group having 1 to 8 carbon atoms, and m is an integer of 1 to 3) The organic hydrazine compound represented; (B) water and/or organic solvent. 如申請專利範圍第1項之金屬表面處理劑，其中，上述有機矽化合物，係下述通式(3) (式中，R為水解性基，R’為碳數1~4之烷基，A為直鏈 狀或分支鏈狀之碳數1~8之伸烷基，R1~R3分別獨立為氫原子、碳數1~20之烷基、碳數1~20之氟烷基、碳數6~10之芳基、碳數2~10之烯基、或下述通式(4)所示之取代基，m為1~3之整數) (式中，R為水解性基，R’為碳數1~4之烷基，B為直鏈狀或分支鏈狀之碳數1~8之伸烷基，m為1~3之整數)。 The metal surface treatment agent according to the first aspect of the invention, wherein the organic ruthenium compound is the following general formula (3) (wherein R is a hydrolyzable group, R' is an alkyl group having 1 to 4 carbon atoms, and A is a linear or branched chain alkyl group having 1 to 8 carbon atoms, and R 1 to R 3 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a formula represented by the following formula (4) Substituent, m is an integer from 1 to 3) (wherein R is a hydrolyzable group, R' is an alkyl group having 1 to 4 carbon atoms, and B is a linear or branched chain alkyl group having 1 to 8 carbon atoms, and m is an integer of 1 to 3) . 如申請專利範圍第2項之金屬表面處理劑，其中，上述有機矽化合物，係下述通式(5) (式中，R為水解性基，R’為碳數1~4之烷基，R1為氫原子、碳數1~20之烷基、碳數1~20之氟烷基、碳數6~10之芳基、碳數2~10之烯基、或下述通式(6)所示之取代基，m為1~3之整數) (式中，R為水解性基，R’為碳數1~4之烷基，m為1~3之整數)。 The metal surface treatment agent according to claim 2, wherein the organic cerium compound is a compound of the following formula (5) (wherein R is a hydrolyzable group, R' is an alkyl group having 1 to 4 carbon atoms, R 1 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, and a carbon number of 6 An aryl group of ~10, an alkenyl group having 2 to 10 carbon atoms, or a substituent represented by the following formula (6), m is an integer of 1 to 3) (wherein R is a hydrolyzable group, R' is an alkyl group having 1 to 4 carbon atoms, and m is an integer of 1 to 3). 如申請專利範圍第1至3項中任一項之金屬表面處理劑，其進一步含有下述通式(7)R4 xSi(OR5)4-x (7) (式中，R4為碳數1~20之非取代或取代之一價烴基，R5為碳數1~8之非取代或取代之一價烴基，x為0~3之整數)所表示之烷氧矽烷或其之部分水解縮合物。 The metal surface treatment agent according to any one of claims 1 to 3, further comprising the following general formula (7) R 4 x Si(OR 5 ) 4-x (7) (wherein R 4 is An alkoxy decane represented by an unsubstituted or substituted one-valent hydrocarbon group having 1 to 20 carbon atoms, R 5 being an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and x is an integer of 0 to 3 or Partial hydrolysis of the condensate. 如申請專利範圍第1至3項中任一項之金屬表面處理劑，其進一步含有有機酞酸酯。 The metal surface treatment agent according to any one of claims 1 to 3, which further contains an organic phthalic acid ester. 如申請專利範圍第1至3項中任一項之金屬表面處理劑，其進一步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 any one of claims 1 to 3, further comprising water-dispersible cerium oxide or organic solvent-dispersible cerium oxide. 如申請專利範圍第1至3項中任一項之金屬表面處理劑，其進一步含有選自Fe、Zr、Ti、V、W、Mo、Al、Sn、Nb、Hf、Y、Ho、Bi、La、Ce及Zn之群中之1種以上之金屬的化合物。 The metal surface treatment agent according to any one of claims 1 to 3, further comprising a member selected from the group consisting of Fe, Zr, Ti, V, W, Mo, Al, Sn, Nb, Hf, Y, Ho, Bi, A compound of one or more metals selected from the group consisting of La, Ce, and Zn. 如申請專利範圍第1至3項中任一項之金屬表面處理劑，其進一步含有含硫羰基之化合物。 The metal surface treatment agent according to any one of claims 1 to 3, which further contains a sulfur-containing carbonyl group-containing compound. 如申請專利範圍第1至3項中任一項之金屬表面處理劑，其進一步含有水溶性樹脂或水分散性樹脂。 The metal surface treatment agent according to any one of claims 1 to 3, further comprising a water-soluble resin or a water-dispersible resin. 如申請專利範圍第1至3項中任一項之金屬表面處理劑，其進一步含有磷酸離子。 The metal surface treatment agent according to any one of claims 1 to 3, which further contains a phosphate ion. 一種鋼材之表面處理方法，其特徵係將鋼材之表面以申請專利範圍第1至10項中任一項之金屬表面處理劑進行表面處理。 A surface treatment method for a steel material characterized in that the surface of the steel material is surface-treated with a metal surface treatment agent according to any one of claims 1 to 10. 如申請專利範圍第11項之表面處理方法，其中，鋼材係金屬被覆鋼材。 The surface treatment method of claim 11, wherein the steel material is a metal coated steel material. 一種表面處理鋼材，其係以申請專利範圍第11或12項之表面處理方法所得。 A surface treated steel material obtained by the surface treatment method of claim 11 or 12. 一種塗裝鋼材之製造方法，其特徵係，以申請專利範圍第1至10項中任一項之金屬表面處理劑處理鋼材之後，再設置上層被膜層。 A method of producing a coated steel material, characterized in that after the steel material is treated with a metal surface treatment agent according to any one of claims 1 to 10, an upper coating layer is further provided. 一種塗裝鋼材，其係以申請專利範圍第14項之塗裝鋼材之製造方法所得。 A coated steel material obtained by the method for producing a coated steel material according to claim 14 of the patent application.
TW102127953A 2012-08-06 2013-08-05 Metal surface treatment agent, surface treatment steel material and surface treatment method thereof, and coating steel material and manufacturing method thereof TWI522493B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2012173658A JP5712980B2 (en) 2012-08-06 2012-08-06 Metal surface treatment agent, surface treated steel material and surface treatment method thereof, and coated steel material and method for producing the same

Publications (2)

Publication Number Publication Date
TW201422845A TW201422845A (en) 2014-06-16
TWI522493B true TWI522493B (en) 2016-02-21

Family

ID=50044987

Family Applications (1)

Application Number Title Priority Date Filing Date
TW102127953A TWI522493B (en) 2012-08-06 2013-08-05 Metal surface treatment agent, surface treatment steel material and surface treatment method thereof, and coating steel material and manufacturing method thereof

Country Status (4)

Country Link
JP (1) JP5712980B2 (en)
KR (1) KR102067841B1 (en)
CN (1) CN103572298B (en)
TW (1) TWI522493B (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9222019B2 (en) * 2013-10-29 2015-12-29 Ecolab Usa Inc. Use of niobate containing compounds as corrosion inhibitors
KR101614307B1 (en) 2014-08-14 2016-04-22 대원강업주식회사 Surface treatment system and its control method
JP6291442B2 (en) * 2015-03-12 2018-03-14 京セラ株式会社 Thermistor sensor casting resin composition and thermistor sensor
JP2017150012A (en) * 2016-02-22 2017-08-31 日本ペイント・サーフケミカルズ株式会社 Metal surface treatment agent
JP6561901B2 (en) * 2016-04-15 2019-08-21 信越化学工業株式会社 Metal surface treatment agent
JP6777492B2 (en) 2016-10-06 2020-10-28 三菱重工業株式会社 Surface treatment equipment and surface treatment method
CN106521473A (en) * 2016-11-18 2017-03-22 安徽工业大学 Copper and copper alloy surface anticorrosion liquid and preparation method thereof
WO2018218432A1 (en) * 2017-05-27 2018-12-06 深圳市恒兆智科技有限公司 Film passivator, metal component, and passivation treatment method therefor
CN108663833A (en) * 2018-05-14 2018-10-16 合肥奇呗数字科技有限公司 A kind of self-cleaning outdoor liquid crystal display
CN111269258B (en) * 2020-03-19 2022-08-19 厦门威亮光学涂层技术有限公司 Sulfur-containing organic silicon compound and preparation method and application thereof
KR102456800B1 (en) 2021-07-05 2022-10-21 삼양화학산업 주식회사 continuous painting method using eco-friendly surface treatment agent
KR102491243B1 (en) * 2022-05-27 2023-01-20 콘티넨탈 오토모티브 게엠베하 Anti corrosion treating car bracket and preparing method thereof

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2668592B2 (en) * 1989-04-03 1997-10-27 富士写真フイルム株式会社 Photosensitive lithographic printing plate
JP2652093B2 (en) * 1991-09-12 1997-09-10 富士写真フイルム株式会社 Photosensitive composition
JPH0873775A (en) 1994-09-02 1996-03-19 Nippon Parkerizing Co Ltd Metal surface treating agent for forming coating film excellent in fingerprint resistance, corrosion resistance and adhesion of coating film and method of treating therewith
JPH08311403A (en) * 1995-05-24 1996-11-26 Toray Dow Corning Silicone Co Ltd Surface treatment agent
CN1149453A (en) * 1995-11-06 1997-05-14 旭化学工业株式会社 Animal growth promoting composition
JPH1060315A (en) 1996-08-14 1998-03-03 Nippon Parkerizing Co Ltd Surface treating agent for zinc-plated steel product or steel structure
JP4568386B2 (en) * 1997-05-14 2010-10-27 日本ペイント株式会社 Rust prevention coating agent and rust prevention treatment method
JP3555845B2 (en) 1999-04-15 2004-08-18 株式会社日鉱マテリアルズ Novel organosilicon compound, method for producing the same, surface treating agent and resin additive using the same
JP4113309B2 (en) * 1999-08-16 2008-07-09 日本パーカライジング株式会社 Surface treatment agent for metal material excellent in corrosion resistance and surface treatment method of metal material
JP4190686B2 (en) * 1999-12-13 2008-12-03 日本ペイント株式会社 Rust prevention coating agent and rust prevention treatment method
JP3857866B2 (en) * 2000-02-29 2006-12-13 日本ペイント株式会社 Non-chromate metal surface treatment agent, surface treatment method and treated painted steel
US6652977B2 (en) * 2001-09-10 2003-11-25 Johnson Diversey, Inc. Primer composition
JP4649654B2 (en) * 2004-09-21 2011-03-16 独立行政法人科学技術振興機構 Functional group-introduced inorganic compound and method for producing composite
JP4242827B2 (en) * 2004-12-08 2009-03-25 日本パーカライジング株式会社 Metal surface treatment composition, surface treatment liquid, surface treatment method, and surface-treated metal material
CN101326308B (en) * 2005-12-15 2010-09-29 日本帕卡濑精株式会社 Surface treatment for metal materials, surface treatment process, and surface- treated metal materials
JP5055822B2 (en) 2006-04-27 2012-10-24 住友金属工業株式会社 Painted steel sheet with excellent coating adhesion
JP5051354B2 (en) * 2007-04-06 2012-10-17 信越化学工業株式会社 Metal surface treatment agent, metal surface treated steel and method for treating the same, painted steel and method for producing the same
JP5343570B2 (en) 2009-01-13 2013-11-13 信越化学工業株式会社 Metal surface treatment agent, surface treated steel material and surface treatment method thereof, and coated steel material and method for producing the same
JP2012041586A (en) * 2010-08-17 2012-03-01 Shin-Etsu Chemical Co Ltd Metal surface treatment agent, surface-treated steel, method for treating the same, coated steel, and method for producing the same
JP2012111983A (en) 2010-11-22 2012-06-14 Shin-Etsu Chemical Co Ltd Metal surface treating agent and metal surface treatment method using the same
JP2012240922A (en) * 2011-05-16 2012-12-10 Shin-Etsu Chemical Co Ltd Organosilicon compound and method for producing the same, compounding agent for rubber, rubber composition, and tire

Also Published As

Publication number Publication date
TW201422845A (en) 2014-06-16
JP2014031556A (en) 2014-02-20
KR20140019236A (en) 2014-02-14
CN103572298B (en) 2017-08-11
CN103572298A (en) 2014-02-12
KR102067841B1 (en) 2020-01-17
JP5712980B2 (en) 2015-05-07

Similar Documents

Publication Publication Date Title
TWI522493B (en) Metal surface treatment agent, surface treatment steel material and surface treatment method thereof, and coating steel material and manufacturing method thereof
KR102406796B1 (en) Organosilicon compound, method for producing same and metal surface treatment agent using same
JP4683582B2 (en) Water-based metal material surface treatment agent, surface treatment method and surface treatment metal material
JP5051354B2 (en) Metal surface treatment agent, metal surface treated steel and method for treating the same, painted steel and method for producing the same
JP5343570B2 (en) Metal surface treatment agent, surface treated steel material and surface treatment method thereof, and coated steel material and method for producing the same
CA2833367C (en) Surface-treated metal material and aqueous metal surface-treatment agent
JP2012111983A (en) Metal surface treating agent and metal surface treatment method using the same
TWI682011B (en) Metal surface treatment agent
JP5673642B2 (en) Metal surface treatment agent, surface treated steel material and surface treatment method thereof, and coated steel material and method for producing the same
JP4973877B2 (en) Metal surface treatment agent, surface-treated steel material and method for treating the same, painted steel material and method for producing the same
JP6569194B2 (en) Surface-treated hot-dip galvanized steel sheet with excellent corrosion resistance
JP2012041586A (en) Metal surface treatment agent, surface-treated steel, method for treating the same, coated steel, and method for producing the same
JP3923418B2 (en) Chromium-free galvanized steel sheet and its manufacturing method
JP5617852B2 (en) Metal surface treatment agent, metal surface treated steel and method for treating the same, painted steel and method for producing the same
JP5673643B2 (en) Metal surface treatment agent, surface treated steel material and surface treatment method thereof, and coated steel material and method for producing the same
JP2017066446A (en) Surface-treatment galvanized steel plate excellent in corrosion resistance
MX2008000635A (en) Metallic material having chromate-free-treated surface excellent in corrosion resistance, heat resistance, anti-fingerprint property, conductivity, coating property and black deposit resistance during processing.