KR102660763B1 - Paint compositions and painted metal plates - Google Patents
Paint compositions and painted metal plates Download PDFInfo
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- KR102660763B1 KR102660763B1 KR1020217030275A KR20217030275A KR102660763B1 KR 102660763 B1 KR102660763 B1 KR 102660763B1 KR 1020217030275 A KR1020217030275 A KR 1020217030275A KR 20217030275 A KR20217030275 A KR 20217030275A KR 102660763 B1 KR102660763 B1 KR 102660763B1
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- 229910052751 metal Inorganic materials 0.000 title claims description 71
- 239000002184 metal Substances 0.000 title claims description 69
- 239000003973 paint Substances 0.000 title claims description 24
- 239000000203 mixture Substances 0.000 title claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 120
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 60
- 239000008199 coating composition Substances 0.000 claims abstract description 59
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- 229920005989 resin Polymers 0.000 claims abstract description 54
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- 229920000647 polyepoxide Polymers 0.000 claims abstract description 53
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 35
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 28
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims description 46
- 239000011248 coating agent Substances 0.000 claims description 45
- 239000000377 silicon dioxide Substances 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 229910000831 Steel Inorganic materials 0.000 claims description 16
- 239000010959 steel Substances 0.000 claims description 16
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
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- WGOZXQULGFEOTE-UHFFFAOYSA-N tributoxysilylmethanamine Chemical compound CCCCO[Si](CN)(OCCCC)OCCCC WGOZXQULGFEOTE-UHFFFAOYSA-N 0.000 description 1
- SNXFCXCGMCBLBI-UHFFFAOYSA-N tributoxysilylmethanethiol Chemical compound CCCCO[Si](CS)(OCCCC)OCCCC SNXFCXCGMCBLBI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- ROWWCTUMLAVVQB-UHFFFAOYSA-N triethoxysilylmethanamine Chemical compound CCO[Si](CN)(OCC)OCC ROWWCTUMLAVVQB-UHFFFAOYSA-N 0.000 description 1
- XSIGLRIVXRKQRA-UHFFFAOYSA-N triethoxysilylmethanethiol Chemical compound CCO[Si](CS)(OCC)OCC XSIGLRIVXRKQRA-UHFFFAOYSA-N 0.000 description 1
- VMFOHNMEJNFJAE-UHFFFAOYSA-N trimagnesium;diphosphite Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])[O-].[O-]P([O-])[O-] VMFOHNMEJNFJAE-UHFFFAOYSA-N 0.000 description 1
- ARKBFSWVHXKMSD-UHFFFAOYSA-N trimethoxysilylmethanamine Chemical compound CO[Si](CN)(OC)OC ARKBFSWVHXKMSD-UHFFFAOYSA-N 0.000 description 1
- QJOOZNCPHALTKK-UHFFFAOYSA-N trimethoxysilylmethanethiol Chemical compound CO[Si](CS)(OC)OC QJOOZNCPHALTKK-UHFFFAOYSA-N 0.000 description 1
- XBWNNHVBLBOOKZ-UHFFFAOYSA-N triphenoxysilylmethanamine Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(CN)OC1=CC=CC=C1 XBWNNHVBLBOOKZ-UHFFFAOYSA-N 0.000 description 1
- BXIOTOUYYLTTNC-UHFFFAOYSA-N triphenoxysilylmethanethiol Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(CS)OC1=CC=CC=C1 BXIOTOUYYLTTNC-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- OJDWSXMZWYSCDJ-UHFFFAOYSA-N tripropoxysilylmethanamine Chemical compound CCCO[Si](CN)(OCCC)OCCC OJDWSXMZWYSCDJ-UHFFFAOYSA-N 0.000 description 1
- NDBGOFIMYAOZJI-UHFFFAOYSA-N tripropoxysilylmethanethiol Chemical compound CCCO[Si](CS)(OCCC)OCCC NDBGOFIMYAOZJI-UHFFFAOYSA-N 0.000 description 1
- AUTOISGCBLBLBA-UHFFFAOYSA-N trizinc;diphosphite Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])[O-].[O-]P([O-])[O-] AUTOISGCBLBLBA-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
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- 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
-
- 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
-
- 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
- C09D5/002—Priming paints
-
- 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
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
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Abstract
본 발명의 도료 조성물은, 비이온성 수분산성 수지 (a)와, 인산 변성 에폭시 수지 (b)와, 멜라민 화합물 (c)와, 실란 커플링제 (d)와, 2가의 금속 이온으로 교환된 실리카 입자 (e)를 포함한다. 그리고, (a), (b) 및 (c) 성분의 합계 100질량부에 대하여, 상기 비이온성 수분산성 수지 (a)의 함유량은 60~94.5질량부이고, 상기 인산 변성 에폭시 수지 (b)의 함유량은 5~39.5질량부이며, 상기 멜라민 화합물 (c)의 함유량은 0.5~10질량부이고, 상기 실란 커플링제 (d)의 함유량은 0.3~5질량부이다.The coating composition of the present invention includes a nonionic water-dispersible resin (a), a phosphoric acid-modified epoxy resin (b), a melamine compound (c), a silane coupling agent (d), and silica particles exchanged with divalent metal ions. Includes (e). And, based on a total of 100 parts by mass of components (a), (b) and (c), the content of the nonionic water-dispersible resin (a) is 60 to 94.5 parts by mass, and the content of the phosphoric acid modified epoxy resin (b) is 60 to 94.5 parts by mass. The content is 5 to 39.5 parts by mass, the content of the melamine compound (c) is 0.5 to 10 parts by mass, and the content of the silane coupling agent (d) is 0.3 to 5 parts by mass.
Description
본 발명은 도료 조성물 및 도장 금속판에 관한 것이다. The present invention relates to paint compositions and painted metal plates.
도장 금속판은, 일반적으로, 도금 강판 등의 금속판의 표면에 도료를 도포함으로써 제조된다. 도료로서는, 환경 부하를 저감시키는 관점 등에서, 용제계 도료 대신에 수계 도료가 이용되는 경우가 있다.Painted metal plates are generally manufactured by applying paint to the surface of a metal plate such as a plated steel plate. As a paint, a water-based paint may be used instead of a solvent-based paint from the viewpoint of reducing environmental load, etc.
그와 같은 수계 도료로서, 에폭시 수지 분산액과, 아크릴 수지 유탁(乳濁)액과, 인몰리브덴산 칼슘 등의 방청(防) 안료를 포함하는 도료 조성물이 제안되고 있다(예를 들면 특허문헌 1을 참조).As such a water-based paint, a paint composition containing an epoxy resin dispersion, an acrylic resin emulsion, and an anti-rust pigment such as calcium phosphomolybdate has been proposed (for example, see Patent Document 1 reference).
그러나, 특허문헌 1의 도료 조성물로부터 얻어지는 도막을 갖는 도장 금속판은, 고온 고습하에서 일정 시간 보존하면, 환경 중의 수분이 도막의 내부에 침입하여 도막이 부풀기 쉽다는 문제가 있다(후술하는 도 1의 (A) 참조). 또, 도료 조성물은, 보관 중의 점도 상승이 적어 양호한 보존 안정성을 가질 것도 요망되고 있다.However, the painted metal plate having a coating film obtained from the coating composition of Patent Document 1 has a problem in that when stored for a certain period of time under high temperature and high humidity, moisture in the environment enters the interior of the coating film and the coating film tends to swell (see Figure 1 (described later) (see A)). In addition, it is desired that the coating composition has a small increase in viscosity during storage and has good storage stability.
본 발명은, 상기 사정을 감안하여 이루어진 것이며, 양호한 보존 안정성을 가지면서, 고온 고습하에서의 도막의 부품을 억제할 수 있는 도료 조성물 및 도장 금속판을 제공하는 것을 목적으로 한다.The present invention has been made in consideration of the above-mentioned circumstances, and its purpose is to provide a coating composition and a painted metal plate that have good storage stability and are capable of suppressing damage to parts of the coating film under high temperature and high humidity.
본 발명은, 이하의 도료 조성물 및 도장 금속판에 관한 것이다.The present invention relates to the following coating composition and painted metal plate.
본 발명의 도료 조성물은, 비이온성의 수분산성 수지 (a)와, 인산 변성 에폭시 수지 (b)와, 멜라민 화합물 (c)와, 실란 커플링제 (d)와, 2가의 금속 이온으로 교환된 실리카 입자 (e)와, 물을 포함하며, 상기 비이온성의 수분산성 수지 (a), 상기 인산 변성 에폭시 수지 (b) 및 상기 멜라민 화합물 (c)의 합계 100질량부에 대하여, 상기 비이온성의 수분산성 수지 (a)의 함유량은 60~94.5질량부이고, 상기 인산 변성 에폭시 수지 (b)의 함유량은 5~39.5질량부이며, 상기 멜라민 화합물 (c)의 함유량은 0.5~10질량부이고, 상기 실란 커플링제 (d)의 함유량은 0.3~5질량부이다.The coating composition of the present invention includes a nonionic water-dispersible resin (a), a phosphoric acid-modified epoxy resin (b), a melamine compound (c), a silane coupling agent (d), and silica exchanged with a divalent metal ion. Containing particles (e) and water, the nonionic water is contained in a total of 100 parts by mass of the nonionic water-dispersible resin (a), the phosphoric acid-modified epoxy resin (b), and the melamine compound (c). The content of the acidic resin (a) is 60 to 94.5 parts by mass, the content of the phosphoric acid modified epoxy resin (b) is 5 to 39.5 parts by mass, the content of the melamine compound (c) is 0.5 to 10 parts by mass, and The content of the silane coupling agent (d) is 0.3 to 5 parts by mass.
본 발명의 도장 금속판은, 금속판과, 상기 금속판 상에 배치된 프라이머층을 가지며, 상기 프라이머층은 본 발명의 도료 조성물의 경화물로 이루어진다.The painted metal plate of the present invention has a metal plate and a primer layer disposed on the metal plate, and the primer layer is made of a cured product of the coating composition of the present invention.
본 발명에 의하면, 양호한 보존 안정성을 가지면서, 고온 고습하에서의 도막의 부품을 억제할 수 있는 도료 조성물 및 도장 금속판을 제공할 수 있다.According to the present invention, it is possible to provide a coating composition and a painted metal plate that have good storage stability and can suppress damage to parts of the coating film under high temperature and high humidity.
도 1의 (A)~(C)는 고온 고습하에서 보존한 후의 도막의 표면을 나타내는 사진이다.Figures 1 (A) to (C) are photographs showing the surface of the coating film after storage at high temperature and high humidity.
비이온성의 수분산성 수지 (a), 인산 변성 에폭시 수지 (b), 멜라민 화합물 (c), 실란 커플링제 (d), 2가의 금속 이온으로 교환된 실리카 입자 (e) 및 물을 소정 비율로 포함하는 본 발명의 도료 조성물(수계 도료 조성물)의 경화물은, 높은 내습성을 가질 수 있다. 이 이유는 명확하지 않지만 이하와 같이 추측된다.Contains a nonionic water-dispersible resin (a), a phosphoric acid-modified epoxy resin (b), a melamine compound (c), a silane coupling agent (d), silica particles exchanged with divalent metal ions (e), and water in a predetermined ratio. The cured product of the coating composition (water-based coating composition) of the present invention can have high moisture resistance. The reason for this is not clear, but is guessed as follows.
도 1의 (A)~(C)는 고온 고습하에서 보존 후의 도막의 표면을 나타내는 사진이다. 이 중, (A)는 비교용의 도막 1((a) 성분만을 포함하는 도막)의 관찰 결과이고, (B)는 비교용의 도막 2((a) 성분에, (b), (c) 및 (d) 성분을 첨가한 도막)의 관찰 결과이며, (C)는 본 발명의 도막((a), (b), (c) 및 (d) 성분에, (e) 성분을 첨가한 도막)의 관찰 결과이다.Figures 1 (A) to (C) are photographs showing the surface of the coating film after storage at high temperature and high humidity. Among these, (A) is the observation result of comparative coating film 1 (a coating film containing only component (a)), and (B) is the observation result of comparative coating film 2 ((a) component plus (b) and (c) and (d) a coating film to which component was added), and (C) is an observation result of the coating film of the present invention (a coating film to which component (e) was added to components (a), (b), (c) and (d). ) is the observation result.
먼저, 본 발명자들은, (a) 성분에, (b), (c) 및 (d) 성분(가교 성분)을 첨가함으로써, 도막의 내습성을 개선할 수 있다는 것을 알아냈다(도 1의 (B) 참조). 또한, 본 발명자들은, (b), (c) 및 (d) 성분에 더하여, 방청 성분을 추가로 첨가함으로써, 도막의 내습성을 더 개선할 수 없는지를 검토했다. 그 결과, 방청 성분으로서 "2가의 금속 이온으로 교환된 실리카 입자 (e)"를 첨가함으로써, 얻어지는 도막의 내습성을 현저하게 높일 수 있다는 것을 알아냈다(도 1의 (C) 참조).First, the present inventors found that the moisture resistance of the coating film could be improved by adding components (b), (c), and (d) (crosslinking components) to component (a) (Figure 1 (B) ) reference). Additionally, the present inventors examined whether the moisture resistance of the coating film could be further improved by additionally adding a rust preventive component in addition to components (b), (c), and (d). As a result, it was found that the moisture resistance of the resulting coating film could be significantly improved by adding "silica particles (e) exchanged with divalent metal ions" as a rust prevention component (see Figure 1(C)).
그리고, 이 검토로부터, 활성이 적절히 높고, 또한 (수중으로의) 금속 이온의 용출량이 많은 금속 이온 교환 실리카일수록, 도막의 내습성 개선 효과가 높다는 것을 알 수 있었다. 또, 도막의 내습성이 높은 것일수록, (b), (c) 및 (d) 성분을 포함하는 조성물의 경시적인 점도 상승을 발생시키기 쉽다는 것, 즉, (b) 성분과 (c) 성분의 가교 반응 등이 일어나기 쉽다는 것을 알 수 있었다.From this study, it was found that the metal ion-exchanged silica with a moderately high activity and a large amount of metal ions eluted (into water) has a higher effect on improving the moisture resistance of the coating film. In addition, the higher the moisture resistance of the coating film, the more likely it is that the composition containing components (b), (c), and (d) will increase in viscosity over time, that is, components (b) and (c). It was found that cross-linking reactions, etc. were likely to occur.
즉, 본 발명의 도료 조성물에서는, "2가의 금속 이온으로 교환된 실리카 입자 (e)"로부터 금속 이온이 적절히 용출되기 쉽고; 또한 이 금속 이온은 활성이 적절히 높기 때문에, 용출된 금속 이온이 인산 변성 에폭시 수지 (b)와 멜라민 화합물 (c)의 가교 반응이나, 실란 커플링제 (d)와 실리카 입자 (e)의 표면의 관능기의 가교 반응 또는 실란 커플링제 (d)와 멜라민 화합물 (c)의 가교 반응을 촉진시킨다(용출된 금속 이온이 촉매로서 작용한다)고 생각된다. 이로써, 가교 반응이 고도로 진행되기 쉽게 하여 높은 가교 밀도를 갖는 경화물이 얻어지기 때문에, 높은 내습성이 얻어진다고 생각된다.That is, in the coating composition of the present invention, metal ions are easily eluted appropriately from the “silica particles (e) exchanged with divalent metal ions”; In addition, since this metal ion has a moderately high activity, the eluted metal ion is used in the crosslinking reaction between the phosphoric acid-modified epoxy resin (b) and the melamine compound (c), or in the functional group on the surface of the silane coupling agent (d) and the silica particle (e). It is thought that it promotes the crosslinking reaction of or between the silane coupling agent (d) and the melamine compound (c) (eluted metal ions act as a catalyst). As a result, it is thought that high moisture resistance is obtained because the crosslinking reaction is facilitated to proceed to a high degree and a cured product with a high crosslink density is obtained.
한편, 가교 반응을 발생시키기 쉬운 도료 조성물은 보존 안정성이 낮아지기 쉽다. 이에 대하여, (a), (b), (c) 및 (d) 성분의 양비(量比)를 조정하는 것, 바람직하게는 추가로 (e) 성분의 종류를 선택함으로써, 경화물의 내습성을 저해하지 않고 보존 안정성을 높일 수 있다.On the other hand, coating compositions that are prone to crosslinking reactions tend to have lower storage stability. In contrast, the moisture resistance of the cured product can be improved by adjusting the amount ratio of components (a), (b), (c), and (d), and preferably by additionally selecting the type of component (e). Storage stability can be improved without damaging it.
즉, 본 발명의 도료 조성물은, 비이온성의 수분산성 수지 (a)와, 인산 변성 에폭시 수지 (b)와, 멜라민 화합물 (c)와, 실란 커플링제 (d)와, 2가의 금속 이온으로 교환된 실리카 입자 (e)와, 물을 포함하고, 또한 (a), (b) 및 (c)의 합계 100질량부에 대하여, (a), (b) 및 (c) 성분의 각 함유량이 소정의 범위로 조정되어 있다. 이하, 본 발명의 도료 조성물에 대하여 구체적으로 설명한다.That is, the coating composition of the present invention is a nonionic water-dispersible resin (a), a phosphoric acid-modified epoxy resin (b), a melamine compound (c), and a silane coupling agent (d) exchanged with a divalent metal ion. It contains silica particles (e) and water, and the respective contents of components (a), (b), and (c) are predetermined for a total of 100 parts by mass of (a), (b), and (c). It is adjusted to the range of . Hereinafter, the coating composition of the present invention will be described in detail.
1. 도료 조성물1. Paint composition
본 발명의 도료 조성물은, 비이온성의 수분산성 수지 (a)와, 인산 변성 에폭시 수지 (b)와, 멜라민 화합물 (c)와, 실란 커플링제 (d)와, 2가의 금속 이온으로 교환된 실리카 입자 (e)와, 물을 포함한다.The coating composition of the present invention includes a nonionic water-dispersible resin (a), a phosphoric acid-modified epoxy resin (b), a melamine compound (c), a silane coupling agent (d), and silica exchanged with a divalent metal ion. Contains particle (e) and water.
1-1. 비이온성의 수분산성 수지 (a)1-1. Nonionic water-dispersible resin (a)
비이온성의 수분산성 수지 (a)는, 비이온성의 친수성기를 갖고, 또한 이온성 관능기를 갖지 않는 수분산성 수지이다. 비이온성의 친수성기는, 수산기, 아미드기, 폴리옥시알킬렌기(예를 들면 폴리옥시에틸렌기) 등일 수 있다. 그중에서도, 비이온성의 친수성기는, 도료 조성물의 보존 안정성을 높이는 관점에서, 폴리옥시에틸렌기인 것이 바람직하다.The nonionic water-dispersible resin (a) is a water-dispersible resin that has a nonionic hydrophilic group and no ionic functional group. The nonionic hydrophilic group may be a hydroxyl group, an amide group, a polyoxyalkylene group (for example, a polyoxyethylene group), etc. Among them, the nonionic hydrophilic group is preferably a polyoxyethylene group from the viewpoint of improving the storage stability of the coating composition.
비이온성의 수분산성 수지 (a)의 예에는, 비이온성의 우레탄 수지, 비이온성의 아크릴 수지, 비이온성의 에폭시 수지, 비이온성의 폴리에스터 수지가 포함된다. 이들 수지는, 비이온성 계면활성제(또는 폴리옥시알킬렌기 등의 비이온성의 친수성기와, 반응성기를 갖는 분산제)의 존재하에서, 모노머를 중합하거나 또는 수지를 교반하여 얻어지는 수지여도 되고, 비이온성의 친수성기를 갖는 모노머를 포함하는 모노머 성분을 중합하여 얻어지는 수지여도 된다.Examples of the nonionic water-dispersible resin (a) include nonionic urethane resin, nonionic acrylic resin, nonionic epoxy resin, and nonionic polyester resin. These resins may be resins obtained by polymerizing monomers or stirring the resin in the presence of a nonionic surfactant (or a dispersant having a nonionic hydrophilic group such as a polyoxyalkylene group and a reactive group), and the nonionic hydrophilic group may be obtained by polymerizing the monomer or stirring the resin. A resin obtained by polymerizing a monomer component containing a monomer may be used.
비이온성의 우레탄 수지는, 예를 들면 폴리이소시아네이트 성분과, 비이온성의 친수성기(예를 들면 수산기)를 갖는 폴리올을 포함하는 폴리올 성분을 반응시켜 얻어지는 중합체일 수 있다.The nonionic urethane resin may be, for example, a polymer obtained by reacting a polyisocyanate component with a polyol component containing a polyol having a nonionic hydrophilic group (for example, a hydroxyl group).
폴리이소시아네이트 성분의 예에는, 시클로헥산디이소시아네이트, 디시클로헥실메탄디이소시아네이트, 이소포론디이소시아네이트 등의 지환식 구조를 갖는 폴리이소시아네이트; 4,4'-디페닐메탄디이소시아네이트, 2,4'-디페닐메탄디이소시아네이트, 페닐렌디이소시아네이트, 톨릴렌디이소시아네이트 등의 방향족 폴리이소시아네이트; 헥사메틸렌디이소시아네이트, 리신디이소시아네이트 등의 지방족 폴리이소시아네이트가 포함된다.Examples of the polyisocyanate component include polyisocyanates having an alicyclic structure such as cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate; Aromatic polyisocyanates such as 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, phenylene diisocyanate, and tolylene diisocyanate; Aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate are included.
비이온성의 친수성기를 갖는 폴리올의 예에는, 3가 이상의 폴리올(비이온성의 친수성기가 수산기인 경우), 폴리옥시에틸렌글리콜이나 폴리옥시에틸렌기와 적어도 2개의 수산기를 갖는 화합물(비이온성의 친수성기가 폴리옥시에틸렌기인 경우)이 포함된다.Examples of polyols having a nonionic hydrophilic group include trivalent or higher polyols (where the nonionic hydrophilic group is a hydroxyl group), polyoxyethylene glycol, or compounds having a polyoxyethylene group and at least two hydroxyl groups (where the nonionic hydrophilic group is a polyoxy group). (in case of ethylene group) is included.
폴리올 성분은, 상기 이외의 다른 폴리올을 더 포함해도 된다. 다른 폴리올의 예에는, 에틸렌글리콜, 프로필렌글리콜, 1,4-부탄디올, 1,6-헥산디올, 트리메틸올프로판, 글리세린 등의 지방족 폴리알코올류; 폴리에틸렌글리콜, 폴리프로필렌글리콜 등의 폴리에테르폴리올류; 아디프산, 세바스산, 프탈산, 이소프탈산 등의 디카복실산과 글리콜로부터 얻어지는 폴리에스터폴리올류가 포함된다.The polyol component may further contain polyols other than those mentioned above. Examples of other polyols include aliphatic polyalcohols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, and glycerin; polyether polyols such as polyethylene glycol and polypropylene glycol; Polyester polyols obtained from dicarboxylic acids such as adipic acid, sebacic acid, phthalic acid, and isophthalic acid, and glycols are included.
비이온성의 아크릴 수지는, 예를 들면, (메트)아크릴산 에스터와, 비이온성의 친수성기를 갖는 중합성 불포화 모노머의 공중합체일 수 있다. 비이온성의 친수성기를 갖는 중합성 불포화 모노머의 예에는, 수산기 함유 (메트)아크릴산 에스터, (메트)아크릴아미드, 폴리옥시알킬렌기를 갖는 중합성 불포화 모노머 등이 포함된다.The nonionic acrylic resin may be, for example, a copolymer of (meth)acrylic acid ester and a polymerizable unsaturated monomer having a nonionic hydrophilic group. Examples of polymerizable unsaturated monomers having a nonionic hydrophilic group include hydroxyl group-containing (meth)acrylic acid ester, (meth)acrylamide, and polymerizable unsaturated monomers having a polyoxyalkylene group.
비이온성의 폴리에스터 수지는, 예를 들면, 비이온성의 친수성기를 갖는 폴리올을 포함하는 폴리올 성분과, 폴리카복실산의 중축합체여도 된다. 비이온성의 친수성기를 갖는 폴리올은, 상술한 바와 동일한 것을 이용할 수 있다. 폴리카복실산의 예에는, 아디프산, 세바스산, 부탄트리카복실산 등의 지방족 폴리카복실산이나, 테레프탈산이나 트리멜리트산 등의 방향족 카복실산이 포함된다.The nonionic polyester resin may be, for example, a polycondensate of a polyol component containing a polyol having a nonionic hydrophilic group and polycarboxylic acid. The same polyols as described above can be used as the polyol having a nonionic hydrophilic group. Examples of polycarboxylic acids include aliphatic polycarboxylic acids such as adipic acid, sebacic acid, and butanetricarboxylic acid, and aromatic carboxylic acids such as terephthalic acid and trimellitic acid.
비이온성의 에폭시 수지는, 예를 들면 에폭시기와 반응할 수 있는 관능기(아미노기나 에폭시기)와 폴리옥시알킬렌기를 갖는 폴리옥시알킬렌 화합물의 존재하에서, 에폭시 수지를 교반하여 얻어지는 수지나; 에폭시기를 2 이상 갖는 화합물과, 폴리에틸렌글리콜 또는 그 모노에스터를 반응시켜 얻어지는 수지 등이 포함된다.Nonionic epoxy resins include, for example, resins obtained by stirring an epoxy resin in the presence of a polyoxyalkylene compound having a polyoxyalkylene group and a functional group (amino group or epoxy group) capable of reacting with an epoxy group; Resins obtained by reacting a compound having two or more epoxy groups with polyethylene glycol or its monoester are included.
그중에서도, 보존 안정성을 높이기 쉽다는 관점에서는, 비이온성의 아크릴 수지, 비이온성의 우레탄 수지가 바람직하다. 또, 얻어지는 도막의 내습성을 높이기 쉽다는 관점에서는, 비이온성의 에폭시 수지, 비이온성의 우레탄 수지가 바람직하다. 즉, 보존 안정성이 양호하고, 또한 도막의 내습성을 높이기 쉬우며, 도막의 밀착성 등도 우수하다는 관점에서는, 비이온성의 우레탄 수지가 특히 바람직하다.Among them, nonionic acrylic resin and nonionic urethane resin are preferable from the viewpoint of easy storage stability. Moreover, from the viewpoint of easy to increase the moisture resistance of the resulting coating film, nonionic epoxy resin and nonionic urethane resin are preferable. That is, nonionic urethane resins are particularly preferred from the viewpoint of good storage stability, easy to increase the moisture resistance of the coating film, and excellent adhesion of the coating film.
비이온성의 수분산성 수지 (a)의 중량 평균 분자량은, 특별히 제한되지 않지만, 예를 들면 50000~1000000인 것이 바람직하다. 비이온성 수분산성 수지 (a)의 중량 평균 분자량이 50000 이상이면, 얻어지는 도막에 충분한 강도 또는 가요성을 부여하기 쉽고, 1000000 이하이면, 도료 조성물의 점도 상승을 억제하기 쉬워 도공성이 저해되기 어렵다.The weight average molecular weight of the nonionic water-dispersible resin (a) is not particularly limited, but is preferably, for example, 50,000 to 1,000,000. If the weight average molecular weight of the nonionic water-dispersible resin (a) is 50,000 or more, it is easy to provide sufficient strength or flexibility to the resulting coating film, and if it is 1,000,000 or less, it is easy to suppress an increase in the viscosity of the coating composition and coatability is unlikely to be impaired.
중량 평균 분자량은, JIS K 0124-2011에 준하여, 젤 퍼미에이션 크로마토그래피로 측정한 크로마토그램으로부터 표준 폴리스티렌의 분자량을 기준으로 하여 산출할 수 있다.The weight average molecular weight can be calculated based on the molecular weight of standard polystyrene from a chromatogram measured by gel permeation chromatography in accordance with JIS K 0124-2011.
비이온성의 수분산성 수지 (a)의 함유량은, (a), (b) 및 (c) 성분의 합계 100질량부에 대하여 60~94.5질량부인 것이 바람직하다. 비이온성의 수분산성 수지 (a)의 함유량이 60질량부 이상이면, 비이온성의 수분산성 수지 (a)는, 예를 들면 인산 변성 에폭시 수지 (b)보다 2가의 금속 이온으로 교환된 실리카 입자 (e)로부터 용출된 금속 이온에 의하여 반응이 촉진되기 어렵기 때문에, 도료 조성물의 보존 안정성을 높이기 쉽다. 비이온성의 수분산성 수지 (a)의 함유량이 94.5질량부 이하이면, 얻어지는 도막의 내습성이나 밀착성, 내식성이 저해되기 어렵다. 비이온성의 수분산성 수지 (a)의 함유량은, 동일한 관점에서, (a), (b) 및 (c) 성분의 합계 100질량부에 대하여 70~89질량부인 것이 보다 바람직하며, 70~85질량부인 것이 보다 바람직하다.The content of the nonionic water-dispersible resin (a) is preferably 60 to 94.5 parts by mass with respect to a total of 100 parts by mass of components (a), (b), and (c). When the content of the nonionic water-dispersible resin (a) is 60 parts by mass or more, the nonionic water-dispersible resin (a) is, for example, silica particles exchanged with divalent metal ions than the phosphoric acid-modified epoxy resin (b) ( Since the reaction is difficult to promote by the metal ion eluted from e), it is easy to increase the storage stability of the coating composition. If the content of the nonionic water-dispersible resin (a) is 94.5 parts by mass or less, the moisture resistance, adhesion, and corrosion resistance of the resulting coating film are unlikely to be impaired. From the same viewpoint, the content of the nonionic water-dispersible resin (a) is more preferably 70 to 89 parts by mass, and 70 to 85 parts by mass, based on a total of 100 parts by mass of the components (a), (b) and (c). It is more desirable to deny it.
1-2. 인산 변성 에폭시 수지 (b)1-2. Phosphoric acid modified epoxy resin (b)
인산 변성 에폭시 수지 (b)는, 도막의 금속판과의 밀착성이나 내습성을 높일 수 있다. 인산 변성 에폭시 수지 (b)는, 에폭시 수지를 인산 결합을 갖는 화합물과 반응시켜 얻어지는 수지이며, 휘발성 아민 등의 염기로 중화함으로써 에멀션을 형성할 수 있다.The phosphoric acid modified epoxy resin (b) can improve the adhesion and moisture resistance of the coating film to the metal plate. The phosphoric acid modified epoxy resin (b) is a resin obtained by reacting an epoxy resin with a compound having a phosphoric acid bond, and can form an emulsion by neutralizing it with a base such as a volatile amine.
원료가 되는 에폭시 수지는 특별히 제한되지 않고, 그 예에는, 비스페놀 A형 에폭시 수지나 비스페놀 F형 에폭시 수지 등의 비스페놀형 에폭시 수지; 비페닐형 에폭시 수지; 노볼락형 에폭시 수지; 나프탈렌형 에폭시 수지; 시클로헥산디메탄올이나 수소 첨가 비스페놀 A 등으로부터 얻어지는 지환식 에폭시 수지가 포함된다. 그중에서도, 밀착성, 내식성의 관점에서, 비스페놀 A형의 에폭시 수지가 바람직하다.The epoxy resin used as a raw material is not particularly limited, and examples thereof include bisphenol-type epoxy resins such as bisphenol A-type epoxy resin and bisphenol F-type epoxy resin; Biphenyl type epoxy resin; Novolak-type epoxy resin; Naphthalene type epoxy resin; Alicyclic epoxy resins obtained from cyclohexanedimethanol, hydrogenated bisphenol A, etc. are included. Among them, from the viewpoint of adhesion and corrosion resistance, bisphenol A type epoxy resin is preferable.
에폭시 수지의 중량 평균 분자량은, 800~50000인 것이 바람직하다. 에폭시 수지의 중량 평균 분자량이 800 이상이면, 얻어지는 도막에 충분한 가요성을 부여하기 쉽고, 50000 이하이면, 도료 조성물의 점도 상승을 억제하기 쉬워 도공성이 저해되기 어렵다.The weight average molecular weight of the epoxy resin is preferably 800 to 50,000. If the weight average molecular weight of the epoxy resin is 800 or more, it is easy to provide sufficient flexibility to the resulting coating film, and if it is 50,000 or less, it is easy to suppress an increase in the viscosity of the coating composition and coatability is unlikely to be impaired.
인산 결합을 갖는 화합물은, 특별히 한정되지 않지만, 그 예에는, 메타인산, 오르토인산, 피로인산 등 인산류; 디에틸포스페이트, 디부틸포스페이트, 디옥틸포스페이트 등의 인산 에스터가 포함된다.The compound having a phosphoric acid bond is not particularly limited, and examples include phosphoric acids such as metaphosphoric acid, orthophosphoric acid, and pyrophosphoric acid; Phosphate esters such as diethyl phosphate, dibutyl phosphate, and dioctyl phosphate are included.
에폭시 수지와 반응시키는 인산 결합을 갖는 화합물의 양(변성량)은, 에폭시 수지의 에폭시기 1몰에 대하여 인산 결합을 갖는 화합물의 인산기의 몰수가, 예를 들면 0.1~1.5몰이 되는 양인 것이 바람직하다.The amount (modified amount) of the compound having a phosphoric acid bond to be reacted with the epoxy resin is preferably such that the number of moles of phosphoric acid groups of the compound having a phosphoric acid bond is, for example, 0.1 to 1.5 moles per mole of epoxy groups of the epoxy resin.
중화에 이용되는 휘발성 아민의 예에는, 트리에틸아민 등이 포함된다.Examples of volatile amines used for neutralization include triethylamine and the like.
인산 변성 에폭시 수지 (b)의 함유량은, (a), (b) 및 (c) 성분의 합계 100질량부에 대하여 5~39.5질량부인 것이 바람직하다. 인산 변성 에폭시 수지 (b)의 함유량이 5질량부 이상이면, 멜라민 화합물 (c)와의 가교 반응 등에 의하여 가교 밀도가 높은 경화물을 형성할 수 있기 때문에, 도막의 금속판과의 밀착성이나 내습성을 높이기 쉽고, 39.5질량부 이하이면, 보존 중에 멜라민 화합물 (c)와의 가교 반응 등에 의한 점도 상승을 발생시키기 어렵기 때문에, 도료 조성물의 보존 안정성이 저해되기 어렵다. 인산 변성 에폭시 수지 (b)의 함유량은, 동일한 관점에서, (a), (b) 및 (c) 성분의 합계 100질량부에 대하여 10~29질량부인 것이 보다 바람직하며, 15~25질량부인 것이 더 바람직하다.The content of the phosphoric acid modified epoxy resin (b) is preferably 5 to 39.5 parts by mass based on a total of 100 parts by mass of components (a), (b), and (c). When the content of the phosphoric acid modified epoxy resin (b) is 5 parts by mass or more, a cured product with a high crosslinking density can be formed through a crosslinking reaction with the melamine compound (c), thereby improving the adhesion of the coating film to the metal plate and moisture resistance. If it is 39.5 parts by mass or less, it is difficult to cause a viscosity increase due to a crosslinking reaction with the melamine compound (c) during storage, so the storage stability of the coating composition is unlikely to be impaired. From the same viewpoint, the content of the phosphoric acid modified epoxy resin (b) is more preferably 10 to 29 parts by mass, and 15 to 25 parts by mass, based on a total of 100 parts by mass of the components (a), (b) and (c). It is more desirable.
또, 인산 변성 에폭시 수지 (b)의 함유량은, 상기와 동일한 관점에서, 비이온성의 수분산성 수지 (a)와 인산 변성 에폭시 수지 (b)의 합계 100질량부에 대하여, 5~40질량부인 것이 바람직하고, 10~30질량부인 것이 보다 바람직하며, 15~30질량부인 것이 더 바람직하다.In addition, from the same viewpoint as above, the content of the phosphoric acid-modified epoxy resin (b) is 5 to 40 parts by mass with respect to a total of 100 parts by mass of the nonionic water-dispersible resin (a) and the phosphoric acid-modified epoxy resin (b). It is preferable, it is more preferable that it is 10-30 mass parts, and it is still more preferable that it is 15-30 mass parts.
1-3. 멜라민 화합물 (c)1-3. Melamine compound (c)
멜라민 화합물 (c)는, 인산 변성 에폭시 수지 (b)의 경화제로서 기능할 수 있다. 이로써, 도료 조성물의 경화물은 양호한 내습성이나 내식성(특히 내습성)을 가질 수 있다.The melamine compound (c) can function as a curing agent for the phosphoric acid modified epoxy resin (b). As a result, the cured product of the coating composition can have good moisture resistance and corrosion resistance (especially moisture resistance).
멜라민 화합물 (c)의 종류는, 특별히 한정되지 않고, 멜라민 경화제로서 공지의 것을 이용할 수 있다. 멜라민 화합물 (c)는, 예를 들면 멜라민과 알데히드를 반응시켜 얻어지는 메틸올화 멜라민 화합물이나, 그 메틸올기의 적어도 일부가 알코올류(예를 들면 메틸알코올, 에틸알코올, n-프로필알코올, 이소프로필알코올, n-부틸알코올, 이소부틸알코올, 2-에틸부탄올, 2-에틸헥산올 등의 1가 알코올)에 의하여 에테르화된 것을 들 수 있다.The type of melamine compound (c) is not particularly limited, and a known melamine curing agent can be used. The melamine compound (c) is, for example, a methylolated melamine compound obtained by reacting melamine with an aldehyde, or at least part of the methylol group is alcohol (e.g., methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol) , monohydric alcohols such as n-butyl alcohol, isobutyl alcohol, 2-ethylbutanol, and 2-ethylhexanol).
메틸올화 멜라민 화합물의 예에는, 트리메틸올멜라민, 헥사메틸올멜라민, 트리부틸올멜라민, 헥사부틸올멜라민이 포함된다. 메틸올화 멜라민 화합물의 에테르화물의 예에는, 메톡시메틸멜라민(예를 들면 헥사메톡시메틸멜라민 등), 에톡시메틸멜라민, 에톡시부틸멜라민, 부톡시부틸멜라민이 포함된다.Examples of methylolated melamine compounds include trimethylolmelamine, hexamethylolmelamine, tributylolmelamine, and hexabutylolmelamine. Examples of etherified products of methylolated melamine compounds include methoxymethylmelamine (for example, hexamethoxymethylmelamine, etc.), ethoxymethylmelamine, ethoxybutylmelamine, and butoxybutylmelamine.
그중에서도, 도료 조성물의 보존 안정성을 높이기 쉽게 하는 관점에서는, 메틸올화 멜라민 화합물의 메틸올기의 적어도 일부를 탄소 원자수 1~4의 1가 알코올로 에테르화하여 얻어지는 멜라민 화합물이 바람직하다.Among them, from the viewpoint of easily increasing the storage stability of the coating composition, a melamine compound obtained by etherifying at least part of the methylol group of a methylolated melamine compound with a monohydric alcohol having 1 to 4 carbon atoms is preferable.
멜라민 화합물 (c)의 함유량은, (a), (b) 및 (c) 성분의 합계 100질량부에 대하여 0.5~10질량부인 것이 바람직하다. 멜라민 화합물 (c)의 함유량이 0.5질량부 이상이면, 인산 변성 에폭시 수지 (b)를 충분히 가교시키기 쉽기 때문에, 도막의 금속판과의 밀착성이나 내습성, 내식성을 높이기 쉽고, 10질량부 이하이면, 보존 중에 인산 변성 에폭시 수지 (b)의 가교 반응 등에 의한 점도 상승을 발생시키기 어렵기 때문에, 보존 안정성이 저해되기 어렵다. 멜라민 화합물 (c)의 함유량은, 동일한 관점에서, (a), (b) 및 (c) 성분의 합계 100질량부에 대하여 1~8질량부인 것이 보다 바람직하며, 3~8질량부인 것이 더 바람직하다.The content of the melamine compound (c) is preferably 0.5 to 10 parts by mass based on a total of 100 parts by mass of components (a), (b), and (c). If the content of the melamine compound (c) is 0.5 parts by mass or more, it is easy to sufficiently crosslink the phosphoric acid-modified epoxy resin (b), so it is easy to improve the adhesion, moisture resistance, and corrosion resistance of the coating film to the metal plate, and if it is 10 parts by mass or less, it can be preserved. Since it is difficult to cause an increase in viscosity due to a crosslinking reaction of the phosphoric acid-modified epoxy resin (b), etc., storage stability is unlikely to be impaired. From the same viewpoint, the content of the melamine compound (c) is more preferably 1 to 8 parts by mass, and more preferably 3 to 8 parts by mass, based on a total of 100 parts by mass of the components (a), (b) and (c). do.
1-4. 실란 커플링제 (d)1-4. Silane coupling agent (d)
실란 커플링제 (d)는, 도막의 금속판과의 밀착성을 높일 수 있다. 또, 실란 커플링제 (d)는, 후술하는 2가의 금속 이온으로 교환된 실리카 입자 (e)의 표면의 관능기와 가교 반응함으로써, 얻어지는 도막의 내습성이나 밀착성을 더 높일 수 있다.The silane coupling agent (d) can increase the adhesion of the coating film to the metal plate. In addition, the silane coupling agent (d) can further improve the moisture resistance and adhesion of the resulting coating film by crosslinking with the functional groups on the surface of the silica particles (e) exchanged with divalent metal ions, which will be described later.
실란 커플링제 (d)는, 분자 내에, 가수분해로 실란올기(Si-OH)를 부여하는 알콕시기 등과, 에폭시기, 비닐이기, 아미노기, 머캅토기 또는 알킬기 등의 유기기를 갖는 화합물을 말한다. The silane coupling agent (d) refers to a compound having in the molecule an alkoxy group that gives a silanol group (Si-OH) by hydrolysis, and an organic group such as an epoxy group, vinyl group, amino group, mercapto group, or alkyl group.
실란 커플링제 (d)의 예에는, 3-글리시독시프로필트리메톡시실란, 3-글리시독시프로필트리에톡시실란, 3-글리시독시프로필메틸디메톡시실란, 3-글리시독시프로필메틸디에톡시실란, 3-글리시독시프로필트리프로폭시실란, 3-글리시독시프로필트리부톡시실란, 3-글리시독시프로필트리페녹시실란, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란 등의, 분자 내에 에폭시기를 갖는 에폭시계 실란 커플링제; 비닐트리메톡시실란, 비닐메톡시실란 등의, 분자 내에 비닐기를 갖는 비닐계 실란 커플링제; 아미노메틸트리메톡시실란, 아미노메틸트리에톡시실란, 아미노메틸트리프로폭시실란, 아미노메틸트리부톡시실란, 아미노메틸트리페녹시실란, 아미노에틸트리메톡시실란, γ-아미노프로필트리메톡시실란 등의, 분자 내에 아미노기를 갖는 아민계 실란 커플링제; 머캅토메틸트리메톡시실란, 머캅토메틸트리에톡시실란, 머캅토메틸트리프로폭시실란, 머캅토메틸트리부톡시실란, 머캅토메틸트리페녹시실란, γ-머캅토프로필메틸디에톡시실란 등의, 분자 내에 머캅토기를 갖는 머캅토계 실란 커플링제 등이 포함된다. 그중에서도, 인산 변성 에폭시 수지 (b)와의 친화성이 양호하고, 또한 멜라민 화합물 (c)와의 가교 반응도 가능하며, 내습성이 높은 경화물을 얻기 쉽다는 관점 등에서, 에폭시계 실란 커플링제가 바람직하다.Examples of the silane coupling agent (d) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyl. Diethoxysilane, 3-glycidoxypropyltripropoxysilane, 3-glycidoxypropyltributoxysilane, 3-glycidoxypropyltriphenoxysilane, 2-(3,4-epoxycyclohexyl)ethyltri Epoxy-based silane coupling agents having an epoxy group in the molecule, such as methoxysilane; Vinyl-based silane coupling agents having a vinyl group in the molecule, such as vinyltrimethoxysilane and vinylmethoxysilane; Aminomethyltrimethoxysilane, Aminomethyltriethoxysilane, Aminomethyltripropoxysilane, Aminomethyltributoxysilane, Aminomethyltriphenoxysilane, Aminoethyltrimethoxysilane, γ-aminopropyltrimethoxysilane Amine-based silane coupling agents having an amino group in the molecule, such as; Mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyltripropoxysilane, mercaptomethyltributoxysilane, mercaptomethyltriphenoxysilane, γ-mercaptopropylmethyldiethoxysilane, etc. , mercapto-based silane coupling agents having a mercapto group in the molecule, etc. Among them, an epoxy-based silane coupling agent is preferable from the viewpoints of having good affinity with the phosphoric acid-modified epoxy resin (b), enabling a crosslinking reaction with the melamine compound (c), and being easy to obtain a cured product with high moisture resistance.
실란 커플링제 (d)의 함유량은, (a), (b) 및 (c) 성분의 합계 100질량부에 대하여 0.3~5질량부인 것이 바람직하다. 실란 커플링제 (d)의 함유량이 0.3질량부 이상이면, 도막의 금속판과의 밀착성이나 내습성, 내식성을 높이기 쉽고, 5질량부 이하이면, 도료 조성물의 보존 안정성이 저해되기 어렵다. 실란 커플링제 (d)의 함유량은, 동일한 관점에서, (a), (b) 및 (c) 성분의 합계 100질량부에 대하여 1~4질량부인 것이 보다 바람직하며, 1.5~3질량부인 것이 더 바람직하다.The content of the silane coupling agent (d) is preferably 0.3 to 5 parts by mass based on a total of 100 parts by mass of components (a), (b), and (c). If the content of the silane coupling agent (d) is 0.3 parts by mass or more, the adhesion, moisture resistance, and corrosion resistance of the coating film to the metal plate are likely to be improved, and if the content is 5 parts by mass or less, the storage stability of the coating composition is unlikely to be impaired. From the same viewpoint, the content of the silane coupling agent (d) is more preferably 1 to 4 parts by mass, and more preferably 1.5 to 3 parts by mass, based on a total of 100 parts by mass of components (a), (b) and (c). desirable.
1-5. 2가의 금속 이온으로 교환된 실리카 입자 (e)1-5. Silica particles exchanged with divalent metal ions (e)
2가의 금속 이온으로 교환된 실리카 입자 (e)는, 실리카 입자 표면의 수산기의 적어도 일부가 이온 교환에 의하여 2가의 금속 이온으로 치환된 실리카 입자이다. 2가의 금속 이온으로 교환된 실리카 입자 (e)는, 도막의 내습성이나 내식성을 높일 수 있다.The silica particles (e) exchanged with divalent metal ions are silica particles in which at least part of the hydroxyl groups on the surface of the silica particles are replaced with divalent metal ions by ion exchange. Silica particles (e) exchanged with divalent metal ions can improve the moisture resistance and corrosion resistance of the coating film.
2가의 금속 이온으로 교환된 실리카 입자 (e)는, 특별히 제한되지 않고, 그 예에는, 칼슘(Ca) 교환 실리카, 마그네슘(Mg) 교환 실리카, 스트론튬(Sr) 교환 실리카, 망간(Mn) 교환 실리카가 포함된다. 그중에서도, 2가의 알칼리 토류 금속 이온으로 교환된 실리카 입자인 것이 바람직하고, 양호한 내습성과 내식성을 갖는 도막을 부여하기 쉽다는 관점에서는, 칼슘(Ca) 교환 실리카, 마그네슘(Mg) 교환 실리카가 바람직하며, 보존 안정성을 더 높이기 쉽다는 관점에서, 마그네슘(Mg) 교환 실리카가 바람직하다.The silica particles (e) exchanged with divalent metal ions are not particularly limited, and examples include calcium (Ca) exchanged silica, magnesium (Mg) exchanged silica, strontium (Sr) exchanged silica, and manganese (Mn) exchanged silica. is included. Among them, silica particles exchanged with divalent alkaline earth metal ions are preferable, and from the viewpoint of ease of providing a coating film with good moisture resistance and corrosion resistance, calcium (Ca) exchanged silica and magnesium (Mg) exchanged silica are preferable. From the viewpoint of easier storage stability, magnesium (Mg) exchanged silica is preferred.
2가의 금속 이온으로 교환된 실리카 입자 (e)의 평균 입자경은, 특별히 제한되지 않지만, 예를 들면 1~5μm일 수 있다. 2가의 금속 이온으로 교환된 실리카 입자 (e)의 평균 입자경은, 예를 들면 레이저 회절·산란법으로 얻어지는 체적 분포에 있어서의 메디안 직경으로서 측정할 수 있다.The average particle diameter of the silica particles (e) exchanged with divalent metal ions is not particularly limited, but may be, for example, 1 to 5 μm. The average particle diameter of the silica particles (e) exchanged with divalent metal ions can be measured, for example, as the median diameter in the volume distribution obtained by a laser diffraction/scattering method.
2가의 금속 이온으로 교환된 실리카 입자 (e)에 있어서 금속 이온 교환량은, 특별히 한정되지 않지만, (금속 이온을 포함하지 않는) 실리카 담체에 대하여 예를 들면 4~8질량%로 할 수 있다. 금속 이온 교환량이 일정 이상이면, (금속 이온의 종류에 따라서도 다르지만) 금속 이온 용출량을 높이기 쉽고, 이로써 인산 변성 에폭시 수지 (b)와 멜라민 화합물 (c)의 가교 반응 등을 촉진하기 쉽다.In the silica particles (e) exchanged with divalent metal ions, the amount of metal ion exchange is not particularly limited, but can be, for example, 4 to 8% by mass relative to the silica carrier (which does not contain metal ions). If the amount of metal ion exchange is above a certain level, it is easy to increase the amount of metal ion elution (although it varies depending on the type of metal ion), and thus it is easy to promote the crosslinking reaction between the phosphoric acid-modified epoxy resin (b) and the melamine compound (c).
금속 이온 교환량은, 예를 들면 금속 이온 교환 실리카의 조제 시의 원료의 투입비로부터 구할 수 있다. 또, 이하의 방법으로 구할 수도 있다.The amount of metal ion exchange can be determined, for example, from the input ratio of the raw materials when preparing metal ion exchange silica. Additionally, it can also be obtained by the following method.
1) 2가의 금속 이온으로 교환된 실리카 입자 (e)를, 1질량%의 염화 나트륨 수용액에 일정량 첨가하여, 23℃에서 30분간 충분히 교반한다.1) A certain amount of silica particles (e) exchanged with divalent metal ions is added to a 1% by mass aqueous solution of sodium chloride, and thoroughly stirred at 23°C for 30 minutes.
2) 교반 후의 수용액에 포함되는 2가의 금속 이온의 양(실리카 담체에 대한 질량%)을, 이온 크로마토그래피에 의하여 측정하여 금속 이온 교환량으로 한다.2) The amount of divalent metal ions (% by mass relative to the silica carrier) contained in the aqueous solution after stirring is measured by ion chromatography to determine the amount of metal ion exchange.
도료 조성물 중에서의 금속 이온의 용출량은, 예를 들면 2가의 금속 이온으로 교환된 실리카 입자 (e)에 있어서의 금속 이온 교환량이나, 금속 이온의 종류, 금속 이온 교환 실리카의 제조 조건 등에 의하여 조정될 수 있다. 금속 이온의 용출량을 적절히 많게 하기 위해서는, 예를 들면 금속 이온 교환량을 적절히 많게 하거나, 금속 이온으로서 2가의 알칼리토류 금속 이온을 선택하는 것이 바람직하다.The amount of metal ions eluted from the coating composition can be adjusted, for example, depending on the amount of metal ions exchanged in the silica particles (e) exchanged with divalent metal ions, the type of metal ion, and the manufacturing conditions of the metal ion exchanged silica. there is. In order to appropriately increase the amount of metal ions eluted, for example, it is desirable to appropriately increase the amount of metal ion exchange or to select a divalent alkaline earth metal ion as the metal ion.
2가의 금속 이온으로 교환된 실리카 입자 (e)의 함유량은, (a), (b) 및 (c) 성분의 합계 100질량부에 대하여 5~70질량부인 것이 바람직하다. 2가의 금속 이온으로 교환된 실리카 입자 (e)의 함유량이 5질량부 이상이면, (b) 성분과 (c) 성분의 가교 반응 등을 충분히 촉진시키기 쉽기 때문에, 도막의 금속판과의 밀착성이나 내습성, 내식성(특히 내습성)을 높이기 쉽고, 70질량부 이하이면, 보존 중에 (b) 성분과 (c) 성분의 가교 반응 등에 의한 점도 상승이 발생하기 어렵기 때문에, 도료 조성물의 보존 안정성이 저해되기 어렵다. 2가의 금속 이온으로 교환된 실리카 입자 (e)의 함유량은, 동일한 관점에서, (a), (b) 및 (c) 성분의 합계 100질량부에 대하여 7.5~55질량부인 것이 보다 바람직하며, 15~45질량부인 것이 더 바람직하다.The content of silica particles (e) exchanged with divalent metal ions is preferably 5 to 70 parts by mass with respect to a total of 100 parts by mass of components (a), (b) and (c). If the content of silica particles (e) exchanged with divalent metal ions is 5 parts by mass or more, it is easy to sufficiently promote the crosslinking reaction of component (b) and component (c), so the adhesion and moisture resistance of the coating film to the metal plate are improved. , it is easy to increase corrosion resistance (especially moisture resistance), and if it is 70 parts by mass or less, it is difficult for a viscosity increase due to a crosslinking reaction of component (b) and component (c) to occur during storage, so the storage stability of the coating composition is impaired. difficult. From the same viewpoint, the content of silica particles (e) exchanged with divalent metal ions is more preferably 7.5 to 55 parts by mass based on a total of 100 parts by mass of components (a), (b) and (c), and is 15 It is more preferable that it is ~45 parts by mass.
1-6. 다른 성분1-6. other ingredients
본 발명의 도료 조성물은, 필요에 따라 (a)~(e) 성분 및 물 이외의 다른 성분을 더 포함할 수 있다. 다른 성분의 예에는, 수용성 유기 용제(예를 들면 메탄올, 에탄올, n-프로판올 등의 알코올류; 아세톤, 메틸에틸케톤 등의 케톤류; 에틸렌글리콜, 디에틸렌글리콜, 프로필렌글리콜 등의 폴리알킬렌글리콜류), 유화제(비이온성 계면활성제, 예를 들면 폴리옥시에틸렌알킬에테르, 폴리옥시알킬렌알킬에테르, 폴리옥시에틸렌 유도체, 소르비탄 지방산 에스터, 폴리옥시에틸렌 소르비탄 지방산 에스터, 폴리옥시에틸렌 소르비톨 지방산 에스터, 글리세린 지방산 에스터, 폴리옥시에틸렌 지방산 에스터 등), (e) 성분 이외의 방청제(예를 들면 인산 아연, 아인산 아연, 인산 아연 마그네슘, 인산 마그네슘, 아인산 마그네슘, 실리카, 인산 지르코늄, 트리폴리인산 2수소 알루미늄, 산화 아연, 인몰리브덴산 아연, 메타붕산 바륨 및 크롬산 스트론튬), pH 조정제(트리에틸아민, 트리에탄올아민, 수산화 나트륨, 탄산 나트륨, 탄산 칼륨 등의 알칼리류나, 염산, 아세트산, 시트르산 등의 산류), 조막(造膜) 조제(부틸셀로솔브, 텍산올, 카르비톨 등의, 비점 150~250℃의 수용성 유기 용제), 안료(산화 티타늄, 카본 블랙, 산화 크롬, 산화 철, 벵갈라 등의 착색 안료, 황산 바륨, 산화 티타늄, 실리카 및 탄산 칼슘 등의 체질 안료)가 포함된다.The coating composition of the present invention may further contain other components other than components (a) to (e) and water, if necessary. Examples of other ingredients include water-soluble organic solvents (e.g., alcohols such as methanol, ethanol, and n-propanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol, and propylene glycol) ), emulsifiers (nonionic surfactants, such as polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, polyoxyethylene derivatives, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, etc.), rust inhibitors other than component (e) (e.g. zinc phosphate, zinc phosphite, magnesium zinc phosphate, magnesium phosphate, magnesium phosphite, silica, zirconium phosphate, aluminum dihydrogen tripolyphosphate, Zinc oxide, zinc phosphomolybdate, barium metaborate, and strontium chromate), pH adjusters (alkalies such as triethylamine, triethanolamine, sodium hydroxide, sodium carbonate, and potassium carbonate, and acids such as hydrochloric acid, acetic acid, and citric acid), film forming agents Preparations (water-soluble organic solvents with a boiling point of 150 to 250°C, such as butylcellosolve, texanol, and carbitol), pigments (colored pigments such as titanium oxide, carbon black, chromium oxide, iron oxide, and Bengala, etc.) body pigments such as barium sulfate, titanium oxide, silica, and calcium carbonate).
다른 성분(수용성 유기 용제를 제외한다)의 합계 함유량은, (a), (b) 및 (c) 성분의 합계 100질량부에 대하여 10질량부 이하일 수 있다.The total content of other components (excluding water-soluble organic solvents) may be 10 parts by mass or less based on a total of 100 parts by mass of components (a), (b), and (c).
본 발명의 도료 조성물은, 임의의 방법으로 얻을 수 있다 예를 들면, 본 발명의 도료 조성물은, (a)~(e) 성분과, 물과, 필요에 따라 유화제 등의 다른 성분을 혼합하여 얻을 수 있다 또한, (a) 및 (b) 성분은, 수분산체의 형태로 사용되어도 된다. 즉, 본 발명의 도료 조성물은, (a) 및 (b) 성분의 수분산체에, (c)~(e) 성분과, 필요에 따라 다른 성분을 혼합하여 얻을 수도 있다.The coating composition of the present invention can be obtained by any method. For example, the coating composition of the present invention can be obtained by mixing components (a) to (e), water, and, if necessary, other components such as an emulsifier. Additionally, components (a) and (b) may be used in the form of an aqueous dispersion. That is, the coating composition of the present invention can be obtained by mixing the water dispersion of components (a) and (b) with components (c) to (e) and, if necessary, other components.
본 발명의 도료 조성물은, 높은 보존 안정성을 가지면서, 내습성이 높은 도막을 부여할 수 있다. 따라서, 도료 조성물은 금속판의 프라이머층용의 도료 조성물로서 바람직하게 이용된다.The coating composition of the present invention can provide a coating film with high moisture resistance while having high storage stability. Therefore, the coating composition is preferably used as a coating composition for the primer layer of a metal plate.
2. 도장 금속판2. Painted metal plate
본 발명의 도장 금속판은, 금속판과, 그 위에 배치된 프라이머층을 갖는다.The painted metal plate of the present invention has a metal plate and a primer layer disposed thereon.
2-1. 금속판2-1. plate
도장 원판이 되는 금속판은, 도장 금속판의 용도에 따라 적절히 선택할 수 있다. 금속판의 예에는, 아연 도금 강판, Zn-Al 합금 도금 강판, Zn-Al-Mg 합금 도금 강판, 알루미늄 도금 강판 등의 도금 강판; 냉연(冷延) 강판, 스테인리스 강판(오스테나이트계, 마르텐사이트계, 페라이트계, 페라이트·마르텐사이트 2상계를 포함한다) 등의 강판; 알루미늄판; 알루미늄 합금판; 및 구리판이 포함된다. 그중에서도, 내식성을 높이는 관점에서, 금속판은 도금 강판인 것이 바람직하고, 용융 도금 강판인 것이 보다 바람직하다. 도금 강판의 도금 부착량은, 특별히 제한되지 않지만, 예를 들면 30~500g/m2일 수 있다.The metal plate that becomes the painted original plate can be appropriately selected depending on the intended use of the painted metal plate. Examples of metal plates include plated steel plates such as galvanized steel plates, Zn-Al alloy plated steel plates, Zn-Al-Mg alloy plated steel plates, and aluminum plated steel plates; Steel sheets such as cold-rolled steel sheets and stainless steel sheets (including austenitic, martensitic, ferritic, and ferrite-martensite dual-phase systems); aluminum plate; Aluminum alloy plate; and copper plates. Among them, from the viewpoint of improving corrosion resistance, the metal plate is preferably a plated steel plate, and more preferably a hot-dip plated steel plate. The plating adhesion amount of the plated steel sheet is not particularly limited, but may be, for example, 30 to 500 g/m 2 .
금속판의 두께는 용도나 가공성에 따라 설정되면 되고, 특별히 제한되지 않지만, 예를 들면 0.1~2mm인 것이 바람직하다.The thickness of the metal plate may be set depending on the purpose or processability and is not particularly limited, but is preferably, for example, 0.1 to 2 mm.
금속판은, 도장 금속판의 내식성 및 도막 밀착성을 높이는 관점에서, 그 표면에 화성 처리가 실시되어 있어도 된다. 화성 처리의 종류는, 특별히 한정되지 않지만, 예를 들면 크로메이트 처리, 크롬 프리 처리, 인산염 처리일 수 있다.The surface of the metal plate may be chemically treated from the viewpoint of improving the corrosion resistance and coating film adhesion of the painted metal plate. The type of chemical treatment is not particularly limited, but may include, for example, chromate treatment, chromium-free treatment, and phosphate treatment.
화성 처리는 공지의 방법으로 실시될 수 있다. 예를 들면, 화성 처리액을 롤 코트법, 스핀 코트법, 스프레이법 등의 방법으로 강판의 표면에 도포하여, 수세하지 않고 건조시키면 된다. 건조 온도 및 건조 시간은, 수분을 증발시킬 수 있으면 특별히 한정되지 않는다. 생산성의 관점에서는, 건조 온도는 도달 기판온도로 60~150℃의 범위 내가 바람직하고, 건조 시간은 2~10초의 범위 내가 바람직하다. 화성 처리 피막의 부착량은, 내식성 및 도막 밀착성의 향상에 유효한 범위 내이면 특별히 한정되지 않는다. 예를 들면, 크로메이트 피막의 경우, 전체 Cr 환산 부착량이 5~100mg/m2가 되도록 부착량을 조정하면 된다. 또, 크롬 프리 피막의 경우, Ti-Mo 복합 피막에서는 10~500mg/m2, 플루오로 애시드계 피막에서는 불소 환산 부착량 또는 총 금속 원소 환산 부착량이 3~100mg/m2의 범위 내가 되도록 부착량을 조정하면 된다. 또, 인산염 피막의 경우 5~500mg/m2가 되도록 부착량을 조정하면 된다.Chemical treatment can be performed by known methods. For example, the chemical conversion solution may be applied to the surface of a steel sheet using a roll coating method, spin coating method, spray method, etc., and then dried without washing with water. Drying temperature and drying time are not particularly limited as long as moisture can be evaporated. From the viewpoint of productivity, the drying temperature is preferably within the range of 60 to 150°C at the reached substrate temperature, and the drying time is preferably within the range of 2 to 10 seconds. The adhesion amount of the chemical conversion film is not particularly limited as long as it is within a range effective for improving corrosion resistance and coating film adhesion. For example, in the case of a chromate film, the adhesion amount can be adjusted so that the total Cr-equivalent adhesion amount is 5 to 100 mg/m 2 . In addition, in the case of chromium-free films, the adhesion amount is adjusted so that it is within the range of 10 to 500 mg/m 2 for Ti-Mo composite films, and 3 to 100 mg/m 2 in terms of fluorine or total metal elements for fluoro acid-based films. Just do it. Additionally, in the case of a phosphate film, the adhesion amount can be adjusted to 5 to 500 mg/m 2 .
2-2. 프라이머층2-2. Primer layer
프라이머층은, 그 위에 배치되는 톱층과 금속판의 사이의 밀착성을 높일 수 있을 뿐만 아니라, 얻어지는 도장 금속판의 내습성이나 내식성을 높일 수 있다. 프라이머층은 본 발명의 도료 조성물의 경화물로 이루어진다.The primer layer can not only improve the adhesion between the top layer disposed thereon and the metal plate, but also improve the moisture resistance and corrosion resistance of the resulting painted metal plate. The primer layer is made of a cured product of the coating composition of the present invention.
프라이머층의 두께는 1~10μm인 것이 바람직하다. 프라이머층의 두께가 1μm 이상이면, 금속판과 톱층의 사이의 밀착성을 높이기 쉽고, 또한 충분한 내습성 및 내식성이 얻어지기 쉽다. 프라이머층의 두께가 10μm 이하이면, 도장 금속판의 외관이나 가공성이 저해되기 어렵다. 프라이머층의 두께는, 상기 관점에서 2~7μm인 것이 보다 바람직하다.The thickness of the primer layer is preferably 1 to 10 μm. If the thickness of the primer layer is 1 μm or more, the adhesion between the metal plate and the top layer is easy to increase, and sufficient moisture resistance and corrosion resistance are easy to be obtained. If the thickness of the primer layer is 10 μm or less, the appearance and processability of the painted metal sheet are unlikely to be impaired. The thickness of the primer layer is more preferably 2 to 7 μm from the above viewpoint.
2-3. 톱층2-3. top tier
본 발명의 도장 금속판은, 프라이머층 상에 배치된 하나 이상의 도막을 더 갖는 것이 바람직하다.The painted metal plate of the present invention preferably further has one or more coating films disposed on the primer layer.
하나 이상의 도막 중 최표면에 있는 톱층은, 열가소성 수지를 포함하는 수지 조성물로 구성될 수 있다.The top layer on the outermost surface of one or more coating films may be composed of a resin composition containing a thermoplastic resin.
열가소성 수지의 종류는, 도장 금속판의 용도에 따라 적절히 설정될 수 있다. 열가소성 수지의 예에는, 아크릴 수지, 폴리에스터, 불소 수지, 아크릴-스티렌 수지, 스티렌 수지, 실리콘 수지가 포함된다. 이들 수지는, 1종류만 포함되어도 되고, 2종류 이상이 포함되어도 된다.The type of thermoplastic resin can be appropriately set depending on the intended use of the painted metal plate. Examples of thermoplastic resins include acrylic resin, polyester, fluorine resin, acrylic-styrene resin, styrene resin, and silicone resin. These resins may be included as one type or as two or more types.
혹은, 톱층은, 경화제와 반응하는 관능기를 갖는 수지(경화성 수지)와, 경화제를 포함하는 수지 조성물의 경화물로 구성되어도 된다.Alternatively, the top layer may be composed of a cured product of a resin composition containing a resin (curable resin) having a functional group that reacts with a curing agent and a curing agent.
경화성 수지의 예에는, 오일 프리의 폴리에스터 수지(수산기 함유 폴리에스터 수지) 등의 경화성 폴리에스터, 수산기 함유 아크릴 수지 등의 경화성 아크릴 수지, 에폭시 수지, 페놀 수지, 요소 수지, 멜라민 수지, 벤조구아나민 수지, 및 이들 수지의 우레탄 변성물, 실리콘 변성물 혹은 에폭시 변성물이 포함된다.Examples of curable resins include curable polyesters such as oil-free polyester resins (hydroxyl group-containing polyester resins), curable acrylic resins such as hydroxyl group-containing acrylic resins, epoxy resins, phenol resins, urea resins, melamine resins, and benzoguanamine. Resins, and urethane-modified, silicone-modified, or epoxy-modified products of these resins are included.
경화제는, 경화성 수지의 종류나 톱층의 소성 조건 등에 따라 적절히 선택될 수 있다. 예를 들면, 수산기를 갖는 경화성 수지 등의 경화제의 예에는, 멜라민 화합물 및 이소시아네이트 화합물이 포함된다. 멜라민 화합물은, 상술한 바와 동일한 것을 이용할 수 있다. 이소시아네이트 화합물의 예에는, 헥사메틸렌디이소시아네이트(HDI) 등의 지방족 이소시아네이트 화합물; 노보넨디이소시아네이트(NBDI), 이소포론디이소시아네이트(IPDI), 시클로헥산디이소시아네이트, 디시클로헥실메탄디이소시아네이트 등의 지환식 이소시아네이트 화합물; 메틸렌디페닐디이소시아네이트(MDI), 톨릴렌디이소시아네이트(TDI), 자일릴렌디이소시아네이트(XDI) 등의 방향족 이소시아네이트 화합물이 포함된다.The curing agent may be appropriately selected depending on the type of curable resin, the firing conditions of the top layer, etc. For example, examples of curing agents such as curable resins having a hydroxyl group include melamine compounds and isocyanate compounds. The same melamine compound as described above can be used. Examples of isocyanate compounds include aliphatic isocyanate compounds such as hexamethylene diisocyanate (HDI); Alicyclic isocyanate compounds such as norbornene diisocyanate (NBDI), isophorone diisocyanate (IPDI), cyclohexane diisocyanate, and dicyclohexylmethane diisocyanate; Aromatic isocyanate compounds such as methylenediphenyl diisocyanate (MDI), tolylene diisocyanate (TDI), and xylylene diisocyanate (XDI) are included.
이들 수지 조성물은, 본 발명의 효과를 나타내는 범위에 있어서, 착색 안료 및 체질 안료 등의 다른 성분을 더 함유하고 있어도 된다. 착색 안료 및 체질 안료는, 상술한 프라이머층에 포함될 수 있는 착색 안료 및 체질 안료와 동일한 것을 이용할 수 있다.These resin compositions may further contain other components such as coloring pigments and extenders within the range that exhibits the effects of the present invention. The coloring pigment and extender may be the same as the coloring pigment and extender that can be included in the primer layer described above.
톱층의 두께는, 구해지는 특성에 따라서도 다르지만, 예를 들면 2~40μm인 것이 바람직하다. 톱층의 두께가 2μm 이상이면, 소기의 의장성이 얻어지기 쉽고, 40μm 이하이면, 외관이나 가공성이 저해되기 어렵다. 톱층의 두께는, 상기 관점에서 5~30μm인 것이 보다 바람직하다.The thickness of the top layer varies depending on the characteristics to be obtained, but is preferably, for example, 2 to 40 μm. If the thickness of the top layer is 2 μm or more, the desired design is easy to obtain, and if it is 40 μm or less, appearance and processability are unlikely to be impaired. The thickness of the top layer is more preferably 5 to 30 μm from the above viewpoint.
하나 이상의 도막은 중간층 등의 다른 층을 더 갖고 있어도 된다.One or more coating films may further have other layers such as an intermediate layer.
중간층은, 예를 들면 톱층과의 외관상의 상승 효과에 의하여, 도장 금속판의 의장성을 높이기 위하여, 프라이머층의 표면, 즉 프라이머층과 톱층의 사이에 배치될 수 있다.The middle layer may be disposed on the surface of the primer layer, that is, between the primer layer and the top layer, in order to enhance the design of the painted metal plate by, for example, a synergistic effect in appearance with the top layer.
중간층은, 상술한 바와 동일하게, 열가소성 수지를 포함하는 수지 조성물, 또는 경화성 수지와 경화제를 포함하는 수지 조성물의 경화물로 구성될 수 있다. 이들 수지 조성물은, 필요에 따라 다른 성분을 더 함유하고 있어도 된다. 중간층에 포함되는 각 성분은, 도장 금속판의 용도에 따라, 프라이머층 및 톱층을 구성하는 수지 조성물의 각 성분으로서 든 것과 동일한 것을 이용할 수 있다.As described above, the intermediate layer may be composed of a resin composition containing a thermoplastic resin, or a cured product of a resin composition containing a curable resin and a curing agent. These resin compositions may further contain other components as needed. Each component contained in the middle layer can be the same as each component included in the resin composition constituting the primer layer and the top layer, depending on the intended use of the painted metal plate.
중간층의 두께는, 소기의 효과를 충분히 얻기 쉽게 하는 관점에서는, 일정 이상인 것이 바람직하고, 도장 금속판의 외관을 손상시키지 않도록 하는 관점에서는, 일정 이하인 것이 바람직하다. 소기의 의장성의 향상 효과를 얻는 관점에서, 중간층의 두께는 예를 들면 5~30μm로 할 수 있다.The thickness of the intermediate layer is preferably above a certain level from the viewpoint of easily obtaining the desired effect, and is preferably below a certain level from the viewpoint of preventing damage to the appearance of the painted metal plate. From the viewpoint of obtaining the desired designability improvement effect, the thickness of the intermediate layer can be, for example, 5 to 30 μm.
3. 도장 금속판의 제조 방법3. Manufacturing method of painted metal plate
본 발명의 도장 금속판은 임의의 방법으로 제조할 수 있다. 본 발명의 도장 금속판의 제조 방법은, 예를 들면, 1) 도장 원판으로서의 금속판 상에 본 발명의 도료 조성물을 도포한 후, 건조 및 경화시켜 프라이머층을 형성하는 공정을 포함하고, 2) 프라이머층 상에 하나 이상의 도막을 형성하는 공정을 더 포함하는 것이 바람직하다.The painted metal plate of the present invention can be manufactured by any method. The method for manufacturing a painted metal plate of the present invention includes, for example, the steps of 1) applying the coating composition of the present invention on a metal plate as a painted base plate, followed by drying and curing to form a primer layer, and 2) primer layer. It is preferable to further include a process of forming one or more coating films on the surface.
1)의 공정에 대하여About the process of 1)
금속판 상에 본 발명의 도료 조성물을 도포한다.The coating composition of the present invention is applied on a metal plate.
도료 조성물을 도포하는 방법은, 특별히 제한되지 않고, 그 예에는, 롤 코트법, 롤러 커튼 코트법, 플로우 코트법, 커튼 플로우법 및 스프레이법이 포함된다.The method of applying the coating composition is not particularly limited, and examples include roll coating, roller curtain coating, flow coating, curtain flow, and spray.
그리고, 금속판의 표면에 도포한 도료 조성물을 건조 및 소성(경화)하여 프라이머층을 형성한다.Then, the paint composition applied to the surface of the metal plate is dried and fired (cured) to form a primer layer.
소성 온도는, 수지 성분이 융착 및/또는 경화될 수 있는 온도이면 되고, 예를 들면 도달 기판온도로 70~250℃로 할 수 있다.The firing temperature may be any temperature at which the resin component can be fused and/or cured, and can be, for example, 70 to 250°C at the reached substrate temperature.
2)의 공정에 대하여About the process of 2)
얻어진 프라이머층 상에, 하나 이상의 도막을 형성한다. 예를 들면, 프라이머층 상에 톱층용 도료 조성물을 도포한다.On the obtained primer layer, one or more coating films are formed. For example, the top layer coating composition is applied on the primer layer.
톱층용 도료 조성물은, 상술한 성분 외에, 용제를 더 포함할 수 있다. 용제는 경화 수지를 용해시킬 수 있는 것이면 되고, 특별히 제한되지 않지만, 그 예에는, N-메틸-2-피롤리돈(NMP)이나 N,N-디메틸포름아미드(DMF), N,N-디메틸아세트아미드(DMAc), N,N-디메틸이미다졸리딘온(DMI), 메틸이소부틸케톤(MIBK) 등의 비(非)프로톤성 극성 용제; 디에틸렌글리콜디메틸에테르(DMDG)나 디에틸렌글리콜디에틸에테르(DEDG) 등의 에테르류; 염화 메틸렌이나 사염화 탄소 등의 할로젠화 지방족 탄화 수소; 자일렌 등의 탄화 수소류; 및 알코올류가 포함된다.The coating composition for top layer may further contain a solvent in addition to the components described above. The solvent may be any solvent that can dissolve the cured resin, and is not particularly limited, but examples include N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), and N,N-dimethyl. Aprotic polar solvents such as acetamide (DMAc), N,N-dimethylimidazolidinone (DMI), and methyl isobutyl ketone (MIBK); Ethers such as diethylene glycol dimethyl ether (DMDG) and diethylene glycol diethyl ether (DEDG); Halogenated aliphatic hydrocarbons such as methylene chloride and carbon tetrachloride; Hydrocarbons such as xylene; and alcohol.
톱층용 도료 조성물의 도포 방법도, 상술한 바와 동일하게 할 수 있다.The application method of the top layer coating composition can also be the same as described above.
이어서, 도포한 톱층용 도료 조성물을 건조 및 소성(경화)하여 톱층을 형성한다. 소성 온도는, 경화 수지가 융착 및/또는 경화될 수 있는 온도이면 되고, 예를 들면 도달 기판온도로 200~260℃로 할 수 있다.Next, the applied top layer coating composition is dried and fired (cured) to form a top layer. The firing temperature may be any temperature at which the cured resin can fuse and/or harden, and can be, for example, 200 to 260°C as the reached substrate temperature.
<실시예><Example>
이하, 본 발명에 대하여 실시예를 참조하여 상세하게 설명하지만, 본 발명은 이들 실시예에 의하여 한정되지 않는다.Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
1. 도료 조성물의 재료1. Materials of paint composition
<비이온성의 수분산성 수지 (a)의 수분산체><Water dispersion of nonionic water-dispersible resin (a)>
수지 A의 수분산체: 비이온성 우레탄 수지의 수분산체, ADEKA사제 HUX-841(고형분 32질량%, 비이온성의 친수성기로서 폴리옥시에틸렌기를 갖는 우레탄 수지)Aqueous dispersion of Resin A: Aqueous dispersion of nonionic urethane resin, HUX-841 manufactured by ADEKA (solid content 32% by mass, urethane resin having a polyoxyethylene group as a nonionic hydrophilic group)
수지 B의 수분산체: 비이온성 아크릴 수지의 수분산체, 구스모토 가세이사제 DXA. 4081(고형분 50질량%, 비이온성의 친수성기로서 폴리옥시에틸렌기를 갖는 아크릴 수지)Aqueous dispersion of Resin B: Aqueous dispersion of nonionic acrylic resin, DXA manufactured by Kusumoto Kasei. 4081 (50 mass% solid content, acrylic resin having a polyoxyethylene group as a nonionic hydrophilic group)
수지 C의 수분산체: 비이온성 에폭시 수지의 수분산체, 요시무라유 가가쿠사제 유카레진 NE316(고형분 45질량%, 비이온성의 친수성기로서 수산기를 갖는 에폭시 수지)Aqueous dispersion of resin C: Aqueous dispersion of nonionic epoxy resin, Yuka Resin NE316 manufactured by Yoshimura Yu Chemical Co., Ltd. (solid content 45% by mass, epoxy resin having a hydroxyl group as a nonionic hydrophilic group)
수지 D의 수분산체: 음이온성 우레탄 수지의 수분산체, 다이이치 고교 세이야쿠사제 슈퍼플렉스 170(고형분 33질량%, 음이온성의 친수성기로서 카복시기를 갖는 우레탄 수지)Aqueous dispersion of Resin D: Aqueous dispersion of anionic urethane resin, Superflex 170 manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (solid content 33% by mass, urethane resin having a carboxyl group as an anionic hydrophilic group)
<인산 변성 에폭시 수지 (b)의 수분산체><Aqueous dispersion of phosphoric acid modified epoxy resin (b)>
오르토인산 60g 및 프로필렌글리콜모노메틸에테르 280g을 투입하고, 비스페놀 A형의 에폭시 수지 (미쓰비시 케미컬사제 jER1055, 분자량 1600, 에폭시 당량: 800~900g/eq) 850g을 서서히 첨가하여, 80℃에서 2시간 반응시켰다. 반응 종료 후, 트리에틸아민 120g과 물 1950g을 더하여, 고형분 28질량%의 인산 변성 에폭시 수지의 수분산체(평균 입자경 0.11μm)를 얻었다.60 g of orthophosphoric acid and 280 g of propylene glycol monomethyl ether were added, and 850 g of bisphenol A type epoxy resin (jER1055 manufactured by Mitsubishi Chemical Corporation, molecular weight 1600, epoxy equivalent: 800 to 900 g/eq) was slowly added, followed by reaction at 80°C for 2 hours. I ordered it. After completion of the reaction, 120 g of triethylamine and 1950 g of water were added to obtain an aqueous dispersion of phosphoric acid-modified epoxy resin with a solid content of 28% by mass (average particle diameter of 0.11 μm).
<멜라민 화합물 (c)><Melamine compound (c)>
헥사메톡시메틸멜라민(미쓰이 사이텍사제 사이멜 303)Hexamethoxymethylmelamine (Cymel 303 manufactured by Mitsui Cytex)
<실란 커플링제 (d)><Silane coupling agent (d)>
글리시독시프로필메틸디에톡시실란(신에쓰 실리콘사제 KBM-403)Glycidoxypropylmethyldiethoxysilane (KBM-403 manufactured by Shin-Etsu Silicone Co., Ltd.)
<금속 이온 교환 실리카><Metal ion exchange silica>
Mg 교환 실리카: 후지 실리시아 가가쿠사제 사일로마스크 52M(평균 입자경 2.7μm, 금속 이온 교환량 6질량%)Mg exchanged silica: Silomask 52M manufactured by Fuji Silicia Chemicals (average particle diameter 2.7 μm, metal ion exchange amount 6 mass%)
Ca 교환 실리카: 후지 실리시아 가가쿠사제 사일로마스크 52(평균 입자경 2.7μm, 금속 이온 교환량 6질량%)Ca exchanged silica: Silomask 52 manufactured by Fuji Silicia Chemicals (average particle diameter 2.7 μm, metal ion exchange amount 6% by mass)
Sr 교환 실리카: 제조예 1에 따라 조제했다. 금속 이온 교환량은 6질량%로 했다.Sr exchanged silica: prepared according to Preparation Example 1. The amount of metal ion exchange was 6% by mass.
(제조예 1)(Production Example 1)
농도 5질량%의 염화 스트론튬 수용액 10000질량부 중에, 10질량부의 실리카(후지 실리시아 가가쿠사제 사일리시아 710)를 첨가했다. 5시간 교반 혼합한 후, 여과하여 고형분을 취출하고, 고형분을 충분히 수세하며 건조하여, 스트론튬 이온 교환 실리카를 얻었다.To 10,000 parts by mass of an aqueous solution of strontium chloride with a concentration of 5% by mass, 10 parts by mass of silica (Silicia 710 manufactured by Fuji Cilicia Chemicals) was added. After stirring and mixing for 5 hours, the solid content was taken out by filtration, and the solid content was sufficiently washed with water and dried to obtain strontium ion exchanged silica.
Mn 교환 실리카: 제조예 2에 따라 조제했다.Mn exchanged silica: prepared according to Preparation Example 2.
(제조예 2)(Production Example 2)
염화 스트론튬을 염화 망간으로 변경한 것 이외에는 제조예 1과 동일한 방법으로 망간 이온 교환 실리카를 얻었다. 금속 이온 교환량은 6질량%로 했다.Manganese ion-exchanged silica was obtained in the same manner as in Preparation Example 1 except that strontium chloride was changed to manganese chloride. The amount of metal ion exchange was 6% by mass.
Li 교환 실리카: 제조예 3에 따라 조제했다.Li-exchanged silica: prepared according to Preparation Example 3.
(제조예 3)(Production Example 3)
염화 스트론튬을 수산화 리튬으로 변경한 것 이외에는 제조예 1과 동일한 방법으로 리튬 이온 교환 실리카를 얻었다. 금속 이온 교환량은 6질량%로 했다.Lithium ion exchanged silica was obtained in the same manner as in Preparation Example 1 except that strontium chloride was changed to lithium hydroxide. The amount of metal ion exchange was 6% by mass.
Al 교환 실리카: 제조예 4에 따라 조제했다.Al exchanged silica: prepared according to Preparation Example 4.
(제조예 4)(Production Example 4)
염화 스트론튬을 염화 알루미늄으로 변경한 것 이외에는 제조예 1과 동일한 방법으로 알루미늄 이온 교환 실리카를 얻었다. 금속 이온 교환량은 6질량%로 했다.Aluminum ion exchanged silica was obtained in the same manner as in Preparation Example 1 except that strontium chloride was changed to aluminum chloride. The amount of metal ion exchange was 6% by mass.
<미교환 실리카><Unexchanged silica>
실리카(이온 교환 없음): 후지 실리시아 가가쿠사제 사일리시아 710(평균 입자경 2.7μm)Silica (no ion exchange): Silicia 710 manufactured by Fuji Silicia Chemicals (average particle diameter 2.7 μm)
2. 도료 조성물2. Paint composition
<도료 조성물 1~39><Paint compositions 1 to 39>
표 1 또는 표 2에 나타내는 고형분 조성이 되도록, 비이온성의 수분산성 수지 (a)의 수분산체, 인산 변성 에폭시 수지 (b)의 수분산체, 멜라민 화합물 (c), 실란 커플링제 (d) 및 금속 이온 교환 실리카 또는 미교환 실리카를 혼합하여 도료 조성물을 얻었다.An aqueous dispersion of the nonionic water-dispersible resin (a), an aqueous dispersion of the phosphoric acid-modified epoxy resin (b), a melamine compound (c), a silane coupling agent (d), and a metal so as to have a solid composition shown in Table 1 or Table 2. A paint composition was obtained by mixing ion exchanged silica or unexchanged silica.
도료 조성물 1~24의 조성을 표 1에 나타내고; 도료 조성물 25~39의 조성을 표 2에 나타낸다.The compositions of paint compositions 1 to 24 are shown in Table 1; The compositions of paint compositions 25 to 39 are shown in Table 2.
3. 도장 금속판의 제작 및 평가3. Fabrication and evaluation of painted metal plates
<도장 금속판 1~39의 제작><Production of painted metal plates 1 to 39>
(1) 금속판(도장 원판)의 준비(1) Preparation of metal plate (painted original plate)
판두께 0.5mm의 냉간 압연 강판을 준비했다. 이 강판을 55질량% Al-45질량% Zn 합금의 도금욕 내에 도입하여, 이 냉간 압연 강판의 양면에 용융 55질량% Al-45질량% Zn 합금의 도금층을 각각 형성했다. 이어서, 얻어진 강판을 용융 상태로부터 25℃/초의 속도로 130℃까지 냉각한 후, 수냉(워터 ??칭)에 의하여 상온(25℃)까지 냉각하여 도금 강판을 얻었다. 얻어진 도금 강판의 편면의 도금 부착량은 80g/m2였다.A cold rolled steel sheet with a thickness of 0.5 mm was prepared. This steel sheet was introduced into a plating bath of 55 mass% Al-45 mass% Zn alloy, and plating layers of molten 55 mass% Al-45 mass% Zn alloy were formed on both sides of the cold rolled steel sheet. Next, the obtained steel sheet was cooled from the molten state to 130°C at a rate of 25°C/sec, and then cooled to room temperature (25°C) by water cooling (water quenching) to obtain a plated steel sheet. The plating adhesion amount on one side of the obtained plated steel sheet was 80 g/m 2 .
얻어진 도금 강판의 표면에, 크롬 프리 화성 처리액을 바 코터로 도포한 후, 건조시켜 화성 처리 피막을 형성했다. 크롬 프리 화성 처리액에는, 티타늄 불화 수소산(H2TiF6): 0.1mol/L 및 지르코늄 불화 수소산(H2ZrF6): 0.1mol/L의 혼합 용액을 이용했다. 화성 처리 피막의 부착량은, Ti 및 Zr의 총 금속 원소 환산 부착량으로 3.5mg/m2였다.The chromium-free chemical treatment liquid was applied to the surface of the obtained plated steel sheet using a bar coater, and then dried to form a chemical treatment film. For the chromium-free chemical treatment solution, a mixed solution of titanium hydrofluoric acid (H 2 TiF 6 ): 0.1 mol/L and zirconium hydrofluoric acid (H 2 ZrF 6 ): 0.1 mol/L was used. The adhesion amount of the chemical conversion film was 3.5 mg/m 2 in terms of the adhesion amount of Ti and Zr in terms of total metal elements.
(2) 프라이머층의 형성(2) Formation of primer layer
얻어진 화성 처리 피막 상에 표 1 또는 표 2에 나타내는 도료 조성물을 바 코터로 도포한 후, 최고 도달 기판온도 150℃ 건조 시간 30초로 소성하여, 막두께 5μm의 프라이머층을 형성했다.The coating composition shown in Table 1 or Table 2 was applied onto the obtained chemical conversion film using a bar coater, and then baked at a maximum substrate temperature of 150°C for a drying time of 30 seconds to form a primer layer with a film thickness of 5 μm.
(3) 톱층의 형성(3) Formation of top layer
(톱 도료 조성물의 조제)(Preparation of top coating composition)
폴리에스터계 클리어 도료(닛폰 페인트·인더스트리얼 코팅스사제 닛페 슈퍼 코트 250HQ, 오일 프리의 경화성 폴리에스터 수지, 멜라민 경화제를 포함하는 도료)에, 당해 수지 고형분 100질량부에 대하여 5질량부의 프탈로시아닌계 청색 안료(크로모파인 4927, 다이니치 세이카제)와, 3질량부의 산화 티타늄(타이페이크 WHITE, R-930, 이시하라 산교 주식회사제)을 첨가 및 혼합하여 균일하게 분산시켜, 톱 도료 조성물을 얻었다.Polyester-based clear paint (Nippe Supercoat 250HQ manufactured by Nippon Paint Industrial Coatings, a paint containing an oil-free curable polyester resin and a melamine hardener), 5 parts by mass of a phthalocyanine-based blue pigment based on 100 parts by mass of the resin solid content. (Chromofine 4927, manufactured by Dainichi Seika) and 3 parts by mass of titanium oxide (Taipei WHITE, R-930, manufactured by Ishihara Sangyo Co., Ltd.) were added and mixed and dispersed uniformly to obtain a top coating composition.
이어서, 얻어진 프라이머층 상에 상기 조제한 톱 도료 조성물을 바 코터로 도포한 후, 최고 도달 기판온도 220℃ 건조 시간 40초로 소성하고, 막두께 15μm의 톱층을 형성하여 도장 금속판을 얻었다.Next, the above-prepared top coating composition was applied onto the obtained primer layer using a bar coater, and then baked at a maximum substrate temperature of 220°C for a drying time of 40 seconds to form a top layer with a film thickness of 15 μm, thereby obtaining a painted metal plate.
(4) 평가(4) Evaluation
도장 금속판의 제작에 이용한 도료 조성물의 보존 안정성을 이하의 방법으로 평가했다.The storage stability of the coating composition used for producing the painted metal plate was evaluated by the following method.
(보존 안정성)(storage stability)
얻어진 도료 조성물의 포드 컵 점도(초)를, 제작 직후와, 40℃ 30%Rh의 환경에서 30일간 보관한 후에, 각각 측정했다. 측정은, 20℃의 환경하에서, No. 4 포드 컵을 이용하여 ASTM D1200·ISO2431에 준거하여 행했다. 그리고, 보존 안정성을 이하의 기준에 근거하여 평가했다.The Ford cup viscosity (seconds) of the obtained coating composition was measured immediately after production and after storage in an environment of 40°C and 30%Rh for 30 days. Measurements were made under No. 20°C environment. 4 This was carried out in accordance with ASTM D1200·ISO2431 using a pod cup. Then, storage stability was evaluated based on the following standards.
◎: 점도 상승이 5초 미만◎: Viscosity rise is less than 5 seconds
○: 점도 상승이 5초 이상 30초 미만○: Viscosity increase is more than 5 seconds and less than 30 seconds.
△: 점도 상승이 30초 이상△: Viscosity increase over 30 seconds
×: 도료가 젤화×: Paint gelatinizes
또, 얻어진 도장 금속판의 톱층의 밀착성, 내습성 및 내식성을 이하의 방법으로 평가했다.Additionally, the adhesion, moisture resistance, and corrosion resistance of the top layer of the obtained painted metal plate were evaluated by the following methods.
(밀착성)(adhesion)
도장 금속판의 톱층의 표면에 1mm 간격의 절개선에 의하여 100개의 칸이 생기도록 바둑판 형상의 절개를 행했다. 형성된 절개부에 테이프를 첩부하고 테이프를 박리한 후, 그 절개부에서의 박리 면적을 구했다. 그리고, 이하의 기준에 따라 금속판과 프라이머층의 사이의 계면의 밀착성을 평가했다.The surface of the top layer of the painted metal plate was cut in a checkerboard shape using cut lines spaced at 1 mm intervals to create 100 cells. After attaching the tape to the formed incision and peeling off the tape, the peeling area at the incision was determined. Then, the adhesion of the interface between the metal plate and the primer layer was evaluated according to the following standards.
◎: 박리 면적 0%(박리 없음)◎: Peeling area 0% (no peeling)
○: 박리 면적이 0% 초과 10% 이하○: Peeling area is more than 0% and less than 10%
△: 박리 면적이 10% 초과 20% 이하△: Peeling area is more than 10% and less than 20%
×: 박리 면적이 20% 초과×: Peeling area exceeds 20%
△ 이상이면 양호하다고 판단했다.If it was △ or higher, it was judged to be good.
(내습성)(moisture resistance)
도장 금속판을 습윤 환경(50℃, 95%Rh)에 1000시간 노출했다. 그 후, 톱층의 평탄부의 부품 발생 면적율을 측정했다. 그리고, 이하의 기준으로 내습성을 평가했다.The painted metal plate was exposed to a humid environment (50°C, 95%Rh) for 1000 hours. After that, the area ratio of parts generated in the flat part of the top layer was measured. Then, moisture resistance was evaluated based on the following standards.
◎: 부품 발생률이 0%(부품 발생 없음)◎: 0% parts generation rate (no parts generation)
○: 부품 발생률이 0% 초과 5% 미만○: Parts occurrence rate greater than 0% but less than 5%
△: 부품 발생률이 5% 이상 20% 미만△: Parts occurrence rate greater than 5% but less than 20%
×: 부품 발생률이 20% 이상×: Parts occurrence rate of 20% or more
△ 이상이면 양호하다고 판단했다.If it was △ or higher, it was judged to be good.
(내식성)(corrosion resistance)
도장 금속판에 대하여, 도금 강판의 도금층에 도달하도록 나이프로 X형의 크로스컷 흠집을 내고, 5% 염수 분무 1시간, 건조 4시간(60℃, 30%Rh), 습윤 3시간(50℃ 95%Rh)을 1사이클로 하여, 120사이클 실시했다. 그리고, 시험 후의 크로스컷부의 최대 부품 폭을 측정했다. 최대 부품 폭은, 크로스컷부로부터의 부품의 침입 깊이의 최대 폭을 나타낸다. 그리고, 이하의 기준으로 내식성을 평가했다.For the painted metal sheet, make an Rh) was set as 1 cycle, and 120 cycles were performed. Then, the maximum component width of the crosscut section after the test was measured. The maximum component width represents the maximum width of the penetration depth of the component from the crosscut portion. Then, corrosion resistance was evaluated based on the following standards.
◎: 최대 부품 폭이 2mm 이하◎: Maximum part width is 2 mm or less
○: 최대 부품 폭이 2mm 초과 4mm 이하○: Maximum part width exceeds 2 mm but does not exceed 4 mm.
△: 최대 부품 폭이 4mm 초과 5mm 이하△: Maximum part width greater than 4 mm and less than or equal to 5 mm
×: 최대 부품 폭이 5mm 초과×: Maximum part width exceeds 5 mm
△ 이상이면 양호하다고 판단했다.If it was △ or higher, it was judged to be good.
도료 조성물 1~24 및 도장 금속판 1~24의 평가 결과를 표 3에 나타내고, 도료 조성물 25~39 및 도장 금속판 25~39의 평가 결과를 표 4에 나타낸다.The evaluation results of the coating compositions 1 to 24 and the painted metal plates 1 to 24 are shown in Table 3, and the evaluation results of the coating compositions 25 to 39 and the painted metal plates 25 to 39 are shown in Table 4.
표 3 및 표 4에 나타내는 바와 같이, 도료 조성물 1~27은 모두 양호한 보존 안정성을 가지면서, 얻어지는 도장 금속판 1~27은 양호한 내습성을 갖는 것을 알 수 있다.As shown in Tables 3 and 4, it can be seen that the coating compositions 1 to 27 all have good storage stability, and the obtained painted metal plates 1 to 27 have good moisture resistance.
특히, 2가의 금속 이온 교환 실리카(e)의 함유량을, (a), (b) 및 (c) 성분의 합계 100질량부에 대하여 7.5~50질량부로 함으로써, 보존 안정성과 내습성을 보다 고도로 양립시킬 수 있는 것을 알 수 있다(도장 금속판 11~15, 18, 25 및 26의 대비).In particular, by setting the content of divalent metal ion exchanged silica (e) to 7.5 to 50 parts by mass based on a total of 100 parts by mass of components (a), (b), and (c), storage stability and moisture resistance are achieved to a higher degree. You can see what can be done (compare painted metal plates 11 to 15, 18, 25 and 26).
또, 2가의 금속 이온 교환 실리카 (e) 중에서도, Mg 교환 실리카를 포함하는 도료 조성물은, 함유량이 많아도 양호한 보존 안정성을 유지할 수 있다는 것을 알 수 있다(도료 조성물 18~21의 대비).Moreover, it can be seen that among divalent metal ion exchanged silicas (e), the coating composition containing Mg exchanged silica can maintain good storage stability even when the content is high (compared to coating compositions 18 to 21).
이에 대하여, (b), (c) 및 (d) 성분의 양이 과도하게 많은 도장 금속판 30, 33 및 38은, 모두 내습성은 양호하지만 도료 조성물의 보존 안정성이 낮은 것을 알 수 있다.In contrast, it can be seen that the painted metal plates 30, 33, and 38, which contain excessive amounts of components (b), (c), and (d), all have good moisture resistance, but the storage stability of the coating composition is low.
또, (b), (c) 및 (d) 성분의 양이 과도하게 적은 도료 조성물 29, 31, 32 및 37은, 모두 보존 안정성은 양호하지만 도장 금속판의 내습성은 낮은 것을 알 수 있다. 또, (e) 성분으로서, 2가의 금속 이온 교환 실리카를 포함하지 않거나, 또는 그 이외의 금속 이온 교환 실리카를 이용한 도료 조성물 34~36은, 모두 보존 안정성은 양호하지만 도장 금속판의 내습성은 낮은 것을 알 수 있었다.In addition, it can be seen that the coating compositions 29, 31, 32, and 37, which contain excessively small amounts of components (b), (c), and (d), all have good storage stability, but the moisture resistance of the painted metal plate is low. In addition, coating compositions 34 to 36 that do not contain divalent metal ion exchanged silica or use other metal ion exchanged silica as component (e) all have good storage stability but low moisture resistance of the painted metal plate. Could know.
또, (a) 성분이 음이온성의 수분산성 수지이면 보존 안정성이 낮아지는 것을 알 수 있다(도료 조성물 18과 39의 대비). 이것은, 음이온성의 수분산성 수지 (a)와 용출된 금속 이온이 반응하기 때문이라고 생각된다.Additionally, it can be seen that if component (a) is an anionic water-dispersible resin, the storage stability is lowered (compared to paint compositions 18 and 39). This is thought to be because the anionic water-dispersible resin (a) reacts with the eluted metal ion.
본 출원은, 2019년 3월 27일 출원된 일본 특허출원 2019-060717에 근거하여 우선권을 주장한다. 당해 출원 명세서 및 도면에 기재된 내용은, 모두 본원 명세서에 원용된다.This application claims priority based on Japanese Patent Application 2019-060717 filed on March 27, 2019. All contents described in the application specification and drawings are incorporated into the present application specification.
<산업상 이용가능성><Industrial applicability>
본 발명에 의하면, 양호한 보존 안정성을 가지면서, 고온 고습하에서의 도막의 부품을 억제할 수 있는 도료 조성물 및 도장 금속판을 제공할 수 있다.According to the present invention, it is possible to provide a coating composition and a painted metal plate that have good storage stability and can suppress damage to parts of the coating film under high temperature and high humidity.
Claims (9)
상기 비이온성의 수분산성 수지 (a), 상기 인산 변성 에폭시 수지 (b) 및 상기 멜라민 화합물 (c)의 합계 100질량부에 대하여,
상기 비이온성의 수분산성 수지 (a)의 함유량은 60~94.5질량부이고,
상기 인산 변성 에폭시 수지 (b)의 함유량은 5~39.5질량부이며,
상기 멜라민 화합물 (c)의 함유량은 0.5~10질량부이고,
상기 실란 커플링제 (d)의 함유량은 0.3~5질량부인, 수계 도료 조성물.A nonionic water-dispersible resin (a), a phosphoric acid-modified epoxy resin (b), a melamine compound (c), a silane coupling agent (d), silica particles exchanged with a divalent metal ion (e), and water. Includes,
For a total of 100 parts by mass of the nonionic water-dispersible resin (a), the phosphoric acid-modified epoxy resin (b), and the melamine compound (c),
The content of the nonionic water-dispersible resin (a) is 60 to 94.5 parts by mass,
The content of the phosphoric acid modified epoxy resin (b) is 5 to 39.5 parts by mass,
The content of the melamine compound (c) is 0.5 to 10 parts by mass,
A water-based coating composition wherein the content of the silane coupling agent (d) is 0.3 to 5 parts by mass.
상기 비이온성의 수분산성 수지 (a), 상기 인산 변성 에폭시 수지 (b) 및 상기 멜라민 화합물 (c)의 합계 100질량부에 대하여, 상기 2가의 금속 이온으로 교환된 실리카 입자 (e)의 함유량은 7.5~55질량부인, 수계 도료 조성물.According to paragraph 1,
The content of the silica particles (e) exchanged with the divalent metal ion is 7.5 to 55 mass densities, water-based paint composition.
상기 비이온성의 수분산성 수지 (a), 인산 변성 에폭시 수지 (b) 및 멜라민 화합물 (c)의 합계 100질량부에 대하여, 상기 2가의 금속 이온으로 교환된 실리카 입자 (e)의 함유량은 20~55질량부인, 수계 도료 조성물According to paragraph 1,
With respect to a total of 100 parts by mass of the nonionic water-dispersible resin (a), the phosphoric acid-modified epoxy resin (b), and the melamine compound (c), the content of the silica particles (e) exchanged with the divalent metal ion is 20 to 20. 55% mass, water-based paint composition
상기 2가의 금속 이온으로 교환된 실리카 입자 (e)는 마그네슘 교환 실리카인, 수계 도료 조성물.According to claim 1 or 2,
The water-based coating composition wherein the silica particles (e) exchanged with the divalent metal ion are magnesium exchanged silica.
상기 비이온성의 수분산성 수지 (a)는 비이온성의 우레탄 수지인, 수계 도료 조성물.According to claim 1 or 2,
The water-based paint composition wherein the nonionic water-dispersible resin (a) is a nonionic urethane resin.
상기 실란 커플링제 (d)가 에폭시계 실란 커플링제인, 수계 도료 조성물.According to claim 1 or 2,
A water-based coating composition wherein the silane coupling agent (d) is an epoxy-based silane coupling agent.
상기 금속판은 도금 강판인, 도장 금속판.In clause 7,
The metal plate is a painted metal plate, which is a plated steel plate.
상기 프라이머층 상에 배치된 하나 이상의 도막을 더 갖는, 도장 금속판.In clause 7,
A painted metal plate further having one or more coating films disposed on the primer layer.
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