JP3069028B2 - Printed laminated steel sheet with improved corrosion resistance - Google Patents
Printed laminated steel sheet with improved corrosion resistanceInfo
- Publication number
- JP3069028B2 JP3069028B2 JP7172920A JP17292095A JP3069028B2 JP 3069028 B2 JP3069028 B2 JP 3069028B2 JP 7172920 A JP7172920 A JP 7172920A JP 17292095 A JP17292095 A JP 17292095A JP 3069028 B2 JP3069028 B2 JP 3069028B2
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- polyethylene terephthalate
- printed
- laminated
- adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910000576 Laminated steel Inorganic materials 0.000 title claims description 31
- 238000005260 corrosion Methods 0.000 title claims description 28
- 230000007797 corrosion Effects 0.000 title claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 77
- 229910000831 Steel Inorganic materials 0.000 claims description 66
- 239000010959 steel Substances 0.000 claims description 66
- -1 polyethylene terephthalate Polymers 0.000 claims description 65
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 63
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 63
- 229920005989 resin Polymers 0.000 claims description 52
- 239000011347 resin Substances 0.000 claims description 52
- 239000010410 layer Substances 0.000 claims description 43
- 239000002245 particle Substances 0.000 claims description 30
- 229920001187 thermosetting polymer Polymers 0.000 claims description 24
- 239000012790 adhesive layer Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 9
- 239000000853 adhesive Substances 0.000 description 41
- 230000001070 adhesive effect Effects 0.000 description 41
- 239000000377 silicon dioxide Substances 0.000 description 35
- 238000007639 printing Methods 0.000 description 25
- 239000000049 pigment Substances 0.000 description 22
- 239000003795 chemical substances by application Substances 0.000 description 20
- 229920005749 polyurethane resin Polymers 0.000 description 18
- 238000000576 coating method Methods 0.000 description 15
- 239000012948 isocyanate Substances 0.000 description 15
- 150000002513 isocyanates Chemical class 0.000 description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 14
- 239000011701 zinc Substances 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 239000003822 epoxy resin Substances 0.000 description 12
- 239000000976 ink Substances 0.000 description 12
- 229920000647 polyepoxide Polymers 0.000 description 12
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 239000007921 spray Substances 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229920001225 polyester resin Polymers 0.000 description 8
- 239000004645 polyester resin Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 230000003449 preventive effect Effects 0.000 description 5
- 230000000717 retained effect Effects 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000007646 gravure printing Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000004640 Melamine resin Substances 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000012463 white pigment Substances 0.000 description 3
- 229910018137 Al-Zn Inorganic materials 0.000 description 2
- 229910018573 Al—Zn Inorganic materials 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 208000028659 discharge Diseases 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- ZVKPGHYZRCHUJO-UHFFFAOYSA-N 4-ethenoxycarbonylbenzoic acid Chemical compound OC(=O)C1=CC=C(C(=O)OC=C)C=C1 ZVKPGHYZRCHUJO-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
-
- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Coating With Molten Metal (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【産業上の利用分野】本発明は、水廻り等の部材や部品
として使用され、耐食性に優れたラミネート鋼板に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated steel sheet having excellent corrosion resistance, which is used as a member or a part for running around water.
【０００２】[0002]
【従来の技術】表面に無地や柄模様を印刷したポリエチ
レンテレフタレートフィルムを鋼板表面に積層したラミ
ネート鋼板は、印刷ポリエチレンテレフタレートフィル
ムが塩化ビニルフィルムに比べて硬度が高く、また安価
であることから、家電製品や暖房機器等の外装部，内装
建材，器物等として使用されている。この種のラミネー
ト鋼板は、顔料を配合した着色接着剤層を鋼板表面に設
け、印刷面が着色接着剤層側となるように印刷ポリエチ
レンテレフタレートフィルムを着色接着剤層の上に積層
することにより製造されている。鋼板の地色は、接着剤
層に配合された顔料によって表面に現れることがない。
しかし、淡色系の色調で着色する場合、配合可能な顔料
が制約される。すなわち、印刷ポリエチレンテレフタレ
ートラミネート鋼板としての色調は、主として印刷ポリ
エチレンテレフタレートフィルムの全面に印刷された色
調に依存するが、印刷層だけで完全に下地鋼板や配合顔
料等の色調を隠蔽することはできない。しかし、一般的
な防錆顔料である鉛系顔料，クロメート系顔料，金属粉
顔料等は、何れも固有の濃色を呈することから、これら
の防錆顔料を用いて防錆効果をもち且つ外観に影響を及
ぼさない白色等の淡色系に着色することは困難である。2. Description of the Related Art Laminated steel sheets in which a polyethylene terephthalate film having a plain or patterned pattern printed on the surface is laminated on the surface of the steel sheet have a higher hardness and are less expensive than printed vinyl terephthalate films. It is used as exterior parts of products and heating equipment, interior building materials, equipment and the like. This type of laminated steel sheet is manufactured by providing a colored adhesive layer containing a pigment on the surface of the steel sheet, and laminating a printed polyethylene terephthalate film on the colored adhesive layer so that the printed surface is on the colored adhesive layer side. Have been. The ground color of the steel sheet does not appear on the surface due to the pigment compounded in the adhesive layer.
However, when coloring with a light color tone, the pigments that can be blended are limited. That is, the color tone of the printed polyethylene terephthalate laminated steel sheet mainly depends on the color tone printed on the entire surface of the printed polyethylene terephthalate film, but the printed layer alone cannot completely hide the color tone of the base steel sheet, the compounded pigment, and the like. However, lead-based pigments, chromate-based pigments, metal powder pigments, and the like, which are common rust-preventive pigments, each exhibit a unique dark color. It is difficult to color to a light color such as white which does not affect the color.
【０００３】[0003]
【発明が解決しようとする課題】このようなことから、
Ｚｎめっき鋼板をベースとする淡色系印刷ポリエチレン
テレフタレートラミネート鋼板では、防錆顔料を配合で
きないため、耐食性が劣っている。たとえば、このラミ
ネート鋼板を塩水噴霧試験に供すると、切断端面や原板
まで達する疵がついた部分では、印刷ポリエチレンテレ
フタレートフィルムの下でＺｎめっき鋼板が腐食し、鋼
板から印刷ポリエチレンテレフタレートフィルムが剥離
し易くなる。そのため、洗濯機や厨房部材等の水廻り製
品として使用することには問題があった。淡色系を呈す
るためには、無色又は白色の顔料を使用する必要があ
る。無色系の防食皮膜としては、樹脂皮膜中にシリカゾ
ルを配合し、金属との密着性を向上させたシリカ−有機
複合樹脂皮膜が知られている。また、酸素，水分，水蒸
気等の腐食性因子の透過を抑制する樹脂皮膜を選択する
ことにより、防食性を発現させることもできる。たとえ
ば、特公平６−５１１７１号公報や特開平６−２２０６
４８号公報では、平均粒径が５０ｎｍ〜３μｍや８ｎｍ
未満のシリカゾルを配合したクロメート皮膜をＺｎめっ
き鋼板表面に設けることによって、耐食性に優れた有機
複合Ｚｎめっき鋼板を提案している。SUMMARY OF THE INVENTION
In a light-colored printed polyethylene terephthalate laminated steel sheet based on a Zn-plated steel sheet, corrosion resistance is inferior because a rust preventive pigment cannot be compounded. For example, when this laminated steel sheet is subjected to a salt spray test, the Zn-plated steel sheet is corroded under the printed polyethylene terephthalate film at the cut end face and the part with the flaw reaching the original sheet, and the printed polyethylene terephthalate film is easily peeled from the steel sheet. Become. Therefore, there has been a problem in using it as a water-wound product such as a washing machine or a kitchen member. In order to exhibit a light color system, it is necessary to use a colorless or white pigment. As a colorless anticorrosion film, a silica-organic composite resin film in which silica sol is blended in a resin film to improve adhesion to a metal is known. In addition, by selecting a resin film that suppresses the transmission of corrosive factors such as oxygen, moisture, and water vapor, corrosion resistance can be exhibited. For example, JP-B-6-51171 and JP-A-6-2206
No. 48, the average particle size is 50 nm to 3 μm or 8 nm.
An organic composite Zn-plated steel sheet having excellent corrosion resistance has been proposed by providing a chromate film containing less than 10% of silica sol on the surface of the Zn-plated steel sheet.
【０００４】しかし、これらのクロメート皮膜を設けた
Ｚｎめっき鋼板を用いても、印刷ポリエチレンテレフタ
レートラミネート鋼板としての耐食性は十分でない。ま
た、接着剤層に平均粒径が数ｎｍから数十ｎｍのシリカ
ゾルを配合しても、十分な耐食性が発現されない。本発
明は、このような問題を解消すべく案出されたものであ
り、樹脂層に配合したシリカ粒子が水分や酸素の透過，
拡散を促進させることを利用することにより、ポリエチ
レンテレフタレートフィルム下或いは下部のＺｎめっき
鋼板に隣接する樹脂層を非腐食性雰囲気に維持し、ラミ
ネート鋼板の耐食性を向上させることを目的とする。However, even if these Zn-plated steel sheets provided with a chromate film are used, the corrosion resistance as a printed polyethylene terephthalate laminated steel sheet is not sufficient. Further, even if silica sol having an average particle diameter of several nm to several tens of nm is blended in the adhesive layer, sufficient corrosion resistance is not exhibited. The present invention has been devised in order to solve such a problem, and the silica particles blended in the resin layer can prevent moisture and oxygen from permeating.
An object of the present invention is to improve the corrosion resistance of a laminated steel sheet by maintaining the resin layer adjacent to the Zn-plated steel sheet below or below the polyethylene terephthalate film in a non-corrosive atmosphere by utilizing the diffusion.
【０００５】[0005]
【課題を解決するための手段】本発明の印刷ラミネート
鋼板は、その目的を達成するため、印刷面を接着剤層側
にして印刷ポリエチレンテレフタレートフィルムが接着
剤層を介してＺｎめっき鋼板表面に積層されたラミネー
ト鋼板において、Ｚｎめっき鋼板に隣接する樹脂層の明
度指数Ｌ値が塗装・乾燥後で７０以上であり、樹脂層膜
厚の５０〜１５０％に相当する平均粒径をもつシリカ粒
子が１〜４０重量％で樹脂層に配合されていることを特
徴とする。接着剤層は、Ｚｎめっき鋼板に直接、或いは
熱硬化型樹脂層を介してＺｎめっき鋼板に設けらること
ができる。明度指数Ｌ値は、ＪＩＳ Ｚ８７３０（色差
表示法）で定められているハンター色差式を使用して求
められる。In order to achieve the object, a printed laminated steel sheet of the present invention has a printed polyethylene terephthalate film laminated on a surface of a Zn-plated steel sheet via an adhesive layer with the printed surface facing the adhesive layer. In the laminated steel sheet, the lightness index L value of the resin layer adjacent to the Zn-plated steel sheet is 70 or more after coating and drying, and silica particles having an average particle diameter corresponding to 50 to 150% of the resin layer film thickness are obtained. It is characterized in that it is contained in the resin layer at 1 to 40% by weight. The adhesive layer may be provided on the Zn-plated steel sheet directly or via a thermosetting resin layer. The lightness index L value is determined using a Hunter color difference equation defined in JIS Z8730 (color difference display method).
【０００６】[0006]
【作用】本発明では、透湿度及び酸素透過度の低いポリ
エチレンテレフタレートフィルムとシリカ粒子との組み
合わせによって優れた耐食性を発現させている。耐食性
は、次のようなメカニズムによって向上するものと考え
られる。Ｚｎめっき鋼板等の塗膜下腐食も局部電池の形
式による電気化学反応であると考えられ、（１）塗膜に
高い電気抵抗を発現させる遮蔽効果及び（２）防錆顔料
による分極効果が防食に有効であるとされている。樹脂
皮膜に配合されるシリカは、防錆顔料ではないことから
分極効果による防食が期待されない。また、樹脂層膜厚
の５０〜１５０％に相当する平均粒径をもつシリカを配
合させるとき、樹脂層中に存在するシリカ粒子と樹脂と
の界面がイオン透過しやすい部位となり、遮蔽効果によ
る防食も期待されない。他方、ポリエチレンテレフタレ
ートフィルムは、透湿度が４６ｇ／ｍ2 ／２４ｈｒ（４
０℃，９０％ＲＨ）と比較的低く、酸素透過度も１２０
ｃｃ／ｍ2 ／２４ｈｒ・ａｔｍ（２０℃，９０％ＲＨ）
と低い。そのため、切断端面や下地鋼に達する疵が付け
られた部分から浸透，拡散した水分や酸素は、ポリエチ
レンテレフタレートフィルムした及び下部のＺｎめっき
鋼板に隣接する樹脂層に閉じ込められた状態になる。According to the present invention, excellent corrosion resistance is exhibited by a combination of a polyethylene terephthalate film having low moisture permeability and oxygen permeability and silica particles. It is considered that the corrosion resistance is improved by the following mechanism. It is considered that under-coat corrosion of Zn-plated steel sheets is also an electrochemical reaction in the form of a local battery, and (1) the shielding effect of developing high electrical resistance in the coating film and (2) the polarization effect of the rust-preventive pigment prevent corrosion. It is said to be effective. Silica incorporated in the resin film is not a rust-preventive pigment, so that anticorrosion due to the polarization effect is not expected. When silica having an average particle diameter corresponding to 50 to 150% of the thickness of the resin layer is blended, the interface between the silica particles present in the resin layer and the resin becomes a site where ions can easily permeate, and the anticorrosion due to the shielding effect is achieved. Is also not expected. On the other hand, a polyethylene terephthalate film, moisture permeability 46g / m 2 / 24hr (4
0 ° C., 90% RH) and oxygen permeability is 120
cc / m 2 / 24hr · atm (20 ℃, 90% RH)
And low. Therefore, moisture and oxygen that have permeated and diffused from the cut end face and the scratched part reaching the base steel are confined in the resin layer formed of the polyethylene terephthalate film and adjacent to the lower Zn-plated steel sheet.
【０００７】そこで、Ｚｎめっき鋼板に隣接する樹脂層
中に存在するシリカ粒子は、ポリエチレンテレフタレー
トフィルム下及び下部のＺｎめっき鋼板に隣接する樹脂
層に閉じ込められた状態にある水分や酸素等を、ポリエ
チレンテレフタレートフィルム下及び下部のＺｎめっき
鋼板に隣接する樹脂層からポリエチレンテレフタレート
フィルムが被覆されていない部位まで透過，拡散させ、
結果として切断端面及び疵付き部分の耐食性が著しく改
善される。このとき、Ｚｎめっき鋼板に隣接する樹脂層
中におけるシリカは、腐食の対象であるＺｎめっき鋼板
に隣接する樹脂層中に閉じ込められた水分や酸素等を透
過，拡散させることに有効に作用する。Ｚｎめっき鋼板
には、接着剤層又は熱硬化型樹脂層の形成に先立って、
通常脱脂処理や化成処理等の前処理が施される。鋼板の
表面性状によっては、前処理を省略することもできる。
Ｚｎめっき鋼板としては、溶融めっき，電気めっき，蒸
着めっき等で製造された純Ｚｎ，Ｚｎ−Ａｌ，Ｚｎ−Ｎ
ｉ，Ｚｎ−Ｆｅ等のＺｎめっき鋼板又はＺｎ系合金めっ
き鋼板が使用される。また、目付け量も、通常使用され
る範囲であれば特に制約されるものではない。Therefore, the silica particles present in the resin layer adjacent to the Zn-plated steel sheet remove moisture and oxygen, etc., trapped in the resin layer adjacent to the Zn-plated steel sheet below and below the polyethylene terephthalate film. Permeation and diffusion from the resin layer below and below the terephthalate film and adjacent to the Zn-plated steel sheet to the area where the polyethylene terephthalate film is not coated,
As a result, the corrosion resistance of the cut end face and the flawed portion is significantly improved. At this time, the silica in the resin layer adjacent to the Zn-plated steel sheet effectively acts to transmit and diffuse moisture, oxygen, and the like confined in the resin layer adjacent to the Zn-plated steel sheet to be corroded. Prior to the formation of the adhesive layer or the thermosetting resin layer on the Zn-plated steel sheet,
Usually, a pretreatment such as a degreasing treatment or a chemical conversion treatment is performed. Depending on the surface properties of the steel sheet, the pretreatment may be omitted.
Examples of the Zn-plated steel sheet include pure Zn, Zn-Al, Zn-N manufactured by hot-dip plating, electroplating, vapor deposition plating, and the like.
i, Zn-plated steel sheets such as Zn-Fe or Zn-based alloy-plated steel sheets are used. Also, the weight per unit area is not particularly limited as long as it is within a range normally used.
【０００８】接着剤としては、印刷ポリエチレンテレフ
タレートフィルムをＺｎめっき鋼板又は熱硬化型樹脂層
に接着できるものである限り、種類に特段の制約を受け
るものではなく、１液型又は２液型の何れをも使用でき
る。接着剤の樹脂は、特に限定されるものでないが、ポ
リエステル系樹脂，ポリウレタン系樹脂等を使用するこ
とができ、接着剤層の乾燥厚みは１〜２０μｍが好まし
い。接着剤層とＺｎめっき鋼板との間に設けられる熱硬
化型樹脂は、特に種類が制約されるものではなく、たと
えばエポキシ系樹脂，ポリエステル系樹脂等が使用され
る。また、硬化剤としても、たとえばメラミン樹脂，イ
ソシアネート樹脂等を使用することができる。熱硬化型
樹脂能の乾燥膜厚としては、２〜２０μｍが好ましい。The type of adhesive is not particularly limited as long as it can bond the printed polyethylene terephthalate film to the Zn-plated steel sheet or the thermosetting resin layer. Can also be used. The resin of the adhesive is not particularly limited, but polyester resin, polyurethane resin and the like can be used, and the dry thickness of the adhesive layer is preferably 1 to 20 μm. The type of thermosetting resin provided between the adhesive layer and the Zn-plated steel sheet is not particularly limited, and for example, an epoxy resin, a polyester resin, or the like is used. Further, as the curing agent, for example, melamine resin, isocyanate resin and the like can be used. The dry film thickness of the thermosetting resin is preferably 2 to 20 μm.
【０００９】Ｚｎめっき鋼板に隣接する樹脂層、すなわ
ち熱硬化型樹脂層が存在しない場合の接着剤層、或いは
熱硬化型樹脂層が存在する場合の熱硬化型樹脂層には、
樹脂層膜厚の５０〜１５０％に相当する平均粒径をもつ
シリカが１〜４０重量％配合される。シリカの平均粒径
が樹脂層膜厚の５０〜１５０％であり、またシリカの配
合量が１〜４０重量％であるとき、ポリエチレンテレフ
タレートフィルム下又は下部のＺｎめっき鋼板に隣接す
る樹脂層から水分や酸素が効率よくポリエチレンテレフ
タレートフィルムが被覆されていない部位まで透過，拡
散する。樹脂層膜厚の５０％未満に相当する平均粒径を
もつシリカや、配合量が１重量％未満では、水分や酸素
の透過，拡散が起こりにくく、十分な耐食性が得られな
い。また、樹脂層膜厚の１５０％に相当する平均粒径を
超えるシリカを使用したり、シリカの配合量が４０重量
％を超えると、Ｚｎめっき鋼板に隣接する樹脂の凝集力
が低下し、印刷ポリエチレンテレフタレートラミネート
鋼板としてのフィルム剥離強度が低下し、使用に耐えな
くなる。The resin layer adjacent to the Zn-plated steel sheet, that is, the adhesive layer when the thermosetting resin layer does not exist, or the thermosetting resin layer when the thermosetting resin layer exists,
Silica having an average particle size corresponding to 50 to 150% of the resin layer film thickness is mixed at 1 to 40% by weight. When the average particle size of the silica is 50 to 150% of the thickness of the resin layer and the compounding amount of the silica is 1 to 40% by weight, moisture from the resin layer adjacent to the Zn-plated steel sheet below or below the polyethylene terephthalate film is reduced. And oxygen efficiently permeate and diffuse to the area not covered with the polyethylene terephthalate film. If the silica has an average particle size corresponding to less than 50% of the resin layer thickness, or if the amount is less than 1% by weight, permeation and diffusion of moisture and oxygen hardly occur, and sufficient corrosion resistance cannot be obtained. Further, when silica having an average particle size exceeding 150% of the resin layer film thickness is used, or when the compounding amount of silica exceeds 40% by weight, the cohesive force of the resin adjacent to the Zn-plated steel sheet is reduced, and printing is performed. The peel strength of the film as a polyethylene terephthalate laminated steel sheet is reduced, and it cannot be used.
【００１０】印刷ポリエチレンテレフタレートラミネー
ト鋼板で淡色を発現するためには、Ｚｎめっき鋼板に隣
接する樹脂層について、ＪＩＳ Ｚ８７３０（色差表示
法）のハンター色差式に従った明度指数Ｌ値がＺｎめっ
き鋼板への塗装・乾燥後で７０以上であることが必要と
される。この点、シリカ以外の顔料としては、アルミナ
等の無色系や酸化チタン等の白系の体質顔料や着色顔料
を顔料をＺｎめっき鋼板に隣接する樹脂層に配合するこ
とができる。熱硬化型樹脂層がある場合の接着剤層とし
ても、無色又は白色の色調をもつ接着剤層が必要とされ
ることから、アルミナ等の無色系や酸化チタン等の白系
の体質顔料や着色顔料が使用される。Ｚｎめっき鋼板に
隣接する樹脂層に配合されるシリカとしては、平均粒径
が数μｍ〜数十μｍの粗粒シリカが使用される。また、
アモルファスシリカや硬質シリカを使用することもでき
る。[0010] In order to express a light color in the printed polyethylene terephthalate laminated steel sheet, the lightness index L value of the resin layer adjacent to the Zn-plated steel sheet according to the Hunter color difference equation of JIS Z8730 (color difference display method) is changed to the Zn-plated steel sheet. After coating and drying, it is required to be 70 or more. In this regard, as a pigment other than silica, a colorless pigment such as alumina or a white pigment such as titanium oxide or a coloring pigment can be blended with the resin layer adjacent to the Zn-plated steel sheet. As an adhesive layer having a thermosetting resin layer, an adhesive layer having a colorless or white color tone is required, so that a colorless pigment such as alumina or a white pigment such as titanium oxide or a coloring pigment is used. Is used. As silica mixed in the resin layer adjacent to the Zn-plated steel sheet, coarse silica having an average particle size of several μm to several tens μm is used. Also,
Amorphous silica and hard silica can also be used.
【００１１】印刷ポリエチレンテレフタレートフィルム
としては、易接着処理を施したポリエチレンテレフタレ
ートフィルムの処理面に柄模様をグラビア印刷し、更に
その上面にベタ印刷層を設けたものが使用される。ポリ
エチレンテレフタレートフィルムには、一般的な透明２
軸延伸ポリエチレンテレフタレートフィルムが使用さ
れ、フィルムの厚みは１０〜５０μｍが好ましい。ポリ
エチレンテレフタレートフィルムへの印刷を施す前に、
ポリエチレンテレフタレートフィルム表面に易接着処理
を施すことが好ましい。易接着処理は、ポリエチレンテ
レフタレートフィルムに対する印刷インク層との接着強
度を改善する。易接着処理としては、コロナ放電処理，
アクリル樹脂やポリエステル樹脂等のコーティング等が
採用される。易接着処理を施したポリエチレンテレフタ
レートフィルムには、柄模様をグラビア印刷し、更にそ
の上面にベタ印刷層を設けることにより意匠性が付与さ
れる。印刷インクには、アクリル系，ポリエステル系，
ポリウレタン系等のベース樹脂に顔料や種々の添加材を
配合したものが使用される。このとき、ハンター色差式
における明度指数Ｌ値がＺｎめっき鋼板への塗装・乾燥
後で７０以上の接着剤層や熱硬化型樹脂層と印刷ポリエ
チレンテレフタレートフィルムのベタ印刷色との組合せ
によって色調が調整される。以上に説明したラミネート
鋼板は、Ｚｎめっき鋼板にクロメート処理，燐酸塩処理
等の前処理を施し、ポリエステル樹脂系，ポリウレタン
系等の接着剤をロールコート法，カーテンフローコート
法，スプレーコート法等で塗布した後、１２０〜２８０
℃で２０〜９０秒間焼き付け・乾燥し、その上に接着剤
層が溶融状態にある段階で印刷ポリエチレンテレフタレ
ートフィルムを積層することにより製造される。また、
熱硬化型樹脂層を設ける場合、接着剤の塗布に先立っ
て、エポキシ系，ポリエステル系等の熱硬化型塗料を同
様に焼き付け、乾燥する。As the printed polyethylene terephthalate film, a film obtained by gravure printing a pattern on the treated surface of a polyethylene terephthalate film subjected to an easy adhesion treatment and further providing a solid printing layer on the upper surface thereof is used. For polyethylene terephthalate film, general transparent 2
An axially stretched polyethylene terephthalate film is used, and the thickness of the film is preferably from 10 to 50 μm. Before printing on polyethylene terephthalate film,
It is preferable that the polyethylene terephthalate film surface is subjected to an easy adhesion treatment. The easy adhesion treatment improves the adhesion strength between the polyethylene terephthalate film and the printing ink layer. Corona discharge treatment, easy adhesion treatment,
A coating such as an acrylic resin or a polyester resin is employed. A design is imparted to the polyethylene terephthalate film subjected to the easy adhesion treatment by gravure printing a pattern and further providing a solid printing layer on the upper surface thereof. Printing inks include acrylic, polyester,
A mixture of a base resin such as a polyurethane resin and a pigment or various additives is used. At this time, the lightness index L value in the Hunter color difference equation is adjusted by the combination of the adhesive layer or the thermosetting resin layer of 70 or more and the solid printing color of the printed polyethylene terephthalate film after coating and drying on the Zn-plated steel sheet. Is done. The laminated steel sheet described above is prepared by subjecting a Zn-plated steel sheet to a pretreatment such as a chromate treatment or a phosphate treatment, and applying a polyester resin-based or polyurethane-based adhesive by a roll coating method, a curtain flow coating method, a spray coating method, or the like. After application, 120-280
It is manufactured by baking and drying at 20 ° C. for 20 to 90 seconds, and laminating a printed polyethylene terephthalate film thereon while the adhesive layer is in a molten state. Also,
When a thermosetting resin layer is provided, a thermosetting paint such as an epoxy-based or polyester-based paint is similarly baked and dried prior to application of the adhesive.
【００１２】[0012]
実施例１：板厚０．５ｍｍの鋼板に片面目付け量４５ｇ
／ｍ2 でめっきした溶融Ｚｎめっき鋼板に塗布型クロメ
ート処理を施し、熱硬化型エポキシ樹脂を乾燥膜厚で６
μｍ塗布し焼き付けた。熱硬化型エポキシ樹脂として
は、メラミン樹脂を硬化剤として平均粒径８μｍのシリ
カ２０重量％及び酸化チタン２０重量％を配合したもの
を使用した。この場合、ハンター色差式における明度指
数Ｌ値が８１であった。この上面に、イソシアネートを
硬化剤とするポリエステル−ポリウレタン樹脂系接着剤
を乾燥膜厚５μｍで塗布・焼き付けし、直ちに積層面を
印刷面側にした印刷ポリエチレンテレフタレートフィル
ムＡを温度２００℃でラミネートした。印刷ポリエチレ
ンテレフタレートフィルムＡとしては、２５μｍ厚みの
コロナ放電処理ポリエチレンテレフタレートフィルムに
石目模様をポリウレタン樹脂系印刷インクでグラビア印
刷した後、更に同種アイボリー色の印刷インクでベタ印
刷したものを使用した。得られたラミネート鋼板は、印
刷ポリエチレンテレフタレートフィルムの色調をもって
いた。また、ラミネート鋼板に碁盤目状の切れ込みをカ
ッターナイフでつけ、エリクセン試験（６ｍｍ押出し）
を行った結果、フィルムの剥離が検出されなかった。ま
た、ラミネート鋼板から図１に示す試験片を切り出し、
ＪＩＳＺ２３７１に準拠した５００時間の塩水噴霧試験
に供したところ、切断端面及びクロスカット部における
フィルムの剥離や浮きも検出されなかった。Example 1: A steel sheet having a thickness of 0.5 mm has a basis weight of 45 g per side.
/ M 2 Plating molten Zn-plated steel sheet subjected to a coating type chromate treatment, the thermosetting epoxy resin in a dry film thickness of 6
μm was applied and baked. As the thermosetting epoxy resin, a resin prepared by blending 20% by weight of silica having an average particle diameter of 8 μm and 20% by weight of titanium oxide using a melamine resin as a curing agent was used. In this case, the lightness index L value in the Hunter color difference equation was 81. On this upper surface, a polyester-polyurethane resin-based adhesive using isocyanate as a curing agent was applied and baked at a dry film thickness of 5 μm, and immediately, a printed polyethylene terephthalate film A having a laminated surface facing the printing surface was laminated at a temperature of 200 ° C. As the printed polyethylene terephthalate film A, one obtained by gravure-printing a stone pattern on a 25 μm-thick corona-discharge treated polyethylene terephthalate film with a polyurethane resin-based printing ink, and then solid-printing with a ivory printing ink of the same type was used. The resulting laminated steel sheet had the color tone of a printed polyethylene terephthalate film. In addition, a cross-cut notch is made on the laminated steel plate with a cutter knife, and an Erichsen test (6 mm extrusion)
As a result, no peeling of the film was detected. Also, a test piece shown in FIG. 1 was cut out from a laminated steel sheet,
When subjected to a salt spray test for 500 hours in accordance with JISZ2371, no peeling or lifting of the film was detected on the cut end face or the cross cut portion.
【００１３】実施例２；鋼板厚み０．４ｍｍ及びＺｎ目
付け量片面３０ｇ／ｍ2 の合金化Ｚｎめっき鋼板に塗布
型クロメート処理を施し、ポリエーテル−ポリウレタン
樹脂系接着剤を乾燥膜厚５μｍで塗布・焼き付けし、直
ちに積層面を印刷面側にした印刷ポリエチレンテレフタ
レートフィルムＢを温度１６０℃でラミネートした。こ
の場合、接着剤としては、エポキシ樹脂を硬化剤とし、
平均粒径５μｍのシリカ１５重量％及び酸化チタン１０
重量％を配合したものを使用した。なお、接着剤層を設
けて状態でのハンター色差式における明度指数Ｌ値は７
９であった。また、印刷ポリエチレンテレフタレートフ
ィルムＢには、ポリエステル樹脂コーティングしたポリ
エチレンテレフタレートフィルムに砂目調の柄をポリウ
レタン樹脂系印刷インク（イソシアネートを硬化剤とす
る２液型）でグラビア印刷した後、更に同種のライトベ
ージュ色の印刷インクでベタ印刷したものを使用した。
得られたラミネート鋼板は、印刷ポリエチレンテレフタ
レートフィルムＢの色調を呈していた。また、碁盤目エ
リクセン試験の結果、フィルムの剥離が検出されなかっ
た。更に、５００時間の塩水噴霧試験に供したところ、
切断端面及びクロスカット部におけるフィルムの剥離や
浮きも検出されなかった。Example 2 A coating type chromate treatment is applied to an alloyed Zn-plated steel sheet having a steel sheet thickness of 0.4 mm and a basis weight of Zn of 30 g / m 2 , and a polyether-polyurethane resin adhesive is applied at a dry film thickness of 5 μm. Immediately after baking, a printed polyethylene terephthalate film B having a laminated surface facing the printed surface was laminated at a temperature of 160 ° C. In this case, as an adhesive, an epoxy resin is used as a curing agent,
15% by weight of silica having an average particle size of 5 μm and titanium oxide 10
What mixed the weight% was used. The lightness index L value in the Hunter color difference equation with the adhesive layer provided is 7
Nine. The printed polyethylene terephthalate film B is gravure-printed on a polyester resin-coated polyethylene terephthalate film with a polyurethane resin-based printing ink (two-pack type using isocyanate as a curing agent) on a polyester resin-coated polyethylene terephthalate film. Solid printing with beige printing ink was used.
The obtained laminated steel sheet had the color tone of the printed polyethylene terephthalate film B. Further, as a result of the cross-cut Erichsen test, no peeling of the film was detected. Further, when subjected to a 500-hour salt spray test,
Neither peeling nor lifting of the film at the cut end face or the cross cut portion was detected.
【００１４】実施例３：５％Ａｌ−Ｚｎめっき鋼板（鋼
板厚み０．６ｍｍ，Ｚｎ目付け量片面３０ｇ／ｍ2 ）に
塗布型クロメート処理を施し、熱硬化型エポキシ樹脂を
乾燥膜厚１０μｍで塗布し焼き付けた。熱硬化型エポキ
シ樹脂としては、イソシアネート樹脂を硬化剤とし、平
均粒径１２μｍのシリカ１５重量％，酸化チタン２５重
量％及びアルミナ５重量％を配合したものを使用した。
この場合、ハンター色差式における明度指数Ｌ値は８５
であった。この上面に、イソシアネートを硬化剤とする
ポリウレタン樹脂系接着剤を乾燥膜厚４μｍで塗布し焼
き付け、直ちに積層面を印刷面側にした印刷ポリエチレ
ンテレフタレートフィルムＡを温度２１０℃でラミネー
トした。得られたラミネート鋼板は、印刷ポリエチレン
テレフタレートフィルムＡの色調を保持していた。碁盤
目エリクセン試験では、フィルムの剥離が検出されなか
った。５００時間の塩水噴霧試験でも、切断端面及びク
ロスカット部にフィルムの剥れ，浮き等が検出されなか
った。Example 3 A 5% Al-Zn plated steel sheet (steel thickness: 0.6 mm, Zn basis weight: 30 g / m 2 on one side) is subjected to a coating type chromate treatment, and a thermosetting epoxy resin is applied to a dry film thickness of 10 μm. I baked it. As the thermosetting epoxy resin, a resin obtained by using an isocyanate resin as a curing agent and blending 15% by weight of silica having an average particle diameter of 12 μm, 25% by weight of titanium oxide, and 5% by weight of alumina was used.
In this case, the lightness index L value in the Hunter color difference equation is 85
Met. On this upper surface, a polyurethane resin-based adhesive using isocyanate as a curing agent was applied at a dry film thickness of 4 μm and baked. Immediately, a printed polyethylene terephthalate film A with the laminated surface facing the printing surface was laminated at a temperature of 210 ° C. The obtained laminated steel sheet retained the color tone of the printed polyethylene terephthalate film A. In the cross-cut Erichsen test, no peeling of the film was detected. Even in the salt spray test for 500 hours, no peeling or floating of the film was detected on the cut end face and the cross cut portion.
【００１５】実施例４：電気Ｚｎめっき鋼板（鋼板厚み
０．６ｍｍ，Ｚｎ目付け量片面１０ｇ／ｍ2 ）に燐酸塩
処理を施し、ポリエステルウレタン樹脂系接着剤を乾燥
膜厚８μｍで塗布し焼き付け、直ちに積層面を印刷面側
にした印刷ポリエチレンテレフタレートフィルムＣを１
５０℃でラミネートした。接着剤としては、イソシアネ
ートを硬化剤とし、平均粒径１０μｍのシリカ１０重量
％及び酸化チタン２０重量％を配合したものを使用し
た。この場合、接着剤層を設けた状態でのハンター色差
式における明度指数Ｌ値は８２であった。なお、印刷ポ
リエチレンテレフタレートフィルムＣとしては、ポリエ
ステル樹脂コーティングした膜厚２５μｍのポリエチレ
ンテレフタレートフィルムに和紙調柄をポリウレタン樹
脂系の印刷インク（イソシアネートを硬化剤とする２液
型）でグラビア印刷した後、更に同種のライトグレー色
の印刷インクでベタ印刷したものを使用した。得られた
ラミネート鋼板は、印刷ポリエチレンテレフタレートフ
ィルムの色調を保持していた。碁盤目エリクセン試験で
は、フィルムの剥離が検出されなかった。５００時間の
塩水噴霧試験でも、切断端面及びクロスカット部にフィ
ルムの剥れ，浮き等が検出されなかった。Example 4: An electro-zinc plated steel sheet (steel thickness: 0.6 mm, Zn basis weight: 10 g / m 2 ) was subjected to phosphate treatment, and a polyester urethane resin-based adhesive was applied at a dry film thickness of 8 μm and baked. Immediately, place the printed polyethylene terephthalate film C with the lamination surface on the printing surface
Laminated at 50 ° C. The adhesive used was a mixture of 10% by weight of silica having an average particle diameter of 10 μm and 20% by weight of titanium oxide, using isocyanate as a curing agent. In this case, the lightness index L value in the Hunter color difference equation with the adhesive layer provided was 82. The printed polyethylene terephthalate film C was prepared by gravure printing a Japanese paper pattern on a polyester resin-coated polyethylene terephthalate film having a thickness of 25 μm with a polyurethane resin-based printing ink (two-pack type using isocyanate as a curing agent), and then further printing. Solid printing using the same type of light gray printing ink was used. The obtained laminated steel sheet retained the color tone of the printed polyethylene terephthalate film. In the cross-cut Erichsen test, no peeling of the film was detected. Even in the salt spray test for 500 hours, no peeling or floating of the film was detected on the cut end face and the cross cut portion.
【００１６】比較例１：溶融Ｚｎめっき鋼板（鋼板厚み
０．５ｍｍ，Ｚｎ目付け量片面４５ｇ／ｍ2 ）に塗布型
クロメート処理を施し、熱硬化型エポキシ樹脂を乾燥膜
厚６μｍで塗布し焼き付けた。熱硬化型エポキシ樹脂に
は、メラミン樹脂を硬化剤とし、酸化チタンを１０重量
％配合したものを使用した。この場合、明度指数Ｌ値は
８０であった。この上面に、イソシアネートを硬化剤と
するポリエステルウレタン樹脂系接着剤を乾燥膜厚５μ
ｍで塗布・焼き付け、直ちに積層面を印刷面側にして印
刷ポリエチレンテレフタレートフィルムＡを２００℃で
ラミネートした。得られたラミネート鋼板は、印刷ポリ
エチレンテレフタレートフィルムＡの色調を保持してい
た。碁盤目エリクセン試験では、フィルムの剥離が検出
されなかった。しかし、５００時間の塩水噴霧試験に供
したところ、切断端面及びクロスカット部において、そ
れぞれフィルムの膨れが切断端面及びクロスカット部に
対して垂直方向に７ｍｍ及び５ｍｍの大きさで発生し
た。Comparative Example 1: A hot-dip galvanized steel sheet (steel thickness: 0.5 mm, Zn basis weight: 45 g / m 2 ) was subjected to a coating type chromate treatment, and a thermosetting epoxy resin was applied to a dry film thickness of 6 μm and baked. . As the thermosetting epoxy resin, a resin containing melamine resin as a curing agent and 10% by weight of titanium oxide was used. In this case, the lightness index L value was 80. On this upper surface, a polyester urethane resin-based adhesive using isocyanate as a curing agent was dried to a thickness of 5 μm.
m, and the printed polyethylene terephthalate film A was immediately laminated at 200 ° C. with the laminated surface facing the printing surface. The obtained laminated steel sheet retained the color tone of the printed polyethylene terephthalate film A. In the cross-cut Erichsen test, no peeling of the film was detected. However, when subjected to a salt spray test for 500 hours, swelling of the film occurred on the cut end face and the cross cut portion in a size of 7 mm and 5 mm in a direction perpendicular to the cut end face and the cross cut portion, respectively.
【００１７】比較例２：合金化Ｚｎめっき鋼板（鋼板厚
み０．４ｍｍ，Ｚｎ目付け量片面３０ｇ／ｍ2）に塗布
型クロメート処理を施し、ポリエーテル−ポリウレタン
樹脂系接着剤を乾燥膜厚５μｍで塗布・焼き付けた。ポ
リエーテル−ポリウレタン樹脂系接着剤としては、エポ
キシ樹脂を硬化剤とし、平均粒径５μｍのシリカ７０重
量％及び酸化チタン１０重量％を配合したものを使用し
た。焼付後、直ちに積層面を印刷面側にした印刷ポリエ
チレンテレフタレートフィルムＢを温度１６０℃でラミ
ネートした。この場合、明度指数Ｌ値は８２であった。
得られたラミネート鋼板は、印刷ポリエチレンテレフタ
レートフィルムの色調を保持していた。しかし、碁盤目
エリクセン試験の結果ではフィルムが剥離し、また５０
０時間の塩水噴霧試験の結果ではラミネート鋼板の平坦
部全面でフィルムに浮きが発生していた。Comparative Example 2: A coating type chromate treatment was performed on an alloyed Zn-plated steel sheet (steel sheet thickness: 0.4 mm, Zn basis weight: 30 g / m 2 ), and a polyether-polyurethane resin-based adhesive was dried at a dry film thickness of 5 μm. Coated and baked. As the polyether-polyurethane resin-based adhesive, an epoxy resin was used as a curing agent, and 70% by weight of silica having an average particle diameter of 5 μm and 10% by weight of titanium oxide were used. Immediately after baking, a printed polyethylene terephthalate film B having a laminated surface facing the printed surface was laminated at a temperature of 160 ° C. In this case, the lightness index L value was 82.
The obtained laminated steel sheet retained the color tone of the printed polyethylene terephthalate film. However, according to the results of the cross-cut Erichsen test, the film peeled off, and
As a result of the 0 hour salt spray test, the film was floated over the entire flat portion of the laminated steel sheet.
【００１８】比較例３：５％Ａｌ−Ｚｎめっき鋼板（鋼
板厚み０．６ｍｍ，Ｚｎ目付け量片面３０ｇ／ｍ2 ）に
塗布型クロメート処理を施し、熱硬化型エポキシ樹脂を
乾燥膜厚５μｍで塗布・焼き付けた。熱硬化型エポキシ
樹脂としては、イソシアネート樹脂を硬化剤として使用
し、平均粒径２０μｍのシリカ３０重量％，酸化チタン
２５重量％及びアルミナ５重量％を配合したものを使用
した。この場合、明度指数Ｌ値は８７であった。この上
面に、イソシアネートを硬化剤とするポリウレタン樹脂
系接着剤を乾燥膜厚４μｍで塗布・焼き付けし、直ちに
積層面を印刷面側にした印刷ポリエチレンテレフタレー
トフィルムＡを２１０℃でラミネートした。得られたラ
ミネート鋼板は、印刷ポリエチレンテレフタレートフィ
ルムＡの色調を保持していた。しかし、表面が不規則に
荒れた外観を呈していた。また、碁盤目エリクセン試験
ではフィルムの剥離が検出され、５００時間の塩水噴霧
試験ではラミネート鋼板の平坦部全面にフィルムの浮き
が検出された。Comparative Example 3: A 5% Al-Zn plated steel sheet (steel thickness: 0.6 mm, Zn basis weight: 30 g / m 2 on one side) was subjected to a coating type chromate treatment, and a thermosetting epoxy resin was applied to a dry film thickness of 5 μm.・ I baked it. As the thermosetting epoxy resin, an isocyanate resin was used as a curing agent, and a mixture of 30% by weight of silica having an average particle diameter of 20 μm, 25% by weight of titanium oxide, and 5% by weight of alumina was used. In this case, the lightness index L value was 87. A polyurethane resin-based adhesive using isocyanate as a curing agent was applied and baked on this upper surface at a dry film thickness of 4 μm, and immediately, a printed polyethylene terephthalate film A with the laminated surface facing the printing surface was laminated at 210 ° C. The obtained laminated steel sheet retained the color tone of the printed polyethylene terephthalate film A. However, the surface had an irregularly rough appearance. In the cross-cut Erichsen test, peeling of the film was detected, and in the salt spray test for 500 hours, floating of the film was detected over the entire flat portion of the laminated steel sheet.
【００１９】比較例４：電気Ｚｎめっき鋼板（鋼板厚み
０．６ｍｍ，Ｚｎ目付け量片面１０ｇ／ｍ2 ）に燐酸塩
処理を施し、ポリエステル−ポリウレタン樹脂系接着剤
を乾燥膜厚８μｍで塗布。焼き付けし、直ちに積層面を
印刷面側にした印刷ポリエチレンテレフタレートフィル
ムＣを１５０℃でラミネートした。ポリエステル−ポリ
ウレタン樹脂系接着剤としては、イソシアネートを硬化
剤とし、平均粒径１０μｍのシリカ０．５重量％，赤色
顔料５重量％及び酸化チタン２０重量％を配合したもの
を使用した。この場合、接着剤層を設けた状態での明度
指数Ｌ値は４５であった。また、印刷ポリエチレンテレ
フタレートフィルムとしては、ポリエステル樹脂コーテ
ィングした膜厚２５μｍのポリエチレンテレフタレート
フィルムに和紙調柄をポリウレタン樹脂系印刷インク
（イソシアネートを硬化剤とする２液型）でグラビア印
刷した後、更に同種のライトグレー色の印刷インクでベ
タ印刷したものを使用した。得られたラミネート鋼板
は、印刷ポリエチレンテレフタレートフィルムに比較し
て赤黒く大きく色調がずれていた。碁盤目エリクセン試
験の結果ではフィルムの剥離が検出されなかったもの
の、５００時間の塩水噴霧試験では切断端面及びクロス
カット部にそれぞれ１０ｍｍ及び８ｍｍの膨れが発生し
ていた。Comparative Example 4: A phosphate treatment was applied to an electro-zinc plated steel sheet (steel thickness: 0.6 mm, Zn basis weight: 10 g / m 2 ), and a polyester-polyurethane resin-based adhesive was applied to a dry film thickness of 8 μm. Immediately after baking, a printed polyethylene terephthalate film C with the laminated surface facing the printed surface was laminated at 150 ° C. As the polyester-polyurethane resin-based adhesive, an adhesive containing 0.5% by weight of silica having an average particle diameter of 10 μm, 5% by weight of a red pigment, and 20% by weight of titanium oxide was used as a curing agent. In this case, the lightness index L value in a state where the adhesive layer was provided was 45. Further, as a printed polyethylene terephthalate film, a Japanese paper pattern is gravure-printed on a 25 μm-thick polyester resin-coated polyethylene terephthalate film with a polyurethane resin-based printing ink (two-pack type using isocyanate as a curing agent), and then the same type. Solid printing with light gray printing ink was used. The obtained laminated steel sheet was red-black and largely out of color as compared with the printed polyethylene terephthalate film. Although no peeling of the film was detected in the result of the cross-cut Erichsen test, in the salt spray test for 500 hours, blisters of 10 mm and 8 mm were generated on the cut end face and the cross cut portion, respectively.
【００２０】実施例５：イソシアネートを硬化剤とする
ポリウレタン樹脂系接着剤１００重量部にカーボンブラ
ック５重量部を配合した黒色接着剤及び酸化チタン５０
重量部を配合した白色接着剤を調製した。これら黒色接
着剤と白色接着剤とを混合し、無彩色系の接着剤を得
た。クロム付着量５０ｍｇ／ｍ2 の塗布型クロメート処
理を施した板厚０．５ｍｍ及びＺｎ目付け量６０ｇ／ｍ
2 の溶融Ｚｎめっき鋼板に乾燥塗膜が６μｍとなるよう
に無彩色接着剤をバーコータで塗装し、到達板温１８０
℃で乾燥させ、Ｌ値の異なる接着剤塗布鋼板を得た。ま
た、各接着剤にストロンチウムクロメートを１０重量部
配合したものを同様に塗布，乾燥し、防錆顔料を配合し
た場合のＬ値が異なる接着剤塗布鋼板を得た。各接着剤
塗布鋼板の色調を調査したところ、図２及び図３に示す
ように防錆顔料配合の有無に応じてＬ値，ａ値，ｂ値が
異なっていた。Example 5 Black adhesive prepared by mixing 5 parts by weight of carbon black with 100 parts by weight of a polyurethane resin adhesive using isocyanate as a curing agent, and titanium oxide 50
A white adhesive containing parts by weight was prepared. These black adhesive and white adhesive were mixed to obtain an achromatic adhesive. A plate thickness of 0.5 mm coated with a coating type chromate having a chromium adhesion amount of 50 mg / m 2 and a Zn basis weight of 60 g / m 2
Achromatic adhesive was applied to the hot-dip Zn-plated steel sheet 2 with a bar coater so that the dry coating film became 6 μm.
It dried at ° C and obtained the adhesive coated steel plates with different L values. In addition, each of the adhesives containing 10 parts by weight of strontium chromate was similarly applied and dried to obtain adhesive-coated steel sheets having different L values when a rust preventive pigment was added. When the color tone of each adhesive-coated steel sheet was examined, the L value, a value, and b value differed depending on the presence or absence of the rust preventive pigment as shown in FIGS. 2 and 3.
【００２１】実施例６：イソシアネートを硬化剤とする
ポリウレタン樹脂系接着剤１００重量部に酸化チタン３
０重量部を配合し、更に平均粒径６μｍ又は１１μｍの
シリカ１０重量部を配合した接着剤を調製した。この接
着剤を実施例５と同じＺｎめっき鋼板に種々の乾燥膜厚
で塗装し、到達板温１８０℃で乾燥させた後、直ちに接
着面と印刷面が積層する様に印刷ポリエチレンテレフタ
レートフィルムをラミネートした。印刷ポリエチレンテ
レフタレートフィルムとしては、コロナ放電処理した２
５μｍ厚みのポリエチレンテレフタレートフィルムに和
紙調柄をポリウレタン樹脂系インク（イソシアネートを
硬化剤としアイボリー調）でグラビア印刷し、更に同種
のインクでベタ印刷したものを使用した。Example 6: Titanium oxide 3 was added to 100 parts by weight of a polyurethane resin adhesive using isocyanate as a curing agent.
0 parts by weight, and further, 10 parts by weight of silica having an average particle diameter of 6 μm or 11 μm was prepared. This adhesive was applied to the same Zn-plated steel sheet as in Example 5 at various dry film thicknesses, dried at a reached plate temperature of 180 ° C, and immediately laminated with a printed polyethylene terephthalate film so that the adhesive surface and the printed surface were laminated. did. As a printed polyethylene terephthalate film, corona discharge treated 2
A gravure print of a Japanese paper pattern on a polyethylene terephthalate film having a thickness of 5 μm with a polyurethane resin-based ink (ivory-like using isocyanate as a curing agent) and a solid print with the same kind of ink were used.
【００２２】また、平均粒径６μｍ及び１１μｍのシリ
カをエポキシ樹脂系熱硬化型プライマー（メラミン硬
化，酸化チタン３０重量部配合）に配合したものを、同
様に前処理したＺｎめっき鋼板に種々の乾燥膜厚で塗装
し、到達板温２１０℃で焼き付けた。この塗装面上に、
実施例５で調製した顔料を配合していない透明接着剤を
乾燥膜厚６μｍで塗布し、到達板温１８０℃で乾燥した
後、直ちに接着面と印刷面が積層するように印刷ポリエ
チレンテレフタレートフィルムをラミネートした。ラミ
ネート前のＬ値を測定した。また、ＪＩＳ Ｚ２３７１
に準拠した塩水噴霧試験を５００時間行った後、切断端
面及びクロスカット部におけるフィルムの膨れ幅を調査
した。調査結果を、表１及び図４〜７に示す。なお、シ
リカを配合していない接着剤を６μｍの厚みで施したも
のでは、Ｌ値が７６，耐食性が切断端面で７ｍｍの膨
れ，クロスカット部で５ｍｍの膨れであった。更に、シ
リカを配合していない厚み６μｍの熱硬化型プライマー
の上に６μｍの透明接着剤を設けたものでは、Ｌ値が７
８，耐食性が切断端面で６ｍｍの膨れ，クロスカット部
で５ｍｍの膨れであった。Further, a mixture of silica having an average particle diameter of 6 μm and 11 μm in an epoxy resin-based thermosetting primer (melamine cured, 30 parts by weight of titanium oxide) is applied to a Zn-coated steel sheet which has been similarly pre-treated, and subjected to various drying. It was applied with a film thickness and baked at an ultimate plate temperature of 210 ° C. On this painted surface,
After applying the transparent adhesive containing no pigment prepared in Example 5 at a dry film thickness of 6 μm and drying at an ultimate plate temperature of 180 ° C., a printed polyethylene terephthalate film is immediately laminated so that the adhesive surface and the printed surface are laminated. Laminated. The L value before lamination was measured. Also, JIS Z2371
After performing a salt spray test in accordance with the above for 500 hours, the swollen width of the film at the cut end face and the cross cut portion was examined. The investigation results are shown in Table 1 and FIGS. When the adhesive containing no silica was applied to a thickness of 6 μm, the L value was 76, the corrosion resistance was 7 mm swelling at the cut end face, and the swelling was 5 mm at the cross cut portion. Further, when a 6 μm transparent adhesive is provided on a 6 μm thick thermosetting primer not containing silica, the L value is 7 μm.
8. Corrosion resistance was 6 mm swelling at the cut end face and 5 mm swelling at the cross cut portion.
【００２３】[0023]
【表１】 [Table 1]
【００２４】実施例７：イソシアネートを硬化剤とする
ポリウレタン樹脂系接着剤１００重量部に酸化チタン３
０重量部を配合し、更に平均粒径６μｍ及び１１μｍの
シリカ０．２〜９０重量部配合した接着剤を調製した。
この接着剤を実施例６と同様に前処理したＺｎめっき鋼
板に乾燥膜厚６μｍ及び１１μｍで塗装し、到達板温１
８０℃で乾燥させた後、直ちに接着面と印刷面が積層す
るように印刷ポリエチレンテレフタレートフィルムをラ
ミネートした。また、実施例６の熱硬化型プライマーに
平均粒径６μｍ及び１１μｍのシリカ０．２〜９０重量
部配合したものを、同様に前処理したＺｎめっき鋼板に
乾燥膜厚６μｍ及び１１μｍで塗装し、到達板温１８０
℃で乾燥させ、直ちに接着面と印刷面が積層するように
印刷ポリエチレンテレフタレートフィルムをラミネート
した。ラミネート前のＬ値を測定した。また、ＪＩＳ
Ｚ２３７１に準拠した塩水噴霧試験を５００時間行った
後、切断端面及びクロスカット部におけるフィルムの膨
れ幅を調査した。調査結果を、表２及び図８〜１１に示
す。Example 7: Titanium oxide 3 was added to 100 parts by weight of a polyurethane resin adhesive using isocyanate as a curing agent.
0 parts by weight, and 0.2 to 90 parts by weight of silica having an average particle diameter of 6 μm and 11 μm were further prepared.
This adhesive was applied to a Zn-coated steel sheet pretreated in the same manner as in Example 6 at a dry film thickness of 6 μm and 11 μm.
After drying at 80 ° C., a printed polyethylene terephthalate film was immediately laminated so that the adhesive surface and the printed surface were laminated. Further, a mixture of the thermosetting primer of Example 6 and 0.2 to 90 parts by weight of silica having an average particle size of 6 μm and 11 μm was coated on a similarly pretreated Zn-plated steel sheet at a dry film thickness of 6 μm and 11 μm, Ultimate plate temperature 180
After drying at ℃, the printed polyethylene terephthalate film was immediately laminated so that the adhesive surface and the printed surface were laminated. The L value before lamination was measured. Also, JIS
After performing the salt spray test according to Z2371 for 500 hours, the swollen width of the film on the cut end face and the cross cut portion was examined. The investigation results are shown in Table 2 and FIGS.
【００２５】[0025]
【表２】 [Table 2]
【００２６】[0026]
【発明の効果】以上に説明したように、本発明のラミネ
ート鋼板は、所定粒径のシリカを樹脂層に配合させるこ
とにより水分や酸素の透過，拡散を促進させて耐食性の
向上を図ると共に、淡色系の色調を付与することができ
る。そのため、水廻りの製品部材等として使用しても、
Ｚｎめっき鋼板の腐食によって印刷ポリエチレンテレフ
タレートフィルムに剥離や膨れが発生せず、長期間にわ
たって意匠性の高い製品として使用される。As described above, the laminated steel sheet according to the present invention promotes the permeation and diffusion of moisture and oxygen by mixing silica having a predetermined particle size into the resin layer, thereby improving the corrosion resistance. A light color tone can be provided. Therefore, even when used as product parts around water,
The printed polyethylene terephthalate film does not peel or swell due to corrosion of the Zn-plated steel sheet, and is used as a product having a high designability for a long period of time.
【図１】 腐食試験に使用した試験片Fig. 1 Specimen used for corrosion test
【図２】 防錆顔料配合に伴うａ値に及ぼすＬ値の影響
を表したグラフFIG. 2 is a graph showing the effect of the L value on the a value associated with the rust preventive pigment formulation.
【図３】 防錆顔料配合に伴うｂ値に及ぼすＬ値の影響
を表したグラフFIG. 3 is a graph showing the effect of the L value on the b value associated with the formulation of the rust preventive pigment.
【図４】 平均粒径６μｍのシリカを配合した接着剤膜
厚が耐食性に及ぼす影響FIG. 4 Effect of adhesive film thickness containing silica having an average particle size of 6 μm on corrosion resistance
【図５】 平均粒径１１μｍのシリカを配合した接着剤
膜厚が耐食性に及ぼす影響FIG. 5: Effect of adhesive film thickness containing silica having an average particle size of 11 μm on corrosion resistance
【図６】 プライマーに配合した平均粒径６μｍのシリ
カの配合量が耐食性に及ぼす影響FIG. 6: Effect of the amount of silica with an average particle size of 6 μm blended in the primer on the corrosion resistance
【図７】 プライマーに配合した平均粒径１１μｍのシ
リカの配合量が耐食性に及ぼす影響FIG. 7: Effect of the amount of silica having an average particle size of 11 μm blended in the primer on the corrosion resistance
【図８】 接着剤に配合した平均粒径６μｍのシリカの
配合量が耐食性に及ぼす影響FIG. 8: Effect of the amount of silica having an average particle size of 6 μm blended in an adhesive on corrosion resistance
【図９】 接着剤に配合した平均粒径１１μｍのシリカ
の配合量が耐食性に及ぼす影響FIG. 9: Effect of the amount of silica having an average particle size of 11 μm blended in an adhesive on corrosion resistance
【図１０】 平均粒径６μｍのシリカを配合したプライ
マー層厚が耐食性に及ぼす影響FIG. 10: Effect of primer layer thickness containing silica having an average particle size of 6 μm on corrosion resistance
【図１１】 平均粒径１１μｍのシリカを配合したプラ
イマー層厚が耐食性に及ぼす影響FIG. 11: Effect of primer layer thickness containing silica having an average particle size of 11 μm on corrosion resistance
フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) B32B 15/08 104 B05D 7/14 C23C 2/26 C23C 28/00 Continuation of the front page (58) Field surveyed (Int. Cl. 7 , DB name) B32B 15/08 104 B05D 7/14 C23C 2/26 C23C 28/00
Claims (3)
レンテレフタレートフィルムが接着剤層を介してＺｎめ
っき鋼板表面に積層されたラミネート鋼板において、Ｚ
ｎめっき鋼板に隣接する樹脂層の明度指数Ｌ値が塗装・
乾燥後で７０以上であり、樹脂層膜厚の５０〜１５０％
に相当する平均粒径をもつシリカ粒子が１〜４０重量％
で樹脂層に配合されている耐食性を改善した印刷ラミネ
ート鋼板。1. A laminated steel sheet in which a printed polyethylene terephthalate film is laminated on a surface of a Zn-plated steel sheet via an adhesive layer with the printed surface facing the adhesive layer,
The lightness index L value of the resin layer adjacent to the n-plated steel sheet
After drying, it is 70 or more, and 50 to 150% of the resin layer thickness.
1 to 40% by weight of silica particles having an average particle size corresponding to
Printed laminated steel sheet with improved corrosion resistance blended in the resin layer.
板に隣接する樹脂層である印刷ラミネート鋼板。2. A printed laminated steel sheet wherein the adhesive layer according to claim 1 is a resin layer adjacent to the Zn-plated steel sheet.
化型樹脂層が設けられている請求項１記載の印刷ラミネ
ート鋼板。3. The printed laminated steel sheet according to claim 1, wherein a thermosetting resin layer is provided between the Zn-plated steel sheet and the adhesive layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7172920A JP3069028B2 (en) | 1995-06-15 | 1995-06-15 | Printed laminated steel sheet with improved corrosion resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7172920A JP3069028B2 (en) | 1995-06-15 | 1995-06-15 | Printed laminated steel sheet with improved corrosion resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH091735A JPH091735A (en) | 1997-01-07 |
| JP3069028B2 true JP3069028B2 (en) | 2000-07-24 |
Family
ID=15950811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7172920A Expired - Fee Related JP3069028B2 (en) | 1995-06-15 | 1995-06-15 | Printed laminated steel sheet with improved corrosion resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3069028B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI990905A (en) * | 1999-04-22 | 2000-10-23 | Tekniseri Oy | A method for manufacturing a surface laminated sheet and a surface diminished sheet |
-
1995
- 1995-06-15 JP JP7172920A patent/JP3069028B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH091735A (en) | 1997-01-07 |
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