JP2006181753A - Decorative film for steel sheet - Google Patents
Decorative film for steel sheet Download PDFInfo
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- JP2006181753A JP2006181753A JP2004375400A JP2004375400A JP2006181753A JP 2006181753 A JP2006181753 A JP 2006181753A JP 2004375400 A JP2004375400 A JP 2004375400A JP 2004375400 A JP2004375400 A JP 2004375400A JP 2006181753 A JP2006181753 A JP 2006181753A
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 91
- 239000010959 steel Substances 0.000 title claims abstract description 91
- 239000010410 layer Substances 0.000 claims abstract description 85
- 229920005989 resin Polymers 0.000 claims abstract description 64
- 239000011347 resin Substances 0.000 claims abstract description 64
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 41
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 35
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 35
- 229920001707 polybutylene terephthalate Polymers 0.000 claims abstract description 34
- 239000000049 pigment Substances 0.000 claims abstract description 27
- 239000012790 adhesive layer Substances 0.000 claims abstract description 25
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- 239000002344 surface layer Substances 0.000 claims abstract description 9
- 150000002009 diols Chemical group 0.000 claims abstract description 7
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- 238000009835 boiling Methods 0.000 abstract description 12
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- 238000002844 melting Methods 0.000 description 6
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- 239000010960 cold rolled steel Substances 0.000 description 4
- 238000004049 embossing Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
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- 229910052804 chromium Inorganic materials 0.000 description 3
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- 239000012463 white pigment Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
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- 239000011248 coating agent Substances 0.000 description 2
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- 229920006267 polyester film Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000004078 waterproofing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910000576 Laminated steel Inorganic materials 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- MFPOUZMIWRBOON-UHFFFAOYSA-N [Mo].[Co].[Zn] Chemical compound [Mo].[Co].[Zn] MFPOUZMIWRBOON-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 229910045601 alloy Inorganic materials 0.000 description 1
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- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
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- 229910003460 diamond Inorganic materials 0.000 description 1
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- 239000003822 epoxy resin Substances 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- CLDVQCMGOSGNIW-UHFFFAOYSA-N nickel tin Chemical compound [Ni].[Sn] CLDVQCMGOSGNIW-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
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- 239000002356 single layer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
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Images
Abstract
Description
本発明は、非晶性共重合ポリエステル樹脂層および顔料配合ポリブチレンテレフタレートを主成分とする層を含む鋼板用化粧フィルム、好ましくはユニットバス化粧鋼板用化粧フィルム、およびその化粧フィルムを被覆した鋼板、好ましくはユニットバス用化粧鋼板に関する。 The present invention relates to a decorative film for a steel sheet comprising an amorphous copolymerized polyester resin layer and a layer containing a pigment-containing polybutylene terephthalate as a main component, preferably a decorative film for a unit bath decorative steel sheet, and a steel sheet coated with the decorative film, Preferably it is related with the decorative steel plate for unit baths.
特許文献１にあるように、化粧金属板被覆用樹脂フィルムはＰＢＴ（ポリブチレンテレフタレート）が使用されている。該化粧金属板は、上記の化粧金属板被覆用樹脂フィルムを、最表面がエンボス加工面となるようにして被覆した態様、また、鋼板との接着性を良くするために、エンボス面と反対側の面（鋼板との貼合面）に低融点ポリエステル層を設ける態様を包含している。 As disclosed in Patent Document 1, PBT (polybutylene terephthalate) is used for the resin film for covering a decorative metal plate. The decorative metal plate is an aspect in which the above-mentioned resin film for coating a decorative metal plate is coated such that the outermost surface is an embossed surface, and in order to improve the adhesion to a steel plate, the side opposite to the embossed surface The aspect which provides a low melting-point polyester layer in the surface (bonding surface with a steel plate) is included.
特許文献２は、基材樹脂層、印刷層、表面保護層（ＰＢＴを主とした樹脂フィルム）が下から順次積層された化粧フィルムに関わり、基材樹脂層が複層からなる樹脂フィルムであって、金属板と接触する層が、樹脂成分中の多価酸成分または多価アルコル成分の一部を他の成分で置換した共重合ポリエステル樹脂フィルムであり、金属板と接触する層の厚さ／金属板と接触しない層の厚さ＝（１／２０）〜１であることを特徴とする。表面（鋼板との貼合面と反対側）にエンボス加工がされ、化粧用フィルムには隠蔽性を付与するために顔料が配合されている。２４０〜２４５℃に熱した鋼板に、化粧用フィルムを貼合している。 Patent Document 2 relates to a decorative film in which a base resin layer, a printing layer, and a surface protective layer (resin film mainly composed of PBT) are sequentially laminated from the bottom, and the base resin layer is a resin film composed of multiple layers. The layer in contact with the metal plate is a copolymerized polyester resin film in which a part of the polyvalent acid component or polyvalent alcohol component in the resin component is replaced with another component, and the thickness of the layer in contact with the metal plate / The thickness of the layer not in contact with the metal plate = (1/20) to 1. The surface (the side opposite to the bonding surface with the steel plate) is embossed, and the cosmetic film is blended with a pigment to provide concealment. A cosmetic film is bonded to a steel plate heated to 240 to 245 ° C.
特許文献３は、完全非晶性ポリエステル層の上部に、接着剤層を設け、前記接着剤層の上部に結晶性ポリエステル層を設けた積層化粧シートに関わり、完全非晶性ポリエステルシートの組成は、コポリマータイプグリコール成分（エチレングリコール７０モル％および１，４−シクロヘキサンジメタノール３０モル％）、ジカルボン酸成分（テレフタル酸結晶成分０％）であると説明されている。 Patent Document 3 relates to a laminated decorative sheet in which an adhesive layer is provided on the upper part of the completely amorphous polyester layer, and a crystalline polyester layer is provided on the upper part of the adhesive layer. The composition of the completely amorphous polyester sheet is And a copolymer type glycol component (70 mol% ethylene glycol and 30 mol% 1,4-cyclohexanedimethanol) and a dicarboxylic acid component (0% terephthalic acid crystal component).
特許文献４は、化粧フィルム及び積層化粧シートに関し、単層の完全非晶性ポリエステルフィルムが鋼板側になるように他のフィルムを貼り合わせる態様が開示されている。
しかしながら上記した特許文献１〜３はいずれも化粧シートの熱水中での耐久性に着目したものではなく、この特性につき言及がなされていない。特許文献４は化粧シートの熱水中での耐久性についても着目がなされているが、完全非晶性ポリエステルフィルムは本来耐熱水性に劣るものであるという認識がなされておらず、この性質を補うための対応策も記載されていない。
Patent Document 4 relates to a decorative film and a laminated decorative sheet, and discloses a mode in which another film is bonded so that a single-layer completely amorphous polyester film is on the steel plate side.
However, none of Patent Documents 1 to 3 described above pay attention to the durability of the decorative sheet in hot water, and no mention is made of this characteristic. Patent Document 4 pays attention to the durability of the decorative sheet in hot water, but it has not been recognized that a completely amorphous polyester film is inherently inferior in hot water resistance, and this property is compensated. No countermeasures for this are described.
本発明は、貼合時の鋼板の温度が２２０℃でも発泡せず接着性が良好であり、沸騰水中での耐久性が良好であり、コーキング剤との接着性が良好である鋼板用化粧フィルム、好ましくはユニットバス化粧鋼板用化粧フィルム、およびその化粧フィルムを被覆した鋼板、好ましくはユニットバス用化粧鋼板を提供することを課題とする。 The present invention is a steel sheet decorative film that does not foam even when the temperature of the steel sheet during bonding is 220 ° C., has good adhesion, has good durability in boiling water, and has good adhesion to a caulking agent. It is an object of the present invention to provide a decorative film for a unit bath decorative steel sheet, and a steel sheet coated with the decorative film, preferably a decorative steel sheet for a unit bath.
本発明は、以下の（１）〜（６）の鋼板用化粧フィルムを要旨としている。
（１）（Ａ）鋼板との貼合面側にポリエチレンテレフタレートのジオール部分であるエチレングリコールの一部を1,4-シクロヘキサンジメタノールに置き換えた、非晶性の共重合ポリエチレンテレフタレート系樹脂を主成分とする接着層を設け、その接着層の上部に、（Ｂ）顔料を配合したポリブチレンテレフタレートを主成分とする層が設けられており、（Ａ）の接着層が、厚み２〜５０μｍで、かつ、全層の厚みの５０％未満のものであることを特徴とする鋼板用化粧フィルム。
（２）上記の（Ｂ）層において、顔料の添加量が１０〜４０重量％である（１）の鋼板用化粧フィルム。
（３）上記（Ｂ）層の上部に、（Ｃ）ポリブチレンテレフタレート５０〜９０重量％およびポリエチレンテレフタレート系樹脂５０〜１０重量％からなる顔料を含有しない表面層を設けたことを特徴とする（１）または（２）の鋼板用化粧フィルム。
（４）上記の（Ｃ）の表面層がエンボス加工されている（３）の鋼板用化粧フィルム。
（５）上記の（Ａ）および（Ｂ）の二層から成る場合は（Ｂ）層の上部に、（Ａ）、（Ｂ）および（Ｃ）の三層から成る場合は（Ｃ）層の上部に、印刷層および保護層がこの順で設けられているか、保護層が設けられていることを特徴とする（１）ないし（４）のいずれかの鋼板用化粧フィルム。
（６）ユニットバス化粧鋼板用化粧フィルムである（１）ないし（５）のいずれかの鋼板用化粧フィルム。
The gist of the present invention is the following decorative films for steel sheets (1) to (6).
(1) (A) Amorphous copolymer polyethylene terephthalate resin in which ethylene glycol, which is the diol part of polyethylene terephthalate, is replaced with 1,4-cyclohexanedimethanol on the side of the surface to be bonded to the steel sheet. An adhesive layer as a component is provided, and a layer mainly composed of (B) a polybutylene terephthalate blended with a pigment is provided above the adhesive layer, and the adhesive layer of (A) has a thickness of 2 to 50 μm. And the decorative film for steel plates characterized by being less than 50% of the thickness of all the layers.
(2) The decorative film for steel sheet according to (1), wherein in the layer (B), the amount of pigment added is 10 to 40% by weight.
(3) A surface layer not containing a pigment composed of 50 to 90% by weight of (C) polybutylene terephthalate and 50 to 10% by weight of a polyethylene terephthalate resin is provided on the layer (B). A decorative film for steel sheet according to 1) or (2).
(4) The decorative film for steel sheet according to (3), wherein the surface layer of (C) is embossed.
(5) In the case of the two layers (A) and (B), the upper part of the layer (B). In the case of the three layers (A), (B) and (C), the layer (C) The decorative film for steel sheet according to any one of (1) to (4), wherein a printed layer and a protective layer are provided in this order or a protective layer is provided on the upper part.
(6) The decorative film for steel plate according to any one of (1) to (5), which is a decorative film for unit bath decorative steel plate.
本発明は、以下の（７）および（８）の化粧フィルム被覆鋼板を要旨としている。
（７）（１）ないし（６）のいずれかの鋼板用化粧フィルムを、その（Ａ）の接着層で高温の鋼板に貼り合わせてなる化粧フィルム被覆鋼板。
（８）ユニットバス用化粧鋼板である（７）の化粧フィルム被覆鋼板。
The gist of the present invention is the decorative film-coated steel sheets of the following (7) and (8).
(7) A decorative film-coated steel sheet obtained by bonding the decorative film for steel sheet according to any one of (1) to (6) to a high-temperature steel sheet with the adhesive layer of (A).
(8) The decorative film-coated steel sheet according to (7), which is a decorative steel sheet for unit bath.
本発明により、貼合時の鋼板の温度が２２０℃でも発泡せず接着性が良好であり、沸騰水中での耐久性が良好であり、コーキング剤との接着性が良好である鋼板用化粧フィルム、好ましくはユニットバス化粧鋼板用化粧フィルム、およびその化粧フィルムを被覆した鋼板、好ましくはユニットバス用化粧鋼板を提供することができる。 According to the present invention, the decorative film for a steel sheet has good adhesiveness without foaming even when the temperature of the steel sheet during bonding is 220 ° C., has good durability in boiling water, and has good adhesiveness with a caulking agent. Preferably, a decorative film for unit bath decorative steel sheet and a steel sheet coated with the decorative film, preferably a decorative steel sheet for unit bath can be provided.
本発明の鋼板用化粧フィルムが対象とする鋼板としては、厚さ０．１０〜１．２ｍｍの普通鋼冷延鋼板が例示される。中でも厚さ０．１０〜０．５０ｍｍの普通鋼の冷延鋼板が好ましい。冷延鋼板の中でも低炭素または極低炭素アルミキルト鋼板が好ましく使用されるか、Ｎｂ、Ｔｉなどを添加した非時効性鋼、３〜１８重量％のクロムを含有するクロム含有鋼板、種々の組成を有するステンレス鋼板なども使用することができる。これらの冷延鋼板の表面に表面処理を施した表面処理鋼板も使用可能である。表面処理としてはめっき、化成処理や塗装処理などがあり、めっきとしては例えば亜鉛めっき、亜鉛−アルミニウム合金めっき、亜鉛−コバルト−モリブデンめっき、錫めっき、ニッケルめっき、クロムめっき、ニッケル−りんめっき，ニッケル−亜鉛めっきニッケル−コバルトめっき、ニッケル−錫めっき、アルミニウムめっきなどかあり、化成処理としては例えばクロメート処理、リン酸塩処理など公知の処理でよい。塗装処理としては種々の塗料をその性質に応じて塗装し、焼き付ける方法で実施される。 Examples of the steel sheet targeted by the decorative film for steel sheet of the present invention include a cold rolled steel sheet having a thickness of 0.10 to 1.2 mm. Of these, a cold-rolled steel plate of ordinary steel having a thickness of 0.10 to 0.50 mm is preferable. Among cold-rolled steel sheets, low-carbon or ultra-low-carbon aluminum quilted steel sheets are preferably used, non-aging steels containing Nb, Ti, etc., chromium-containing steel sheets containing 3 to 18% by weight of chromium, various compositions A stainless steel plate or the like having can also be used. A surface-treated steel sheet having a surface treated on the surface of these cold-rolled steel sheets can also be used. Surface treatment includes plating, chemical conversion treatment and coating treatment. Examples of plating include zinc plating, zinc-aluminum alloy plating, zinc-cobalt-molybdenum plating, tin plating, nickel plating, chromium plating, nickel-phosphorus plating, nickel. -There are zinc plating nickel-cobalt plating, nickel-tin plating, aluminum plating and the like, and the chemical conversion treatment may be a known treatment such as chromate treatment, phosphate treatment, etc. The coating process is carried out by a method in which various paints are applied and baked according to their properties.
本発明の鋼板用化粧フィルムは、Ａ層：非晶性共重合ポリエステル樹脂の接着層、およびＢ層：顔料を配合したポリブチレンテレフタレートを主成分とする層、必要に応じＣ層：ポリエチレンテレフタレート系樹脂を配合したポリブチレンテレフタレートの顔料を含有しないクリア層の二層または三層構造を基本としている。この二層または三層構造の好ましい具体的態様は、Ａ層がＰＥＴＧ（完全非晶性ＰＥＴ系樹脂）である。二層または三層構造の積層フィルムの製法は、特に限定されないが、Ｔダイキャスト法、二層または三層共押出法が好ましいものとして例示される。 The decorative film for steel sheet of the present invention comprises an A layer: an amorphous copolyester resin adhesive layer, and a B layer: a layer mainly composed of polybutylene terephthalate containing a pigment, and optionally a C layer: polyethylene terephthalate system. It is based on a two-layer or three-layer structure of a clear layer that does not contain a polybutylene terephthalate pigment blended with a resin. In a preferred specific embodiment of this two-layer or three-layer structure, the A layer is PETG (fully amorphous PET resin). Although the manufacturing method of the laminated film of 2 layer or 3 layer structure is not specifically limited, T die-cast method and 2 layer or 3 layer coextrusion method are illustrated as a preferable thing.
Ａ層：接着層に用いる非晶性共重合ポリエステル樹脂について説明する。
接着層の非晶性共重合ポリエステル樹脂は、再度加熱処理を行っても再結晶化により物性低下を起こさず、結晶性〔DSC法によって測定された結晶性（JIS K7121）〕成分を全くもたないか、結晶性成分をほとんどもたないものである。
非晶性ポリエステル系樹脂の製造方法は、すでに当業界において広く知られており、例えば米国特許5,340,907号に開示されている。
本発明で用いる非晶性共重合ポリエステル樹脂は、ポリエチレンテレフタレートのジオール部分であるエチレングリコールの一部を1,4-シクロヘキサンジメタノールに置き換えた、非晶性の共重合ポリエチレンテレフタレート系樹脂であり、本発明の実施例では、非晶性共重合ポリエステル樹脂として用いるのは、ポリエチレンテレフタレートのジオール部分であるエチレングリコールの一部を1,4-シクロヘキサンジメタノールに置き換えた、非晶性の共重合ポリエチレンテレフタレート系樹脂であるＰＥＴＧであり、イーストマン・ケミカル社、商品名「イースター」を用いている。
A layer: The amorphous copolyester resin used for the adhesive layer will be described.
The amorphous copolyester resin of the adhesive layer has no crystallinity [crystallinity measured by DSC method (JIS K7121)] component, and does not cause deterioration of physical properties due to recrystallization even when heat-treated again. Or have little crystalline component.
A method for producing an amorphous polyester resin is already widely known in the art and disclosed in, for example, US Pat. No. 5,340,907.
The amorphous copolyester resin used in the present invention is an amorphous copolyethylene terephthalate resin in which a part of ethylene glycol, which is a diol portion of polyethylene terephthalate, is replaced with 1,4-cyclohexanedimethanol, In the examples of the present invention, an amorphous copolymerized polyethylene resin in which a part of ethylene glycol, which is a diol portion of polyethylene terephthalate, is replaced with 1,4-cyclohexanedimethanol is used as an amorphous copolymerized polyester resin. It is PETG which is a terephthalate resin, and uses the product name “Easter” from Eastman Chemical Company.
非晶性共重合ポリエステル樹脂層は沸騰水中での耐久性が悪い。本発明では後述するＢ層と多層化するので、本発明の鋼板用化粧フィルムの厚みの主体をＢ層に担わせ、非晶性共重合ポリエステル樹脂層の厚みを薄くすることができ、鋼板用化粧フィルムに求められる強度が確保できる。さらに、非晶性共重合ポリエステル樹脂層の厚みが薄くなれば、沸騰水中での耐久性に問題はない。非晶性共重合ポリエステル樹脂層の厚みは低温接着性と、沸騰水中での耐久性の兼ね合いで厚み２〜５０μｍで、かつ、全層の厚みの５０％未満の範囲で決められる。２μｍ未満では接着性が悪く、５０μｍを超えるか、或いは、全層の厚みの５０％以上では耐沸騰水性が悪いためにアバタ状になる。 The amorphous copolyester resin layer has poor durability in boiling water. In the present invention, since it is multi-layered with the B layer described later, the main component of the thickness of the decorative film for steel sheet of the present invention can be borne by the B layer, and the thickness of the amorphous copolymerized polyester resin layer can be reduced. The strength required for the decorative film can be secured. Furthermore, if the thickness of the amorphous copolymerized polyester resin layer is reduced, there is no problem in durability in boiling water. The thickness of the amorphous copolymerized polyester resin layer is determined in the range of 2 to 50 μm in terms of low-temperature adhesiveness and durability in boiling water, and less than 50% of the total thickness. If it is less than 2 μm, the adhesiveness is poor, and if it exceeds 50 μm, or if it is 50% or more of the total thickness, the water resistance to boiling is poor, resulting in an avatar shape.
Ｂ層：顔料を配合したポリブチレンテレフタレートを主成分とする層について、説明する。
Ｂ層はポリブチレンテレフタレートを主成分とし、これに隠蔽性を付与するために顔料が配合された組成物から構成されている。
Ｂ層に用いられるポリブチレンテレフタレート以外の樹脂としては、ポリエチレンテレフタレート等のポリエステルが挙げられる。ポリブチレンテレフタレート樹脂の固有粘度は１．０〜２．０の範囲であることが好ましい。固有粘度は定法を用い、樹脂をフェノール／テトラクロロエタンの１：１混合溶液に溶解させた後、３０℃の恒温浴槽中でウベローデ粘度計により、比粘度を測定し、固有粘度を求めることかできる。固有粘度が１．０未満の場合は金属板に被覆して恒温多湿の雰囲気中に長期間経時した際に十分な耐衝撃性（耐水劣化性）が得られず、一方、固有粘度が２０を超える場合は、樹脂を加熱溶融し押出機から押し出してフィルムに製膜する際に高粘度となり過ぎて押出機のトルクが上がるため製膜困難となる。より好ましい固有粘度の範囲は、耐水劣化性および製膜性の観点から１．２〜１．５である。
上記のブチレンテレフタレートを主成分とする樹脂フィルムの厚さは特に限定するものではないが、２０〜３００μｍ、中でも７０〜２００μｍであることか好ましい。
B layer: The layer which has as a main component the polybutylene terephthalate which mix | blended the pigment is demonstrated.
The B layer is composed of a composition in which polybutylene terephthalate is a main component and a pigment is blended to impart concealability thereto.
Examples of the resin other than polybutylene terephthalate used for the B layer include polyesters such as polyethylene terephthalate. The intrinsic viscosity of the polybutylene terephthalate resin is preferably in the range of 1.0 to 2.0. Intrinsic viscosity can be determined by using a conventional method, and after dissolving the resin in a 1: 1 mixed solution of phenol / tetrachloroethane, the specific viscosity can be determined by measuring the specific viscosity with a Ubbelohde viscometer in a constant temperature bath at 30 ° C. . When the intrinsic viscosity is less than 1.0, sufficient impact resistance (water resistance) cannot be obtained when the metal plate is coated and kept for a long time in a constant temperature and humidity atmosphere. When exceeding, when resin is heat-melted and extruded from the extruder to form a film, the viscosity becomes too high and the torque of the extruder increases, making film formation difficult. A more preferable range of the intrinsic viscosity is 1.2 to 1.5 from the viewpoint of water resistance and film forming property.
The thickness of the resin film containing butylene terephthalate as a main component is not particularly limited, but is preferably 20 to 300 μm, and more preferably 70 to 200 μm.
顔料の種類およびその配合量について、本発明においては、化粧フィルムに顔料を含有させて隠蔽性を付与することができる。隠蔽性の評価は、分光測色計（コニカミノルタセインシング社製 ＣＭ−２５００ｄ）を用いて、標準白色板と標準黒色板上に試料（フィルム）を置き、色差（ΔＥ値）を測定する。標準白色板に試料を置いて測定した場合の色差（ΔＥ値）の測定値と、標準黒色板に試料を置いて測定した場合の色差（ΔＥ値）の差が、１以下であれば、隠蔽性良好、１を超えると、隠蔽性が劣る、と評価する。
顔料の添加量は１０〜４０重量％の範囲が好ましい。１０重量％未満では色差（ΔＥ値）の差が１を超えると化粧フィルムを鋼板と積層して得られるラミネート鋼板の外観が、基材である鋼板の色調に影響されるおそれがある。また、４０重量％を超えると樹脂成分の割合が少なく、製膜性が悪化する。コストアップにもなる。
About the kind of pigment, and its compounding quantity, in this invention, a pigment can be included in a decorative film and concealment property can be provided. The hiding property is evaluated by placing a sample (film) on a standard white plate and a standard black plate using a spectrocolorimeter (CM-2500d manufactured by Konica Minolta Sewing Co., Ltd.) and measuring the color difference (ΔE value). If the difference between the color difference (ΔE value) measured when the sample is placed on the standard white plate and the color difference (ΔE value) measured when the sample is placed on the standard black plate is 1 or less, concealment It is evaluated that the concealability is inferior when the property is good and exceeds 1.
The addition amount of the pigment is preferably in the range of 10 to 40% by weight. If the difference in color difference (ΔE value) exceeds 1 at less than 10% by weight, the appearance of the laminated steel sheet obtained by laminating the decorative film with the steel sheet may be affected by the color tone of the steel sheet as the substrate. Moreover, when it exceeds 40 weight%, there are few ratios of a resin component, and film forming property deteriorates. It also increases the cost.
含有させる顔料の種類に特に制限はなく、例えば、白色顔料としての酸化チタンを配合することにより隠蔽性を付与することができ、あるいは、黒色顔料としてのカーボンブラックを配合することにより隠蔽性を付与することもでき、さらには、白色顔料と他の有色顔料を配合することにより所望の色調と濃度の隠蔽性を付与することもできる。本発明において、化粧フィルムに顔料を含有させる方法に特に制限はなく、例えば、ポリブチレンテレフタレート系樹脂をベース樹脂とするマスターバッチをあらかじめ調製しておき、ポリブチレンテレフタレート系樹脂に該マスターバッチを混合し、Ｔダイなどから押し出して製膜することにより、顔料を含有させることができる。 There are no particular restrictions on the type of pigment to be included. For example, it is possible to impart concealment by blending titanium oxide as a white pigment, or concealment by blending carbon black as a black pigment. Furthermore, the desired color tone and density can be concealed by blending a white pigment and another colored pigment. In the present invention, there is no particular limitation on the method of adding a pigment to the decorative film. For example, a master batch based on a polybutylene terephthalate resin is prepared in advance, and the master batch is mixed with the polybutylene terephthalate resin. Then, a pigment can be contained by extrusion from a T die or the like to form a film.
Ｃ層：ポリエチレンテレフタレート系樹脂を配合したポリブチレンテレフタレートの、顔料を含有しないクリア層について説明する。
ポリブチレンテレフタレート系樹脂からなるフィルムを使用した場合に、エンボス加工によって深く鮮明な凹凸模様が得られ、この樹脂フィルムを金属板に被覆した場合、飛躍的に意匠性に優れた化粧金属板が得られる。一方、化粧鋼板の重ね合わせ部などの防水のために、シリコーン系など硬化性のコーキング剤を使用するが、ポリブチレンテレフタレート系樹脂はコーキング剤との接着性が悪い。本発明においては、ＰＢＴ系樹脂にＰＥＴ系樹脂をブレンドすることによって、接着性が向上する。
すなわち、ポリエチレンテレフタレート系樹脂を配合したポリブチレンテレフタレートの顔料を含有しないクリア層は、ポリブチレンテレフタレート５０〜９０重量％およびポリエチレンテレフタレート系樹脂５０〜１０重量％の樹脂組成物を用いた、顔料を配合しないクリア層が好ましい例として挙げられる。ポリエチレンテレフタレートの配合割合が１０重量％以上でコーキング剤の接着性が向上するが、５０重量％を超えるとポリブチレンテレフタレートの特性が希釈されすぎてしまう。配合するポリエチレンテレフタレート系樹脂は、ホモ−ＰＥＴであっても、共重合ＰＥＴであってもよい。実施例では、ＰＢＴ（７０％）とＰＥＴ（３０％）のブレンド物であり、ＰＥＴはイソフタル酸変成の共重合ＰＥＴを使用している。
クリア層の厚さは特に限定するものではないが、２０〜３０μｍ、中でも４〜１５μｍであることが好ましい。
Layer C: A clear layer of polybutylene terephthalate containing a polyethylene terephthalate resin and containing no pigment will be described.
When a film made of polybutylene terephthalate resin is used, a deep and clear concavo-convex pattern is obtained by embossing, and when this resin film is coated on a metal plate, a decorative metal plate with greatly improved design is obtained. It is done. On the other hand, a curable caulking agent such as silicone is used for waterproofing the overlapping portion of the decorative steel plate, but the polybutylene terephthalate resin has poor adhesion to the caulking agent. In the present invention, the adhesiveness is improved by blending the PBT resin with the PET resin.
That is, a clear layer containing no polybutylene terephthalate pigment blended with a polyethylene terephthalate resin is blended with a pigment using a resin composition of 50 to 90% by weight of polybutylene terephthalate and 50 to 10% by weight of a polyethylene terephthalate resin. A clear layer that is not used is a preferred example. When the blending ratio of polyethylene terephthalate is 10% by weight or more, the adhesion of the caulking agent is improved. However, when it exceeds 50% by weight, the characteristics of polybutylene terephthalate are excessively diluted. The polyethylene terephthalate resin to be blended may be homo-PET or copolymerized PET. In the examples, a blend of PBT (70%) and PET (30%) is used, and PET uses copolymerized PET modified with isophthalic acid.
The thickness of the clear layer is not particularly limited, but is preferably 20 to 30 μm, and more preferably 4 to 15 μm.
また、化粧フィルムが（Ａ）および（Ｂ）の二層から成る場合は（Ｂ）層の上部に、（Ａ）、（Ｂ）および（Ｃ）の三層から成る場合は（Ｃ）層の上部に、印刷層および保護層を順次設けるようにしてもよい。保護層としては、二軸延伸ＰＥＴ系樹脂フィルムが使用可能である。保護層は接着剤層を介在させて設けることができる。ＰＥＴ系樹脂フィルムは微細結晶を生成することにより、硬く平滑な表面が得られやすく、印刷性に優れている。そのため、グラビア、オフセット、スクリーン印刷などによる全面着色印刷層、または部分着色印刷層を設けた複合樹脂フィルムも使用可能である。また、化粧フィルムが（Ａ）および（Ｂ）の二層から成る場合は（Ｂ）層の上部に、（Ａ）、（Ｂ）および（Ｃ）の三層から成る場合は（Ｃ）層の上部に、全面着色印刷層、または部分着色印刷層を設けることも可能である。 When the decorative film is composed of two layers (A) and (B), the upper part of the layer (B), and when the decorative film is composed of three layers (A), (B) and (C), the layer (C) A print layer and a protective layer may be sequentially provided on the upper portion. As the protective layer, a biaxially stretched PET resin film can be used. The protective layer can be provided with an adhesive layer interposed. A PET-based resin film is easy to obtain a hard and smooth surface by producing fine crystals, and is excellent in printability. Therefore, a composite resin film provided with an entire colored printing layer by gravure, offset, screen printing, or a partially colored printing layer can also be used. When the decorative film is composed of two layers (A) and (B), the upper part of the layer (B), and when the decorative film is composed of three layers (A), (B) and (C), the layer (C) It is also possible to provide an entire colored printing layer or a partially colored printing layer on the upper part.
エンボス加工方法について、上記のＰＢＴ系樹脂にＰＥＴ系樹脂をブレンドした樹脂フィルムのエンボス加工方法としては、加熱溶融した樹脂をＴダイからエンボス加工を施したキャスティングロール上に押出して片面にエンボス目を有するフィルムに製膜する方法、フィルムを直接チルドロールの間に通す方法、フィルムを加熱してチルドロールの間に通す方法、回転スクリーンロールに通して真空で吸引する力でエンボス加工する方法、フィルムをパーフォレーター（目打ち機）に通すホットニードルプロセス、刻印ロールを使用して圧縮する方法など、いずれの方法を用いてエンボス加工してもよい。また、金属板に上記のブレンドした樹脂フィルムを積層した後、樹脂の融点±１０℃の温度範囲に加熱した金属板と共に、彫刻ロールを使用して圧着してエンボス加工してもよい。エンボス形状としては、ランダムマント、四角形、ダイヤモンド形、深絞り形、梨地、砂目（ＳＧ目と呼称）なと、種々に模様を製品のニーズに応じて選択することができる。 Regarding the embossing method, as a method for embossing a resin film in which a PET resin is blended with the PBT resin, the heat-melted resin is extruded from a T-die onto an embossed casting roll, and an embossed pattern is formed on one side. A method of forming a film having a film, a method of passing a film directly between chilled rolls, a method of heating a film and passing it between chilled rolls, a method of embossing by a vacuum drawn through a rotating screen roll, a film You may emboss using any method, such as the hot needle process which passes through a perforator (piercing machine), and the method of compressing using a stamping roll. Moreover, after laminating the above-mentioned blended resin film on a metal plate, it may be embossed by pressure bonding using an engraving roll together with the metal plate heated to a temperature range of the melting point of the resin ± 10 ° C. As the embossed shape, various patterns such as a random cloak, a square shape, a diamond shape, a deep drawing shape, a satin texture, and a grain texture (referred to as SG eyes) can be selected according to the needs of the product.
積層方法について、鋼板用化粧フィルムを、上記のようにしてエンボス加工を施した化粧フィルムの場合も、その（Ａ）の接着層で高温の鋼板に貼り合わせる。公知の熱融着法などを用いて鋼板に積層する。化粧フィルム被覆鋼板はユニットバス用化粧鋼板として用いるのに適している。
化粧フィルムを鋼板にラミネートする方法には、超音波溶接、スピンウェルド等の接着方法を用いることができる。あるいは、火気に対して安全で臭気もなく、価格的にも安価な一般的な接着剤、例えば、酢酸ビニル樹脂系、エチレン−ビニルアセテート樹脂系、尿素樹脂系、ウレタン樹脂系、エポキシ樹脂系、ポリエステル樹脂系、シアノアクリレ−ト樹脂系なとの接着剤を介してラミネートしてもよいが、単に樹脂の融点以上に加熱しておいた鋼板上に圧着する方法（加熱圧着法）でラミネー卜してもよい。すなわち、鋼板をポリブチレンテレフタレート樹脂の融点以上の温度に加熱し、化粧フィルムの（Ａ）の接着層面を金属板に当接し、１対のラミネートロールで両者を挟み付け、直ちに水中に浸漬して急冷する。
鋼板との接着力を高度に要求されるものに対しては、化粧フィルムの（Ａ）の接着層の面に接着剤層を設けるか、または金属板に接着剤層を設け、接着剤層を介在させて金属板と化粧フィルムを積層させることも可能である。また、加熱圧着法で化粧フィルムと鋼板とをラミネートさせる場合には、強固な密着力を得ることができるように鋼板との表面を予め処理しておくことが好ましい。表面処理方法としては、電解クロム酸処理、接着プライマー処理などの方法を採用することができる。
About the lamination | stacking method, also in the case of the decorative film which embossed as mentioned above, the decorative film for steel plates is bonded together to a high temperature steel plate with the adhesive layer of (A). It laminates on a steel plate using a well-known heat fusion method. The decorative film-coated steel sheet is suitable for use as a decorative steel sheet for a unit bath.
As a method of laminating the decorative film on the steel plate, an adhesion method such as ultrasonic welding or spin weld can be used. Or, a general adhesive that is safe against fire, has no odor, and is inexpensive, such as vinyl acetate resin, ethylene-vinyl acetate resin, urea resin, urethane resin, epoxy resin, Lamination may be done via an adhesive such as polyester resin or cyanoacrylate resin, but simply laminating by means of crimping on a steel plate heated above the melting point of the resin (thermocompression bonding). May be. That is, the steel sheet is heated to a temperature equal to or higher than the melting point of the polybutylene terephthalate resin, the adhesive layer surface (A) of the decorative film is brought into contact with the metal plate, the two are sandwiched by a pair of laminating rolls, and immediately immersed in water. Cool quickly.
For those that require a high degree of adhesive strength with the steel plate, an adhesive layer is provided on the surface of the adhesive layer (A) of the decorative film, or an adhesive layer is provided on the metal plate, It is also possible to laminate a metal plate and a decorative film by interposing. Moreover, when laminating a decorative film and a steel plate by a thermocompression bonding method, it is preferable to treat the surface of the steel plate in advance so as to obtain a strong adhesion. As the surface treatment method, methods such as electrolytic chromic acid treatment and adhesion primer treatment can be employed.
本発明の詳細を実施例で説明する。本発明はこれらの実施例によって何ら限定されることはない。 Details of the present invention will be described in the examples. The present invention is not limited in any way by these examples.
実施例において使用した樹脂
ＰＥＴＧ：イーストマンケミカルジャパン（株） イースター６７６３
ジオール成分 ・・ エチレングリコール：６７ｍｏｌ％
１，４−シクロヘキサンジメタノール：３３ｍｏｌ％
融点： − （完全非晶性のため測定不能）
固有粘度：０．７５
ＰＢＴ：東レ（株） トレコン１２００Ｓ
融点：２２５℃
固有粘度：１．２３
ＰＥＴ：ユニチカ（株） ＭＡ１３４４
イソフタル酸変性共重合ＰＥＴ
ジカルボン酸成分 ・・ テレフタル酸：９２ｍｏｌ％
イソフタル酸： ８ｍｏｌ％
融点：２３４℃
固有粘度：０．７１
Resin PETG used in Examples: Eastman Chemical Japan Co., Ltd. Easter 6763
Diol component ・ ・ Ethylene glycol: 67 mol%
1,4-cyclohexanedimethanol: 33 mol%
Melting point:-(not measurable due to complete amorphousness)
Intrinsic viscosity: 0.75
PBT: Toray Industries, Inc. Toraycon 1200S
Melting point: 225 ° C
Intrinsic viscosity: 1.23
PET: Unitika MA1344
Isophthalic acid modified copolymer PET
Dicarboxylic acid component ・ ・ Terephthalic acid: 92 mol%
Isophthalic acid: 8 mol%
Melting point: 234 ° C
Intrinsic viscosity: 0.71
表１に示すように、実施例として三層構造の化粧フィルム（厚み１２５μｍ）を用いた。
１）Ａ層（接着層）は、厚み６μｍのＰＥＴＧ（完全非晶性ＰＥＴ）用いた。これは、ＰＥＴＧ：ＰＥＴのジオール部分の一部をＣＨＤＭ（1,4-シクロヘキサンジメタノール）に置き換えた、共重合ＰＥＴで、完全非晶性である。ＰＥＴＧ層は沸騰水中での耐久性が悪いので、厚みを６μｍにした。
２）Ｂ層（白色顔料としての酸化チタンを２２．５重量％配合したＰＢＴ）として厚みを１１３μｍにした。
３）Ｃ層（表面層）として、ＰＢＴ系樹脂７０重量％とＰＥＴ系樹脂３０重量％のブレンド樹脂を用いた。厚みは６μｍとした。
上記の三種類の樹脂を、三台の押出機とＴダイを備えた押出成型機に供給して、エンボス加工を施したキャスティングロール上にＣ層（表面層）側が位置するように熔融樹脂を押し出しし、Ｃ層（表面層）側にエンボス加工が施された三層共押出の化粧フィルムを得た。
こうして得られた化粧フィルムを公知の熱融着法を用いて、２２０℃に加熱した鋼板にＡ層（接着層）が接するように積層して化粧フィルム被覆鋼板を得た。
As shown in Table 1, a decorative film having a three-layer structure (thickness: 125 μm) was used as an example.
1) As the A layer (adhesive layer), PETG (fully amorphous PET) having a thickness of 6 μm was used. This is a copolymerized PET in which part of the diol portion of PETG: PET is replaced with CHDM (1,4-cyclohexanedimethanol) and is completely amorphous. Since the PETG layer has poor durability in boiling water, the thickness was set to 6 μm.
2) Layer B (PBT containing 22.5% by weight of titanium oxide as a white pigment) had a thickness of 113 μm.
3) As the C layer (surface layer), a blend resin of 70% by weight of PBT resin and 30% by weight of PET resin was used. The thickness was 6 μm.
Supply the above three types of resins to an extruder equipped with three extruders and a T-die, and melt resin so that the C layer (surface layer) side is positioned on the embossed casting roll. Extruded to obtain a three-layer co-extruded decorative film embossed on the C layer (surface layer) side.
The decorative film thus obtained was laminated using a known heat-sealing method so that the A layer (adhesive layer) was in contact with the steel sheet heated to 220 ° C. to obtain a decorative film-coated steel sheet.
表１に示すように、比較例として３種類の化粧フィルム（厚み１２５μｍ）を用いた。 As shown in Table 1, three types of decorative films (thickness 125 μm) were used as comparative examples.
上記実施例および比較例で得られた化粧シートに対し、下記に示される方法で各種物性を試験した。得られた結果を表１に示す。
１）発泡の有無：所定の温度に加熱した鋼板に化粧フィルムを積層した後の発泡の有無を、目視によって確認する。
貼合温度が２４０℃の場合、外部の気温・湿度の条件（例えば、秋〜春にかけて）によっては発泡しない。夏場など、温度・湿度が高い場合に発泡する。２５０℃では、夏場以外でも発泡する場合がある。
２）密着性の評価
金属基板に樹脂フィルムをラミネートした化粧板から６０×６０ｍｍの試験片を採取し、カッターナイフを使用して、樹脂フィルム上から幅５ｍｍの井桁の切り込みを金属基板面に達するまで入れた。
この試片について、エリクセン試験機を用いて、半径10mmの球形のポンチを鋼板側から6mm押し付け、フィルム貼合鋼板を変形させた際のフィルムの剥離状態を評価することで、樹脂フィルムと金属基板との密着性の評価をした。
実用上問題ないと思われる範囲を○。実用上問題あるものを×とする。
３）耐沸騰水性
本発明の化粧板をユニットバスの内装材として用いられる高温多湿の状態で長時間経時させた場合を想定し、沸騰水中に３時間浸漬した場合の樹脂フィルムの耐水劣化性をフィルム表面が「あばた状」になるか否かで評価した。あばた状になるものを×、そうでないものを○とする。この点がＰＥＴＧの最大の問題点であることがわかる。
４）シーリング剤の密着性
シーラント４８５５（コーキング剤、信越化学工業（株）製）をフィルム面にとぐろ状に塗布し、２４時間放置した後に剥離しない場合：○、剥離する場合：×
化粧鋼板同士の重ね合わせ部分などに、防水のためシリコーン系など硬化性のコーキング剤を塗布する。ＰＢＴ系樹脂にＰＥＴ系樹脂をブレンドすることによって、接着性が向上することがわかる。
1) Presence or absence of foaming: The presence or absence of foaming after laminating a decorative film on a steel sheet heated to a predetermined temperature is visually confirmed.
When bonding temperature is 240 degreeC, it does not foam depending on external temperature and humidity conditions (for example, from autumn to spring). Foams when the temperature and humidity are high, such as in summer. At 250 ° C., foaming may occur even outside summer.
2) Evaluation of adhesion A test piece of 60 × 60 mm was taken from a decorative board in which a resin film was laminated on a metal substrate, and a 5 mm wide notch cut from the resin film was reached on the metal substrate surface using a cutter knife. I put it.
About this specimen, using an Erichsen tester, a spherical punch with a radius of 10 mm was pressed 6 mm from the steel plate side, and the peeled state of the film when the film bonded steel plate was deformed was evaluated. The adhesion was evaluated.
A range that seems to have no problem in practical use. A thing with a problem in practical use is set as x.
3) Boiling water resistance Assuming that the decorative board of the present invention is aged for a long time in a hot and humid state used as an interior material of a unit bath, the water deterioration resistance of the resin film when immersed in boiling water for 3 hours is shown. Evaluation was made based on whether or not the surface of the film became “butterfly”. The thing which becomes an abalone form is set as x, and the thing which is not so is set as ○. It can be seen that this is the biggest problem with PETG.
4) Adhesiveness of sealing agent When sealant 4855 (caulking agent, manufactured by Shin-Etsu Chemical Co., Ltd.) is applied in a film shape and left undisturbed after standing for 24 hours: ○, when peeling: ×
A silicone-based curable caulking agent is applied to the overlapping parts of decorative steel sheets for waterproofing. It can be seen that the adhesion is improved by blending the PBT resin with the PET resin.
表１に示すように本発明の鋼板用化粧フィルムは、より低温（２２０℃）で鋼板と積層することができた。そして得られた本発明の化粧フィルム被覆鋼板は、発泡の有無、金属基板との密着性、耐性沸騰水性およびシーリング剤との密着性のいずれにおいても優れた特性を示す。 As shown in Table 1, the decorative film for steel sheet of the present invention could be laminated with the steel sheet at a lower temperature (220 ° C.). The obtained decorative film-coated steel sheet of the present invention exhibits excellent characteristics in any of the presence / absence of foaming, adhesion to a metal substrate, resistant boiling water and adhesion to a sealing agent.
本発明の鋼板用化粧フィルムは、貼合時の鋼板の温度が２２０℃でも発泡せず接着性が良好であり、沸騰水中での耐久性が良好であり、コーキング剤との接着性が良好であり、ユニットバスに好適に適用させることができる。 The decorative film for steel sheet of the present invention has good adhesiveness without foaming even when the temperature of the steel sheet at the time of bonding is 220 ° C., has good durability in boiling water, and has good adhesion with a caulking agent. Yes, it can be suitably applied to a unit bus.
Claims (8)
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| JP2004375400A JP4681875B2 (en) | 2004-12-27 | 2004-12-27 | Steel sheet decorative film |
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| JP2010094890A (en) * | 2008-10-16 | 2010-04-30 | Mitsubishi Plastics Inc | Laminated sheet for resin-coated metal plates, manufacturing process of the laminated sheet, designed laminated sheet coated metal plate, prefabricated bath member, building upholstery material, and steel furniture member |
| JP2010173312A (en) * | 2009-02-02 | 2010-08-12 | Mitsubishi Plastics Inc | Laminated sheet for resin-coated metal plate, laminated sheet-covered metal plate, prefabricated bath member, building interior member, steel furniture member, and method for manufacturing laminated sheet for resin-coated metal plate |
| WO2012148099A3 (en) * | 2011-04-27 | 2013-01-03 | (주)엘지하우시스 | Environmentally friendly deco sheet having outstanding moulding properties and glossiness |
| WO2015026066A1 (en) * | 2013-08-19 | 2015-02-26 | (주)엘지하우시스 | Deco sheet |
| WO2019187947A1 (en) * | 2018-03-27 | 2019-10-03 | 積水化成品工業株式会社 | Foam particle, foam molded body, preparation method thereof and resin complex |
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| AU2016240880B2 (en) | 2015-03-31 | 2018-09-13 | Jfe Steel Corporation | Laminated metal sheet for container |
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| JP2010094890A (en) * | 2008-10-16 | 2010-04-30 | Mitsubishi Plastics Inc | Laminated sheet for resin-coated metal plates, manufacturing process of the laminated sheet, designed laminated sheet coated metal plate, prefabricated bath member, building upholstery material, and steel furniture member |
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| WO2019187947A1 (en) * | 2018-03-27 | 2019-10-03 | 積水化成品工業株式会社 | Foam particle, foam molded body, preparation method thereof and resin complex |
| JP2019172735A (en) * | 2018-03-27 | 2019-10-10 | 積水化成品工業株式会社 | Foam particle, foam molded body, manufacturing method therefor, and resin composite |
| JP2022117952A (en) * | 2021-02-01 | 2022-08-12 | イクレ ジョ | Heat adhesion pet film |
| JP7239753B2 (en) | 2021-02-01 | 2023-03-14 | イクレ ジョ | Thermal adhesion PET film |
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