JP4141641B2 - Embossing processing method and manufacturing method of decorative metal plate - Google Patents
Embossing processing method and manufacturing method of decorative metal plate Download PDFInfo
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- JP4141641B2 JP4141641B2 JP2000579665A JP2000579665A JP4141641B2 JP 4141641 B2 JP4141641 B2 JP 4141641B2 JP 2000579665 A JP2000579665 A JP 2000579665A JP 2000579665 A JP2000579665 A JP 2000579665A JP 4141641 B2 JP4141641 B2 JP 4141641B2
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- 238000004049 embossing Methods 0.000 title claims description 42
- 229910052751 metal Inorganic materials 0.000 title claims description 28
- 239000002184 metal Substances 0.000 title claims description 28
- 238000003672 processing method Methods 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 229920005989 resin Polymers 0.000 claims description 151
- 239000011347 resin Substances 0.000 claims description 151
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 33
- 238000001816 cooling Methods 0.000 claims description 22
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 20
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 20
- -1 polybutylene terephthalate Polymers 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 14
- 238000012545 processing Methods 0.000 claims description 12
- 238000005259 measurement Methods 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 230000035515 penetration Effects 0.000 claims description 7
- 238000004458 analytical method Methods 0.000 claims description 5
- 238000013459 approach Methods 0.000 claims description 5
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- 239000004431 polycarbonate resin Substances 0.000 claims description 5
- 230000000930 thermomechanical effect Effects 0.000 claims description 5
- 238000011946 reduction process Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 description 18
- 230000003746 surface roughness Effects 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 12
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 12
- 238000007747 plating Methods 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 229910000576 Laminated steel Inorganic materials 0.000 description 4
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
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- 229910052799 carbon Inorganic materials 0.000 description 3
- 229920006026 co-polymeric resin Polymers 0.000 description 3
- 239000010960 cold rolled steel Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
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- 239000004417 polycarbonate Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 229910000655 Killed steel Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004830 Super Glue Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- MFPOUZMIWRBOON-UHFFFAOYSA-N [Mo].[Co].[Zn] Chemical compound [Mo].[Co].[Zn] MFPOUZMIWRBOON-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 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
- 238000005452 bending Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 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
- 239000008397 galvanized steel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- MXNUCYGENRZCBO-UHFFFAOYSA-M sodium;ethene;2-methylprop-2-enoate Chemical compound [Na+].C=C.CC(=C)C([O-])=O MXNUCYGENRZCBO-UHFFFAOYSA-M 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C59/04—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing using rollers or endless belts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0036—Heat treatment
- B32B38/004—Heat treatment by physically contacting the layers, e.g. by the use of heated platens or rollers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/06—Embossing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
- B32B2307/7265—Non-permeable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2419/00—Buildings or parts thereof
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Shaping Of Tube Ends By Bending Or Straightening (AREA)
- Laminated Bodies (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
【技術分野】
【０００１】
本発明はユニットバス等の耐水性を必要とする建材等に使用するエンボス加工性に優れた樹脂フィルム又はシート（以下、「樹脂フィルム」という。）のエンボス加工処理方法、及び化粧金属板の製造方法に関する。
【背景技術】
【０００２】
化粧金属板はユニットバス等の耐水性を必要とする建材等に広く用いられている。この場合、樹脂フィルムを表面に被覆することは、素材の金属板に防食効果を付与することが主目的であるが、同時に化粧金属板に高級感を持たせるという目的もあり、従来からエンボス模様を付加することが広く行われてきた。
このような目的に使用される、エンボス模様を付加するフィルムの素材は、従来から、主としてエンボス加工が容易であること、低価格であること等の観点から、たとえば軟質塩化ビニル樹脂等が多く使用されてきた。
しかし、軟質塩化ビニル樹脂は成形を容易にするためにＤＢＰ（ジブチルフタレート）、ＤＯＰ（ジオクチルフタレート）等のフタル酸類を可塑剤として添加、混合して軟質化している関係で、浴槽のような温度の高くなる箇所には使用し難く、またそれらを含む製品の廃棄には種々の問題がある。さらに、金属板にエンボス加工処理した樹脂フィルムを接着、ラミネート処理して使用する場合における製品の美感は、使用する金属板、金属板と樹脂との組合せ等によって異なる場合が少なくない。換言すれば、その用途の製品に使用する樹脂の種類とエンボス加工処理条件等によって、美感、特に高級感のような審美性的感性は左右され易いという問題があるために、エンボス加工処理は使用する樹脂との関係で最適条件で行うことが好ましい。
可塑剤を排除した硬質の塩化ビニル樹脂フィルムは、加工性が劣る上にエンボス加工処理が一般に困難であるほかに、エンボス処理によって得た樹脂の美観が得られ難いという問題がある。また塩化ビニル樹脂に代えて、オレフィン系樹脂のポリエチレン、ポリプロピレン樹脂等を使用する場合にはこれらの樹脂のエンボス加工性は良好であるものの、金属板上に積層した後に加工した場合に加工部分が白色化して美感を損なうという問題がある。
この問題を解決するために、ゴム成分を添加配合するという提案があるが、ゴム成分を添加するとポリエチレン樹脂は塩化ビニル樹脂同様の軟質樹脂に変性してしまうという問題が新たに発生する。また、ポリブチレンテレフタレート樹脂は耐水性及び水中に放置後の強度劣化が少ないという優れた特性を有するために、この分野の被覆材としては極めて有望であるが、通常の処理条件ではエンボス加工性が悪いためにこの目的のためには実用化されていなかった。
本発明は、上記、これらの課題を解決することを目的とし、従来の軟質塩化ビニル樹脂と同等以上のエンボス加工性に優れた樹脂フィルム及びその樹脂フィルムを被覆した高級感のある感性の豊かな化粧金属板を提供することを目的とする。
【発明の開示】
【０００３】
本発明は以下の特徴を有する。
すなわち、
（Ａ）
「下記（１）〜（３）のいずれかの樹脂フィルムの中から下記式で与えられるＴＭＡ（Ｔｈｅｒｍｏ Ｍｅｃｈａｎｉｃａｌ Ａｎａｌｙｓｉｓ）関係値が３０以下である樹脂フィルムを選択して、
彫刻ロールによる圧下処理でエンボス処理加工を行う場合において、冷却ロールが樹脂フィルムと接触する部分の表面温度Ｔｒを、ＴＭＡにより測定される軟化開始温度であるＴｓｓを基準として、Ｔｓｓ±１０（℃）の範囲に設定してエンボス加工処理することを特徴とするエンボス加工処理方法。
（１）固有粘度（ＩＶ）が１．０〜１．４のポリブチレンテレフタレート（ＰＢＴ）樹脂フィルム、
（２）ＰＢＴ樹脂３０重量部とポリエチレンテレフタレート（ＰＥＴ）樹脂７０重量部とのブレンド樹脂フィルム、
（３）ＰＢＴ樹脂７０重量部とポリカーボネート樹脂３０重量部とのブレンド樹脂フィルム、
ＴＭＡ関係値（℃）＝Ｔｓｅ−Ｔｓｓ、
ここで、
軟化開始温度Ｔｓｓ（℃）は、ＴＭＡにより測定され、
２ｍｍφで先端Ｒ＝０．２以下（先端角６０°）の針に荷重１００ｇをかけ、１０℃／ｍｉｎで昇温した時の針のフィルムへの進入深さをＪＩＳ−Ｋ−７１９６に準じて測定して得られた曲線における、
針が進入を始めるよりも低温側に認められる直線部分の高温側への延長と、
進入速度が最大となる部分の接線の低温側への延長との交点により求められる温度であり、
軟化終了温度Ｔｓｅ（℃）は、上記進入速度が最大となる部分の接線の高温側への延長と、
軟化終了後の高温側に認められる直線部分の低温側への延長との交点により求められる温度である。」
（Ｂ）
「下記（１）〜（３）のいずれかの樹脂フィルムの中から下記式で与えられるＴＭＡ（Ｔｈｅｒｍｏ Ｍｅｃｈａｎｉｃａｌ Ａｎａｌｙｓｉｓ）関係値が３０以下である樹脂フィルムを選択して、
彫刻ロールによる圧下処理でエンボス処理加工を行う場合において、冷却ロールが樹脂フィルムと接触する部分の表面温度Ｔｒを、ＴＭＡにより測定される軟化開始温度であるＴｓｓを基準として、Ｔｓｓ±１０（℃）の範囲に設定してエンボス加工処理し、
この樹脂フィルムを金属板に被覆することを特徴とする化粧金属板の製造方法。
（１）固有粘度（ＩＶ）が１．０〜１．４のポリブチレンテレフタレート（ＰＢＴ）樹脂フィルム、
（２）ＰＢＴ樹脂３０重量部とポリエチレンテレフタレート（ＰＥＴ）樹脂７０重量部とのブレンド樹脂フィルム、
（３）ＰＢＴ樹脂７０重量部とポリカーボネート樹脂３０重量部とのブレンド樹脂フィルム、
ここで、
軟化開始温度Ｔｓｓ（℃）は、ＴＭＡにより測定され、
２ｍｍφで先端Ｒ＝０．２以下（先端角６０°）の針に荷重１００ｇをかけ、１０℃／ｍｉｎで昇温した時の針のフィルムへの進入深さをＪＩＳ−Ｋ−７１９６に準じて測定して得られた曲線における、
針が進入を始めるよりも低温側に認められる直線部分の高温側への延長と、
進入速度が最大となる部分の接線の低温側への延長との交点により求められる温度であり、
軟化終了温度Ｔｓｅ（℃）は、上記進入速度が最大となる部分の接線の高温側への延長と、
軟化終了後の高温側に認められる直線部分の低温側への延長との交点により求められる温度である。」
【０００４】
本発明の発明者等は樹脂フィルムの特性とエンボス加工性の関係について鋭意検討した結果、Ｔｈｅｒｍｏ Ｍｅｃｈａｎｉｃａｌ Ａｎａｌｙｓｉｓ（ＴＭＡ）による軟化開始温度Ｔｓｓ（℃）と軟化終了温度Ｔｓｅ（℃）から計算されるＴＭＡ関係値である（Ｔｓｅ−Ｔｓｓ）の値が３０以下の樹脂であり、樹脂フィルムとして、好ましくはポリブチレンテレフタレート樹脂を含有する樹脂フィルムを使用し、エンボス加工処理する冷却ロールが樹脂フィルムと接触する部分の表面温度Ｔｒを、前記、ＴＭＡにより測定される軟化開始温度であるＴｓｓを基準として、Ｔｓｓ±１０（℃）の範囲に設定することとした場合に、これらの樹脂フィルムのエンボス加工性が飛躍的に向上するとともに、そのエンボス処理したフィルムを化粧金属板に接着、ラミネート処理した場合に、製品に従来品以上の高級感を付与できることを見出した。
この結果、このような特性を有する樹脂フィルムを積層加工（ラミネート加工）し、折り曲げ等の加工を施した場合にも加工部分が白色化して意匠性を損なうという問題はなく、塩化ビニル樹脂と同等のエンボス加工性を向上させることができ、さらに耐水性及び水中に放置後の強度劣化が少ないという、ポリブチレンテレフタレート樹脂の優れた特性をそのまま維持することができた。
以下に本発明についてその内容を説明する。
【０００５】
（使用する樹脂フィルム等）
樹脂フィルム等の厚さは特に限定しないが、例えば０．０２〜０．３０ｍｍ、好ましくは０．０８０〜０．１５０ｍｍのポリブチレンテレフタレート（ＰＢＴ）樹脂、ＰＢＴと他の樹脂との種々の割合のブレンド樹脂、たとえばポリエチレンテレフタレート（ＰＥＴ）樹脂、ポリカーボネート樹脂、アイオノマー樹脂等とのブレンド、又はこれらの３種以上の樹脂のブレンド、あるいはＰＢＴと他の樹脂又は化合物との共重合体、たとえばイソフタル酸、アジピン酸との共重合体の樹脂フィルム等、さらに上記種々の樹脂フィルム等を異なる厚さの比率で積層した複合樹脂フィルム等を使用することができる。これらの樹脂フィルム等の中には着色樹脂等が入っていても差し支えない。２種以上のブレンド樹脂を使用する理由は、例えば衝撃強度には優れているが金属との接着性が劣る樹脂に対して、その接着性のみの改良を図るために金属との接着性の良好な樹脂をブレンドするようなケースであり、複合樹脂を使用するのは、金属との接着面に接着特性の優れた樹脂を使用するためである。
【０００６】
これらの樹脂フィルムに使用する樹脂は、下記式で与えられるＴＭＡ関係値が３０以下の範囲にあることが必要である。
ＴＭＡ関係値（℃）＝Ｔｓｅ−Ｔｓｓ ここで、Ｔｓｓ（℃）はＴＭＡにより測定される軟化開始温度であり、またＴｓｅ（℃）はＴＭＡにより測定される軟化終了温度である。
このようなＴＭＡ関係値の樹脂フィルムを原料樹脂フィルムとし、彫刻ロールを使用して圧下エンボス加工処理する場合には、溶融樹脂が最初に接する冷却ロール表面の原料樹脂フィルムと接触している部分の温度を、ＴＭＡにより測定される軟化開始温度であるＴｓｓを基準として、Ｔｓｓ±１０（℃）の範囲に設定してエンボス処理加工することが必要である。
【０００７】
樹脂のＴＭＡ関係値を３０以下に限定する理由は、従来用いられていた塩化ビニル樹脂フィルムのエンボス加工後の平均表面粗度がＲａで、４．０μｍであったから、従来品との比較においてエンボス性を良好とする平均表面粗度基準をＲａで４．０μｍとしたためである。このようなＴＭＡ関係値の樹脂フィルム等を使用するとエンボス加工性が改良される理由は、軟化開始点から軟化終了点の範囲が比較的小さい樹脂を軟化開始点に近い一定の温度範囲内で処理した場合には、エンボス加工処理に伴って発生する圧縮エネルギーや摩擦エネルギーをこの温度範囲で樹脂が効果的に吸収することができるために、冷却後も樹脂が高度の歪みを維持できるからではないかと考えられる。
【０００８】
また、このようなＴＭＡ関係値の樹脂フィルムを原料樹脂フィルムとし、彫刻ロールを使用して圧下エンボス加工処理する場合に、冷却ロールの表面が原料樹脂フィルムと接触している部分の温度Ｔｒを、ＴＭＡにより測定される軟化開始温度であるＴｓｓを基準として、Ｔｓｓ±１０（℃）の範囲にする理由は、このような温度範囲でエンボス加工処理した樹脂フィルムを化粧金属板に接着、ラミネート処理した場合には、その製品の高級感がきわめて優れているからである。エンボス加工処理温度と、化粧金属板とのラミネート樹脂フィルムの有する感性の関係については、まだ不明な点が多いが、加工処理温度を樹脂の軟化温度近傍でコントロールすることにより、フィルムの粘着等も生じずに歪みを与えることが高級感の発生につながるのではないかと考えられる。
一般的に、ＴＭＡ関係値と、樹脂フィルムのエンボス加工後の平均表面粗度Ｒａの関係は逆相関関係となる傾向がある。この平均表面粗度Ｒａは商品の意匠的価値（意匠性）と大きな関係があって、４以上の範囲が適正値であると考えられている。なお、この平均表面粗度Ｒａのさらに好ましい範囲は５〜８である。
【０００９】
（エンボス加工処理方法）
樹脂フィルム等のエンボス加工処理方法は、例えば複層フィルムを直接チルドロールの間に通す方法、ブラウン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の力でエンボス加工する方法、複層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等の種々の方法があるが、本発明の場合はＴダイから供給した樹脂フィルムを、Ｔｓｓ±１０（℃）の温度範囲に調節した冷却ロールを使用して、又は冷却ロールと彫刻ロールで圧下する方法でエンボス加工処理される。エンボス形状としてはランダムマット、四角形、ダイヤモンド型、深絞り型、砂目等の種々の模様を、製品のニーズに応じて使用することができる。
【００１０】
（エンボス性の良否判定）
本発明における樹脂フィルム等のエンボス性の良否はその樹脂フィルムのエンボス加工後の表面粗度Ｒａ（μｍ）によって判断される。一般に良好なエンボス性とは樹脂の融点前後の温度で彫刻ロール等で圧下、エンボス加工したときに、容易にエンボス模様が樹脂フィルムの表面に形成され、かつその後、温度を上げた場合にも長時間、そのエンボス模様を維持していることをいう。
表面粗度の測定は、樹脂フィルムを室温に冷却した後、表面粗度Ｒａ（μｍ）を東京精密社製ＳＵＲＦＣＯＭ表面粗さ計を用いて、ＪＩＳ Ｂ０６０１に準拠して測定し、平均表面粗度が４．０以上をエンボス性良好とした。なお、この測定は、エンボス加工処理の終了した樹脂フィルムから、任意に５枚の樹脂試験片を採取して、その各試片について４個所の異なる場所の表面粗度を測定し、その平均値を計算して表面粗度Ｒａ（μｍ）とした。
また、エンボス性の高級感の有無の判定をするためには、エンボス加工処理フィルムを化粧金属板上に貼付した後に水中に沈めて目視判定する。この場合に使用する金属板としては、鋼板、アルミニウム板、銅板等、広く金属板であれば用いることができる。鋼板としては、厚さ０．１０〜１．２０ｍｍの普通鋼冷延鋼板が好ましい。中でも、厚さ０．１０〜０．５０ｍｍの普通鋼冷延鋼板が好ましい。冷延製品の中でも低炭素又は極低炭素アルミキルド鋼板が好ましく使用されるが、Ｎｂ、Ｔｉ等を添加した非時効性鋼、３〜１８ｗｔ％のクロムを含むクロム含有鋼板、種々の組成を有するステンレス鋼板等も使用することができる。これら圧延鋼板の表面は表面処理がされているものでも差し支えない。
表面処理方法としては、めっき処理、塗装処理等があり、めっき処理としては、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、ニッケル・りんめっき、ニッケル・コバルトめっき、ニッケル・錫めっき等があり、また塗装処理としては種々の塗料をその性質に応じて焼き付け、塗装する方法で行われる。
【００１１】
エンボス加工処理した樹脂フィルムを金属板上に被覆する場合には、エポキシ系、ポリエステル系、シアノアクリレート系等の接着剤を使用しても良いが、単にＤＳＣにより測定した樹脂の融点Ｔｍｐ（℃）以上に加熱しておいた金属板上に圧着する方法で接着しても良い。加熱圧着法で樹脂フィルムと金属板を接着させる場合には強固な接着力を得ることができるように金属板の表面を処理しておくことが好ましい。金属板の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等の方法を採用することができる。
ＴＭＡ関係値の計算に必要な諸元の測定は以下の条件で行った。
理学電機（株）製のＴＭＡ、ＴＡＳ−３００を用いて、２ｍｍφで先端Ｒ＝０．２以下（先端角６０°）の針に荷重１００ｇをかけ、１０℃／ｍｉｎで昇温した時の針のフィルムへの進入深さをＪＩＳ−Ｋ−７１９６に準じて測定した。図３にＴＭＡ関係値の測定曲線の一例を示す。ここで針の進入度は進入深さをフィルム厚みで割った値である。
軟化終了温度Ｔｓｅは、図３に示すように進入度が急激に変化する曲線と、軟化終了後のベース線の接線交点により求められる温度である。同様に軟化開始温度Ｔｓｓは、Ｔｓｅで用いた曲線の接線と、その近傍のベース線の接線交点により求められる温度である。
また、ＤＳＣによるＴｍｐの測定は以下の条件で行った。
パーキンエルマー社製の示差熱量計ＤＳＣ−７を使用し、精秤した約５ｍｇの試料を窒素ガス雰囲気下において２０℃／分で昇温させ、吸熱ピークをＤＳＣの融点Ｔｍｐとした。
実施例 以下に、実施例について本発明をさらに具体的に説明する。
【００１２】
【実施例】
（実施例１）
図１に示すように、ＴＭＡ関係値が７．２であって、その固有粘度（ＩＶ）が１．４のＰＢＴ（ポリブチレンテレフタレート）樹脂を溶融して、Ｔダイ（樹脂供給口）１からフィルム厚さが０．１００ｍｍになるように彫刻ロール３上に押し出した。フィルム状の溶融樹脂２を、彫刻ロール３と補助ロール５とで挟み、フィルム厚さ０．１００ｍｍにエンボス加工処理した固化フィルム６を製造した。この第１態様の処理方式は彫刻ロール（平均表面粗さＲａ＝１１μｍの凹凸が付与された砂目ロール）３が冷却ロールを兼用している場合である。彫刻ロール３がフィルム状の樹脂と接する部分の表面温度は、使用した樹脂のＴｓｓが２２１．４℃であるため、ロール表面温度が２１５℃になるように彫刻ロール（冷却ロール）３内部に通水する冷却水温を調節・設定した。エンボス加工処理した同化フィルム６を、その後さらに室温まで冷却し、５枚の試片を間隔をおいて採取し、エンボス性の指標である表面粗度Ｒａを測定して、その平均値を計算した結果、６．７μｍであった。
【００１３】
（実施例２）
図２に示すように、ＴＭＡ関係値が３．３であって、その固有粘度（ＩＶ）が１．０のＰＢＴ樹脂を溶融して、Ｔダイ１からフィルム厚さが０．１００ｍｍになるように冷却ロール４上に押し出した。
フィルム状の溶融樹脂２を、彫刻ロール３と冷却ロール４とで挟み、フィルム厚さ０．１００ｍｍにエンボス加工処理した固化フィルム６を製造した。
この第２態様の方式は彫刻ロール（平均表面粗さＲａ＝１１μｍの凹凸が付与されたＳＧ目ロール）の３に対向するロールが冷却ロールとなっている場合である。冷却ロール４が樹脂と接する表面温度は、使用した樹脂のＴｓｓが２２０．５℃であるため、ロール表面温度が２１５℃になるように冷却ロール４内部に通水する冷却水温を調節・設定した。エンボス加工処理した固化フィルム６を、その後さらに室温まで冷却し、５枚の試片を間隔をおいて採取し、エンボス件の指標である表面粗度Ｒａを測定して、その平均値を計算した結果、７．０μｍであった。
【００１４】
（実施例３〜１０）
ＴＭＡ関係値の異なる樹脂について、溶融樹脂をＴダイから処理ロール上に押し出して、実施例１又は２の態様のエンボス加工方式で、０．１００ｍｍのフィルム厚さでエンボス加工処理した。この場合の冷却ロールが樹脂と接する表面温度Ｔｒはあらかじめ測定しておいた、使用樹脂のＴＭＡによるＴｓｓに基づいてその都度、Ｔｓｓ±１０（℃）以内に設定した。
実施例３はＩＶ＝１．０のＰＢＴ樹脂を使用して態様１で処理した場合、実施例４はＩＶ＝１．４のＰＢＴ樹脂を使用して態様２で処理した場合、実施例５と６はブレンド樹脂の場合で、実施例５はポリエチレンテレフタレート（ＰＥＴ）樹脂７０重量部とＰＢＴ樹脂３０重量部のブレンド、実施例６はＰＢＴ７０重量部とポリカーボネート（ＰＣ）樹脂３０重量部のブレンドの場合である。
実施例７は２層フィルムの例で、ＰＢＴ樹脂フィルムとイソフタル酸の１０モル％／ＰＥＴ樹脂の共重合樹脂フィルムの複合積層フィルム（厚さ比は４：１）、実施例８はＰＥＴ樹脂単味の場合、実施例９はＰＣ樹脂単味、実施例１０はイソフタル酸とＰＥＴ樹脂の共重合体の場合であり、その他の条件は表１に示した。
【００１５】
（比較例１）
ＴＭＡ関係値が３０を超えている場合の例で、ＰＢＴ樹脂とＰＥＴ樹脂の等重量ブレンド樹脂を実施例１と同様の方法でエンボス加工処理し、その後さらに室温まで冷却し、５枚の試片を間隔をおいて採取し、エンボス性の指標である表面粗度Ｒａを測定して、その平均値を計算した結果、３．２μｍであった。
【００１６】
（比較例２〜９）
比較例２〜８はＴＭＡ関係値は３０以内であるが、冷却ロールの温度ＴｒがＴｓｓ±１０（℃）の範囲を外れた場合で、このうち比較例２〜４は高位にずれた場合、比較例５〜７は低位に外れた場合である。比較例３はエンボス処理中に樹脂がロールに粘着してしまって試料を採取することはできなかった。比較例４の共重合体はイソフタル酸１１モル％とＰＥＴ樹脂の共重合体、比較例７はアジピン酸１０モル％とＰＥＴの共重合体の場合である。また、比較例８と９は複層フィルムの場合で、比較例８はＰＢＴ樹脂フィルムとイソフタル酸の１０モル％／ＰＥＴ樹脂の共重合樹脂フィルムの複合積層フィルム（厚さ比は４：１）、比較例９はＰＣ樹脂フィルムとイソフタル酸の１０モル％／ＰＥＴ樹脂の共重合樹脂フィルムの複合積層フィルム（厚さ比は４：１）で、ＴＭＡ関係値が３０を超えた場合である。なお、その他の条件は表２に示した。
【００１７】
次に、このようにエンボス加工処理した樹脂フィルムについて、鋼板との組合せにおける高級感の有無を以下のようにして調べた。
まず、炭素分が０．０３０％のアルミキルド冷延鋼板であって厚さ０．５０ｍｍの鋼板に０．００２ｍｍの厚さに亜鉛めっき処理をし、この亜鉛めっき鋼板を３０×２０ｃｍの大きさに切断する。この鋼板をＤＳＣにより測定したＴｍｐ±１０℃に加熱して、その表面上にエンボス加工した樹脂フィルムを貼付する。
このようなラミネート鋼板を３枚ずつ用意し、これを太陽光線の入らない室内のテーブル上に置き、試料の１ｍ上から２０Ｗの白色蛍光灯５本で照射する。年齢、性別の異なる５人の人に、観測場所及び角度を変えて以下のような評価点をつけてもらい、その評価点の平均値を求めて総合評価する。
評価点は、従来の塩ビラミネート鋼板と比較したときに、塩ビラミネート鋼板と同等以上の高級感がある場合を５点、塩ビラミネート鋼板より多少劣るがやや高級感の得られる場合を４点、塩ビラミネート鋼板に比較して安っぽいという感触の場合を３点とする。
このような評価をした場合、概ね表面粗度との関係があり、ＴＭＡ関係値が３０以下の樹脂フィルムを使用して、冷却ロール温度をＴＭＡによるＴｓｓ±１０（℃）の温度範囲で処理した試料は、いずれも十分な高級感を有していた。これに対して、これらの要件にマッチしない比較例の試料の場合にはいずれも高級感は得られなかったり、不充分であった。これらの結果を表１、表２に示した。
【００１８】
【表１】
【表２】
【産業上の利用可能性】
ＴＭＡ関係値が３０以下である樹脂フィルムを原料とし、冷却ロールが樹脂フィルムと接触する部分の表面温度Ｔｒを、ＴＭＡにより測定される軟化開始温度であるＴｓｓを基準として、Ｔｓｓ±１０（℃）の範囲に設定してエンボス加工処理した場合には、従来の塩ビ樹脂と同等以上のエンボス面を得ることができ、高級感が得られる。
【００２１】
【図面の簡単な説明】
図１は、実施例に係るエンボス処理加工方法の第１態様のロール配置図である。
図２は、実施例に係るエンボス処理加工方法の第２態様のロール配置図である。
図３は、ＴＭＡ関係値の測定曲線の一例である。【Technical field】
[0001]
The present invention relates to a method for embossing a resin film or sheet (hereinafter referred to as “resin film”) excellent in embossing workability, which is used for building materials that require water resistance such as a unit bath, and the production of a decorative metal plate. Regarding the method.
[Background]
[0002]
The decorative metal plate is widely used for building materials that require water resistance such as a unit bath. In this case, the main purpose of coating the resin film on the surface is to give the material metal plate an anticorrosive effect, but at the same time it has the purpose of giving the decorative metal plate a high-class feeling, and the embossed pattern has been conventionally used. It has been widely performed.
Conventionally, the material of the film to which the embossed pattern is added is used mainly for such purposes, mainly from the viewpoint of easy embossing and low cost. It has been.
However, soft vinyl chloride resin is softened by adding and mixing phthalic acids such as DBP (dibutyl phthalate) and DOP (dioctyl phthalate) as a plasticizer in order to facilitate molding. It is difficult to use in places where the height is high, and there are various problems in disposal of products containing them. Furthermore, the aesthetics of the product when the embossed resin film is bonded and laminated to the metal plate is often used depending on the metal plate used, the combination of the metal plate and the resin, or the like. In other words, embossing treatment is used because there is a problem that aesthetics, especially high-grade aesthetic sensibility, are easily affected by the type of resin used in the product for that application and the embossing treatment conditions. It is preferable to carry out under optimum conditions in relation to the resin used.
A hard vinyl chloride resin film from which a plasticizer is excluded has problems in that the processability is inferior and the embossing treatment is generally difficult, and the aesthetic appearance of the resin obtained by the embossing treatment is difficult to obtain. In addition, when using olefin resin polyethylene, polypropylene resin, etc. instead of vinyl chloride resin, the embossability of these resins is good, but when processed after being laminated on a metal plate, the processed part is There is a problem of whitening and impairing aesthetics.
In order to solve this problem, there is a proposal of adding and blending a rubber component. However, when the rubber component is added, a new problem arises in that the polyethylene resin is modified into a soft resin similar to vinyl chloride resin. Polybutylene terephthalate resin is very promising as a coating material in this field because it has excellent properties such as water resistance and little deterioration in strength after standing in water. It was not put into practical use for this purpose because of its badness.
The present invention aims to solve the above-mentioned problems, and has a resin film excellent in embossing workability equal to or higher than that of a conventional soft vinyl chloride resin and a rich and high-quality sensibility coated with the resin film. An object is to provide a decorative metal plate.
DISCLOSURE OF THE INVENTION
[0003]
The present invention has the following features.
That is,
(A)
“A resin film having a TMA (Thermo Mechanical Analysis) relationship value given by the following formula is selected from the resin films of any of the following (1) to (3) :
When embossing processing is performed by a reduction process using an engraving roll, the surface temperature Tr of the portion where the cooling roll comes into contact with the resin film is defined as Tss ± 10 (° C.) based on Tss, which is the softening start temperature measured by TMA. The embossing processing method is characterized in that the embossing processing is performed by setting the range.
(1) a polybutylene terephthalate (PBT) resin film having an intrinsic viscosity (IV) of 1.0 to 1.4,
(2) a blend resin film of 30 parts by weight of PBT resin and 70 parts by weight of polyethylene terephthalate (PET) resin,
(3) Blend resin film of 70 parts by weight of PBT resin and 30 parts by weight of polycarbonate resin,
TMA-related value (° C.) = Tse−Tss,
here,
The softening start temperature Tss (° C.) is measured by TMA,
The penetration depth of the needle into the film when a load of 100 g is applied to a needle with a tip of R = 0.2 or less (tip angle 60 °) at 2 mmφ and the temperature is raised at 10 ° C./min according to JIS-K-7196. In the curve obtained by measurement,
The extension of the straight line portion that is recognized on the low temperature side from the start of the needle to the high temperature side,
It is the temperature obtained by the intersection with the extension of the tangent of the part where the approach speed is maximum to the low temperature side,
The softening end temperature Tse (° C.) is the extension of the tangential line where the entry speed is maximum to the high temperature side,
This is the temperature obtained by the intersection with the extension of the straight line portion observed on the high temperature side after the end of softening to the low temperature side. "
(B)
“A resin film having a TMA (Thermo Mechanical Analysis) relationship value given by the following formula is selected from the resin films of any of the following (1) to (3) :
When embossing processing is performed by a reduction process using an engraving roll, the surface temperature Tr of the portion where the cooling roll comes into contact with the resin film is defined as Tss ± 10 (° C.) based on Tss, which is the softening start temperature measured by TMA. Set to the range of embossing processing,
A method for producing a decorative metal plate, comprising coating a metal plate with the resin film.
(1) a polybutylene terephthalate (PBT) resin film having an intrinsic viscosity (IV) of 1.0 to 1.4,
(2) a blend resin film of 30 parts by weight of PBT resin and 70 parts by weight of polyethylene terephthalate (PET) resin,
(3) Blend resin film of 70 parts by weight of PBT resin and 30 parts by weight of polycarbonate resin,
here,
The softening start temperature Tss (° C.) is measured by TMA,
The penetration depth of the needle into the film when a load of 100 g is applied to a needle with a tip of R = 0.2 or less (tip angle 60 °) at 2 mmφ and the temperature is raised at 10 ° C./min according to JIS-K-7196. In the curve obtained by measurement,
The extension of the straight line portion that is recognized on the low temperature side from the start of the needle to the high temperature side,
It is the temperature obtained by the intersection with the extension of the tangent of the part where the approach speed is maximum to the low temperature side,
The softening end temperature Tse (° C.) is the extension of the tangential line where the entry speed is maximum to the high temperature side,
This is the temperature obtained by the intersection with the extension of the straight line portion observed on the high temperature side after the end of softening to the low temperature side. "
[0004]
As a result of intensive studies on the relationship between the properties of the resin film and the embossability, the inventors of the present invention, as a result, TMA calculated from the softening start temperature Tss (° C) and the softening end temperature Tse (° C) by Thermo Mechanical Analysis (TMA). The relational value (Tse-Tss) is a resin having a value of 30 or less, preferably a resin film containing polybutylene terephthalate resin is used as the resin film, and the cooling roll to be embossed is in contact with the resin film. When the surface temperature Tr of the portion is set to a range of Tss ± 10 (° C.) with reference to Tss, which is the softening start temperature measured by TMA, the embossability of these resin films is A dramatic improvement and embossed film on the decorative metal plate It has been found that a high-grade feeling can be imparted to a product when compared to conventional products.
As a result, even when a resin film having such characteristics is laminated (laminated) and subjected to processing such as bending, there is no problem that the processed portion is whitened and the design is not impaired, and is equivalent to vinyl chloride resin. It was possible to improve the embossability of the polybutylene terephthalate resin as it was, and to maintain the excellent properties of water resistance and strength deterioration after standing in water.
The contents of the present invention will be described below.
[0005]
(Resin film used)
The thickness of the resin film or the like is not particularly limited, but for example, 0.02 to 0.30 mm, preferably 0.080 to 0.150 mm of polybutylene terephthalate (PBT) resin, various ratios of PBT and other resins. Blend resins such as polyethylene terephthalate (PET) resins, polycarbonate resins, ionomer resins and the like, or blends of three or more of these resins, or copolymers of PBT with other resins or compounds, such as isophthalic acid, A resin film of a copolymer with adipic acid or the like, and a composite resin film obtained by laminating the above various resin films at different thickness ratios can be used. These resin films or the like may contain colored resins or the like. The reason for using two or more kinds of blended resins is that, for example, a resin having excellent impact strength but poor adhesion to metal has good adhesion to metal in order to improve only the adhesion. This is a case in which various resins are blended, and the composite resin is used because a resin having excellent adhesive properties is used for the adhesive surface with the metal.
[0006]
The resin used for these resin films is required to have a TMA-related value given by the following formula in the range of 30 or less.
TMA-related value (° C.) = Tse−Tss where Tss (° C.) is a softening start temperature measured by TMA, and Tse (° C.) is a softening end temperature measured by TMA.
When a resin film having such a TMA relation value is used as a raw material resin film and subjected to a rolling embossing process using an engraving roll, a portion of the part in contact with the raw material resin film on the surface of the cooling roll with which the molten resin comes into contact first. It is necessary to set the temperature to a range of Tss ± 10 (° C.) with respect to Tss, which is a softening start temperature measured by TMA, and perform embossing processing.
[0007]
The reason why the TMA-related value of the resin is limited to 30 or less is that the average surface roughness after embossing of the vinyl chloride resin film that has been used in the past was Ra, which was 4.0 μm. This is because the average surface roughness standard for improving the property is 4.0 μm in Ra. The reason why embossability is improved when using a resin film having such a TMA-related value is that a resin having a relatively small range from the softening start point to the softening end point is processed within a certain temperature range close to the softening start point. This is not because the resin can effectively absorb the compressive energy and frictional energy that accompany the embossing treatment in this temperature range, so that the resin can maintain a high degree of strain even after cooling. It is thought.
[0008]
In addition, when a resin film having such a TMA relation value is used as a raw material resin film and subjected to a rolling embossing process using an engraving roll, the temperature Tr of the portion where the surface of the cooling roll is in contact with the raw material resin film is The reason for setting Tss ± 10 (° C.) based on Tss, which is the softening start temperature measured by TMA, is that the resin film embossed in such a temperature range is bonded to a decorative metal plate and laminated. In some cases, the quality of the product is very good. There are still many unclear points regarding the embossing processing temperature and the sensitivity of the laminated resin film to the decorative metal plate, but by controlling the processing temperature in the vicinity of the softening temperature of the resin, film adhesion, etc. It is thought that imparting distortion without causing a high-class feeling.
In general, the relationship between the TMA relationship value and the average surface roughness Ra after embossing of the resin film tends to be inversely correlated. This average surface roughness Ra has a large relationship with the design value (designability) of the product, and a range of 4 or more is considered to be an appropriate value. In addition, the more preferable range of this average surface roughness Ra is 5-8.
[0009]
(Embossing processing method)
Embossing treatment method for resin film, etc., for example, a method of passing a multilayer film directly between chilled rolls, a method of heating a brown film between chilled rolls, a embossing with a rotating screen roll by vacuum force There are various methods such as a method of performing, a hot needle process in which a multilayer film is passed through a perforator (a perforator), and a method of compressing using a marking roll. In the present invention, a resin film supplied from a T die Is embossed using a cooling roll adjusted to a temperature range of Tss ± 10 (° C.) or by a method of rolling down with a cooling roll and an engraving roll. As the embossed shape, various patterns such as a random mat, a square shape, a diamond shape, a deep drawing shape, and a grain pattern can be used according to the needs of the product.
[0010]
(Embossing quality judgment)
The quality of the embossing property of the resin film or the like in the present invention is determined by the surface roughness Ra (μm) after the embossing of the resin film. In general, good embossability means that an embossed pattern is easily formed on the surface of a resin film when it is pressed and embossed with a sculpture roll at a temperature around the melting point of the resin. It means that the embossed pattern is maintained for a time.
The surface roughness is measured by cooling the resin film to room temperature, and then measuring the surface roughness Ra (μm) according to JIS B0601 using a SURFCOM surface roughness meter manufactured by Tokyo Seimitsu Co., Ltd. Of 4.0 or more was considered good embossing property. In this measurement, five resin test pieces are arbitrarily sampled from the resin film that has been subjected to the embossing treatment, and the surface roughness at four different locations is measured for each test piece. Was calculated as the surface roughness Ra (μm).
Moreover, in order to determine the presence or absence of embossed luxury, the embossed film is attached on a decorative metal plate, and then submerged in water for visual determination. As a metal plate used in this case, a wide metal plate such as a steel plate, an aluminum plate, or a copper plate can be used. As the steel plate, a plain steel cold-rolled steel plate having a thickness of 0.10 to 1.20 mm is preferable. Among these, a plain steel cold-rolled steel sheet having a thickness of 0.10 to 0.50 mm is preferable. Among cold-rolled products, low-carbon or ultra-low-carbon aluminum killed steel plates are preferably used, but non-aging steels added with Nb, Ti, etc., chromium-containing steel plates containing 3-18 wt% chromium, stainless steels having various compositions Steel plates and the like can also be used. The surface of these rolled steel plates may be surface-treated.
As the surface treatment method, there are plating treatment, coating treatment, and the like. As the plating treatment, for example, zinc plating, zinc-aluminum alloy plating, zinc-cobalt-molybdenum plating, tin plating, nickel plating, nickel / phosphorous plating, nickel There are cobalt plating, nickel / tin plating, and the coating process is performed by baking and coating various paints according to the properties.
[0011]
When coating an embossed resin film on a metal plate, an epoxy, polyester or cyanoacrylate adhesive may be used, but the resin melting point Tmp (° C) measured by DSC. You may adhere | attach by the method of crimping | bonding on the metal plate heated above. When the resin film and the metal plate are bonded by the thermocompression bonding method, it is preferable to treat the surface of the metal plate so that a strong adhesive force can be obtained. As the surface treatment method of the metal plate, methods such as electrolytic chromic acid treatment and adhesion primer treatment can be employed.
Measurements of specifications necessary for calculating TMA-related values were performed under the following conditions.
Using TMA and TAS-300 manufactured by Rigaku Denki Co., Ltd. Needle when a load of 100 g is applied to a needle with 2 mmφ and tip R = 0.2 or less (tip angle 60 °) and the temperature is raised at 10 ° C./min. The penetration depth into the film was measured according to JIS-K-7196. FIG. 3 shows an example of a measurement curve of TMA related values. Here, the penetration degree of the needle is a value obtained by dividing the penetration depth by the film thickness.
The softening end temperature Tse is a temperature obtained by a tangent intersection of a curve in which the degree of approach changes rapidly as shown in FIG. 3 and the base line after the softening ends. Similarly, the softening start temperature Tss is a temperature obtained from the tangent intersection of the tangent of the curve used in Tse and the base line in the vicinity thereof.
The Tmp measurement by DSC was performed under the following conditions.
A differential calorimeter DSC-7 manufactured by Perkin Elmer was used, and a precisely weighed sample of about 5 mg was heated at 20 ° C./min in a nitrogen gas atmosphere, and the endothermic peak was defined as the melting point Tmp of DSC.
Examples Hereinafter, the present invention will be described more specifically with reference to examples.
[0012]
【Example】
(Example 1)
As shown in FIG. 1, a PBT (polybutylene terephthalate) resin having a TMA relation value of 7.2 and an intrinsic viscosity (IV) of 1.4 is melted, and the T die (resin supply port) 1 The film was extruded onto the
[0013]
(Example 2)
As shown in FIG. 2, a PBT resin having a TMA-related value of 3.3 and an intrinsic viscosity (IV) of 1.0 is melted so that the film thickness from the T die 1 becomes 0.100 mm. And extruded onto the cooling roll 4.
A film-like
The system of this second aspect is a case where the roll opposite to 3 of the engraving roll (SG roll having an unevenness with an average surface roughness Ra = 11 μm) is a cooling roll. The surface temperature at which the cooling roll 4 is in contact with the resin was adjusted and set to the temperature of the cooling water passing through the cooling roll 4 so that the roll surface temperature was 215 ° C. because the Tss of the resin used was 220.5 ° C. . The embossed solidified film 6 was then further cooled to room temperature, 5 specimens were taken at intervals, the surface roughness Ra, which is an index of the embossing, was measured, and the average value was calculated. As a result, it was 7.0 μm.
[0014]
(Examples 3 to 10)
For resins having different TMA-related values, the molten resin was extruded from a T-die onto a treatment roll and embossed with a film thickness of 0.100 mm by the embossing method of the embodiment of Example 1 or 2. In this case, the surface temperature Tr at which the cooling roll is in contact with the resin was set within Tss ± 10 (° C.) each time based on the Tss measured by TMA of the resin used in advance.
Example 3 was treated with
Example 7 is an example of a two-layer film, and a composite laminated film (thickness ratio is 4: 1) of a PBT resin film and a copolymer resin film of 10 mol% of isophthalic acid / PET resin, and Example 8 is a single PET resin film. In the case of taste, Example 9 is a case of simple PC resin, Example 10 is a case of a copolymer of isophthalic acid and PET resin, and other conditions are shown in Table 1.
[0015]
(Comparative Example 1)
In the case where the TMA-related value exceeds 30, an equal weight blended resin of PBT resin and PET resin is embossed in the same manner as in Example 1, and then cooled to room temperature, and 5 specimens The surface roughness Ra, which is an embossing index, was measured and the average value was calculated. As a result, it was 3.2 μm.
[0016]
(Comparative Examples 2-9)
In Comparative Examples 2 to 8, the TMA-related value is 30 or less, but when the temperature Tr of the cooling roll is out of the range of Tss ± 10 (° C.), among these, Comparative Examples 2 to 4 are shifted to a high level. Comparative Examples 5 to 7 are cases in which they are out of the low range. In Comparative Example 3, the resin stuck to the roll during the embossing treatment, and a sample could not be collected. The copolymer of Comparative Example 4 is a copolymer of 11 mol% isophthalic acid and a PET resin, and Comparative Example 7 is a copolymer of 10 mol% adipic acid and PET. Comparative Examples 8 and 9 are multi-layer films, and Comparative Example 8 is a composite laminated film of PBT resin film and isophthalic acid 10 mol% / PET resin copolymer resin film (thickness ratio is 4: 1). Comparative Example 9 is a composite laminated film (thickness ratio is 4: 1) of a PC resin film and a copolymer resin film of 10 mol% of isophthalic acid / PET resin, with a TMA-related value exceeding 30. Other conditions are shown in Table 2.
[0017]
Next, the resin film thus embossed was examined for the presence or absence of a high-grade feeling in combination with a steel plate as follows.
First, an aluminum killed cold-rolled steel sheet having a carbon content of 0.030%, a 0.50 mm-thick steel sheet was galvanized to a thickness of 0.002 mm, and the galvanized steel sheet was sized to 30 × 20 cm. Disconnect. The steel sheet is heated to Tmp ± 10 ° C. measured by DSC, and an embossed resin film is stuck on the surface.
Three such laminated steel plates are prepared, placed on a table in a room where sunlight does not enter, and irradiated with five white fluorescent lamps of 20 W from 1 m above the sample. Five people with different ages and genders are given the following evaluation points by changing the observation place and angle, and the average value of the evaluation points is obtained and comprehensively evaluated.
The evaluation score is 5 points when there is a high-grade feeling equal to or higher than that of the conventional PVC-laminated steel sheet, 4 points when it is slightly inferior to the PVC-laminated steel sheet, but a slightly high-grade feeling is obtained. Three points are given for the feeling of being cheap compared to the laminated steel plate.
When such an evaluation was made, there was a general relationship with the surface roughness, and a TMA-related value of 30 or less was used, and the cooling roll temperature was processed in a temperature range of Tss ± 10 (° C.) by TMA. All the samples had a sufficient high-class feeling. On the other hand, in the case of the samples of the comparative examples that do not match these requirements, a high-class feeling was not obtained or was insufficient. These results are shown in Tables 1 and 2.
[0018]
[Table 1]
[Table 2]
[Industrial applicability]
Using a resin film having a TMA-related value of 30 or less as a raw material, the surface temperature Tr of the portion where the cooling roll is in contact with the resin film is Tss ± 10 (° C.) with reference to Tss, which is the softening start temperature measured by TMA When the embossing treatment is performed with this range set, it is possible to obtain an embossed surface equal to or higher than that of a conventional vinyl chloride resin, and a high-quality feeling can be obtained.
[0021]
[Brief description of the drawings]
FIG. 1 is a roll layout diagram of a first aspect of an embossing processing method according to an embodiment.
FIG. 2 is a roll layout diagram of a second aspect of the embossing processing method according to the embodiment.
FIG. 3 is an example of a measurement curve of TMA related values.
Claims (2)
彫刻ロールによる圧下処理でエンボス処理加工を行う場合において、冷却ロールが樹脂フィルムと接触する部分の表面温度Ｔｒを、ＴＭＡにより測定される軟化開始温度であるＴｓｓを基準として、Ｔｓｓ±１０（℃）の範囲に設定してエンボス加工処理することを特徴とするエンボス加工処理方法。
（１）固有粘度（ＩＶ）が１．０〜１．４のポリブチレンテレフタレート（ＰＢＴ）樹脂フィルム、
（２）ＰＢＴ樹脂３０重量部とポリエチレンテレフタレート（ＰＥＴ）樹脂７０重量部とのブレンド樹脂フィルム、
（３）ＰＢＴ樹脂７０重量部とポリカーボネート樹脂３０重量部とのブレンド樹脂フィルム、
ＴＭＡ関係値（℃）＝Ｔｓｅ−Ｔｓｓ、
ここで、
軟化開始温度Ｔｓｓ（℃）は、ＴＭＡにより測定され、
２ｍｍφで先端Ｒ＝０．２以下（先端角６０°）の針に荷重１００ｇをかけ、１０℃／ｍｉｎで昇温した時の針のフィルムへの進入深さをＪＩＳ−Ｋ−７１９６に準じて測定して得られた曲線における、
針が進入を始めるよりも低温側に認められる直線部分の高温側への延長と、
進入速度が最大となる部分の接線の低温側への延長との交点により求められる温度であり、
軟化終了温度Ｔｓｅ（℃）は、上記進入速度が最大となる部分の接線の高温側への延長と、
軟化終了後の高温側に認められる直線部分の低温側への延長との交点により求められる温度である。 A resin film having a TMA (Thermo Mechanical Analysis) relation value given by the following formula is selected from the following (1) to (3) :
When embossing processing is performed by a reduction process using an engraving roll, the surface temperature Tr of the portion where the cooling roll comes into contact with the resin film is defined as Tss ± 10 (° C.) based on Tss, which is the softening start temperature measured by TMA. The embossing processing method is characterized in that the embossing processing is performed by setting the range.
(1) a polybutylene terephthalate (PBT) resin film having an intrinsic viscosity (IV) of 1.0 to 1.4,
(2) a blend resin film of 30 parts by weight of PBT resin and 70 parts by weight of polyethylene terephthalate (PET) resin,
(3) Blend resin film of 70 parts by weight of PBT resin and 30 parts by weight of polycarbonate resin,
TMA-related value (° C.) = Tse−Tss,
here,
The softening start temperature Tss (° C.) is measured by TMA,
The penetration depth of the needle into the film when a load of 100 g is applied to a needle with a tip of R = 0.2 or less (tip angle 60 °) at 2 mmφ and the temperature is raised at 10 ° C./min according to JIS-K-7196. In the curve obtained by measurement,
The extension of the straight line portion that is recognized on the low temperature side from the start of the needle to the high temperature side,
It is the temperature obtained by the intersection with the extension of the tangent of the part where the approach speed is maximum to the low temperature side,
The softening end temperature Tse (° C.) is the extension of the tangential line where the entry speed is maximum to the high temperature side,
This is the temperature obtained by the intersection with the extension of the straight line portion observed on the high temperature side after the end of softening to the low temperature side.
彫刻ロールによる圧下処理でエンボス処理加工を行う場合において、冷却ロールが樹脂フィルムと接触する部分の表面温度Ｔｒを、ＴＭＡにより測定される軟化開始温度であるＴｓｓを基準として、Ｔｓｓ±１０（℃）の範囲に設定してエンボス加工処理し、
この樹脂フィルムを金属板に被覆することを特徴とする化粧金属板の製造方法。
（１）固有粘度（ＩＶ）が１．０〜１．４のポリブチレンテレフタレート（ＰＢＴ）樹脂フィルム、
（２）ＰＢＴ樹脂３０重量部とポリエチレンテレフタレート（ＰＥＴ）樹脂７０重量部とのブレンド樹脂フィルム、
（３）ＰＢＴ樹脂７０重量部とポリカーボネート樹脂３０重量部とのブレンド樹脂フィルム、
ここで、
軟化開始温度Ｔｓｓ（℃）は、ＴＭＡにより測定され、
２ｍｍφで先端Ｒ＝０．２以下（先端角６０°）の針に荷重１００ｇをかけ、１０℃／ｍｉｎで昇温した時の針のフィルムへの進入深さをＪＩＳ−Ｋ−７１９６に準じて測定して得られた曲線における、
針が進入を始めるよりも低温側に認められる直線部分の高温側への延長と、
進入速度が最大となる部分の接線の低温側への延長との交点により求められる温度であり、
軟化終了温度Ｔｓｅ（℃）は、上記進入速度が最大となる部分の接線の高温側への延長と、
軟化終了後の高温側に認められる直線部分の低温側への延長との交点により求められる温度である。 A resin film having a TMA (Thermo Mechanical Analysis) relation value given by the following formula is selected from the following (1) to (3) :
When embossing processing is performed by a reduction process using an engraving roll, the surface temperature Tr of the portion where the cooling roll comes into contact with the resin film is defined as Tss ± 10 (° C.) based on Tss, which is the softening start temperature measured by TMA. Set to the range of embossing processing,
A method for producing a decorative metal plate, comprising coating a metal plate with the resin film.
(1) a polybutylene terephthalate (PBT) resin film having an intrinsic viscosity (IV) of 1.0 to 1.4,
(2) a blend resin film of 30 parts by weight of PBT resin and 70 parts by weight of polyethylene terephthalate (PET) resin,
(3) Blend resin film of 70 parts by weight of PBT resin and 30 parts by weight of polycarbonate resin,
here,
The softening start temperature Tss (° C.) is measured by TMA,
The penetration depth of the needle into the film when a load of 100 g is applied to a needle with a tip of R = 0.2 or less (tip angle 60 °) at 2 mmφ and the temperature is raised at 10 ° C./min according to JIS-K-7196. In the curve obtained by measurement,
The extension of the straight line portion that is recognized on the low temperature side from the start of the needle to the high temperature side,
It is the temperature obtained by the intersection with the extension of the tangent of the part where the approach speed is maximum to the low temperature side,
The softening end temperature Tse (° C.) is the extension of the tangential line where the entry speed is maximum to the high temperature side,
This is the temperature obtained by the intersection with the extension of the straight line portion observed on the high temperature side after the end of softening to the low temperature side.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30915398 | 1998-10-29 | ||
| PCT/JP1999/006059 WO2000026282A1 (en) | 1998-10-29 | 1999-10-29 | Resin film excellent in embossing capability, embossing method, decorative metal sheet coated with the resin film |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005109251A Division JP2005281699A (en) | 1998-10-29 | 2005-04-05 | Resin film excellent in embossing processability, embossing processing method, and decorative metal sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP4141641B2 true JP4141641B2 (en) | 2008-08-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000579665A Expired - Fee Related JP4141641B2 (en) | 1998-10-29 | 1999-10-29 | Embossing processing method and manufacturing method of decorative metal plate |
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| Country | Link |
|---|---|
| JP (1) | JP4141641B2 (en) |
| AU (1) | AU6368299A (en) |
| TW (1) | TWI248452B (en) |
| WO (1) | WO2000026282A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7470386B2 (en) | 2004-04-26 | 2008-12-30 | Sipix Imaging, Inc. | Roll-to-roll embossing tools and processes |
| CN115697679A (en) * | 2020-08-28 | 2023-02-03 | 可隆工业株式会社 | Polyester film and method for producing same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60255416A (en) * | 1984-06-01 | 1985-12-17 | Mitsui Toatsu Chem Inc | Preparation of thermoplastic resin sheet with embossed pattern having large unevenness |
| JPH0668032B2 (en) * | 1986-04-21 | 1994-08-31 | 三井石油化学工業株式会社 | Skin material |
| JPH0939094A (en) * | 1995-08-03 | 1997-02-10 | Toyo Kohan Co Ltd | Production of laminated sheet |
| JPH10235734A (en) * | 1997-02-26 | 1998-09-08 | Sekisui Chem Co Ltd | Method of manufacturing embossed sheet |
-
1999
- 1999-10-28 TW TW088118631A patent/TWI248452B/en not_active IP Right Cessation
- 1999-10-29 JP JP2000579665A patent/JP4141641B2/en not_active Expired - Fee Related
- 1999-10-29 AU AU63682/99A patent/AU6368299A/en not_active Abandoned
- 1999-10-29 WO PCT/JP1999/006059 patent/WO2000026282A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2000026282A1 (en) | 2000-05-11 |
| AU6368299A (en) | 2000-05-22 |
| TWI248452B (en) | 2006-02-01 |
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