JP2018059012A - Polyester resin-based film for decorative sheet, and decorative sheet - Google Patents
Polyester resin-based film for decorative sheet, and decorative sheet Download PDFInfo
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- JP2018059012A JP2018059012A JP2016198611A JP2016198611A JP2018059012A JP 2018059012 A JP2018059012 A JP 2018059012A JP 2016198611 A JP2016198611 A JP 2016198611A JP 2016198611 A JP2016198611 A JP 2016198611A JP 2018059012 A JP2018059012 A JP 2018059012A
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- 229920001225 polyester resin Polymers 0.000 title claims abstract description 105
- 239000004645 polyester resin Substances 0.000 title claims abstract description 100
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 32
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 17
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 10
- 229920000728 polyester Polymers 0.000 claims description 8
- 238000003860 storage Methods 0.000 claims description 6
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical group OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 2
- 238000009864 tensile test Methods 0.000 claims description 2
- 238000010586 diagram Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 238000004049 embossing Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- -1 polytetramethylene Polymers 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 229920005672 polyolefin resin Polymers 0.000 description 4
- 238000007646 gravure printing Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000011120 plywood Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical class CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920006127 amorphous resin Polymers 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000010068 moulding (rubber) Methods 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
【解決課題】熱加工性に優れた化粧シート用ポリエステル樹脂系フィルム及び化粧シートを提供すること。【解決手段】少なくとも非晶性ポリエステル系樹脂（Ａ）と軟質ポリエステル系樹脂（Ｂ）を含有し、前記非晶性ポリエステル系樹脂（Ａ）と前記軟質ポリエステル系樹脂（Ｂ）の質量比が９５：５〜４０：６０であることを特徴とする化粧シート用ポリエステル樹脂系フィルム。【選択図】なし[Problem to be solved] It is an object of the present invention to provide a polyester resin film for decorative sheets and a decorative sheet with excellent heat processability. [Solution] Contains at least an amorphous polyester resin (A) and a soft polyester resin (B), and the mass ratio of the amorphous polyester resin (A) and the soft polyester resin (B) is 95. :5 to 40:60. A polyester resin film for decorative sheeting. [Selection diagram] None
Description
本発明は、化粧シート用ポリエステル樹脂系フィルムに関し、更に詳しくは熱加工性に優れた化粧シート用のポリエステル樹脂系基材フィルム及びこれを用いた化粧シートに関する。 The present invention relates to a polyester resin film for a decorative sheet, and more particularly to a polyester resin base film for a decorative sheet excellent in heat processability and a decorative sheet using the same.
家具類や建築内装材等に用いられる化粧合板のような化粧材は、合板等の木材や鋼板等の下地材に、印刷・着色を施した化粧シートを貼り付けたものがよく知られており、この化粧シートの素材としては、紙、プラスチックフィルムが広く用いられている。 Cosmetic materials such as decorative plywood used for furniture and architectural interior materials are well known in that printed decorative sheets are pasted on base materials such as wood and steel plates such as plywood. As a material for the decorative sheet, paper and plastic film are widely used.
中でも、化粧シート用のプラスチックフィルムの素材としては、剛性と柔軟性のバランスが良好であるため、ポリオレフィン系の素材を用いたものが多くなってきている。 Among them, as a material for a plastic film for a decorative sheet, since a balance between rigidity and flexibility is good, those using a polyolefin-based material are increasing.
しかし、ポリオレフィン系樹脂は、一般的に結晶構造を有するために、融点を境にしてフィルム硬度が大きく変わる。そのため、フィルム硬度の調整は難しくなり、エンボス加工に適した加工温度の範囲が限られ、加工条件の設定が難しい。 However, since the polyolefin-based resin generally has a crystal structure, the film hardness varies greatly with the melting point as a boundary. Therefore, it is difficult to adjust the film hardness, the processing temperature range suitable for embossing is limited, and it is difficult to set processing conditions.
また化粧シート用の素材としては、ポリオレフィン以外にポリエステル樹脂も用いられている。たとえば、特許文献１には、非晶質ポリエステル樹脂を主成分とする基材フィルム層と、特定の非晶質ポリエステル樹脂と結晶性を有する特定の晶質ポリエステル樹脂からなる保護フィルム層を積層した化粧シートの技術が開示されている。 In addition to polyolefin, polyester resin is also used as a material for the decorative sheet. For example, in Patent Document 1, a base film layer mainly composed of an amorphous polyester resin and a protective film layer made of a specific amorphous polyester resin and a specific crystalline polyester resin having crystallinity are laminated. Techniques for decorative sheets are disclosed.
ポリエステル樹脂を使用した化粧シート用の基材フィルムは、結晶性や非晶性のポリエステル樹脂を適宜調整した技術が発明されているが、いずれもプレス成形やエンボス加工性などの熱加工性としては十分なものではなかった。 The base film for decorative sheets using polyester resin has been invented by adjusting the crystalline or amorphous polyester resin as appropriate, but all of them have thermal processability such as press molding and embossability. It was not enough.
本発明者等は、鋭意検討したところ、非晶性ポリエステル系樹脂（Ａ）と軟質ポリエステル系樹脂（Ｂ）を特定の比率で混合することで、熱加工性に優れる技術、特にエンボス加工性に優れる化粧シート用ポリエステル樹脂系フィルムを見出し、以下の本発明に至った。 As a result of diligent investigations, the present inventors have mixed amorphous polyester resin (A) and soft polyester resin (B) at a specific ratio, thereby achieving excellent heat workability, particularly embossability. The present inventors have found an excellent polyester resin film for decorative sheets and have reached the following present invention.
本発明は、熱加工性に優れた化粧シート用ポリエステル樹脂系フィルム及び化粧シートを提供することを主な目的とする。 The main object of the present invention is to provide a polyester resin film for a decorative sheet and a decorative sheet that are excellent in heat processability.
すなわち、本発明は、
［１］少なくとも非晶性ポリエステル系樹脂（Ａ）と軟質ポリエステル系樹脂（Ｂ）を含有し、前記非晶性ポリエステル系樹脂（Ａ）と前記軟質ポリエステル系樹脂（Ｂ）の質量比が９５：５〜４０：６０であることを特徴とする化粧シート用ポリエステル樹脂系フィルム。
［２］前記非晶性ポリエステル系樹脂（Ａ）は、シクロヘキサンジメタノール変性ポリエステル系樹脂であることを特徴とする［１］に記載の化粧シート用ポリエステル樹脂系フィルム。
［３］前記非晶性ポリエステル系樹脂（Ａ）は、１，４−シクロヘキサンジメタノール残基を６０ｍｏｌ％（グリコール成分全体に対する）以下含有することを特徴とする［１］又は［２］に記載の化粧シート用ポリエステル樹脂系フィルム。
［４］前記軟質ポリエステル系樹脂（Ｂ）は、ＪＩＳ Ｋ７１２７に準拠する引張試験において降伏点を有しないことを特徴とする［１］〜［３］のいずれか１項に記載の化粧シート用ポリエステル樹脂系フィルム。
［５］前記フィルムは、貯蔵弾性率（周波数１０Ｈｚ）より得られる７．０×１０６における温度（Ｔ１）と、３．０×１０６における温度（Ｔ２）において、下記式（１）より得られるΔＴが、３０（℃）以上であることを特徴とする［１］〜［４］のいずれか１項に記載の化粧シート用ポリエステル樹脂系フィルム。
式（１）・・・ Ｔ２（℃）−Ｔ１（℃）＝ ΔＴ（℃）
［６］［１］〜［５］のいずれか１項に記載の化粧シート用ポリエステル樹脂系フィルムを基材層として含む化粧シート。
を提供するものである。
That is, the present invention
[1] At least the amorphous polyester resin (A) and the soft polyester resin (B) are contained, and the mass ratio of the amorphous polyester resin (A) to the soft polyester resin (B) is 95: A polyester resin film for a decorative sheet, which is 5 to 40:60.
[2] The polyester resin film for decorative sheets according to [1], wherein the amorphous polyester resin (A) is a cyclohexanedimethanol-modified polyester resin.
[3] The amorphous polyester resin (A) contains 1,4-cyclohexanedimethanol residue in an amount of 60 mol% or less (relative to the entire glycol component), according to [1] or [2] Polyester resin film for decorative sheets.
[4] The polyester for decorative sheets according to any one of [1] to [3], wherein the soft polyester resin (B) does not have a yield point in a tensile test based on JIS K7127. Resin film.
[5] The film is obtained from the following formula (1) at a temperature (T1) at 7.0 × 10 6 and a temperature (T2) at 3.0 × 10 6 obtained from the storage elastic modulus (frequency 10 Hz). The polyester resin film for decorative sheets according to any one of [1] to [4], wherein ΔT is 30 (° C.) or more.
Formula (1) ... T2 (° C)-T1 (° C) = ΔT (° C)
[6] A decorative sheet comprising the polyester resin film for a decorative sheet according to any one of [1] to [5] as a base material layer.
Is to provide.
本発明によれば、熱加工性、特にエンボス加工性に優れた化粧シート用ポリエステル樹脂系フィルム及び化粧シートを提供することが可能となる。 ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the polyester resin-type film for decorative sheets and decorative sheet excellent in heat workability, especially embossing property.
本発明の一つの態様は、少なくとも非晶性ポリエステル系樹脂（Ａ）と軟質ポリエステル系樹脂（Ｂ）を含有し、前記非晶性ポリエステル系樹脂（Ａ）と前記軟質ポリエステル系樹脂（Ｂ）の質量比が９５：５〜４０：６０である化粧シート用ポリエステル樹脂系フィルム（以下「本発明の化粧シート用ポリエステル樹脂系フィルム」ということもある。）である。 One embodiment of the present invention contains at least an amorphous polyester resin (A) and a soft polyester resin (B), and the amorphous polyester resin (A) and the soft polyester resin (B). It is a polyester resin film for decorative sheets (hereinafter also referred to as “the polyester resin film for decorative sheets of the present invention”) having a mass ratio of 95: 5 to 40:60.
本発明の化粧シート用ポリエステル樹脂系フィルムは、非晶性ポリエステル系樹脂（Ａ）と軟質ポリエステル系樹脂（Ｂ）の質量比を、９５：５〜４０：６０とすることが好ましく、９０：１０〜４０：６０とすることがより好ましく、９０：１０〜４５：５５とすることが更に好ましく、８５：１５〜４５：５５とすることがとりわけ好ましい。非晶性ポリエステル系樹脂（Ａ）と軟質ポリエステル系樹脂（Ｂ）の質量比を上記とすることで、フィルムの貯蔵弾性率の数値が７．０×１０６（Ｔ１）〜３．０×１０６（Ｔ２）となる温度域を広範囲とすることができる。これにより、化粧シート用ポリエステル樹脂系フィルムが適度な弾性の状態を広い温度域で保つことが可能となり、熱加工性（エンボス加工性など）を良好とすることができる。 In the polyester resin film for a decorative sheet of the present invention, the mass ratio of the amorphous polyester resin (A) and the soft polyester resin (B) is preferably 95: 5 to 40:60, and 90:10 It is more preferable to set to 40:60, still more preferably 90:10 to 45:55, and particularly preferably 85:15 to 45:55. By setting the mass ratio of the amorphous polyester-based resin (A) and the soft polyester-based resin (B) as described above, the storage elastic modulus of the film is 7.0 × 10 6 (T1) to 3.0 × 10. 6 (T2) can be a wide temperature range. Thereby, it becomes possible for the polyester resin film for decorative sheets to maintain an appropriate elastic state in a wide temperature range, and heat workability (such as embossability) can be improved.
［非晶性ポリエステル系樹脂］
非晶性ポリエステル系樹脂（Ａ）は、通常の成形加工条件下では殆ど結晶化することのない程度に結晶化速度を遅くしたポリエステル系樹脂であり、具体的には、例えば、テレフタル酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸と、エチレングリコール、テトラメチレングリコール等の脂肪族ジオールとの縮合重合反応において、ジカルボン酸成分としてたとえばセバシン酸、エイコ酸、ドデカンジオン酸、ダイマー酸、シクロヘキサンジカルボン酸等の長鎖脂肪族ジカルボン酸及び／又は脂環族ジカルボン酸を導入したり、及び／又は、グリコール成分として例えばポリエチレングリコール、ポリテトラメチレングリコール、シクロヘキサンジメタノール等のポリエーテル系ジオール及び／又は脂環族ジオールを導入する等して製造された共重合ポリエステル系樹脂を挙げることができる。最も代表的なものは、通称ＰＥＴＧ等として市販されているグリコール変性ポリエステル系樹脂であり、本発明の目的にも好ましく使用することができ、より好ましくは、シクロヘキサンジメタノール変性ポリエステル系樹脂を使用することができる。
なお、非晶性ポリエステル系樹脂（Ａ）としては、実質的に非晶性であれば良く、ごく一部に結晶構造を有していても良い。
[Amorphous polyester resin]
Amorphous polyester-based resin (A) is a polyester-based resin having a crystallization rate reduced to such an extent that it hardly crystallizes under normal molding processing conditions. Specifically, for example, terephthalic acid, naphthalene, etc. In the condensation polymerization reaction between an aromatic dicarboxylic acid such as dicarboxylic acid and an aliphatic diol such as ethylene glycol or tetramethylene glycol, as the dicarboxylic acid component, for example, sebacic acid, eicoic acid, dodecanedioic acid, dimer acid, cyclohexanedicarboxylic acid, etc. Long chain aliphatic dicarboxylic acid and / or alicyclic dicarboxylic acid and / or polyether component diol such as polyethylene glycol, polytetramethylene glycol, cyclohexanedimethanol and / or alicyclic as glycol component Made by introducing a group diol, etc. Copolymeric polyester resins. The most typical one is a glycol-modified polyester resin marketed under the common name PETG or the like, and can be preferably used for the purpose of the present invention, and more preferably a cyclohexanedimethanol-modified polyester resin is used. be able to.
The amorphous polyester resin (A) may be substantially non-crystalline and may have a very small crystal structure.
また、非晶性ポリエステル系樹脂（Ａ）は、ポリエチレンテレフタレートのグリコール成分に、シクロヘキサンジメタノールを共重合したグリコール変性ポリエチレンテレフタレートを使用した場合は、グリコール成分全体に対するシクロヘキサンジメタノール残基の割合が、６０ｍｏｌ％以下が好ましく、５０ｍｏｌ％以下がより好ましく、４０ｍｏｌ％以下がさらに好ましい。また、下限は特に限定しないが、５ｍｏｌ％以上が好ましく、１０ｍｏｌ％以上がより好ましく、２０ｍｏｌ％以上がさらに好ましい。グリコール成分におけるシクロヘキサンジメタノール残基の割合を上記範囲とすることで、樹脂の結晶化度を低減できるため、加熱したときの樹脂の硬度の変化がなだらかとなり、熱加工性という観点から好ましい。 In addition, when the non-crystalline polyester resin (A) is a glycol component of polyethylene terephthalate and a glycol-modified polyethylene terephthalate copolymerized with cyclohexane dimethanol is used, the ratio of the cyclohexane dimethanol residue to the entire glycol component is 60 mol% or less is preferable, 50 mol% or less is more preferable, and 40 mol% or less is more preferable. Moreover, although a minimum is not specifically limited, 5 mol% or more is preferable, 10 mol% or more is more preferable, and 20 mol% or more is further more preferable. By making the ratio of the cyclohexanedimethanol residue in the glycol component within the above range, the degree of crystallinity of the resin can be reduced. Therefore, the change in the hardness of the resin when heated is gentle, which is preferable from the viewpoint of thermal processability.
前記非晶性ポリエステル系樹脂（Ａ）の市販品としては、イーストマンケミカル社の「ＰＥＴＧ６７６３（商品名）」やＳＫケミカル社の「ＳＫＹＧＲＥＥＮ Ｓ２００８（商品名）」などが挙げられる。 Examples of commercially available amorphous polyester resins (A) include “PETG6763 (trade name)” manufactured by Eastman Chemical Co., “SKYGREEN S2008 (trade name)” manufactured by SK Chemical Co., Ltd.
［軟質ポリエステル系樹脂］
本発明の軟質ポリエステル系樹脂（Ｂ）は、温度１７５℃における溶融粘度が５０００〜４００００Ｐａ・ｓの範囲内にあり且つ破断点伸度が３００％以上であるポリエステル系樹脂のことをいう。また、このような軟質ポリエステル系樹脂（Ｂ）としては、例えば、テレフタル酸、イソフタル酸、ナフタレン−１，４−ジカルボン酸、ナフタレン−２，６−ジカルボン酸等の芳香族ジカルボン酸又はこれらのエステル形成誘導体を主成分とするジカルボン酸成分と、エチレングリコールを主成分とするものであり、全グリコール成分中にエチレングリコールが６０ｍｏｌ％以上含有されているグリコール成分との共重合体が挙げられる。
[Soft polyester resin]
The soft polyester resin (B) of the present invention refers to a polyester resin having a melt viscosity in the range of 5000 to 40000 Pa · s at a temperature of 175 ° C. and an elongation at break of 300% or more. Examples of such soft polyester resins (B) include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, and esters thereof. Examples thereof include a copolymer of a dicarboxylic acid component having a forming derivative as a main component and a glycol component having ethylene glycol as a main component and containing 60 mol% or more of ethylene glycol in all glycol components.
また、軟質ポリエステル系樹脂（Ｂ）としては、結晶性ポリエステル系樹脂、非晶性ポリエステル系樹脂のどちらも限定することなく使用することができる。中でも、非晶性ポリエステル系樹脂は、加熱したときの樹脂の硬度の変化がなだらかであるため、熱加工性という観点から好ましい。このような軟質ポリエステル系樹脂（Ｂ）としては、市販されているものを用いることができ、例えば、ベルポリエステルプロダクツ社製の「ＴＫ−ＦＬＸ」が挙げられる。 As the soft polyester resin (B), either a crystalline polyester resin or an amorphous polyester resin can be used without limitation. Among these, amorphous polyester resins are preferable from the viewpoint of thermal processability because the hardness of the resin changes gently when heated. As such a soft polyester resin (B), a commercially available product can be used, and examples thereof include “TK-FLX” manufactured by Bell Polyester Products.
軟質ポリエステル系樹脂（Ｂ）としては、グリコール成分中にエチレングリコールを６０〜７０ｍｏｌ％の範囲で含有したものを好ましく使用することができる。 As a soft polyester-type resin (B), what contained ethylene glycol in the range of 60-70 mol% in a glycol component can be used preferably.
前記軟質ポリエステル系樹脂（Ｂ）の市販品としては、ベルポリエステルプロダクツ社の「ＰＲＩＴ３０（商品名）」、同社「ＴＫ−ＦＬＸ（商品名）」などが挙げられる。 As a commercial item of the said soft polyester-type resin (B), "PRIT30 (brand name)" of Bell Polyester Products, the company "TK-FLX (brand name)", etc. are mentioned.
また、本発明の化粧シート用ポリエステル樹脂系フィルムは、当該フィルムの全質量に対して、非晶性ポリエステル系樹脂（Ａ）と軟質ポリエステル系樹脂（Ｂ）の合計質量を５０質量％以上とすることが好ましく、７０質量％以上とすることがより好ましく、９０質量％以上とすることが更に好ましい。非晶性ポリエステル系樹脂（Ａ）と軟質ポリエステル系樹脂（Ｂ）の合計質量を上記の範囲とすることにより、熱加工性（エンボス加工性など）をより良好とすることができる。 Moreover, the polyester resin-type film for decorative sheets of this invention makes the total mass of an amorphous polyester-type resin (A) and a soft polyester-type resin (B) 50 mass% or more with respect to the total mass of the said film. Preferably, it is more preferable to set it as 70 mass% or more, and it is still more preferable to set it as 90 mass% or more. By setting the total mass of the amorphous polyester resin (A) and the soft polyester resin (B) within the above range, the heat workability (such as embossability) can be further improved.
本発明の化粧シート用ポリエステル樹脂系フィルムは、貯蔵弾性率（周波数１０Ｈｚ）より得られる７．０×１０６における温度（Ｔ１）と、３．０×１０６における温度（Ｔ２）において、下記式（１）から得られるΔＴが３０（℃）以上であることが好ましい。下記式（１）より得られるΔＴが３０（℃）以上とすることにより、化粧シート用ポリエステル樹脂系フィルムを熱加工（エンボス加工など）する際、フィルムが適度な弾性の状態を広い温度域で保つことが可能となり、熱加工性（エンボス加工性など）を良好とすることがでる。また、ΔＴは、３２℃以上であることがより好ましく、３５℃以上であることが更に好ましい。
式（１）・・・ Ｔ２（℃）−Ｔ１（℃）＝ ΔＴ（℃）
The polyester resin film for decorative sheets of the present invention has the following formula at a temperature (T1) at 7.0 × 10 6 and a temperature (T2) at 3.0 × 10 6 obtained from the storage elastic modulus (frequency: 10 Hz). ΔT obtained from (1) is preferably 30 (° C.) or more. When ΔT obtained from the following formula (1) is 30 (° C.) or more, when the polyester resin film for decorative sheet is heat-processed (embossed, etc.), the film has an appropriate elastic state in a wide temperature range. It becomes possible to maintain the heat processing property (such as embossing property). ΔT is more preferably 32 ° C. or higher, and further preferably 35 ° C. or higher.
Formula (1) ... T2 (° C)-T1 (° C) = ΔT (° C)
更に本発明の化粧シート用ポリエステル樹脂系フィルムは、本発明の効果を著しく阻害しない範囲で他の樹脂や、改質剤、充填剤、可塑剤、滑剤、熱安定剤、酸化防止剤、帯電防止剤、難燃剤、紫外線吸収剤、光安定剤、抗菌・防カビ剤、顔料、染料などを適宜添加することができる。 Furthermore, the polyester resin film for decorative sheets of the present invention is not limited to other resins, modifiers, fillers, plasticizers, lubricants, heat stabilizers, antioxidants, antistatic agents, as long as the effects of the present invention are not significantly impaired. An agent, a flame retardant, an ultraviolet absorber, a light stabilizer, an antibacterial / antifungal agent, a pigment, a dye, and the like can be appropriately added.
本発明の化粧シート用ポリエステル樹脂系フィルムは、熱加工性、特にエンボス加工性に優れていることから、特に化粧シート用基材フィルムとして好適に使用することができる。 Since the polyester resin film for decorative sheets of the present invention is excellent in heat processability, particularly embossability, it can be suitably used particularly as a base film for decorative sheets.
＜化粧シート用ポリエステル樹脂系フィルムの製造方法＞
本発明の化粧シート用ポリエステル樹脂系フィルムの製造方法は、特に限定されることはなく、例えば、本発明の化粧シート用ポリエステル樹脂系で用いるポリエステル系樹脂の組成物を溶融混練して溶融樹脂組成物を得る工程、該溶融樹脂組成物を押出成形する工程、および、成形された溶融樹脂組成物を冷却する工程を有していてもよい。
<Method for producing polyester resin film for decorative sheet>
The method for producing a polyester resin film for a decorative sheet of the present invention is not particularly limited. For example, a composition of a polyester resin used in the polyester resin system for a decorative sheet of the present invention is melt-kneaded to obtain a molten resin composition. You may have the process of obtaining a thing, the process of extruding this molten resin composition, and the process of cooling the shape | molded molten resin composition.
溶融混練には、単軸押出機、二軸押出機などの公知の混合機を用いることができる。本発明の化粧シート用ポリエステル樹脂系で用いるポリエステル系樹脂の組成物の溶融温度は、樹脂の種類、混合比率、添加剤の有無や種類に応じて適宜決定されるが、溶融温度の下限は、例えば１６０℃以上、好ましくは、１８０℃以上であり、また、溶融温度の上限は、例えば２９０℃以下、好ましくは２７０℃以下である。かかる溶融温度の範囲内で成形することにより、ポリエステル系樹脂の熱劣化を生じることなく、外観良好なポリエステル系樹脂フィルムを成形することができる。 For melt kneading, a known mixer such as a single screw extruder or a twin screw extruder can be used. The melting temperature of the polyester resin composition used in the polyester resin system for decorative sheets of the present invention is appropriately determined according to the type of resin, the mixing ratio, the presence or absence of additives, and the type, but the lower limit of the melting temperature is For example, it is 160 ° C. or higher, preferably 180 ° C. or higher, and the upper limit of the melting temperature is, for example, 290 ° C. or lower, preferably 270 ° C. or lower. By molding within such a melting temperature range, a polyester resin film having a good appearance can be molded without causing thermal degradation of the polyester resin.
押出成形では、例えば、Ｔダイなどの金型を用いて、溶融樹脂の組成物を押出成形する。押出成形された溶融樹脂の組成物を冷却するには、例えば、冷却されたキャストロールなどの冷却機に、溶融樹脂の組成物を接触させ、急冷する。これにより、溶融樹脂の組成物が固化され、ポリエステル系樹脂フィルムが得られる。冷却温度は、溶融温度よりも低温であれば限定されないが、冷却温度の上限は、例えば８０℃以下、好ましくは、６０℃以下であり、また、冷却温度の下限は、例えば０℃以上、好ましくは、１０℃以上である。 In extrusion molding, for example, a molten resin composition is extruded using a mold such as a T-die. In order to cool the extruded molten resin composition, for example, the molten resin composition is brought into contact with a cooled cooling machine such as a cast roll and rapidly cooled. Thereby, the composition of molten resin is solidified and a polyester-type resin film is obtained. The cooling temperature is not limited as long as it is lower than the melting temperature, but the upper limit of the cooling temperature is, for example, 80 ° C. or less, preferably 60 ° C. or less, and the lower limit of the cooling temperature is, for example, 0 ° C. or more, preferably Is 10 ° C. or higher.
本発明のもう１つの態様は、本発明の化粧シート用ポリエステル樹脂系フィルムを基材層として含む化粧シートである。
このような化粧シートとしては、例えば、上記の化粧シート用ポリエステル樹脂系フィルム表層側に印刷層を形成し、その上に透明な表面層を積層したものが挙げられる。具体的には、本発明の化粧シート用ポリエステル樹脂系フィルムの片面または両面にコロナ処理を施し、プライマーを塗布し、この処理済みシート上にグラビア印刷により木目調の印刷を行い、さらに透明シートを貼り合わせてエンボス処理を施すことにより、本発明にかかる化粧シートを製造することができる。
Another aspect of the present invention is a decorative sheet comprising the polyester resin film for decorative sheet of the present invention as a base material layer.
Examples of such a decorative sheet include those in which a printing layer is formed on the surface of the polyester resin film for decorative sheets and a transparent surface layer is laminated thereon. Specifically, one side or both sides of the polyester resin film for decorative sheets of the present invention is subjected to corona treatment, a primer is applied, and a woodgrain printing is performed on the treated sheet by gravure printing, and a transparent sheet is further formed. The decorative sheet according to the present invention can be produced by pasting and embossing.
一般に化粧シートの表面には、化粧材の耐候性、耐摩耗性、耐擦傷性等を向上させるため表面層を設けることが多いが、この層はポリオレフィン系樹脂、ポリエステル系樹脂、アクリル系樹脂、ウレタン系樹脂等を積層又はコーティングすることにより形成できる。この表面層にエンボスを施してもよい。 In general, the surface of the decorative sheet is often provided with a surface layer in order to improve the weather resistance, abrasion resistance, scratch resistance, etc. of the decorative material. This layer is a polyolefin resin, polyester resin, acrylic resin, It can be formed by laminating or coating urethane resin or the like. You may emboss this surface layer.
印刷層は、顔料等を分散させたインクを用いて、グラビア印刷、オフセット印刷、オフセットグラビア印刷、シルクスクリーン印刷等の印刷をして形成する方法の他に、転写法によっても形成することができる。この印刷層と化粧材用基材シートとの密着性を向上するため、印刷を施す化粧材用基材シート面にコロナ処理を行っておくことが望ましい。また、前記基材シートと印刷層との間にプライマー層を設けると両者の接着性が更に向上するので好ましい。このプライマー層としては、例えば、塩素化ポリオレフィン樹脂、ポリエステル樹脂、エチレン−ビニルアルコール共重合体等を主成分とし、これに必要に応じ充填剤を添加した溶液を化粧シート用ポリエステル樹脂系フィルムの基材フィルム上に塗布等することにより形成される層が挙げられる。 The printing layer can be formed by a transfer method in addition to a method of performing printing such as gravure printing, offset printing, offset gravure printing, and silk screen printing using an ink in which a pigment or the like is dispersed. . In order to improve the adhesion between the printed layer and the base material sheet for decorative material, it is desirable to perform corona treatment on the surface of the base material sheet for decorative material to be printed. In addition, it is preferable to provide a primer layer between the substrate sheet and the printing layer because the adhesion between the two is further improved. As the primer layer, for example, a solution containing a chlorinated polyolefin resin, a polyester resin, an ethylene-vinyl alcohol copolymer or the like as a main component and a filler added thereto as necessary is used as a base for a polyester resin film for a decorative sheet. Examples thereof include a layer formed by coating on a material film.
以下に実施例および比較例を示し、本発明をさらに具体的に説明するが、本発明は、以下の実施例および比較例に限定されない。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples and comparative examples.
＜使用した材料＞
（非晶性ポリエステル樹脂）
Ａ：ＳＫケミカル社製、商品名「ＳＫＹＧＲＥＥＮ Ｓ２００８」
（軟質ポリエステル樹脂）
Ｂ−１：ベルポリエステルプロダクツ社製、商品名「ＰＲＩＴ３０」（結晶性）
Ｂ−２：ベルポリエステルプロダクツ社製、商品名「ＴＫ−ＦＬＸ」（非晶性）
（ポリオレフィン系樹脂）
Ｃ：日本ポリプロ社製、商品名「ＭＡ３Ｕ」（ポリプロピレン樹脂）
<Materials used>
(Amorphous polyester resin)
A: Product name “SKYGREEN S2008” manufactured by SK Chemical Co., Ltd.
(Soft polyester resin)
B-1: Bell Polyester Products, trade name “PRIT30” (crystalline)
B-2: Bell Polyester Products, trade name “TK-FLX” (amorphous)
(Polyolefin resin)
C: Product name “MA3U” (polypropylene resin), manufactured by Nippon Polypro Co., Ltd.
＜評価方法＞
＜Ｔ１、Ｔ２の測定方法＞
粘弾性の測定装置（アイティ計測（株）製、粘弾性スペクトロメーターＤＶＡ−２００）にて、測定の温度範囲を−１００〜２００℃、周波数１０Ｈｚ、昇温速度３℃／ｍｉｎで引張測定により貯蔵弾性率を測定した。貯蔵弾性率が７．０×１０６の温度をＴ１、貯蔵弾性率が３．０×１０６の温度をＴ２とした。
<Evaluation method>
<Measurement method of T1, T2>
Using a viscoelasticity measuring device (made by IT Measurement Co., Ltd., viscoelasticity spectrometer DVA-200), the temperature range of measurement is -100 to 200 ° C, the frequency is 10 Hz, and the temperature rising rate is 3 ° C / min. The elastic modulus was measured. The temperature at which the storage elastic modulus was 7.0 × 10 6 was T1, and the temperature at which the storage elastic modulus was 3.0 × 10 6 was T2.
＜熱加工性の評価＞
得られた化粧シート用フィルムをプレス機上で加熱軟化させた後、凹凸を有するエンボス版で加圧し、加工温度９０〜１５０℃の範囲において賦形した。
熱加工性の評価は、下記の基準で評価した。
○：均一にエンボス加工できて、エンボス版の離型性も良好
△：エンボスの均一性は若干劣るが、エンボス版の離型性は良好
×：エンボス加工が均一でない、またはエンボス版の離型性が悪い
<Evaluation of thermal processability>
The obtained decorative sheet film was heated and softened on a press machine, and then pressed with an embossed plate having irregularities, and shaped in a processing temperature range of 90 to 150 ° C.
Evaluation of thermal workability was evaluated according to the following criteria.
○: Embossing is uniform and the release property of the embossed plate is good. Δ: The uniformity of the embossed plate is slightly inferior, but the release property of the embossed plate is good. ×: Embossing is not uniform or the release of the embossed plate is released. Bad nature
＜化粧シート用フィルムの作成＞
（実施例１）
非晶性ポリエステル系樹脂（Ａ）を８５質量％、軟質ポリエステル系樹脂（Ｂ−１）を１５質量％の割合でドライブレンドし、得られた混合物を５０ｍｍφの押出機を使用したＴダイ成形機に投入し、樹脂温度２６０℃の条件で押出し、冷却水を通した金属製成形ロールとゴム製成形ロールでニップ成形を行い、厚み１００μｍの実施例１に係る化粧シート用フィルムを作製し、上記の評価を行った。結果は表１に示す。
<Creation of film for decorative sheet>
Example 1
A T-die molding machine using an amorphous polyester resin (A) and a dry blending of 85% by mass of soft polyester resin (B-1) at a ratio of 15% by mass, and the resulting mixture using a 50 mmφ extruder. , Extruded under conditions of a resin temperature of 260 ° C., nip-molded with a metal molding roll and a rubber molding roll through which cooling water was passed, to prepare a decorative sheet film according to Example 1 having a thickness of 100 μm, and Was evaluated. The results are shown in Table 1.
（実施例２）
配合した樹脂を、非晶性ポリエステル系樹脂（Ａ）を７５質量％、軟質ポリエステル系樹脂（Ｂ−２）を２５質量％とした以外は、実施例１と同様の条件で、実施例２に係る化粧シート用フィルムを作製し、上記の評価を行った。結果は表１に示す。
(Example 2)
Example 2 was carried out under the same conditions as in Example 1 except that the blended resin was changed to 75% by mass of the amorphous polyester resin (A) and 25% by mass of the soft polyester resin (B-2). Such a film for a decorative sheet was prepared and evaluated as described above. The results are shown in Table 1.
（実施例３）
配合した樹脂を、非晶性ポリエステル系樹脂（Ａ）を５０質量％、軟質ポリエステル系樹脂（Ｂ−２）を５０質量％とした以外は、実施例１と同様の条件で、実施例３に係る化粧シート用フィルムを作製し、上記の評価を行った。結果は表１に示す。
(Example 3)
Example 3 is the same as Example 1 except that the blended resin is 50% by mass of amorphous polyester resin (A) and 50% by mass of soft polyester resin (B-2). Such a film for a decorative sheet was prepared and evaluated as described above. The results are shown in Table 1.
（比較例１）
配合した樹脂を、非晶性ポリエステル樹脂（Ａ）を１００質量％とした以外は、実施例１と同様の条件で、比較例１に係る化粧シート用フィルムを作製し、上記の評価を行った。結果は表１に示す。
(Comparative Example 1)
A film for decorative sheet according to Comparative Example 1 was produced under the same conditions as in Example 1 except that the amorphous resin (A) was changed to 100% by mass, and the above evaluation was performed. . The results are shown in Table 1.
（比較例２）
配合した樹脂を、非晶性ポリエステル樹脂（Ａ）を３５質量％、軟質ポリエステル樹脂（Ｂ−１）６５質量％とした以外は、実施例１と同様の条件で、比較例２に係る化粧シート用フィルムを作製し、上記の評価を行った。結果は表１に示す。
(Comparative Example 2)
A decorative sheet according to Comparative Example 2 under the same conditions as in Example 1 except that the blended resin was 35% by mass of amorphous polyester resin (A) and 65% by mass of soft polyester resin (B-1). Films were prepared and evaluated as described above. The results are shown in Table 1.
（比較例３）
配合した樹脂を、ポリプロピレン樹脂（Ｃ）を１００質量％とした以外は、実施例１と同様の条件で、比較例３に係る化粧シート用フィルムを作製し、上記の評価を行った。結果は表１に示す。
(Comparative Example 3)
The film for decorative sheets which concerns on the comparative example 3 was produced on the conditions similar to Example 1 except having mix | blended resin 100 mass% of polypropylene resin (C), and said evaluation was performed. The results are shown in Table 1.
＜結果＞
表１より、実施例１〜３に係る化粧シート用フィルムはいずれも、本発明に規定するΔＴが好ましい範囲であり、熱加工性（エンボス加工性）に優れる結果であった。
一方、比較例１〜３の化粧シート用フィルムは、本発明に規定する配合比率から外れるため、ΔＴが小さい値となり、熱加工性が優れない結果となった。
<Result>
From Table 1, all the films for decorative sheets according to Examples 1 to 3 have a ΔT defined in the present invention in a preferable range, and are excellent in heat workability (embossability).
On the other hand, since the films for decorative sheets of Comparative Examples 1 to 3 deviated from the blending ratio specified in the present invention, ΔT was a small value, and the thermal processability was not excellent.
Claims (6)
式（１）・・・ Ｔ２（℃）−Ｔ１（℃）＝ ΔＴ（℃）
The film has ΔT obtained from the following formula (1) at a temperature (T1) at 7.0 × 10 6 obtained from the storage elastic modulus (frequency 10 Hz) and a temperature (T2) at 3.0 × 10 6 . It is 30 (degreeC) or more, The polyester resin film for decorative sheets of any one of Claims 1-4 characterized by the above-mentioned.
Formula (1) ... T2 (° C)-T1 (° C) = ΔT (° C)
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| JP2016198611A JP2018059012A (en) | 2016-10-07 | 2016-10-07 | Polyester resin-based film for decorative sheet, and decorative sheet |
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| JP2016198611A JP2018059012A (en) | 2016-10-07 | 2016-10-07 | Polyester resin-based film for decorative sheet, and decorative sheet |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020085286A1 (en) * | 2018-10-26 | 2020-04-30 | 三菱瓦斯化学株式会社 | Thermoplastic resin laminate |
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| JP2002129483A (en) * | 2000-10-20 | 2002-05-09 | Okamoto Ind Inc | Copolyester wallpaper |
| JP2003246916A (en) * | 2001-12-18 | 2003-09-05 | Riken Technos Corp | Flexible polyester decorative sheet composition and flexible polyester decorative sheet |
| JP2004091795A (en) * | 1998-02-06 | 2004-03-25 | Riken Technos Corp | Resin sheet |
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| JP2004091795A (en) * | 1998-02-06 | 2004-03-25 | Riken Technos Corp | Resin sheet |
| JP2002129483A (en) * | 2000-10-20 | 2002-05-09 | Okamoto Ind Inc | Copolyester wallpaper |
| JP2003246916A (en) * | 2001-12-18 | 2003-09-05 | Riken Technos Corp | Flexible polyester decorative sheet composition and flexible polyester decorative sheet |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020085286A1 (en) * | 2018-10-26 | 2020-04-30 | 三菱瓦斯化学株式会社 | Thermoplastic resin laminate |
| CN112912247A (en) * | 2018-10-26 | 2021-06-04 | 三菱瓦斯化学株式会社 | Thermoplastic resin laminate |
| KR20210080414A (en) * | 2018-10-26 | 2021-06-30 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Thermoplastic resin laminate |
| JPWO2020085286A1 (en) * | 2018-10-26 | 2021-09-16 | 三菱瓦斯化学株式会社 | Thermoplastic resin laminate |
| JP7272369B2 (en) | 2018-10-26 | 2023-05-12 | 三菱瓦斯化学株式会社 | Thermoplastic resin laminate |
| US11951720B2 (en) | 2018-10-26 | 2024-04-09 | Mitsubishi Gas Chemical Company, Inc. | Thermoplastic resin laminate |
| TWI841615B (en) * | 2018-10-26 | 2024-05-11 | 日商三菱瓦斯化學股份有限公司 | Thermoplastic resin laminate |
| KR102791358B1 (en) * | 2018-10-26 | 2025-04-03 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Thermoplastic resin laminate |
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