JPS63189227A - Manufacture of releasable polyester film - Google Patents
Manufacture of releasable polyester filmInfo
- Publication number
- JPS63189227A JPS63189227A JP2185387A JP2185387A JPS63189227A JP S63189227 A JPS63189227 A JP S63189227A JP 2185387 A JP2185387 A JP 2185387A JP 2185387 A JP2185387 A JP 2185387A JP S63189227 A JPS63189227 A JP S63189227A
- Authority
- JP
- Japan
- Prior art keywords
- polyester film
- heat treatment
- film
- polyolefin
- aqueous liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920006267 polyester film Polymers 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 229920000098 polyolefin Polymers 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000002425 crystallisation Methods 0.000 claims abstract description 10
- 230000008025 crystallization Effects 0.000 claims abstract description 10
- 238000011282 treatment Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 4
- -1 ethylene, propylene, butadiene Chemical class 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 13
- 229920001577 copolymer Polymers 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 9
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 239000000839 emulsion Substances 0.000 abstract description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 abstract description 2
- 239000007900 aqueous suspension Substances 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 2
- 229920002554 vinyl polymer Polymers 0.000 abstract description 2
- 150000001336 alkenes Chemical class 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000000465 moulding Methods 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000009775 high-speed stirring Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920001634 Copolyester Polymers 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000009998 heat setting Methods 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
- 238000007759 kiss coating Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 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 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- ZUHPIMDQNAGSOV-UHFFFAOYSA-N 2-benzyl-2-phenylpropanedioic acid Chemical compound C=1C=CC=CC=1C(C(=O)O)(C(O)=O)CC1=CC=CC=C1 ZUHPIMDQNAGSOV-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UUAGPGQUHZVJBQ-UHFFFAOYSA-N Bisphenol A bis(2-hydroxyethyl)ether Chemical compound C=1C=C(OCCO)C=CC=1C(C)(C)C1=CC=C(OCCO)C=C1 UUAGPGQUHZVJBQ-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000012773 agricultural material Substances 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000007860 aryl ester derivatives Chemical class 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は離型性ポリエステルフィルムの製造法に関し、
更に詳しくは滑り性を保持しかつ離型性に優れ、例えば
種々の条件下で流延又は注型される熱硬化型モールディ
ング樹脂、触媒反応型モールディング樹脂、ドライフォ
トレジスト或は焼成前のセラミックなどに対し優れた離
型性を長時間わたって維持・発現し得る二軸配向ポリエ
ステルフィルムからなる離型性フィルムの製造法に関す
る。[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a method for producing a releasable polyester film,
More specifically, it maintains slipperiness and has excellent mold releasability, such as thermosetting molding resins that are cast or cast under various conditions, catalytic reaction molding resins, dry photoresists, or ceramics before firing. The present invention relates to a method for producing a releasable film made of a biaxially oriented polyester film that can maintain and exhibit excellent releasability over a long period of time.
〈従来技術〉
芳香族二塩基酸或はそのエステル形成性誘導体とジオー
ル或はそのエステル形成性誘導体とから合成されるポリ
エステル（例えばポリエチレンテレフタレート、その共
重合体、ポリアルキレンナフタレート、又はそれと小割
合の他樹脂とのブレンド体等）をダイから溶融押出し、
急冷し、更に二軸延伸配向・結晶化したフィルムは、物
理的特性、耐熱性、ガス遮断性、Ｎ気的特性、耐薬品性
などに優れていることから磁気テープ、・Ｘ線写真。<Prior art> Polyesters synthesized from aromatic dibasic acids or their ester-forming derivatives and diols or their ester-forming derivatives (e.g., polyethylene terephthalate, copolymers thereof, polyalkylene naphthalates, or small proportions thereof) Blends with other resins, etc.) are melt extruded from a die,
Films that are rapidly cooled, then biaxially stretched and crystallized have excellent physical properties, heat resistance, gas barrier properties, N gas properties, and chemical resistance, so they can be used for magnetic tape, X-ray photography, etc.
箔巻きメタライズドコンデンサー、ケミカルマット、ジ
アゾ−フィルム、ＯＨＰ、ＦＰＣ，包装材及び農業用資
材などとして極めて多岐に亘って用いられている。It is used in a wide variety of applications such as foil-wrapped metallized capacitors, chemical mats, diazo films, OHPs, FPCs, packaging materials, and agricultural materials.
その使途分野の一つとして、ドライフォトレジスト用離
型フィルム、反応型のモールディング樹脂成形の際の隔
壁離型フィルム等の離型材の分野がある。これは二軸配
向ポリエステルフィルムが二軸方向に延伸され、結晶配
向を受けて高い表面凝集性を有しているため、一般に塗
料、接着剤及びインキの受容性に乏しく、この不活性な
表面状態を効果的に利用する用途分野であると云える。One of the fields in which it is used is in the field of mold release materials such as mold release films for dry photoresists and barrier wall mold release films used in reactive molding resin molding. This is because the biaxially oriented polyester film is stretched biaxially and has high surface cohesion due to crystal orientation, so it generally has poor receptivity to paints, adhesives, and inks, and this inert surface state It can be said that this is an application field that effectively utilizes.
しかし、ポリエステルフィルムにも改善すべき課題があ
る。例えばＦＲＰ成形の離型材料に用いた場合、ＦＲＰ
の硬化条件によっては、部分的に離型効果が乏しく、樹
脂と離型材とが付着する個所が現われたり、また、シー
トモールディング樹脂が加温されたような場合には、離
型材フィルムと樹脂の間に接着が生じることもあり、必
ずしも満足できるものではない。However, polyester films also have issues that need to be improved. For example, when used as a mold release material for FRP molding, FRP
Depending on the curing conditions, the mold release effect may be poor in some areas and the resin and mold release agent may adhere to each other, or if the sheet molding resin is heated, the mold release material film and the resin may not adhere to each other. Adhesion may occur between the two, which is not always satisfactory.
上述の問題は、同じ離型材料を繰り返し２〜３回使用す
る場合に特に生じ易く、また硬化促進のために、樹脂の
モールディング温度を高くしたような際にも生じ易い。The above-mentioned problem is particularly likely to occur when the same mold release material is used two or three times, and also when the molding temperature of the resin is raised to accelerate curing.
一方、ポリエステルフィルムに代る離型性能を備えたシ
ート材料としては、シリコン離型紙、ポリ四弗化エチレ
ン樹脂シートなどがある。もっとも、前者は耐熱性の点
で問題があり、紙個有の特性として湿潤状態での強度低
下が大きく、可撓性引き裂きに対しても弱いと云う問題
があって適切とは云えない。四弗化エチレン樹脂シート
材料の離型性はよいが、フィルムとしては不透明で内部
の性状を観察出来ないこと、高価格で汎用材料とは云え
ない。また、その共重合体は透明性、耐熱性が優れてい
るものの、熱変形が大きい欠点があるから、好適な離型
材料と云えない。On the other hand, sheet materials with mold release performance that can replace polyester films include silicone release paper and polytetrafluoroethylene resin sheets. However, the former is not suitable because it has problems in terms of heat resistance, the inherent characteristics of paper such as a large decrease in strength in a wet state, and weakness against flexible tearing. Tetrafluoroethylene resin sheet material has good mold releasability, but as a film it is opaque and the internal properties cannot be observed, and it is expensive and cannot be called a general-purpose material. Further, although the copolymer has excellent transparency and heat resistance, it has the disadvantage of large thermal deformation, so it cannot be said to be a suitable mold release material.
そこで、二軸配向ポリエステルフィルムの特性を利用し
て、その表面により一層の離型性を賦与する試みがなさ
れてきた。例えば、シリコーン樹脂を表面に薄く塗設せ
しめるものである。もっとも、この被覆フィルムは、製
造時に離型剤がフィルム表面に均一に拡がらず、斑点状
態となる傾向がある。不均一に塗膜が形成されると離型
剤が加工製品に転写される事があり、この被覆フィルム
の欠点の１つとなる。Therefore, attempts have been made to utilize the characteristics of biaxially oriented polyester films to impart even greater release properties to their surfaces. For example, a thin layer of silicone resin is applied to the surface. However, in this coated film, the release agent does not spread uniformly over the surface of the film during manufacture, and tends to become speckled. If the coating is formed unevenly, the release agent may be transferred to the processed product, which is one of the drawbacks of this coated film.
〈発明の目的〉
本発明の目的は、改善された離型性能を有するポリエス
テルフィルムの製造法を提供することにある。<Object of the Invention> An object of the present invention is to provide a method for producing a polyester film having improved mold release performance.
〈発明の構成・効果〉
本発明の目的は、本発明によれば、未延伸ポリエステル
フィルムに二軸延伸配向処理と結晶化熱処理を施して二
軸配向ポリエステルフィルムを製造する方法において、
延伸配向が完了していないポリエステルフィルム又は延
伸配向が完了しているが熱処理結晶化が完了していない
ポリエステルフィルムの少くとも片面にポリオレフィン
系水性液を塗設し、次いで乾燥処理と、延伸配向・熱処
理又は熱処理とを施して配向結晶化を完了させることを
特徴とする離型性ポリエステルフィルムの製造法によっ
て達成される。<Configuration/Effects of the Invention> According to the present invention, an object of the present invention is to provide a method for producing a biaxially oriented polyester film by subjecting an unstretched polyester film to a biaxial stretching orientation treatment and a crystallization heat treatment,
An aqueous polyolefin liquid is coated on at least one side of a polyester film that has not been completely stretched or oriented, or a polyester film that has been stretched and oriented but has not been heat-treated and crystallized, and then subjected to drying treatment, stretching and orientation. This is achieved by a method for producing a releasable polyester film characterized by completing oriented crystallization by heat treatment or heat treatment.
本発明で用いるポリオレフィン系水性液は、エチレン、
プロピレン、ブテン、ペンテン、ヘキセン、ブタジェン
、シクロペンタジェン、ヘキサジエン、イソブチン、イ
ソプレン等の如き不飽和脂肪族炭化水素の単独重合体或
はこれらの共重合体、又はこれらと他のビニル単量体と
の共重合体の水溶液、エマルジョン、水懸濁液などであ
る。オレフィン系重合体は２０００以上の分子量を有す
ることが好ましい。The polyolefin aqueous liquid used in the present invention includes ethylene,
Homopolymers of unsaturated aliphatic hydrocarbons such as propylene, butene, pentene, hexene, butadiene, cyclopentadiene, hexadiene, isobutyne, isoprene, etc., or copolymers thereof, or these and other vinyl monomers. copolymers, aqueous solutions, emulsions, aqueous suspensions, etc. It is preferable that the olefin polymer has a molecular weight of 2000 or more.
かかる水性液は、その製造法によって特に制限されるこ
とはなく、例えば（イ）オレフィン系重合体の加熱溶融
物を界面活性剤を含む熱水中に高速撹拌上添加して微分
散させる方法：（ワ）オレフィン系重合体の有機溶剤溶
液を界面活性剤を含む水中に高速撹拌上添加して微分散
させ、必要なら脱溶剤させる方法；（／す機械的に超微
粉砕したオレフィン系重合体を界面活性剤を含む水中に
安定分散化させる方法；に）アクリル酸やビニルスルホ
ン酸又はそれらのアルカリ金属塩、アミン塩、アンモニ
ウム塩、水酸基含有アクリレート、メチロール化アクリ
ルアミド等の親水ビニル単ｍ体とオレフィンの共重合体
を水に溶解、乳化２分散させる方法；（ホ）ポリオレフ
ィン系重合体と他の親水性高分子の混合物を水に乳化２
分散させる方法等で製造されたものを用いることができ
る。その際、ポリオレフィン系重合体の量は、水性液中
に含まれる全固形分に対し、５０〜１００ｗｔ％が好ま
しく、更には７０〜１００ｗｔ％が好ましい。また水性
液中の固形分濃度は、塗布方法にもよるが、１〜２０ｗ
ｔ％程度が好ましく、更には２〜１０ｗｔ％が程度が好
ましい。このポリオレフィン系水性液は、本発明の最も
大きな特徴である離型性の付与と云う効果を妨げない限
り、着色料、フィラー、触媒安定剤などの添加剤を添加
することは特に問題はない。Such an aqueous liquid is not particularly limited by its manufacturing method, and for example, (a) a method of finely dispersing a heated melt of an olefin polymer by adding it to hot water containing a surfactant with high speed stirring: (W) A method of adding an organic solvent solution of an olefin polymer to water containing a surfactant under high-speed stirring, finely dispersing it, and removing the solvent if necessary; A method for stably dispersing acrylic acid or vinyl sulfonic acid in water containing a surfactant; Method for dissolving and emulsifying an olefin copolymer in water 2 Dispersing method; (e) Emulsifying a mixture of a polyolefin polymer and other hydrophilic polymer in water 2
Those manufactured by a dispersion method or the like can be used. In this case, the amount of the polyolefin polymer is preferably 50 to 100 wt%, more preferably 70 to 100 wt%, based on the total solid content contained in the aqueous liquid. In addition, the solid content concentration in the aqueous liquid is 1 to 20w, depending on the application method.
It is preferably about t%, more preferably about 2 to 10 wt%. There is no particular problem in adding additives such as colorants, fillers, catalyst stabilizers, etc. to this polyolefin aqueous liquid as long as they do not interfere with the effect of imparting mold release properties, which is the most significant feature of the present invention.
ポリオレフィン系水性液の塗布方法は特別な方法をとる
必要は全くなく、公知のコーティング法を用いることで
何ら差し支えはない。即ちリバースコーティング、キス
コーティング、エアーナイフコーティング、スプレーコ
ーティング、ブラシユコーティング及びグラビアコーテ
ィングなどが適用できる。ポリオレフィン系水性液の塗
布後、溶媒を蒸発させることで、ポリエステルフィルム
表面上にポリオレフィン系重合体の被膜を形成すること
ができる。水溶媒の加熱蒸発はフィルムが形態を保持し
得る温度以下で行うことが好ましい。There is no need to use any special method for applying the polyolefin aqueous liquid, and any known coating method may be used. That is, reverse coating, kiss coating, air knife coating, spray coating, brush coating, gravure coating, etc. can be applied. After applying the polyolefin aqueous liquid, the solvent can be evaporated to form a polyolefin polymer coating on the surface of the polyester film. The heating and evaporation of the water solvent is preferably carried out at a temperature below which the film can maintain its shape.
本発明においてポリオレフィン系水性液を塗布するポリ
エステルフィルムは、延伸配向が完了していないポリエ
ステルフィルム、或は延伸配向が完了しているが熱処理
結晶化が完了していないポリエステルフィルムである。In the present invention, the polyester film to which the aqueous polyolefin liquid is applied is a polyester film that has not been completely stretched and oriented, or a polyester film that has been completely stretched and oriented but not yet heat-treated and crystallized.
ここで、゛延伸配向が完了していないポリエステルフィ
ルム″とは、未延伸（非結晶性）のポリエステルフィル
ム、−軸方向に延伸配向されたポリエステルフィルム。Here, the term "polyester film that has not been completely stretched and oriented" refers to an unstretched (non-crystalline) polyester film and a polyester film that has been stretched and oriented in the -axial direction.
所定の二軸延伸配向度には延伸（配向）されていない二
軸延伸ポリエステルフィルム（例えば、縦延伸−横延伸
−再縦延伸（及び／又は再横延伸）で所定の二軸延伸配
向度を有するフィルムを製造する場合の再縦延伸（及び
／又は再横延伸）に供する二軸延伸ポリエステルフィル
ム）等を包含する。このうち−軸方向に延伸配向された
ポリエステルフィルム、特に縦方向（長手方向）に延伸
配向されたポリエステルフィルムが好ましい。A biaxially stretched polyester film that has not been stretched (orientated) to a predetermined biaxial stretching orientation degree (for example, a biaxially stretched polyester film that has not been stretched (orientated) to a predetermined biaxial stretching orientation degree by longitudinal stretching-transverse stretching-re-longitudinal stretching (and/or re-transverse stretching) (biaxially stretched polyester film) which is subjected to longitudinal re-stretching (and/or transverse re-stretching) when producing a film with Among these, a polyester film stretched and oriented in the -axial direction, particularly a polyester film stretched and oriented in the longitudinal direction (longitudinal direction), is preferred.
ポリオレフィン系水性液の塗布に際し、ポリエステルフ
ィルムに、被覆物とのより高度な密着性を得るために予
めコロナ処理、プラズマ処理などの活性化処理やマット
加工、エンボッシング加工。When applying a polyolefin aqueous liquid, the polyester film is subjected to activation treatments such as corona treatment and plasma treatment, matte finishing, and embossing in advance to obtain higher adhesion to the coating.
サンドブラスト加工などを施すことは何らさしつかえな
く、むしろ好ましいことである。There is nothing wrong with applying sandblasting or the like, and it is actually preferable.
本発明において、ポリオレフィン系重合体の被覆厚みは
、効能が発現する最低限の膜厚でよく、いたづらに大き
な膜厚にする必要はない。好ましい厚みとしては０．０
１μ〜２μ位の範囲が適切である。In the present invention, the coating thickness of the polyolefin polymer may be the minimum thickness that exhibits its efficacy, and there is no need to make it extremely thick. The preferred thickness is 0.0
A range of about 1μ to 2μ is appropriate.
本発明においてポリエステルとは、芳香族二塩基酸或は
そのエステル形成性誘導体（例えば低級アルキルエステ
ル、アリールエステル等）とジオール或はそのエステル
形成性誘導体（例えば低級脂肪酸エステル、エチレンオ
キサイド等）とから合成される線状飽和ポリエステルで
ある。この芳香族二塩基酸としては例えばテレフタル酸
、イソフタル酸、２．６−ナフタリンジカルボン酸、
１．５−ナフタリンジカルボン酸、４．４’−（又は
３．４’−）ジフェニルジカルボン酸、 ４．４’
−（又は３．４’−）ジフェニルスルホンジカルボン酸
、４．４’−（又は３．４’−）ジフェニルエーテルジ
カルボン酸、 ４．４’ −（又は３．４’−）ジフ
ェニルエタンジカルボン酸等を挙げることができる。こ
れらのうちテレフタル酸、２，６−ナフタリンジカルボ
ン酸が好ましい。また、ジオールとしては、例えばエチ
レングリコール、トリメチレングリコール、テトラメチ
レングリコール、ヘキサメチレングリコール、オクタメ
チレングリコール。In the present invention, polyester refers to an aromatic dibasic acid or its ester-forming derivative (e.g., lower alkyl ester, aryl ester, etc.) and a diol or its ester-forming derivative (e.g., lower fatty acid ester, ethylene oxide, etc.). It is a linear saturated polyester that is synthesized. Examples of the aromatic dibasic acid include terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid,
1.5-naphthalene dicarboxylic acid, 4.4'-(or 3.4'-)diphenyldicarboxylic acid, 4.4'
-(or 3.4'-) diphenylsulfonedicarboxylic acid, 4.4'-(or 3.4'-) diphenyletherdicarboxylic acid, 4.4'-(or 3.4'-) diphenylethanedicarboxylic acid, etc. can be mentioned. Among these, terephthalic acid and 2,6-naphthalene dicarboxylic acid are preferred. Examples of diols include ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, and octamethylene glycol.
１．４−シクロヘキサンジメタツール、ネオペンチルグ
リコール、ジエチレングリコール等の如き脂肪族ジオー
ル、ハイドロキノン、レゾルシン。1. Aliphatic diols such as 4-cyclohexane dimetatool, neopentyl glycol, diethylene glycol, etc., hydroquinone, resorcinol.
２．２−ビス（４−ヒドロキシフェニル）プロパン。2.2-bis(4-hydroxyphenyl)propane.
ビス（４−ヒドロキシフェニル）スルホン、２．２−ビ
ス（４−ヒドロキシエトキシフェニル）プロパン等の如
き芳香族ジオールなどを挙げることができる。これらの
うちエチレングリコールが特に好ましい。Aromatic diols such as bis(4-hydroxyphenyl)sulfone, 2,2-bis(4-hydroxyethoxyphenyl)propane, and the like can be mentioned. Among these, ethylene glycol is particularly preferred.
ポリエステルの好ましい具体例としては、ポリエチレン
テレフタレート、エチレンテレフタレートを主たる繰返
し単位（好ましくは８０％以上の繰返し単位）とするコ
ポリエステル、ポリエチレン−２，６−ナフタレート、
エチレン−２，６−ナフタレートを主たる繰返し単位（
好ましくは８０％以上の繰返し単位）とするコポリエス
テル等を例示することができる。Preferred specific examples of polyesters include polyethylene terephthalate, copolyesters containing ethylene terephthalate as a main repeating unit (preferably 80% or more repeating units), polyethylene-2,6-naphthalate,
The main repeating unit is ethylene-2,6-naphthalate (
Examples include copolyesters having a repeating unit of preferably 80% or more.
本発明におけるポリエステルは、ポリマーが実質的に線
状である量範囲で３官能以上の多官能化合物を共重合せ
しめてもよく、またポリマー末端を単官能化合物を用い
て変性してもよい。The polyester in the present invention may be copolymerized with a trifunctional or higher polyfunctional compound in an amount such that the polymer is substantially linear, or the terminal end of the polymer may be modified with a monofunctional compound.
本発明におけるポリエステルは、当然のことながらフィ
ルム形成能を有するものであり、例えばポリエチレンテ
レフタレートでは通常０．４以上、□ 好ましくは０
．５以上の固有粘度（オルソクロロフェノール、２５℃
）を有するものである。The polyester in the present invention naturally has a film-forming ability, and for example, polyethylene terephthalate usually has a film-forming ability of 0.4 or more, preferably 0.
．． Intrinsic viscosity of 5 or more (orthochlorophenol, 25℃
).
本発明における未延伸ポリエステルフィルムは、かかる
ポリエステルをダイから溶融押出し、急冷することで製
造できる。通常は、ダイから押出した溶融物をギヤステ
ィングドラムで急冷することで製造される。この未延伸
ポリエステルフィルムは、例えば当業界に知られた方法
で、二軸延伸配向処理及び結晶化熱処理を施して二軸配
向ポリエステルフィルムとする。この結晶化熱処理はヒ
ートセットとも呼ばれる処理である。二軸延伸配向は逐
次二軸延伸配向処理が好ましく、延伸倍率は一軸方向の
倍率が少くとも２倍、更には２．５倍以上であって面積
倍率が６倍以上、更には９倍以上であることが好ましい
。ヒートセットは１７０”Ｃ以上の４温度、更には１９
０℃以上の温度で数秒ないし数分間、更には５秒ないし
２０秒間行なうことが好ましい。The unstretched polyester film in the present invention can be produced by melt-extruding the polyester through a die and rapidly cooling it. Usually, it is manufactured by rapidly cooling the melt extruded from a die using a gearing drum. This unstretched polyester film is subjected to a biaxial stretching orientation treatment and a crystallization heat treatment, for example, by methods known in the art to obtain a biaxially oriented polyester film. This crystallization heat treatment is also called heat setting. The biaxial stretching orientation is preferably a sequential biaxial stretching orientation treatment, and the stretching ratio in the uniaxial direction is at least 2 times, more preferably 2.5 times or more, and the area magnification is 6 times or more, furthermore 9 times or more. It is preferable that there be. Heat set at 4 temperatures above 170"C, and even 19
It is preferable to carry out the reaction at a temperature of 0° C. or higher for several seconds to several minutes, more preferably for 5 seconds to 20 seconds.
本発明によれば、滑り性を保持しかつ離型性に優れた離
型性ポリエステルフィルムを得ることができ、該フィル
ムは例えば種々の条件下で流延又は注型される熱硬化型
モールディング樹脂、触媒反応型モールディング樹脂、
ドライフォトレジスト或は焼成前のセラミックなどに対
し優れた離型性を長時間にわたって維持２発現すること
ができる。According to the present invention, it is possible to obtain a releasable polyester film that maintains slipperiness and has excellent mold releasability, and the film can be used with thermosetting molding resins that are cast or cast under various conditions, for example , catalytic molding resin,
It is possible to maintain and exhibit excellent mold releasability over a long period of time for dry photoresist or ceramics before firing.
〈実施例〉 以下、実施例を挙げて本発明を更に説明する。<Example> The present invention will be further explained below with reference to Examples.
なお、ポリエステルフィルムの離型性は下記の方法によ
って評価した。In addition, the mold releasability of the polyester film was evaluated by the following method.
離型性：
スコッチ粘着テープ＃５４との接着力を１字剥離法によ
り測定し、５０ｇ／α巾以下を（０）：５０〜１５０ｇ
／ｃｍ巾を（△） ： １５０ｇ／ｃＷＩ巾以上を（
×）とした。Release property: Adhesive force with Scotch adhesive tape #54 was measured by single-character peeling method, and 50 g/α width or less (0): 50 to 150 g
/cm width (△): 150g/cWI width or more (
x).
参考例［ポリオレフィン系水性液の調製］く水性液Ａ〉
数平均分子［４８００のエチレン−プロピレン（５０：
５０）共重合体のｎ−ヘキサン溶液を９０℃のポリオキ
シエチレンノニル−フェニルエーテル１０％水溶液に高
速撹拌上添加して分散させたｌ、ｎ−ヘキサンを留去さ
せ、得られる水分散体を水で固形分濃度２％に希釈した
。Reference example [Preparation of polyolefin aqueous liquid] Aqueous liquid A> Number average molecule [4800 ethylene-propylene (50:
50) Add the n-hexane solution of the copolymer to a 10% aqueous polyoxyethylene nonyl-phenyl ether solution at 90°C with high speed stirring, distill off the dispersed l,n-hexane, and collect the resulting aqueous dispersion. It was diluted with water to a solids concentration of 2%.
く水性液Ｂ〉
エチレン−メタクリル！！（９５：５）共重合体をメタ
クリル酸と等当量の苛性カリを含む熱水溶液中に高速撹
拌上分散させた後、水で固形分濃度２％に希釈した。Aqueous liquid B> Ethylene-methacrylic! ! The (95:5) copolymer was dispersed with high speed stirring in a hot aqueous solution containing potassium hydroxide in an equivalent amount to methacrylic acid, and then diluted with water to a solid content concentration of 2%.
〈水性液Ｃ〉
エチレン−プロピレン−アクリル酸−酢酸ビニル（５０
： ４０： ７ ： ３ ’）共重合体の溶液をアクリ
ル酸と等当量のアンモニアを含む温水中に高速浣拌下添
加分散させた後、溶媒を留去した。次いで水で固形分濃
度２％に希釈させた後、アンモニア水でＩ）、Ｈ７，５
に調整した。<Aqueous liquid C> Ethylene-propylene-acrylic acid-vinyl acetate (50
: 40: 7: 3') A solution of the copolymer was added and dispersed in hot water containing an equivalent amount of ammonia to acrylic acid under high speed stirring, and then the solvent was distilled off. Next, after diluting with water to a solid content concentration of 2%, I), H7,5 with ammonia water
Adjusted to.
〈水性液Ｄ〉
水性液８９０重量部にブライマルＨＡ −１６（アクリ
ル系エマルジョン、日本アクリル製）の２％希釈液１０
重量部を加えた。<Aqueous liquid D> 890 parts by weight of aqueous liquid and 10% diluted solution of Brimal HA-16 (acrylic emulsion, manufactured by Nippon Acrylic)
Added parts by weight.
比較例１
２５℃のオルソクロロフェノール中で測定した固有粘度
０．６５のポリエチレンテレフタレートをエクストルー
ダーでダイから溶融押出し、これを４０℃に冷却したキ
ャスティングドラム上で静電印加を行いつつ急冷し、厚
さ３１０μｍの未延伸フィルムとし、続いてこれを９３
℃に加熱した金属ロール上で長手方向に３．５倍に延伸
し、次いでテンター内で９８℃の予熱ゾーンを通過させ
、１０５℃で横方向に３．５倍に延伸し、更に２２０℃
で７秒間熱固定を行い、２５μｍの厚さの二軸配向フィ
ルムを得た。Comparative Example 1 Polyethylene terephthalate with an intrinsic viscosity of 0.65 measured in orthochlorophenol at 25°C was melt-extruded from a die using an extruder, and then rapidly cooled on a casting drum cooled to 40°C while applying an electrostatic charge. This was made into an unstretched film with a thickness of 310 μm, and then this was
Stretched 3.5 times in the longitudinal direction on metal rolls heated to 100°C, then passed through a preheating zone at 98°C in a tenter, stretched 3.5 times in the transverse direction at 105°C, and further stretched at 220°C.
Heat setting was performed for 7 seconds to obtain a biaxially oriented film with a thickness of 25 μm.
このフィルムの離型テストの結果を表１に示す。Table 1 shows the results of the mold release test for this film.
実施例１
比較例１と同じ二軸配向フィルムの製法において、縦延
伸が終了した一軸延伸フイルムに前記の水性液Ａをキス
コート法で均一に塗布し、２００℃で約１０秒間乾燥し
た。塗布量は約４ｇ／ｍ（ウェット）であった。このフ
ィルムはしわもな（Ｄ−□ ル状に巻け、巻姿は良
好であった。このフィルムの離型テストの結果を表１に
示す。Example 1 In the same method for producing a biaxially oriented film as in Comparative Example 1, the aqueous liquid A was uniformly applied to a uniaxially oriented film that had been longitudinally stretched using a kiss coating method, and dried at 200° C. for about 10 seconds. The coating amount was approximately 4 g/m (wet). This film could be rolled into a wrinkle-free (D-□) shape, and the winding appearance was good. Table 1 shows the results of the release test for this film.
実施例２〜４ 実施例１において水性液Ａの代りに水性液Ｂ。Examples 2-4 In Example 1, aqueous liquid B was substituted for aqueous liquid A.
Ｃ，Ｄを用いること以外は実施例１と全く同様にして得
た二軸配向フィルムの離型性を表１に示す。Table 1 shows the releasability of the biaxially oriented film obtained in the same manner as in Example 1 except for using C and D.
これら二軸配向フィルムのロールの巻姿は良好であった
。The roll appearance of these biaxially oriented films was good.
表１
表１から、本発明のフィルムは高い離型性を有すること
が明らかである。Table 1 From Table 1, it is clear that the film of the present invention has high mold release properties.
Claims (1)
結晶化熱処理を施して二軸配向ポリエステルフィルムを
製造する方法において、延伸配向が完了していないポリ
エステルフィルム又は延伸配向が完了しているが熱処理
結晶化が完了していないポリエステルフィルムの少くと
も片面にポリオレフィン系水性液を塗設し、次いで乾燥
処理と、延伸配向・熱処理又は熱処理とを施して配向結
晶化を完了させることを特徴とする離型性ポリエステル
フィルムの製造法。 ２、ポリオレフィン系水性液を一軸延伸配向ポリエステ
ルフィルムの少くとも片面に塗設する特許請求の範囲第
１項記載の製造法。[Claims] 1. In a method for producing a biaxially oriented polyester film by subjecting an unstretched polyester film to a biaxial stretching orientation treatment and a crystallization heat treatment, a polyester film whose stretching orientation has not been completed or whose stretching orientation has been completed. Applying an aqueous polyolefin liquid to at least one side of a polyester film that has undergone heat treatment but has not yet undergone crystallization, and then performs drying treatment, stretching orientation/heat treatment, or heat treatment to complete oriented crystallization. A method for producing a releasable polyester film characterized by: 2. The manufacturing method according to claim 1, wherein a polyolefin aqueous liquid is coated on at least one side of a uniaxially stretched oriented polyester film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2185387A JPS63189227A (en) | 1987-02-03 | 1987-02-03 | Manufacture of releasable polyester film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2185387A JPS63189227A (en) | 1987-02-03 | 1987-02-03 | Manufacture of releasable polyester film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63189227A true JPS63189227A (en) | 1988-08-04 |
| JPH0562897B2 JPH0562897B2 (en) | 1993-09-09 |
Family
ID=12066667
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2185387A Granted JPS63189227A (en) | 1987-02-03 | 1987-02-03 | Manufacture of releasable polyester film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63189227A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03277677A (en) * | 1990-03-27 | 1991-12-09 | Hitachi Chem Co Ltd | Adhesive film for chemical plating and manufacture of printed wiring board |
| JP2009101680A (en) * | 2007-10-04 | 2009-05-14 | Unitika Ltd | Mold release sheet |
| JP2010158816A (en) * | 2009-01-08 | 2010-07-22 | Unitika Ltd | Mold releasing sheet |
| JP2012020429A (en) * | 2010-07-13 | 2012-02-02 | Unitika Ltd | Slippery polyester film and method of manufacturing the same |
| JP2014133420A (en) * | 2014-04-25 | 2014-07-24 | Unitika Ltd | Method of manufacturing easily slidable polyester film |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006150812A (en) * | 2004-11-30 | 2006-06-15 | Mitsubishi Polyester Film Copp | Release film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60192631A (en) * | 1984-03-14 | 1985-10-01 | ダイアホイルヘキスト株式会社 | Polyester film |
| JPS61255941A (en) * | 1985-05-10 | 1986-11-13 | Diafoil Co Ltd | Polyester film having coated layer |
-
1987
- 1987-02-03 JP JP2185387A patent/JPS63189227A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60192631A (en) * | 1984-03-14 | 1985-10-01 | ダイアホイルヘキスト株式会社 | Polyester film |
| JPS61255941A (en) * | 1985-05-10 | 1986-11-13 | Diafoil Co Ltd | Polyester film having coated layer |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03277677A (en) * | 1990-03-27 | 1991-12-09 | Hitachi Chem Co Ltd | Adhesive film for chemical plating and manufacture of printed wiring board |
| JP2009101680A (en) * | 2007-10-04 | 2009-05-14 | Unitika Ltd | Mold release sheet |
| JP2010158816A (en) * | 2009-01-08 | 2010-07-22 | Unitika Ltd | Mold releasing sheet |
| JP2012020429A (en) * | 2010-07-13 | 2012-02-02 | Unitika Ltd | Slippery polyester film and method of manufacturing the same |
| JP2014133420A (en) * | 2014-04-25 | 2014-07-24 | Unitika Ltd | Method of manufacturing easily slidable polyester film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0562897B2 (en) | 1993-09-09 |
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