JP6519267B2 - Release film - Google Patents
Release film Download PDFInfo
- Publication number
- JP6519267B2 JP6519267B2 JP2015066626A JP2015066626A JP6519267B2 JP 6519267 B2 JP6519267 B2 JP 6519267B2 JP 2015066626 A JP2015066626 A JP 2015066626A JP 2015066626 A JP2015066626 A JP 2015066626A JP 6519267 B2 JP6519267 B2 JP 6519267B2
- Authority
- JP
- Japan
- Prior art keywords
- release
- release film
- adhesive tape
- film
- release layer
- 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.)
- Active
Links
- 239000002390 adhesive tape Substances 0.000 claims description 27
- -1 polysiloxane Polymers 0.000 claims description 25
- 229920001296 polysiloxane Polymers 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 15
- 229920002050 silicone resin Polymers 0.000 claims description 14
- 238000012644 addition polymerization Methods 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 229920006267 polyester film Polymers 0.000 claims description 10
- 229920000742 Cotton Polymers 0.000 claims description 7
- 238000004299 exfoliation Methods 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 238000003475 lamination Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 239000010408 film Substances 0.000 description 58
- 239000010410 layer Substances 0.000 description 27
- 230000032683 aging Effects 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000012788 optical film Substances 0.000 description 9
- 125000003342 alkenyl group Chemical group 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000012790 adhesive layer Substances 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229910004283 SiO 4 Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 150000001282 organosilanes Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 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 group C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
Description
本発明は離型フィルムに関する。さらに詳しくは、安定した剥離力を有するシリコーン系離型フィルムに関する。 The present invention relates to a release film. More specifically, the present invention relates to a silicone-based release film having a stable peeling force.
液晶ディスプレイ（以下、ＬＣＤと呼ぶことがある）の製造プロセスにおいて、位相差フィルムや偏光板などの光学用フィルム部材に粘着剤層を付与するための透明粘着シートの重要性が高まっている。 In the manufacturing process of a liquid crystal display (hereinafter sometimes referred to as LCD), the importance of a transparent pressure-sensitive adhesive sheet for applying a pressure-sensitive adhesive layer to an optical film member such as a retardation film or a polarizing plate is increasing.
これらの用途に使用される透明粘着シートは光の透過性や透明性が重要であり、粘着層が２枚の離型フィルムに挟まれた構造により提供されている。すなわち基材としてのポリエステルフィルム上に離型層としてシリコーン樹脂を塗工した離型フィルムの離型層側へ、有機溶剤で希釈した粘着剤を塗工および乾燥させた後、もう一枚の離型フィルムを貼り合わせた構造であり、一方の離型フィルムを剥がしながら偏光板や位相差板とラミネートすることにより、これら光学用フィルムに粘着剤層を付与している。 The transparency and transparency of light are important for the transparent pressure-sensitive adhesive sheet used for these applications, and the pressure-sensitive adhesive layer is provided by a structure in which it is sandwiched between two release films. That is, after a pressure-sensitive adhesive diluted with an organic solvent is coated and dried on the release layer side of a release film in which a silicone resin is applied as a release layer on a polyester film as a substrate, another sheet is released. A pressure-sensitive adhesive layer is applied to these optical films by laminating it with a polarizing plate or a retardation plate while peeling off one of the mold release films.
この際に２枚の離型フィルムの剥離力に差を持たせて、まず軽い剥離力側の離型フィルムを確実に剥離し、光学用フィルム部材に貼合する。次に、比較的重い剥離力側の離型フィルムを剥すが、このとき剥離力が重すぎて粘着層を変形させるようなことがあってはならない。これら両側の２枚の離型フィルムの剥離力を適正な値とし、かつ経時や熱負荷により変化させないことが工程上重要であり、特に重い剥離力側の離型フィルムは、重すぎても軽すぎても実害に繋がる。 At this time, the release force of the two release films is given a difference, and the release film on the side of the light release force is reliably released first, and is bonded to the optical film member. Next, the release film on the relatively heavy release side is peeled off, but at this time, the release force should not be too heavy to deform the adhesive layer. It is important in the process to set the peel force of these two release films on both sides to an appropriate value and not change it with time or heat load, and in particular, the release film on the heavy release force side is light even if it is too heavy Too much will lead to harm.
離型フィルムの剥離力は、被着体である粘着剤の種類、厚さ、粘着剤の乾燥条件や粘着剤塗工後のエージング条件（一般的に、４０〜６０℃にて１〜２週間程度）などにより変化する。すなわち、同じ粘着剤を使用しても、粘着剤層が厚い場合や粘着剤の乾燥温度が高温になった場合、粘着剤塗工後のエージング時間が長くなると剥離は重くなる。 The release force of the release film is determined by the type and thickness of the pressure-sensitive adhesive which is the adherend, the drying conditions of the pressure-sensitive adhesive and the aging conditions after coating with the pressure-sensitive adhesive (generally, 1 to 2 weeks at 40 to 60 ° C. Change depending on the degree). That is, even if the same pressure-sensitive adhesive is used, when the pressure-sensitive adhesive layer is thick or when the drying temperature of the pressure-sensitive adhesive becomes high, the peeling becomes heavy as the aging time after the application of the pressure-sensitive adhesive is prolonged.
離型フィルムに使用されるシリコーン樹脂は一般に付加重合型のシリコーン樹脂であり、ＳｉＨ基とアルケニル基の付加重合反応により架橋された離型層が形成される。アルケニル基が残存すると硬化が不十分となるため、通常ＳｉＨ基／アルケニル基の比が１〜３の範囲で配合されており、ＳｉＨが多い状態となっている（特許文献１参照）。このため残存するＳｉＨが、粘着剤中の主成分（アクリル樹脂やウレタン樹脂等）や添加剤（シランカップリング剤や硬化剤）と反応するために重剥離化するものと考えられている。 The silicone resin used for the release film is generally an addition polymerization type silicone resin, and a release layer crosslinked is formed by the addition polymerization reaction of an SiH group and an alkenyl group. When the alkenyl group remains, the curing becomes insufficient. Therefore, the ratio of SiH group / alkenyl group is usually blended in the range of 1 to 3, and the SiH state is high (see Patent Document 1). For this reason, it is believed that residual SiH causes heavy peeling in order to react with the main components (acrylic resin, urethane resin, etc.) and additives (silane coupling agent, curing agent) in the adhesive.
この重剥離化を防ぐために、アルケニル基に対するＳｉＨ基の当量比をなるべく小さくして、残存するＳｉＨ基の量をできるだけ少なくすることが行われているが、その効果は十分ではなく、かえってアルケニル基が残存して硬化が不十分となるという問題があった。 In order to prevent this heavy exfoliation, the equivalent ratio of the SiH group to the alkenyl group is reduced as much as possible to reduce the amount of the remaining SiH group as much as possible. However, the effect is not sufficient. And there is a problem that the curing becomes insufficient.
すなわち、比較的重い剥離力を有し、かつ、剥離力が安定な離型フィルムが望まれている。 That is, a release film having a relatively heavy peeling force and having a stable peeling force is desired.
本発明の目的は、比較的重く、安定した剥離力を有する離型フィルムを提供することである。 An object of the present invention is to provide a release film which is relatively heavy and has a stable peeling force.
本発明は、課題を解決するために以下の手段を用いる。 The present invention uses the following means to solve the problems.
第１の発明は、二軸延伸ポリエステルフィルムの少なくとも片面に離型層が積層された離型フィルムであって、離型層がメチル水素化ポリシロキサンとメチルアルケニルポリシロキサンからなる付加重合型シリコーン樹脂及び重剥離化剤とからなり、離型層に粘着テープを貼り合わせ後の粘着テープ剥離力が１００ｍＮ／５０ｍｍ以上であり、下記（１）式で示される加熱重剥離化率が３０％未満であり、下記（２）式で示されるヘイズ減少が１％以下であることを特徴とする離型フィルムである。
加熱重剥離化率（％）＝｛（Ｈｂ−Ｈａ）／Ｈａ｝×１００ （１）
Ｈａ：粘着テープ貼り合わせ後、室温で２４時間放置後の粘着テープ剥離力（ｍＮ／５０ｍｍ）。
The first invention is a release film having a release layer laminated on at least one side of a biaxially stretched polyester film, wherein the release layer is an addition polymerization type silicone resin composed of methyl hydrogenated polysiloxane and methyl alkenyl polysiloxane. And a heavy release agent, and the adhesive tape peel force after bonding the adhesive tape to the release layer is 100 mN / 50 mm or more, and the heating heavy release ratio shown by the following formula (1) is less than 30% The release film is characterized in that the haze reduction represented by the following formula (2) is 1% or less.
Heating heavy exfoliation rate (%) = {(Hb-Ha) / Ha} x 100 (1)
Ha: Adhesive tape peeling force (mN / 50 mm) after leaving to stand at room temperature for 24 hours after adhesive tape lamination.
Ｈｂ：粘着テープ貼り合わせ後、７０℃２４時間加熱し、室温にまで放熱した状態における粘着テープ剥離力（ｍＮ／５０ｍｍ）。 Hb: Adhesive tape peeling force (mN / 50 mm) in a state of heating at 70 ° C. for 24 hours after adhering the adhesive tape and radiating heat to room temperature.
ヘイズ減少（％）＝Ｈｚｂ−Ｈｚａ （２）
Ｈｚａ：エタノールを浸み込ませた綿布で拭き取った後の離型フィルムのヘイズ（％）
Ｈｚｂ：上記拭き取り前の離型フィルムのヘイズ（％）
第２の発明は、二軸延伸ポリエステルフィルムの少なくとも片面にメチル水素化ポリシロキサンとメチルアルケニルポリシロキサンからなる付加重合型シリコーン樹脂及び重剥離化剤とからなる離型層を形成した後、７０℃以上１００℃未満の温度で２４時間以上のエージング処理を施すことを特徴とする離型フィルムの製造方法である。
Haze reduction (%) = Hzb-Hza (2)
Hza: Haze of release film after wiping off with a cotton cloth soaked with ethanol (%)
Hzb: Haze (%) of release film before wiping
In the second invention, after forming a release layer composed of an addition polymerization type silicone resin composed of methyl hydrogenated polysiloxane and methyl alkenyl polysiloxane and a heavy release agent on at least one side of a biaxially stretched polyester film, 70 ° C. It is a manufacturing method of the release film characterized by performing an aging process for 24 hours or more at the temperature of less than 100 degreeC.
本発明により、比較的重く、安定した剥離力を有する離型フィルムを提供することができる。 According to the present invention, it is possible to provide a relatively heavy release film having a stable peeling force.
以下に具体例を挙げつつ、本発明について詳細に説明する。 The present invention will be described in detail by way of specific examples.
本発明は、二軸延伸ポリエステルフィルムの少なくとも片面に離型層が積層された離型フィルムであって、離型層がメチル水素化ポリシロキサンとメチルアルケニルポリシロキサンからなる付加重合型シリコーン樹脂及び重剥離化剤とからなり、離型層に粘着テープを貼り合わせ後の粘着テープ剥離力が１００ｍＮ／５０ｍｍ以上であり、下記（１）式で示される加熱重剥離化率が３０％未満であり、下記（２）式で示されるヘイズ減少が１％以下であることを特徴とする離型フィルムである。 The present invention is a release film in which a release layer is laminated on at least one surface of a biaxially stretched polyester film, wherein the release layer comprises an addition polymerization silicone resin and a heavy metal consisting of methyl hydrogenated polysiloxane and methyl alkenyl polysiloxane. The adhesive tape peel force after bonding the adhesive tape to the release layer is 100 mN / 50 mm or more, and the heating heavy release rate shown by the following equation (1) is less than 30%, It is a release film characterized by the haze reduction shown by following (2) Formula being 1% or less.
加熱重剥離化率（％）＝｛（Ｈｂ−Ｈａ）／Ｈａ｝×１００ （１）
Ｈａ：粘着テープ貼り合わせ後、室温で２４時間放置後の粘着テープ剥離力（ｍＮ／５０ｍｍ）。
Heating heavy exfoliation rate (%) = {(Hb-Ha) / Ha} x 100 (1)
Ha: Adhesive tape peeling force (mN / 50 mm) after leaving to stand at room temperature for 24 hours after adhesive tape lamination.
Ｈｂ：粘着テープ貼り合わせ後、７０℃２４時間加熱し、室温にまで放熱した状態における粘着テープ剥離力（ｍＮ／５０ｍｍ）。 Hb: Adhesive tape peeling force (mN / 50 mm) in a state of heating at 70 ° C. for 24 hours after adhering the adhesive tape and radiating heat to room temperature.
ヘイズ減少（％）＝Ｈｚｂ−Ｈｚａ （２）
Ｈｚａ：エタノールを浸み込ませた綿布で拭き取った後の離型フィルムのヘイズ（％）。
Haze reduction (%) = Hzb-Hza (2)
Hza: Haze (%) of the release film after wiping off with a cotton cloth impregnated with ethanol.
Ｈｚｂ：拭き取り前の離型フィルムのヘイズ（％）。 Hzb: haze (%) of the release film before wiping off.
本発明の離型フィルムは、エージング工程にて長時間の高温処理を行うため、耐熱性に優れた基材を使用する必要があり、耐熱性に優れた二軸延伸ポリエステルフィルムを用いることが重要であり、なかでも二軸延伸ポリエチレンテレフタレートフィルムが機械強度、耐熱性、寸法安定性などのバランスから好ましい。 Since the release film of the present invention is subjected to high temperature treatment for a long time in the aging step, it is necessary to use a substrate excellent in heat resistance, and it is important to use a biaxially stretched polyester film excellent in heat resistance Among them, biaxially stretched polyethylene terephthalate film is preferable in view of the balance of mechanical strength, heat resistance, dimensional stability and the like.
これらの二軸延伸ポリエステルフィルムは、常法によって製造されたものでよく、厚さは１２〜１８８μｍの範囲が好ましく、表面粗さは特に限定されるものではないが、中心線平均表面粗さＲａが５〜５０ｎｍ程度のものを使用する。 These biaxially stretched polyester films may be produced by an ordinary method, the thickness is preferably in the range of 12 to 188 μm, and the surface roughness is not particularly limited, but the center line average surface roughness Ra Is about 5 to 50 nm.
本発明における離型層に使用される樹脂は、メチル水素化ポリシロキサンとメチルアルケニルポリシロキサンからなる付加重合型シリコーン樹脂である。これらポリシロキサンはジメチルポリシロキサンを基本構造とし、一部、メチル基の代わりに水素またはアルケニル基が導入されたものである。 The resin used for the release layer in the present invention is an addition polymerization type silicone resin composed of methyl hydrogenated polysiloxane and methyl alkenyl polysiloxane. These polysiloxanes have dimethylpolysiloxane as a basic structure, and in some cases, hydrogen or an alkenyl group is introduced instead of a methyl group.
メチル水素化ポリシロキサンのＳｉＨが、メチルアルケニルポリシロキサンのアルケニル基と白金触媒の存在下で付加重合反応により架橋し、強固な離型層を形成する。上記アルケニル基としては、ビニル基、アリル基、ブテニル基、ヘキセニル基などを例示することができるが、合成の容易性からビニル基によるメチルビニルポリシロキサンを使用することが好ましい。 The SiH of the methylhydrogenated polysiloxane is crosslinked by the addition polymerization reaction in the presence of the alkenyl group of the methylalkenylpolysiloxane and the platinum catalyst to form a strong release layer. Examples of the alkenyl group include vinyl group, allyl group, butenyl group and hexenyl group, but it is preferable to use methylvinylpolysiloxane with a vinyl group because of ease of synthesis.
使用される重剥離化剤としては、アルキド樹脂やアクリル樹脂、オルガノシランなどが挙げられる。オルガノシランとしては、シリコーンレジン、シランカップリング剤などがあり、いずれを用いても良いが、本発明においては、Ｍ単位（Ｒ３ＳｉＯ１／２）およびＱ単位（ＳｉＯ４／２)からなるＭＱレジンが好ましく、その構造中に付加重合型のシリコーン樹脂の中のアルケニル基、またはＳｉＨ基との架橋が得られる反応基を有していることが好ましい。 The heavy release agent to be used includes alkyd resin, acrylic resin, organosilane and the like. Examples of organosilanes include silicone resins and silane coupling agents, any of which may be used, but in the present invention, they are composed of M units (R 3 SiO 1/2 ) and Q units (SiO 4/2 ). MQ resin is preferable, and it is preferable to have a reactive group capable of obtaining crosslinking with an alkenyl group or an SiH group in an addition polymerization type silicone resin in the structure.
離型層の乾燥後塗工厚さは、好ましくは０．０２〜０．３μｍ、より好ましくは０．０３〜０．１μｍである。塗工厚さを０．０２〜０．３μｍとすることで、経済性良く離型性能を発現することができる。 The coating thickness after drying of the release layer is preferably 0.02 to 0.3 μm, more preferably 0.03 to 0.1 μm. By setting the coating thickness to 0.02 to 0.3 μm, the mold release performance can be expressed with good economy.
離型層を塗工、乾燥後、７０℃以上にて数日間以上、好ましくは９０℃にて数日間以上エージングすることにより、剥離力を安定化することができる。 The release force can be stabilized by aging the release layer at 70 ° C. or more for several days or more, preferably 90 ° C. for several days or more after coating and drying.
すなわち、本発明の離型フィルムは、離型層に粘着テープ（日東電工社製３１Ｂ）貼り合わせ後の粘着テープ剥離力が１００ｍＮ／５０ｍｍ以上であり、下記（１）式で示される加熱重剥離化率が３０％未満であることを特徴とする。 That is, the release film of the present invention has an adhesive tape peeling force of 100 mN / 50 mm or more after bonding an adhesive tape (31B manufactured by Nitto Denko Corporation) to the release layer, and the heating weight peeling shown by the following formula (1) Conversion rate is less than 30%.
加熱重剥離化率（％）＝｛（Ｈｂ−Ｈａ）／Ｈａ｝×１００ （１）
Ｈａ：粘着テープ貼り合わせ後、室温で２４時間放置後の粘着テープ剥離力（ｍＮ／５０ｍｍ）。
Heating heavy exfoliation rate (%) = {(Hb-Ha) / Ha} x 100 (1)
Ha: Adhesive tape peeling force (mN / 50 mm) after leaving to stand at room temperature for 24 hours after adhesive tape lamination.
Ｈｂ：粘着テープ貼り合わせ後、７０℃２４時間加熱し、室温にまで放熱した状態における粘着テープ剥離力（ｍＮ／５０ｍｍ）。 Hb: Adhesive tape peeling force (mN / 50 mm) in a state of heating at 70 ° C. for 24 hours after adhering the adhesive tape and radiating heat to room temperature.
加熱重剥離率が３０％を超えると、光学フィルム部材に粘着層とともに貼合されたあと、光学フィルム部材が熱処理を受けた場合に剥離が重くなり、剥離が困難になるか、剥離ができても粘着層にダメージを与えることになり好ましくない。 When the heating heavy peeling rate exceeds 30%, after the optical film member is bonded to the optical film member together with the adhesive layer, the peeling becomes heavy when the optical film member is subjected to heat treatment, and peeling becomes difficult or peeling is possible. It is not preferable because it damages the adhesive layer.
高温でエージングを行うと、二軸延伸ポリエチレンテレフタレートフィルムにはエチレンテレフタレートの基本ユニットが３つ環状に結合した環状三量体であるオリゴマー析出による白化が生じる場合がある。離型フィルムにオリゴマーが析出すると、位相差フィルムや偏光板などの光学用フィルム部材に粘着剤層を付与するための透明粘着シートにおいて重要である光の透過性や透明性を損ねることとなり、実用上の問題が発生するため、エージングは１００℃未満で実施することが重要である。 When aging is carried out at a high temperature, the biaxially stretched polyethylene terephthalate film may cause whitening due to oligomer precipitation which is a cyclic trimer in which three basic units of ethylene terephthalate are cyclically bonded. If oligomers are precipitated on the release film, the light transmission and transparency that are important in a transparent adhesive sheet for applying an adhesive layer to an optical film member such as a retardation film or a polarizing plate will be impaired, It is important to carry out the aging at less than 100 ° C., as the above problems occur.
本発明の離型フィルムは、二軸延伸ポリエステルフィルムより析出するオリゴマー成分での汚染がない離型フィルムであって、離型フィルムの離型層表面、および背面に発生したオリゴマーを、エタノールを浸み込ませた綿布にて拭き取りをした後のヘイズ減少、すなわち（２）式が、１％以下であることを特徴とする。 The release film of the present invention is a release film free from contamination with an oligomer component precipitated from a biaxially oriented polyester film, and the ethanol generated on the release layer surface of the release film and the back surface is immersed in ethanol. It is characterized in that the haze reduction after wiping with embedded cotton cloth, that is, the expression (2) is 1% or less.
ヘイズ減少（％）＝Ｈｚｂ−Ｈｚａ （２）
Ｈｚａ: エタノールを浸み込ませた綿布で拭き取った後の離型フィルムのヘイズ値（％）
Ｈｚｂ：拭き取り前の離型フィルムのヘイズ値（％）
ヘイズ減少が１％を超える場合は、拭き取り前の離型フィルムに多量のオリゴマーが析出した状態であることを示しており、光学用フィルム部材に係わる離型フィルムに使用できない。ヘイズ減少は好ましくは０．５％未満である。
Haze reduction (%) = Hzb-Hza (2)
Hza: Haze value of release film after wiping off with a cotton cloth impregnated with ethanol (%)
Hzb: Haze value of release film before wiping (%)
When the haze reduction exceeds 1%, it indicates that a large amount of oligomers are precipitated on the release film before wiping, and it can not be used for the release film related to the optical film member. The haze reduction is preferably less than 0.5%.
本発明の離型フィルムは、二軸延伸ポリエステルフィルムの少なくとも片面にメチル水素化ポリシロキサンとメチルアルケニルポリシロキサンからなる付加重合型シリコーン樹脂及び重剥離化剤からなる離型層を形成し、７０℃以上１００℃未満の温度で２４時間以上のエージング処理を施すことにより製造することができる。エージング処理時間の上限は特には設けられないが、経済性の観点からは１ヶ月程度と推測される。 The release film of the present invention forms a release layer consisting of an addition polymerization type silicone resin consisting of methyl hydrogenated polysiloxane and methyl alkenyl polysiloxane and a heavy release agent on at least one side of a biaxially stretched polyester film, It can manufacture by giving the aging process for 24 hours or more at the temperature of less than 100 degreeC. Although the upper limit of the aging treatment time is not particularly set, it is estimated that it is about one month from the viewpoint of economy.
以下、実施例により本発明を詳述するが、本発明はこれらの実施例のみに限定されるものではない。 Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples.
（１）加熱重剥離化率（％）
離型層に粘着テープ（日東電工社製３１Ｂ）を５ｋｇゴムローラーで押さえながら一往復させて貼り合わせ、室温（２３±２℃）で２４時間放置後、引張り試験機にて、３００ｍｍ／ｍｉｎの速度で１８０°に引き剥した時の粘着テープ剥離力（ｍＮ／５０ｍｍ）をＨａとした。粘着テープ貼り合わせ後、熱風オーブンで７０℃２４時間加熱し、室温（２３±２℃）にまで放熱した状態における粘着テープ剥離力（ｍＮ／５０ｍｍ）をＨｂとした。加熱重剥離化率を下記（１）式で計算した。
(1) Heating heavy peeling rate (%)
A pressure-sensitive adhesive tape (31B manufactured by Nitto Denko Corporation) is reciprocated on the mold release layer while holding down with a 5 kg rubber roller, and after standing for 24 hours at room temperature (23 ± 2 ° C), 300 mm / min The adhesive tape peel force (mN / 50 mm) when peeled off at a speed of 180 ° was taken as Ha. After laminating the adhesive tape, the adhesive tape peeling force (mN / 50 mm) in a state of radiating heat to room temperature (23 ± 2 ° C.) by heating in a hot air oven for 24 hours was defined as Hb. The heating heavy exfoliation rate was calculated by the following equation (1).
加熱重剥離化率（％）＝｛（Ｈｂ−Ｈａ）／Ｈａ｝×１００ （１）
（２）ヘイズ減少（％）
離型フィルムの離型層表面、および背面を、エタノールを浸み込ませた綿布で拭き取った後のヘイズ減少を下記（２）式で計算した。ヘイズの測定は、日本電色工業製ヘイズメーターＮＤＨ２０００（ＪＩＳ Ｋ−７１３６に準拠、ＮＤＨ−２０００測定方法３）にて行った。
Heating heavy exfoliation rate (%) = {(Hb-Ha) / Ha} x 100 (1)
(2) Haze reduction (%)
The haze reduction after wiping off the release layer surface and release layer of the release film with a cotton cloth impregnated with ethanol was calculated by the following equation (2). The measurement of the haze was performed by Nippon Denshoku Industries haze meter NDH2000 (according to JIS K-7136, NDH-2000 measurement method 3).
ヘイズ減少（％）＝Ｈｚｂ−Ｈｚａ （２）
Ｈｚａ: エタノールを浸み込ませた綿布で拭き取った後の離型フィルムのヘイズ値（％）
Ｈｚｂ：拭き取り前の離型フィルムのヘイズ値（％）
［実施例１］
付加重合型シリコーン樹脂であるメチルビニルポリシロキサンおよびメチル水素化ポリシロキサンの溶剤溶液（ＫＳ３７０３、信越化学工業（株）製）３．５重量部、重剥離化剤として、ビニル基を有するＭ単位（Ｒ３ＳｉＯ１／２）およびＱ単位（ＳｉＯ４／２）からなるＭＱレジンの溶剤溶液（ＫＳ３８００、信越化学工業（株）製）１．５重量部、硬化剤として白金の錯体溶液（ＰＬ−５０Ｔ、信越化学工業（株）製）０．０９重量部、トルエン／ヘプタン（５０／４５）混合液９５重量部を混合した離型層塗工液Ａを作成した。
Haze reduction (%) = Hzb-Hza (2)
Hza: Haze value of release film after wiping off with a cotton cloth impregnated with ethanol (%)
Hzb: Haze value of release film before wiping (%)
Example 1
3.5 parts by weight of a solvent solution (KS 3703, Shin-Etsu Chemical Co., Ltd. product) of methyl vinyl polysiloxane and methyl hydrogenated polysiloxane which are addition polymerization type silicone resins, M unit having vinyl group as heavy release agent ( 1.5 parts by weight of a solvent solution (KS 3800, manufactured by Shin-Etsu Chemical Co., Ltd.) of MQ resin consisting of R 3 SiO 1/2 ) and Q unit (SiO 4/2 ), a complex solution of platinum (PL-) as a curing agent A release layer coating liquid A was prepared by mixing 50 T, 0.09 parts by weight of Shin-Etsu Chemical Co., Ltd., and 95 parts by weight of a toluene / heptane (50/45) mixed liquid.
厚さ３８μｍの東レ（株）社製ポリエチレンテレフタレートフィルム、“ルミラー”（登録商標）Ｒ７５Ｘの片面に、離型層塗工液Ａを１５００ｍｍ幅の通常のグラビアコーターで塗布し、１５０℃オーブンで２０秒間脱溶剤および硬化反応させ、巻き取ったフィルムロールを８５℃×７日間エージングし離型フィルムを得た。 Release layer coating solution A is applied on one side of a 38 μm thick Toray Industries, Inc. polyethylene terephthalate film “Lumirror” (registered trademark) R75X with a conventional gravure coater having a width of 1500 mm, and 20 in an oven at 150 ° C. The solvent removal and curing reaction were conducted for a second, and the wound film roll was aged at 85 ° C. for 7 days to obtain a release film.
［実施例２］
実施例１において、エージングを７０℃×７日間とした以外は、実施例１と同様にして離型フィルムを得た。
Example 2
A release film was obtained in the same manner as in Example 1 except that the aging was changed to 70 ° C. × 7 days in Example 1.
［実施例３］
実施例１において、エージングを１００℃×７日間とした以外は、実施例１と同様にして離型フィルムを得た。
[Example 3]
A release film was obtained in the same manner as in Example 1 except that the aging was changed to 100 ° C. × 7 days.
［実施例４］
実施例１において、付加重合型シリコーン樹脂であるメチルビニルポリシロキサンおよびメチル水素化ポリシロキサンのトルエン溶液（ＫＳ３７０３、信越化学工業（株）製）４．０重量部、重剥離化剤としてビニル基を有するＭ単位（Ｒ３ＳｉＯ１／２）およびＱ単位（ＳｉＯ４／２）からなるＭＱレジンの溶剤溶液（ＫＳ３８００、信越化学工業（株）製）１．０重量部を混合し、硬化剤として白金の錯体溶液（ＰＬ−５０Ｔ、信越化学工業（株）製）０．０９重量部、トルエン／ヘプタン（５０／４５）混合液９５重量部を混合した離型層塗工液Ｂを使用した以外は、実施例１と同様にして離型フィルムを得た。
Example 4
In Example 1, 4.0 parts by weight of a toluene solution (KS 3703, Shin-Etsu Chemical Co., Ltd. product) of methyl vinyl polysiloxane and methyl hydrogenated polysiloxane which are addition polymerization type silicone resins, and a vinyl group as a heavy release agent 1.0 part by weight of a solvent solution (KS 3800, manufactured by Shin-Etsu Chemical Co., Ltd.) of an MQ resin consisting of M units (R 3 SiO 1/2 ) and Q units (SiO 4/2 ) having each other is mixed and used as a curing agent Except using a mold release layer coating liquid B in which 0.09 parts by weight of a complex solution of platinum (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) and 95 parts by weight of a toluene / heptane (50/45) mixed liquid are mixed A release film was obtained in the same manner as in Example 1.
［実施例５］
実施例４において、エージングを７０℃×７日間とした以外は、実施例４と同様にして離型フィルムを得た。
[Example 5]
A release film was obtained in the same manner as in Example 4 except that the aging was changed to 70 ° C. × 7 days in Example 4.
［実施例６］
実施例４において、エージングを１００℃×７日間とした以外は、実施例４と同様にして離型フィルムを得た。
[Example 6]
A release film was obtained in the same manner as in Example 4 except that the aging was changed to 100 ° C. × 7 days.
［比較例１］
実施例１において、エージングを５５℃×７日間とした以外は、実施例１と同様にして離型フィルムを得た。
Comparative Example 1
A release film was obtained in the same manner as in Example 1 except that aging was carried out at 55 ° C. for 7 days.
［比較例２］
実施例１において、エージングを１４０℃×７日間とした以外は、実施例１と同様にして離型フィルムを得た。
Comparative Example 2
A release film was obtained in the same manner as in Example 1 except that the aging was changed to 140 ° C. × 7 days in Example 1.
［比較例３］
実施例１において、エージングを施さなかったこと以外は、実施例１と同様にして離型フィルムを得た。
Comparative Example 3
A release film was obtained in the same manner as in Example 1 except that aging was not performed in Example 1.
［比較例４］
実施例４において、エージングを５５℃×７日間とした以外は、実施例４と同様にして離型フィルムを得た。
Comparative Example 4
A release film was obtained in the same manner as in Example 4 except that aging was carried out at 55 ° C. for 7 days.
［比較例５］
実施例４において、エージングを１４０℃×７日間とした以外は、実施例４と同様にして離型フィルムを得た。
［比較例６］
実施例４において、エージングを施さなかったこと以外は、実施例４と同様にして離型フィルムを得た。
Comparative Example 5
A release film was obtained in the same manner as in Example 4 except that the aging was changed to 140 ° C. × 7 days in Example 4.
Comparative Example 6
A release film was obtained in the same manner as in Example 4 except that aging was not performed in Example 4.
実施例１〜６、比較例１〜６を、加熱重剥離化率、およびヘイズ減少で評価した結果は、表１に示す。 Table 1 shows the results of evaluating Examples 1 to 6 and Comparative Examples 1 to 6 by the rate of thermal heavy peeling and the reduction in haze.
本発明の離型フィルムは、剥離が比較的重いにもかかわらず、安定した剥離力を有し、高温加熱後にも重剥離化が起きにくく、優れた離型特性を有するので、ＬＣＤの製造プロセスにおいて、位相差フィルムや偏光板などの光学用フィルム部材に粘着剤層を付与するための透明粘着シート離型に好適に用いられる。
The release film of the present invention has a stable release force despite the relatively heavy release, and it is difficult for heavy release to occur even after high temperature heating, and has excellent release characteristics, so the LCD manufacturing process In the above, it is suitably used for transparent adhesive sheet release for applying an adhesive layer to an optical film member such as a retardation film or a polarizing plate.
Claims (2)
加熱重剥離化率（％）＝｛（Ｈｂ−Ｈａ）／Ｈａ｝×１００ （１）
Ｈａ：粘着テープ貼り合わせ後、室温で２４時間放置後の粘着テープ剥離力（ｍＮ／５０ｍｍ）。
Ｈｂ：粘着テープ貼り合わせ後、７０℃２４時間加熱し、室温にまで放熱した状態における粘着テープ剥離力（ｍＮ／５０ｍｍ）。
ヘイズ減少（％）＝Ｈｚｂ−Ｈｚａ （２）
Ｈｚａ：エタノールを浸み込ませた綿布で拭き取った後の離型フィルムのヘイズ（％）。
Ｈｚｂ：拭き取り前の離型フィルムのヘイズ（％）。 A release film in which a release layer is laminated on at least one surface of a biaxially stretched polyester film, wherein the release layer is composed of an addition polymerization silicone resin and an MQ resin consisting of methyl hydrogenated polysiloxane and methyl alkenyl polysiloxane. And the adhesive tape peeling force after bonding the adhesive tape to the release layer is 100 mN / 50 mm or more, and the heating heavy peeling ratio shown by the following formula (1) is less than 30%, and by the following formula (2) haze reduction is shown Ri der than 1%, release film for adhesive sheet thickness of the release layer is characterized 0.02~0.3μm der Rukoto.
Heating heavy exfoliation rate (%) = {(Hb-Ha) / Ha} x 100 (1)
Ha: Adhesive tape peeling force (mN / 50 mm) after leaving to stand at room temperature for 24 hours after adhesive tape lamination.
Hb: Adhesive tape peeling force (mN / 50 mm) in a state of heating at 70 ° C. for 24 hours after adhering the adhesive tape and radiating heat to room temperature.
Haze reduction (%) = Hzb-Hza (2)
Hza: Haze (%) of the release film after wiping off with a cotton cloth impregnated with ethanol.
Hzb: haze (%) of the release film before wiping off.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015066626A JP6519267B2 (en) | 2015-03-27 | 2015-03-27 | Release film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015066626A JP6519267B2 (en) | 2015-03-27 | 2015-03-27 | Release film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2016185674A JP2016185674A (en) | 2016-10-27 |
| JP6519267B2 true JP6519267B2 (en) | 2019-05-29 |
Family
ID=57203682
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2015066626A Active JP6519267B2 (en) | 2015-03-27 | 2015-03-27 | Release film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6519267B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019044056A1 (en) * | 2017-08-30 | 2019-03-07 | 東レフィルム加工株式会社 | Mold release film |
| JP7322440B2 (en) * | 2019-03-15 | 2023-08-08 | 三菱ケミカル株式会社 | release film |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000062122A (en) * | 1998-06-10 | 2000-02-29 | Mitsubishi Kagaku Polyester Film Kk | Mold release film |
| JP2000141568A (en) * | 1998-11-09 | 2000-05-23 | Mitsubishi Polyester Film Copp | Release film |
| JP5171332B2 (en) * | 2008-03-18 | 2013-03-27 | リンテック株式会社 | Release sheet, polarizing plate with release sheet, and substrate-less double-sided adhesive sheet |
| JP5319328B2 (en) * | 2009-02-27 | 2013-10-16 | 帝人デュポンフィルム株式会社 | Release film for ceramic sheet production |
| KR101783879B1 (en) * | 2010-01-13 | 2017-10-10 | 다우 코닝 도레이 캄파니 리미티드 | Silicone-based releasable adhesive composition, sheet-form substrate having releasable adhesive layer formed by curing this composition, and use of such as a protective film or fixing sheet |
| JP5756315B2 (en) * | 2011-03-29 | 2015-07-29 | リンテック株式会社 | Release agent composition and release film for molding ceramic green sheet |
| JP5799893B2 (en) * | 2012-05-25 | 2015-10-28 | 信越化学工業株式会社 | Emulsion heavy release additive for release sheet, emulsion composition for release sheet, and release sheet |
-
2015
- 2015-03-27 JP JP2015066626A patent/JP6519267B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2016185674A (en) | 2016-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI694929B (en) | Release film having excellent peelability | |
| JP6251111B2 (en) | Double-sided adhesive film and protective member for information display screen using the same | |
| KR101522941B1 (en) | Silicone release film and manufacturing method thereof | |
| KR101836212B1 (en) | Release film having excellent peelability | |
| KR101927851B1 (en) | Mold releasable composition, release film comprising the same, and method for manufacturing a release sheet using the same | |
| JP2015024542A (en) | Surface protective film and optical component with surface protective film affixed | |
| JP2013208897A (en) | Silicone release film having improved release and anti-blocking characteristics | |
| JP2017170672A (en) | Release film, and resin composition and coating composition used in the same | |
| JP6519267B2 (en) | Release film | |
| KR101844051B1 (en) | Protective film | |
| JP6694981B2 (en) | Release film with excellent releasability | |
| KR20200121021A (en) | Fluoro release film | |
| JP6566247B2 (en) | Double-sided adhesive film and protective member for information display screen using the same | |
| WO2017047405A1 (en) | Composite polarizing plate and liquid crystal panel using same | |
| JP2006007689A (en) | Mold releasing film | |
| JP4210732B2 (en) | Antireflection film | |
| KR102392098B1 (en) | Release film and manufacturing method thereof | |
| KR20140118168A (en) | Release film | |
| JP6383968B2 (en) | Double-sided adhesive film and protective member for information display screen using the same | |
| KR102459382B1 (en) | Release film | |
| JP2016102136A5 (en) | ||
| KR20180094678A (en) | Released film | |
| KR20180086821A (en) | Tihgt release silicone coating flim | |
| JP2020116888A (en) | Peeling sheet | |
| KR20170038639A (en) | Release film and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20180219 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20181005 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20181023 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20181217 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190129 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20190402 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20190408 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6519267 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |