JP2020059252A - Release film - Google Patents
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Abstract
Description
本発明は樹脂層成型時の濡れ性と樹脂層の剥離性に優れた離型フィルムに関する。 The present invention relates to a release film having excellent wettability during resin layer molding and releasability of the resin layer.
離型フィルムは、従来より粘着剤、接着剤、貼薬剤等よりなる粘着面を保護する目的、或は硬化性樹脂、例えばウレタン樹脂、エポキシ樹脂、不飽和ポリエステル樹脂等の硬化反応性、形成性を保護する目的等で用いられ、また、近年積層セラミックコンデンサー用のグリーンシート成型時のライナーとして特に需要が旺盛である。かかる離型フィルムとして、従来から、プラスチックフィルムの少なくとも片面にポリジメチルシロキサンの付加重合硬化物または縮重合硬化物よりなる皮膜を設けたものが用いられている。この硬化物は非粘着で離型効果に優れ、また熱安定性に優れるという利点を有するが、塗布面の表面自由エネルギーを著しく低下させるため樹脂コーティングの濡れ性に乏しく樹脂層成型時に濡れ性不良に起因する塗工欠陥を発生させやすい。一方、表面自由エネルギーを向上させるためにオレフィン等を離型層として用いると、樹脂層の剥離強度が増大し、樹脂層の破れや剥離不良が発生するという問題点がある。従って、樹脂層成形時の濡れ性と剥離性に優れた離型フィルムが求められている。上記課題に対して、特許文献１には架橋剤成分量の調整によりシリコーン離型層の濡れ性を向上させる技術が開示されているが、未だ濡れ性は不十分であり、更に濡れ性を上げようとすれば、架橋基の残留による重剥離化が発生する問題がある。また、特許文献２にはシリコーン離型層にポリビニルアルコール樹脂を混和し、剥離強度と濡れ性を調整する技術が開示されているが、シリコーン樹脂とポリビニルアルコールの相溶性が悪いため、微小領域ではシリコーン樹脂が偏析する箇所が発生し、局所的な濡れ性不良となるため、樹脂コーティング時の塗工欠陥を防止するに至らない。 Release films are used for the purpose of protecting the adhesive surface, which is conventionally composed of adhesives, adhesives, patches, etc., or curing reactivity of curable resins such as urethane resins, epoxy resins, unsaturated polyester resins, and formability. It is used for the purpose of protecting the ceramics, and in recent years, there is particularly strong demand as a liner for forming a green sheet for a laminated ceramic capacitor. As such a release film, conventionally, a plastic film provided with a film made of an addition polymerization cured product or a polycondensation cured product of polydimethylsiloxane on at least one surface has been used. This cured product has the advantages that it is non-adhesive, has an excellent release effect, and has excellent thermal stability, but the wettability of the resin coating is poor because the surface free energy of the coated surface is significantly reduced, and the wettability is poor during resin layer molding. Easily causes coating defects. On the other hand, when olefin or the like is used as a release layer to improve the surface free energy, the peel strength of the resin layer increases, and there is a problem in that the resin layer breaks or peeling failure occurs. Therefore, there is a demand for a release film having excellent wettability and releasability when molding a resin layer. With respect to the above problems, Patent Document 1 discloses a technique for improving the wettability of the silicone release layer by adjusting the amount of the crosslinking agent component, but the wettability is still insufficient, and the wettability is further increased. In such a case, there is a problem that heavy exfoliation occurs due to the residual crosslinking group. Further, Patent Document 2 discloses a technique of mixing a polyvinyl alcohol resin into a silicone release layer to adjust the peel strength and wettability, but since the compatibility between the silicone resin and polyvinyl alcohol is poor, in a minute region. A location where the silicone resin segregates occurs, resulting in poor local wettability, so that coating defects during resin coating cannot be prevented.
本発明の目的は、かかる問題を解消し、樹脂層成型時の濡れ性と剥離性に優れた離型フィルムを提供することにある。 An object of the present invention is to solve the above problems and provide a release film having excellent wettability and releasability when molding a resin layer.
本発明者等は、かかる課題を達成するために鋭意検討した結果、特定の単位よりなるポリシロキサン成分を含有する離型層を使用することにより、樹脂層成型時の濡れ性と剥離性に優れた離型フィルムが得られることを見出し、上記課題を解決するに至った。すなわち、上記課題はプラスチックフィルムの少なくとも片面に、ポリシロキサン成分を離型層全固形分に対し７０重量％以上含む離型層が設けられており、かつ、該ポリシロキサン成分が下記式（１）で示される単位と下記式（２）で示される単位よりなり、両者のモル比が８０：２０〜２０：８０の範囲である離型フィルムにより達成される。 The present inventors have conducted extensive studies in order to achieve such a subject, and as a result, by using a release layer containing a polysiloxane component composed of a specific unit, excellent wettability and releasability during resin layer molding are obtained. It has been found that a release film can be obtained and the above problems have been solved. That is, the problem is that a release layer containing a polysiloxane component in an amount of 70% by weight or more based on the total solid content of the release layer is provided on at least one surface of the plastic film, and the polysiloxane component is represented by the following formula (1). And a unit represented by the following formula (2), and the molar ratio of both is in the range of 80:20 to 20:80.
本発明によれば、樹脂層成型時の濡れ性と剥離性に優れた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 release film having excellent wettability and releasability when molding a resin layer.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
［プラスチックフィルム］
本発明におけるプラスチックフィルムは、特に限定されないが、例えばポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステル、ポリカーボネート、ポリエチレン、ポリプロピレン等のポリオレフィン、ポリスチレントリアセチルセルロース、アクリル、ポリイミド等からなるシートあるいはフィルムを例示することができる。中でも、機械特性、耐熱性に優れ、またこれらの特性と価格とのバランスが良いという観点から、ポリエステルからなるフィルムが好ましく、ポリエチレンテレフタレート、ポリエチレンナフタレートからなるフィルムがより好ましい。また、かかるフィルムとしては、二軸延伸フィルムであることが、機械特性、耐熱性にさらに優れるため好ましい。プラスチックフィルムとしてポリエステルフィルムを用いる場合には、該ポリエステルフィルムは従来から知られている方法で製造できる。例えば、ポリエステルを乾燥後溶融し、ダイ（例えばＴダイ、Ｉダイ等）から冷却ドラム上に押出し冷却して未延伸フィルムとし、該未延伸フィルムを二軸方向に延伸し、更に熱固定することによって製造することができる。フィルムの厚みは、特に制限がないが、１２〜２５０μｍが好ましい。ポリエステルフィルムとしては滑剤を含まないフィルムが表面平坦性の点で好ましいが、表面粗さ制御のため滑剤、例えば炭酸カルシウム、カオリン、シリカ、酸化チタン等の如き無機微粒子および／または触媒残渣の析出微粒子等を含有させたフィルムであっても良く、またドデシルベンゼンスルホン酸ソーダの如き帯電防止剤、色調調整剤等の如き他の添加剤を含有させたフィルムであっても良い。
[Plastic film]
The plastic film in the present invention is not particularly limited, and examples thereof include a sheet or film made of polyester such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate, polyethylene, polyolefin such as polypropylene, polystyrene triacetyl cellulose, acrylic, polyimide and the like. You can Among them, a film made of polyester is preferable, and a film made of polyethylene terephthalate or polyethylene naphthalate is more preferable, from the viewpoints of excellent mechanical properties and heat resistance and a good balance between these properties and price. Further, as such a film, a biaxially stretched film is preferable because it is further excellent in mechanical properties and heat resistance. When a polyester film is used as the plastic film, the polyester film can be produced by a conventionally known method. For example, after the polyester is dried and melted, it is extruded from a die (for example, T die, I die, etc.) onto a cooling drum to be cooled to obtain an unstretched film, and the unstretched film is biaxially stretched and heat-fixed. Can be manufactured by. The thickness of the film is not particularly limited, but is preferably 12 to 250 μm. As the polyester film, a film containing no lubricant is preferable in terms of surface flatness, but for controlling the surface roughness, a lubricant, for example, inorganic fine particles such as calcium carbonate, kaolin, silica, titanium oxide, etc. and / or fine particles for depositing catalyst residue And the like, or a film containing other additives such as an antistatic agent such as sodium dodecylbenzene sulfonate and a color tone adjusting agent.
［離型層］
本発明における離型層は、ポリシロキサンを離型層全固形分に対し７０重量％以上含み、かつ、該ポリシロキサン成分が下記式（１）で示される単位と下記式（２）で示される単位よりなり、両者のモル比が８０：２０〜２０：８０の範囲である離型層である。
[Release layer]
The release layer in the present invention contains polysiloxane in an amount of 70% by weight or more based on the total solid content of the release layer, and the polysiloxane component is represented by the unit represented by the following formula (1) and the following formula (2). The release layer is composed of units and the molar ratio of both is in the range of 80:20 to 20:80.
ポリシロキサンの離型層固形分全体に対する重量は７０重量％以上であり、７５重量％以上が好ましく、８０重量％以上がより好ましい。離型層全固形分に対するポリシロキサン重量が下限未満であると離型性が発現せず、樹脂層剥離強度が重剥離となり許容されない。なお、ポリシロキサンの離型層固形分全体に対する重量の上限は、特に規定されないが、９８重量％以下が好ましく、９５重量％以下がより好ましく、９２重量％以下がさらに好ましい。 The weight of the polysiloxane with respect to the total solid content of the release layer is 70% by weight or more, preferably 75% by weight or more, and more preferably 80% by weight or more. If the polysiloxane weight relative to the total solid content of the release layer is less than the lower limit, the releasability is not exhibited and the resin layer peel strength is heavy release, which is not acceptable. The upper limit of the weight of the polysiloxane to the total solid content of the release layer is not particularly limited, but is preferably 98% by weight or less, more preferably 95% by weight or less, and further preferably 92% by weight or less.
式（１）において、Ｒ１がアルキル基以外の官能基の場合は離型性が発現せず、また炭素数が５より大きいと架橋反応性が著しく低下するため許容されない。また、単位（１）と単位（２）とのモル比は８０：２０〜２０：８０であり、７０：３０〜４０：６０が好ましく、７０：３０〜５０：５０がより好ましい。モル比が上記範囲を外れると塗膜硬度と離型性のバランスが崩れるため、所望の濡れ性と剥離性を両立できない。なお、ポリシロキサン成分は、主たるポリシロキサン成分が前記の単位（１）および単位（２）であればよく、本発明の効果を阻害しない範囲において、他のポリシロキサン成分を含んでいてもよい。ポリシロキサン成分中の単位（１）および単位（２）の合計の割合は、８０重量％以上が好ましく、９０重量％以上がより好ましい。 In the formula (1), when R1 is a functional group other than an alkyl group, releasability is not exhibited, and when the number of carbon atoms is more than 5, the cross-linking reactivity is remarkably reduced, which is not acceptable. The molar ratio of the unit (1) to the unit (2) is 80:20 to 20:80, preferably 70:30 to 40:60, more preferably 70:30 to 50:50. When the molar ratio is out of the above range, the balance between the coating film hardness and the releasability is lost, so that the desired wettability and releasability cannot both be achieved. The main polysiloxane component may be the unit (1) and the unit (2) described above, and may contain other polysiloxane components as long as the effects of the present invention are not impaired. The total proportion of units (1) and units (2) in the polysiloxane component is preferably 80% by weight or more, more preferably 90% by weight or more.
［離型層厚み］
本発明における離型層の厚みは０．０１〜１．０μｍが好ましく、より好ましくは０．０１〜０．５μｍであり、更に好ましくは０．０１〜０．１μｍである。離型層厚みが０．０１μｍを下回るとプラスチックフィルム表面が完全に被覆されず、離型性が失われる場合がある。また、離型層厚みが１．０μｍを超えると離型フィルムを工程でロールｔｏロール搬送する際の曲げや引張に塗膜が耐えられず、塗膜の割れや脱落が発生し、また、塗膜硬化に必要な熱量が増大し、さらに、本発明における離型層を使用する場合必要な熱量が大きいため、生産性が著しく低下する場合がある。
[Release layer thickness]
The thickness of the release layer in the present invention is preferably 0.01 to 1.0 μm, more preferably 0.01 to 0.5 μm, and further preferably 0.01 to 0.1 μm. If the thickness of the release layer is less than 0.01 μm, the surface of the plastic film may not be completely covered and the releasability may be lost. Further, if the release layer thickness exceeds 1.0 μm, the coating film cannot withstand bending and tension during roll-to-roll conveyance of the release film in the process, and the coating film is cracked or comes off. The amount of heat required for film curing increases, and when the release layer of the present invention is used, the amount of heat required is large, which may significantly reduce productivity.
［界面活性剤］
本発明における離型層を設けるためのコーティング組成物には、プラスチックフィルムへの濡れを促進するために界面活性剤を添加することができる。かかる界面活性剤はアニオン系界面活性剤、カチオン系界面活性剤、ノニオン界面活性等が挙げられるが、好ましくはノニオン系界面活性剤である。なお、イオン性界面活性剤はシランの硬化反応を阻害する可能性があるため好ましくない。
[Surfactant]
A surfactant can be added to the coating composition for providing the release layer in the invention in order to promote wetting of the plastic film. Examples of such a surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and the like, but a nonionic surfactant is preferable. The ionic surfactant is not preferable because it may hinder the curing reaction of silane.
［シリカ粒子］
本発明における離型層には架橋反応促進および低分子シラン成分の揮散防止のためにシリカ粒子を添加するのが好ましい。離型層に添加するシリカ粒子は離型面の表面粗さへの影響を小さくするために小粒径のものが良く、一次粒子径は好ましくは１〜１００ｎｍ、より好ましくは２〜８０ｎｍ、さらに好ましくは３〜５０ｎｍである。一途粒子径が１００ｎｍより大きくなると、離型面の表面平滑性が悪化する場合があり、一次粒子径が１ｎｍより小さくなると、表面積が増大し、シリカ粒子表面の反応活性が向上し、被着体との相互作用が増大するため重剥離化する場合がある。
[Silica particles]
Silica particles are preferably added to the release layer in the present invention in order to accelerate the crosslinking reaction and prevent volatilization of the low-molecular silane component. The silica particles added to the release layer preferably have a small particle size in order to reduce the influence on the surface roughness of the release surface, and the primary particle size is preferably 1 to 100 nm, more preferably 2 to 80 nm, and further It is preferably 3 to 50 nm. If the particle size is larger than 100 nm, the surface smoothness of the release surface may be deteriorated. If the primary particle size is smaller than 1 nm, the surface area is increased and the reaction activity of the silica particle surface is improved, so that the adherend is adhered. Heavy peeling may occur due to increased interaction with.
シリカ粒子の量は、離型層全重量に対して、０．５〜１０重量％が好ましく、２〜５重量％であることがより好ましい。シリカ粒子の量が離型層全重量に対して０．５重量％未満であると、架橋反応が進まない場合があり、他方１０重量％を超えると離型層最表面においてシリカ粒子の占有面積が増大し重剥離化する場合があるため好ましくない。 The amount of silica particles is preferably 0.5 to 10% by weight, more preferably 2 to 5% by weight, based on the total weight of the release layer. If the amount of silica particles is less than 0.5% by weight based on the total weight of the release layer, the crosslinking reaction may not proceed. On the other hand, if it exceeds 10% by weight, the area occupied by the silica particles on the outermost surface of the release layer is large. Is sometimes increased, resulting in heavy exfoliation, which is not preferable.
［その他の添加剤］
更に、本発明における離型層には、本発明の効果を消失させない範囲において、例えば帯電防止剤、紫外線吸収剤、顔料、有機フィラー、潤滑剤、ブロッキング防止剤等の他の添加剤を混合することができる。
[Other additives]
Furthermore, the release layer in the present invention is mixed with other additives such as an antistatic agent, an ultraviolet absorber, a pigment, an organic filler, a lubricant, an antiblocking agent, etc. within a range that does not eliminate the effects of the present invention. be able to.
［離型フィルムの製造方法］
本発明の離型フィルムは特に限定されないが、例えば以下の様態で製造することができる。すなわち、下記式（３）で示されるトリアルコキシシランと下記式（４）で示されるテトラアルコキシシランを加水分解することにより水へ溶解させた水性コーティング組成物を、プラスチックフィルムの少なくとも片面に塗布し、次いで乾燥させることで、離型フィルムを製造できる。塗布は、通常の塗布工程、すなわちポリエステルフィルムに、該フィルムの製造工程と切離して塗布する工程で行ってもよい。しかし、この工程では、芥、塵埃などを巻込み易いから、クリーンな雰囲気での塗工が望ましい。かかる観点よりポリエステルフィルム製造工程での塗工が好ましい。特に、この工程中で結晶配向が完了する前のポリエステルフィルムに水性コーティング組成物として塗布することが好ましい。
Ｒ１−Ｓｉ（−ＯＲ２）３ （３）
（式中、Ｒ１は炭素数１〜５のアルキル基、Ｒ２は炭素数１〜２のアルキル基を表す。）
Ｓｉ（−ＯＲ３）４ （４）
（式中、Ｒ３は炭素数１〜２のアルキル基を表す。）
[Release film manufacturing method]
The release film of the present invention is not particularly limited, but can be produced, for example, in the following manner. That is, an aqueous coating composition prepared by dissolving a trialkoxysilane represented by the following formula (3) and a tetraalkoxysilane represented by the following formula (4) in water by hydrolysis is applied to at least one surface of a plastic film. Then, the release film can be produced by drying. The application may be performed in a normal application step, that is, a step of applying the polyester film separately from the production step of the film. However, in this step, since it is easy to entrain refuse and dust, coating in a clean atmosphere is desirable. From this viewpoint, coating in the polyester film manufacturing process is preferable. In particular, it is preferable to apply as an aqueous coating composition to the polyester film before the crystal orientation is completed in this step.
R1-Si (-OR2) 3 (3)
(In the formula, R1 represents an alkyl group having 1 to 5 carbon atoms, and R2 represents an alkyl group having 1 to 2 carbon atoms.)
Si (-OR3) 4 (4)
(In the formula, R3 represents an alkyl group having 1 to 2 carbon atoms.)
ここで、結晶配向が完了する前のポリエステルフィルムとは、ポリエステルを熱溶融してそのままフィルム状となした未延伸フィルム：未延伸フィルムを縦方向（長手方向）または横方向（幅方向）の何れか一方に配向せしめた一軸延伸フィルム；さらには縦方向及び横方向の二方向に低倍率延伸配向せしめたフィルム（最終的に縦方向または横方向に再延伸せしめて配向結晶可を完了せしめる前の二軸延伸フィルム）等を含むものである。 Here, the polyester film before the crystal orientation is completed means an unstretched film obtained by heat-melting polyester into a film as it is: in either the longitudinal direction (longitudinal direction) or the lateral direction (width direction) of the unstretched film. A uniaxially stretched film oriented in one direction; a film oriented in a low-magnification stretch direction in both the longitudinal direction and the transverse direction (before the final re-stretching in the longitudinal direction or the transverse direction to complete the oriented crystal formation). Biaxially stretched film) and the like.
塗布方法としては、公知の任意の塗工法が適用できる。例えば、キスコート法、バースコート法、ダイコート法、リバースコート法、オフセットグラビアコート法、マイヤバーコート法、グラビアコート法、ロールブラッシュ法、スプレーコート法、エアーナイフコート法、含浸法及びカーテンコート法などを単独又は組み合わせて適用するとよい。 As a coating method, any known coating method can be applied. For example, a kiss coat method, a bar coat method, a die coat method, a reverse coat method, an offset gravure coat method, a myer bar coat method, a gravure coat method, a roll brush method, a spray coat method, an air knife coat method, an impregnation method and a curtain coat method. May be applied alone or in combination.
水性コーティング組成物を塗布された、結晶配向完了する前のポリエステルフィルムは、乾燥され、延伸、熱固定等の工程に導かれる。例えば水性コーティング組成物を塗布した縦一軸延伸ポリエステルフィルムは、ステンターに導かれて横延伸及び熱固定される。この間、水性コーティング組成物は乾燥され熱架橋される。 The polyester film coated with the water-based coating composition and before the completion of the crystal orientation is dried and introduced into a process such as stretching and heat setting. For example, a longitudinally uniaxially stretched polyester film coated with an aqueous coating composition is introduced into a stenter and transversely stretched and heat set. During this time, the aqueous coating composition is dried and heat crosslinked.
ポリエステルフィルムの配向結晶化条件、例えば延伸等の条件は、従来から当業界に蓄積された条件で行うことができるが、熱固定温度は、フィルムの融解サブピーク温度（Ｔｓｍ）が好ましくは１８０℃以上、より好ましくは２００℃以上、さらに好ましくは２１０℃以上になるように調整することが好ましい。ここで融解サブピーク温度（Ｔｓｍ）とは、示差走査熱量計測定（ＤＳＣ）によるポリエステルの結晶融解前に現れる微小な吸熱ピークであり、この融解サブピーク（Ｔｓｍ）はフィルムの熱固定温度に相当する温度に微小ピークとして観測され、熱固定処理で形成された結晶構造のうち不完全な部分（擬結晶）が融解するために生じるものである。Ｔｓｍが１８０℃を下回ると、本発明における離型層を硬化させるために必要な熱量が大きいため、塗膜硬化に充分な熱量が供給されず、架橋不足となり、所望の離型性が発現しないことがある。 The orientation and crystallization conditions of the polyester film, such as stretching, can be performed under the conditions accumulated in the art in the past, but the heat setting temperature is preferably a melting subpeak temperature (Tsm) of the film of 180 ° C. or higher. It is preferable that the temperature is adjusted to 200 ° C. or higher, more preferably 210 ° C. or higher. Here, the melting sub-peak temperature (Tsm) is a minute endothermic peak that appears before crystalline melting of polyester by differential scanning calorimetry (DSC), and this melting sub-peak (Tsm) is a temperature corresponding to the heat setting temperature of the film. It is observed as a minute peak in the crystal, and is caused by melting of an incomplete portion (pseudocrystal) of the crystal structure formed by the heat setting treatment. When Tsm is lower than 180 ° C., the amount of heat required to cure the release layer in the present invention is large, so that sufficient amount of heat to cure the coating film cannot be supplied, resulting in insufficient cross-linking, and desired releasability is not exhibited. Sometimes.
［表面粗さ］
本発明の離型フィルムの離型層を形成した側の表面粗さは、Ｒａが１〜３０ｎｍであることが好ましく、１〜２０ｎｍであることがより好ましく、１〜１５ｎｍであることがさらに好ましい。また、Ｒｚが１０〜８００ｎｍであることが好ましく、１０〜６００ｎｍであることがより好ましく、１０〜５００ｎｍであることがさらに好ましい。表面粗さが該範囲にあることで、離型フィルムのハンドリング性が良好となり、かつ、離型面上に形成する樹脂層の平滑性を満足させることができる。
[Surface roughness]
Ra of the surface roughness of the release film of the present invention on which the release layer is formed is preferably 1 to 30 nm, more preferably 1 to 20 nm, and further preferably 1 to 15 nm. . Further, Rz is preferably 10 to 800 nm, more preferably 10 to 600 nm, and further preferably 10 to 500 nm. When the surface roughness is within this range, the release film has good handleability and can satisfy the smoothness of the resin layer formed on the release surface.
以下、実施例を掲げて本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
［実施例１〜８及び比較例１〜４］
平均粒子径が０．７μｍの炭酸カルシウム粒子を０．１重量％を含むポリエチレンテレフタレート（［η］＝０．６４ｄｌ／ｇ、Ｔｇ＝７８℃）を、２０℃に維持した回転冷却ドラム上に溶融押出して未延伸フィルムを得、次に機械軸方向に３．６倍延伸したのち、一軸延伸フィルムの片面に表１に記載の水性コーティング組成物をロールコーターで塗布した。次いで１１５℃で乾燥し、１４５℃で横方向に４．０倍延伸し、さらに２３０℃で熱処理し、厚み３０μｍの離型フィルムを得た。
[Examples 1 to 8 and Comparative Examples 1 to 4]
Polyethylene terephthalate ([η] = 0.64 dl / g, Tg = 78 ° C.) containing 0.1% by weight of calcium carbonate particles having an average particle size of 0.7 μm was melted on a rotary cooling drum maintained at 20 ° C. An unstretched film was extruded to obtain an unstretched film. Then, the unstretched film was stretched 3.6 times in the machine axis direction, and then the aqueous coating composition shown in Table 1 was applied to one surface of the uniaxially stretched film by a roll coater. Then, it was dried at 115 ° C., stretched 4.0 times in the transverse direction at 145 ° C., and further heat-treated at 230 ° C. to obtain a release film having a thickness of 30 μm.
［比較例５］
水性コーティング組成物を、水性付加重合型ポリジメチルシロキサン（信越化学製、ＫＭ−３９５１）６重量部と白金触媒０．０６重量部を水９３．９重量部で希釈したコーティング組成物とした以外は実施例１と同条件で離型フィルムを得た。
なお、物性の評価は以下の方法により実施した。
[Comparative Example 5]
Except that the aqueous coating composition was a coating composition prepared by diluting 6 parts by weight of an aqueous addition-polymerization type polydimethylsiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., KM-3951) and 0.06 part by weight of a platinum catalyst with 93.9 parts by weight of water. A release film was obtained under the same conditions as in Example 1.
The evaluation of physical properties was performed by the following methods.
１）離型層厚み
離型フィルムサンプルを三角形の小片に切り出した後、コーティングにより、厚み２ｎｍのＰｔ（白金）層を離型層表面に形成した。得られたサンプルを多軸包埋カプセルに固定して、エポキシ樹脂を用いて包埋処理し、ミクロトームＵＬＴＲＡＣＵＴ−Ｓを用いて、フィルムの面方向に垂直な方向にスライスして、厚さ５０ｎｍの超薄サンプルを得た。次いで、得られた超薄サンプルをグリッドに載台して、２％オスミウム酸により、６０℃、２時間の条件で蒸気染色した。蒸気染色後の超薄サンプルを用いて、透過電子顕微鏡ＬＥＭ−２０００により、加速電圧１００ｋｖの条件でフィルム断面を観測し、離型層の厚みを測定した。測定は、任意の１０点について実施し、それらの平均値を離型層の厚み（単位：μｍ）とした。
1) Release Layer Thickness A release film sample was cut into triangular pieces, and a Pt (platinum) layer having a thickness of 2 nm was formed on the surface of the release layer by coating. The obtained sample was fixed in a multiaxial embedding capsule, embedded using an epoxy resin, and sliced in a direction perpendicular to the plane direction of the film using a microtome ULTRACUT-S to give a thickness of 50 nm. An ultra thin sample was obtained. Then, the obtained ultra-thin sample was mounted on a grid and vapor-stained with 2% osmic acid at 60 ° C. for 2 hours. Using the ultrathin sample after vapor dyeing, the film cross section was observed with a transmission electron microscope LEM-2000 under the condition of an acceleration voltage of 100 kv, and the thickness of the release layer was measured. The measurement was carried out at arbitrary 10 points, and the average value thereof was taken as the thickness (unit: μm) of the release layer.
２）表面粗さ（Ｒａ、Ｒｚ）
非接触式三次元表面粗さ計（ＺＹＧＯ社製：Ｎｅｗ Ｖｉｅｗ５０２２）を用いて測定倍率２５倍、測定面積２８３μｍ×２１３μｍ（＝０．０６０３ｍｍ２）の条件にて測定し、該粗さ計に内蔵された表面解析ソフトＭｅｔｒｏ Ｐｒｏにより中心面平均粗さ（Ｒａ）および十点平均粗さ（Ｒｚ）を求めた。
2) Surface roughness (Ra, Rz)
Measured using a non-contact type three-dimensional surface roughness meter (New View 5022 manufactured by ZYGO Co., Ltd.) under the conditions of a measurement magnification of 25 times and a measurement area of 283 μm × 213 μm (= 0.0603 mm 2 ), and built in the roughness meter. The center plane average roughness (Ra) and the ten-point average roughness (Rz) were determined by the surface analysis software Metro Pro.
３）融解サブピーク温度（Ｔｓｍ）
フィルム約２０ｍｇを測定用のアルミニウム製パンに封入して示差走査熱量計（ＴＡ Ｉｎｓｔｒｕｍｅｎｔｓ社製、ＤＳＣＱ１００）に装着し、昇温速度２０℃／分でＤＳＣ曲線を描かせ、融解による明瞭な吸熱ピークより低温側の吸熱ピークを融解サブピーク温度とした。また、融解サブピークが結晶融解ピークに近接しピークとして明瞭でない場合には、ＤＳＣ曲線の２次微分曲線が０となる点をサブピーク温度とした。
3) Melting sub-peak temperature (Tsm)
Approximately 20 mg of the film was enclosed in an aluminum pan for measurement, mounted on a differential scanning calorimeter (DSCQ100, manufactured by TA Instruments), and a DSC curve was drawn at a heating rate of 20 ° C./min to give a clear endothermic peak due to melting. The endothermic peak on the lower temperature side was defined as the melting subpeak temperature. Further, when the melting sub-peak is close to the crystal melting peak and is not clear as a peak, the point at which the second derivative curve of the DSC curve becomes 0 was defined as the sub-peak temperature.
４）離型層均一性
作成した離型フィルム表面を目視で観察し、離型層の均一性を評価した。なお、評価基準は下記の通りである。
○：離型層表面１ｍ２に長径０．５ｍｍ以上の塗布欠陥が観察されない。
△：離型層表面１ｍ２に長径１ｍｍ以上の塗布欠陥が観察されない。
×：離型層表面１ｍ２に長径１ｍｍ以上の塗布欠陥が１つ以上観察される。
4) Uniformity of Release Layer The surface of the produced release film was visually observed to evaluate the uniformity of the release layer. The evaluation criteria are as follows.
◯: No coating defect having a major axis of 0.5 mm or more is observed on 1 m 2 of the surface of the release layer.
Δ: No coating defect having a major axis of 1 mm or more is observed on 1 m 2 of the release layer surface.
X: One or more coating defects with a major axis of 1 mm or more are observed on 1 m 2 of the release layer surface.
５）樹脂層塗工時欠陥数
作成した離型フィルムの離型層を形成した面上に、ポリビニルブチラール（積水化学製、ＢＭ−２）をトルエンーエタノール１：１（ｗ／ｗ）混合液に溶解させた溶液を、アプリケータを用いて樹脂層の厚みが０．５μｍとなるように塗布、乾燥させ、樹脂層を形成した。形成した樹脂層のハジキ欠陥を顕微鏡で１ｃｍ□検査し、欠点数を計測した。該欠点数が６個／１ｃｍ□以上であるとＭＬＣＣチップを製造した際に電気特性不良率が高くなる。
5) Number of defects during coating of resin layer Polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., BM-2) was mixed with toluene-ethanol 1: 1 (w / w) on the surface of the release film prepared, on which the release layer was formed. The solution dissolved in was applied and dried using an applicator so that the thickness of the resin layer was 0.5 μm, and the resin layer was formed. A cissing defect of the formed resin layer was inspected with a microscope for 1 cm □, and the number of defects was measured. If the number of defects is 6 pieces / cm 2 or more, the defective rate of electrical characteristics becomes high when an MLCC chip is manufactured.
６）樹脂層剥離強度
作成した離型フィルムの離型層を形成した面上に、ポリビニルブチラール（積水化学製、ＢＭ−２）をトルエンーエタノール１：１（ｗ／ｗ）混合液に溶解させた溶液を、アプリケータを用いて樹脂層の厚みが３．０μｍとなるように樹脂層を形成した。形成した樹脂層を剥離角度９０度、剥離速度３００ｍｍ／分、サンプル幅２５ｍｍで剥離し、その際の剥離抵抗を測定した。剥離強度が７．０ｇ／２５ｍｍを超えると樹脂層の伸びや破断が発生するため、実用上問題がある。
6) Peel strength of resin layer Polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd., BM-2) was dissolved in a toluene-ethanol 1: 1 (w / w) mixed solution on the surface of the formed release film on which the release layer was formed. A resin layer was formed from the solution using an applicator so that the thickness of the resin layer was 3.0 μm. The formed resin layer was peeled at a peeling angle of 90 degrees, a peeling speed of 300 mm / min, and a sample width of 25 mm, and the peeling resistance at that time was measured. If the peel strength exceeds 7.0 g / 25 mm, elongation and breakage of the resin layer occur, which is a practical problem.
表１から明らかの如く、本発明の離型フィルムは、樹脂層塗工時の濡れ性と剥離性に優れている。 As is clear from Table 1, the release film of the present invention is excellent in wettability and releasability during coating of the resin layer.
本発明の離型フィルムは、濡れ性と剥離性に優れるため、各種の用途に使用できるため、産業上の利用価値は極めて高い。 Since the release film of the present invention has excellent wettability and releasability, it can be used in various applications, and thus has an extremely high industrial utility value.
Claims (11)
Ｒ１−Ｓｉ（−ＯＲ２）３ （３）
（式中、Ｒ１は炭素数１〜５のアルキル基、Ｒ２は炭素数１〜２のアルキル基を表す。）
Ｓｉ（−ＯＲ３）４ （４）
（式中、Ｒ３は炭素数１〜２のアルキル基を表す。） A method for producing a release film comprising a release layer provided on at least one surface of a plastic film, the release layer comprising a trialkoxysilane represented by the following formula (3) and a tetraalkoxy represented by the following formula (4): A method for producing a release film, which is a release layer formed by applying a coating composition of silane and drying.
R1-Si (-OR2) 3 (3)
(In the formula, R1 represents an alkyl group having 1 to 5 carbon atoms, and R2 represents an alkyl group having 1 to 2 carbon atoms.)
Si (-OR3) 4 (4)
(In the formula, R3 represents an alkyl group having 1 to 2 carbon atoms.)
The manufacturing method according to any one of claims 8 to 10, wherein an endothermic subpeak temperature (Tsm) obtained by differential scanning calorimetry (DSC) of the plastic film is 180 ° C or higher.
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| CN115010977A (en) * | 2022-06-13 | 2022-09-06 | 江苏皇冠新材料科技有限公司 | Release material for MLCC and preparation method thereof |
| WO2024058163A1 (en) * | 2022-09-16 | 2024-03-21 | 東洋紡株式会社 | Mold release film and method for producing same |
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| WO2024058163A1 (en) * | 2022-09-16 | 2024-03-21 | 東洋紡株式会社 | Mold release film and method for producing same |
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