JP6480295B2 - Release film with excellent releasability - Google Patents

Release film with excellent releasability Download PDF

Info

Publication number
JP6480295B2
JP6480295B2 JP2015187549A JP2015187549A JP6480295B2 JP 6480295 B2 JP6480295 B2 JP 6480295B2 JP 2015187549 A JP2015187549 A JP 2015187549A JP 2015187549 A JP2015187549 A JP 2015187549A JP 6480295 B2 JP6480295 B2 JP 6480295B2
Authority
JP
Japan
Prior art keywords
film
release agent
release
fine particles
agent 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
Application number
JP2015187549A
Other languages
Japanese (ja)
Other versions
JP2017061081A (en
Inventor
洋之 宮坂
洋之 宮坂
林　益史
益史 林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujimori Kogyo Co Ltd
Original Assignee
Fujimori Kogyo Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=58418357&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=JP6480295(B2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Fujimori Kogyo Co Ltd filed Critical Fujimori Kogyo Co Ltd
Priority to JP2015187549A priority Critical patent/JP6480295B2/en
Priority to KR1020160095209A priority patent/KR101876195B1/en
Priority to CN201610602186.7A priority patent/CN106553395B/en
Priority to TW105125127A priority patent/TWI694929B/en
Priority to TW109114124A priority patent/TWI725831B/en
Publication of JP2017061081A publication Critical patent/JP2017061081A/en
Priority to KR1020180076804A priority patent/KR101968935B1/en
Publication of JP6480295B2 publication Critical patent/JP6480295B2/en
Application granted granted Critical
Priority to KR1020190041141A priority patent/KR102053851B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/14—Layered products comprising a layer of synthetic resin next to a particulate layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/16—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/201—Adhesives in the form of films or foils characterised by their carriers characterised by the release coating composition on the carrier layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)

Description

本発明は、各種の粘着製品や粘着剤層を有する光学部材において、粘着剤層の保護に使用される離型フィルムに関する。さらに詳細には、剥離力が小さく、粘着剤層に貼合した状態で時間経過しても、剥離力が大きくなり難く、かつ、粘着剤層へのシリコーン成分の移行が少ないため、貼合した粘着剤層の粘着力を低下させない、剥離性に優れた離型フィルムに関するものである。   The present invention relates to a release film used for protecting an adhesive layer in an optical member having various adhesive products and an adhesive layer. More specifically, the peeling force is small, and even when time passes in the state of being bonded to the pressure-sensitive adhesive layer, the peeling force is hardly increased, and the transfer of the silicone component to the pressure-sensitive adhesive layer is small, and thus bonding is performed. The present invention relates to a release film that does not decrease the adhesive strength of the pressure-sensitive adhesive layer and has excellent peelability.

従来から、各種の用途に対して、離型フィルム（剥離フィルムと呼ばれることもある）が使用されている。中でもセラミック積層コンデンサー、セラミック基板等の各種セラミック製電子部品の製造時に使用されるグリーンシートの成形用離型フィルム、偏光板、光学フィルター、フラットパネルディスプレーなどの製造時に使用される粘着剤層を有する光学部材用の離型フィルム、タッチパネル部材や光学部材同士を貼合するための、光学部材貼合用の粘着剤層用の離型フィルムなどに、広く使用されている。   Conventionally, release films (sometimes referred to as release films) have been used for various applications. Above all, it has a pressure-sensitive adhesive layer used in the production of green sheet molding release films, polarizing plates, optical filters, flat panel displays, etc. used in the production of various ceramic electronic parts such as ceramic multilayer capacitors and ceramic substrates. Widely used for release films for optical members, touch panel members, release films for adhesive layers for bonding optical members, and the like.

セラミック積層コンデンサー、セラミック基板等の各種セラミック製電子部品の製造時に使用されるグリーンシートは、セラミック積層コンデンサーの小型化及び大容量化に伴い、薄膜化が進んでいる。グリーンシートを離型フィルムから剥離する際に、離型フィルムの剥離力が大きい場合には、グリーンシートが破損することから、従来に比べて剥離力の小さい離型フィルムが求められている。   Green sheets used in the production of various ceramic electronic components such as ceramic multilayer capacitors and ceramic substrates are becoming thinner as ceramic multilayer capacitors become smaller and larger in capacity. When a green sheet is peeled from a release film, if the release force of the release film is large, the green sheet is damaged. Therefore, a release film having a smaller peel force than the conventional one is required.

一方、液晶ディスプレイを構成する部材である偏光板、位相差板などの光学部材においては、該光学部材に形成された光学部材同士又は他の部材と貼り合わせる用途の粘着剤層を保護するために、離型フィルムが使用されている。
当該用途に使用される離型フィルムは、ディスプレイの大型化に伴い、偏光板などの光学部材及び離型フィルムの寸法が大きくなり、剥離面積が大きくても軽く剥離できることが必要とされている。そのため、従来に比べて剥離力の小さい離型フィルムが求められている。また、タッチパネルの構成部材や光学部材同士を貼合するための、光学部材用の粘着剤層については、タブレットＰＣ、タブレット端末、タッチパネルなどの薄型化に伴い、薄膜の粘着剤層でも光学部材の段差（例えば、携帯端末のカバーガラス等に用いられる額縁印刷の段差など）に追従できるように、凝集力の弱い粘着剤層が使用されている。しかし、凝集力の弱い粘着剤層を用いた場合、離型フィルムの剥離力が大き過ぎると光学部材用の粘着剤層が変形してしまうことから、従来に比べて剥離力の小さい離型フィルムが求められている。 On the other hand, in an optical member such as a polarizing plate and a retardation plate that are members constituting a liquid crystal display, in order to protect an adhesive layer for use in bonding with optical members formed on the optical member or with other members A release film is used.
The release film used for the application needs to be able to be peeled lightly even if the peel area is large, as the size of the optical member such as a polarizing plate and the release film increase as the display becomes larger. Therefore, there is a demand for a release film having a smaller peeling force than conventional ones. Moreover, about the adhesive layer for optical members for bonding the structural member and optical members of a touch panel, with thinning of tablet PC, a tablet terminal, a touch panel, etc., even a thin adhesive layer of an optical member A pressure-sensitive adhesive layer having a weak cohesive force is used so as to follow a step (for example, a step of frame printing used for a cover glass of a portable terminal). However, when a pressure-sensitive adhesive layer having a weak cohesive force is used, the release film having a smaller peeling force than conventional ones will be deformed if the release force of the release film is too large. Is required.

このように、セラミックグリーンシートの成形用離型フィルム、及び各種の粘着剤層を有する光学部材用の離型フィルムでは、従来に比べて剥離力の小さい離型フィルムが求められている。こうしたことを背景にして、特許文献１では、分子中にビニル基を１個のみ持つシリコーンを含有する硬化シリコーンを用いた離型フィルムが提案されている。
また、特許文献２では、ポリエステルフィルムの片面にオリゴマーの析出防止層を施し、その上に無溶剤系の付加反応硬化型シリコーンを含有する離型層を有し、テープ剥離力が１５ｍＮ／ｃｍ以下であり、かつ、シリコーン系成分の移行性評価接着率が９０％以上の離型フィルムが提案されている。
さらに、特許文献３では、官能基を有しないポリジメチルシロキサンなどの、軽剥離成分を添加していない付加反応型シリコーンを用い、５０〜６５℃の環境下で２０時間以上熱処理を施した離型フィルムであって、アクリル系粘着剤の剥離力が０．１５Ｎ／５０ｍｍ以下で残留接着率が９０％以上の離型フィルムが提案されている。 As described above, a release film for forming a ceramic green sheet and a release film for an optical member having various pressure-sensitive adhesive layers are required to have a release film having a smaller peeling force than conventional ones. Against this background, Patent Document 1 proposes a release film using a cured silicone containing silicone having only one vinyl group in the molecule.
Further, in Patent Document 2, an oligomer precipitation preventing layer is applied to one side of a polyester film, and a release layer containing a solventless addition reaction curable silicone is provided thereon, and the tape peeling force is 15 mN / cm or less. In addition, a release film having a migration evaluation adhesion rate of silicone components of 90% or more has been proposed.
Furthermore, in patent document 3, the release which performed the heat processing for 20 hours or more in 50-65 degreeC environment using the addition reaction type silicone which does not add the light peeling component, such as polydimethylsiloxane which does not have a functional group. A release film having a peeling force of acrylic pressure-sensitive adhesive of 0.15 N / 50 mm or less and a residual adhesive rate of 90% or more has been proposed.

特許文献１〜３においては、いずれも、剥離力が小さく、かつ、貼合した粘着剤層の粘着力を低下させない離型フィルムが提案されている。しかし、特許文献１に記載の離型フィルムでは、分子中にビニル基を１個のみ持つシリコーンを含有する硬化シリコーンを用いるため、ビニル基を完全に反応させないと、ビニル基を１個のみ持つシリコーンが粘着剤層に移行してしまい、粘着剤層の粘着力が低下してしまうことが懸念される。
また、特許文献２に記載の離型フィルムについては、オリゴマーの析出防止層を設けていることが、従来の離型フィルムと異なる。しかし、無溶剤系の付加反応硬化型シリコーンを使用しているため、剥離性能に関しては、従来の離型フィルムの範疇となってしまう。さらに、特許文献３に記載の離型フィルムでは、軽剥離成分を添加していない付加反応型シリコーンをエージングすることにより軽剥離化したものである。この場合、軽剥離の割には、貼合した粘着剤層の粘着力を低下させない離型フィルムが得られるが、さらに剥離力を低減することが困難である。 In each of Patent Documents 1 to 3, a release film is proposed that has a small peeling force and does not reduce the adhesive strength of the bonded adhesive layer. However, since the release film described in Patent Document 1 uses a cured silicone containing silicone having only one vinyl group in the molecule, silicone having only one vinyl group unless the vinyl group is completely reacted. Is likely to move to the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive force of the pressure-sensitive adhesive layer is reduced.
Moreover, about the release film of patent document 2, it is different from the conventional release film that the precipitation prevention layer of an oligomer is provided. However, since solvent-free addition reaction curable silicone is used, the release performance falls within the category of conventional release films. Furthermore, the release film described in Patent Document 3 is lightly peeled by aging addition-reactive silicone to which no lightly peeling component is added. In this case, a release film that does not decrease the adhesive strength of the bonded adhesive layer is obtained for light peeling, but it is difficult to further reduce the peeling force.

また、特許文献４に記載の離型フィルムは、ポリエステルフィルムに所定の粒子径の不活性粒子を含むシリコーン剥離層を、所定の厚さに施したものである。シリコーン剥離層を厚くした際に生じるブロッキング（離型フィルムをロール状に巻いた時に、離型フィルムの背面と剥離層が疑似接着をしてしまい、うまく巻き取れない現象）を、所定粒子径の不活性粒子をシリコーン剥離層に入れることで解決したものである。しかし、不活性粒子により、シリコーン剥離層が不連続になってしまうため、溶剤が接触すると、不活性粒子とシリコーンの界面に溶剤が浸透し、シリコーンが脱落する恐れがある。また、シリコーン剥離層の厚さに比べて粒子径の大きな不活性粒子を添加するために、離型フィルムを粘着剤層の表面保護に使用した場合に、不活性粒子が、粘着剤層側に付着し、粘着剤層の粘着力を低下させることがある。   The release film described in Patent Document 4 is obtained by applying a silicone release layer containing inert particles having a predetermined particle diameter to a polyester film to a predetermined thickness. Blocking that occurs when the silicone release layer is thickened (a phenomenon in which when the release film is rolled into a roll, the back surface of the release film and the release layer are pseudo-bonded and cannot be wound well) This is solved by putting inert particles in the silicone release layer. However, since the silicone release layer is discontinuous due to the inert particles, when the solvent comes into contact with the solvent, the solvent may permeate the interface between the inert particles and the silicone, and the silicone may fall off. In addition, when adding a release film to protect the surface of the pressure-sensitive adhesive layer in order to add inert particles having a particle size larger than the thickness of the silicone release layer, the inert particles are placed on the pressure-sensitive adhesive layer side. It may adhere and reduce the adhesive strength of the adhesive layer.

特開２００８−２６５２２７号公報JP 2008-265227 A 特開２０１２−１３６６１２号公報JP 2012-136612 A 特開２００６−００７６８９号公報JP 2006-007689 A 特開２０１３−２０８８９７号公報JP2013-208897A

本発明は、剥離力が小さく、粘着剤層に貼合した状態で時間が経過しても、剥離力が大きくなり難く、かつ、粘着剤層へのシリコーン成分の移行が少ないため、貼合した粘着剤層の粘着力を低下させない、剥離性に優れた離型フィルムを提供することを課題とする。   In the present invention, the peeling force is small, and even when time passes in the state of being bonded to the pressure-sensitive adhesive layer, the peeling force is hardly increased, and the silicone component is less transferred to the pressure-sensitive adhesive layer, and thus bonded. It is an object of the present invention to provide a release film that does not decrease the adhesive strength of the pressure-sensitive adhesive layer and has excellent peelability.

こうした課題を解決すべく鋭意検討を行った結果、粘着剤層の粘着力を低下させないためには、シリコーン系離型剤（剥離剤と呼ばれることもある）を使用した離型フィルムを、粘着剤層へのシリコーン移行の少ないものにする必要があることが判明した。また、粘着剤層へのシリコーン移行の少ないシリコーン系離型剤を使用した場合でも、剥離力を小さくすることを検討した結果、離型剤層の厚さを特定の厚さ以上にすることにより、剥離力を小さくできることが判明した。しかし、離型剤層の厚さを厚くした場合には、離型フィルムをロール形状に巻き取り、離型剤層が、離型フィルムの背面に合わさった際にブロッキングを起こしてしまい、離型フィルムをロール状にきれいに巻き取れないことが判明した。離型フィルムに使用される基材フィルムは、その製造工程において、基材フィルムをロール形状に巻き取ってもブロッキングを起こさないようにするために、基材フィルムには、滑剤粒子を含有させて成膜している。このため、離型フィルムの背面において、基材フィルムの表面は、凹凸構造を有しているが、離型剤層の厚さを厚くすることにより、基材フィルム表面の凹凸構造を、離型剤層が埋めてしまうことが、ブロッキングを起こした原因と考えられる。   As a result of intensive studies to solve these problems, in order not to reduce the adhesive strength of the pressure-sensitive adhesive layer, a release film using a silicone-based release agent (sometimes called a release agent) is used. It has been found that there is a need for less silicone transfer to the layer. In addition, even when using a silicone release agent with little silicone migration to the pressure-sensitive adhesive layer, as a result of studying to reduce the peel force, by increasing the thickness of the release agent layer to a specific thickness or more It was found that the peel force can be reduced. However, when the thickness of the release agent layer is increased, the release film is wound into a roll shape, and when the release agent layer is combined with the back surface of the release film, blocking occurs, and the release agent layer is released. It was found that the film could not be wound up in a roll. In the production process, the base film used for the release film contains lubricant particles in order to prevent blocking even when the base film is wound into a roll shape. A film is being formed. For this reason, on the back surface of the release film, the surface of the base film has an uneven structure. By increasing the thickness of the release agent layer, the uneven structure on the surface of the base film is released. The filling of the agent layer is considered to cause the blocking.

また、剥離性と耐ブロッキング性とを両立させる方法を鋭意検討し、本発明を完成させることができた。本発明は、粘着剤層へのシリコーン成分の移行の少ない離型剤を使用した場合でも、剥離力を小さくするために、離型剤層の厚さを０．４μｍ以上としている。また、本発明は、離型剤層と、離型フィルム背面とのブロッキングを防ぐために、離型剤層に適度な表面粗さの凹凸形状を形成することにより、剥離性と耐ブロッキング性とを両立させることを技術思想としている。離型剤層に適度な凹凸形状を形成する手段として、離型剤層に、微粒子として、無機微粒子および／またはポリマー微粒子を含有させている。但し、基材フィルムに単に微粒子を含有した離型剤層を設けるだけでは、溶剤が接触すると、微粒子と離型剤との隙間から離型剤層と基材フィルムとの界面に溶剤が浸透し、離型剤層が基材フィルムから剥離する恐れがある。このため、本発明では、溶剤が離型剤層と基材フィルムとの界面まで浸透しないよう、基材フィルムに単に微粒子を含有した離型剤層を設けるのではなく、その間に微粒子を含有しない離型剤層を設けることで、耐溶剤性も改善され、かつ、剥離性と耐ブロッキング性を両立できることがわかり、本発明を完成させた。   In addition, the present invention has been completed by intensively studying a method for achieving both peelability and blocking resistance. In the present invention, the thickness of the release agent layer is set to 0.4 μm or more in order to reduce the peeling force even when a release agent with little migration of the silicone component to the pressure-sensitive adhesive layer is used. Moreover, in order to prevent blocking between the release agent layer and the back surface of the release film, the present invention forms a concavo-convex shape having an appropriate surface roughness on the release agent layer, thereby providing releasability and blocking resistance. The technical idea is to achieve both. As a means for forming an appropriate uneven shape in the release agent layer, the release agent layer contains inorganic fine particles and / or polymer fine particles as fine particles. However, by simply providing a release agent layer containing fine particles on the base film, when the solvent comes into contact with the solvent, the solvent penetrates into the interface between the release agent layer and the base film from the gap between the fine particles and the release agent. The release agent layer may be peeled off from the base film. For this reason, in the present invention, in order to prevent the solvent from penetrating to the interface between the release agent layer and the base film, the base film is not simply provided with a release agent layer containing fine particles, and no fine particles are contained therebetween. By providing the release agent layer, it was found that the solvent resistance was improved and that both the peelability and the blocking resistance were compatible, and the present invention was completed.

本発明は、基材フィルムの少なくとも一方の面に、微粒子を含有しない第１の離型剤層と、微粒子として、無機微粒子および／またはポリマー微粒子を含有する第２の離型剤層とが、この順に積層された離型フィルムであって、前記第１の離型剤層の厚さと、前記第２の離型剤層の厚さと、を合わせた総厚さが、０．４〜２．０μｍであり、前記微粒子の頂点が、前記第２の離型剤層の表面から突出してなり、前記第２の離型剤層の表面から前記微粒子の頂点までの平均の突出高さが、前記総厚さ以上であり、かつ、前記第２の離型剤層が、シリコーン系離型剤を含むことを特徴とする離型フィルムを提供する。 In the present invention, the first release agent layer containing no fine particles on at least one surface of the base film, and the second release agent layer containing inorganic fine particles and / or polymer fine particles as fine particles, The release films are laminated in this order, and the total thickness of the thickness of the first release agent layer and the thickness of the second release agent layer is 0.4-2. 0 μm, the tops of the fine particles protrude from the surface of the second release agent layer, and the average protrusion height from the surface of the second release agent layer to the tops of the fine particles is A release film having a total thickness or more and wherein the second release agent layer contains a silicone release agent is provided.

前記無機微粒子が、シリカ、炭酸カルシウム、リン酸カルシウム、硫酸バリウム、カオリン、ガラス粉末、タルクからなる無機粒子群から選択された１種以上であり、前記ポリマー微粒子が、シリコーン系樹脂、アクリル系樹脂、ポリアミド系樹脂、ポリエステル系樹脂、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリスチレン系樹脂、エポキシ系樹脂からなる高分子樹脂粒子群から選択された１種以上であることが好ましい。   The inorganic fine particles are at least one selected from the group of inorganic particles consisting of silica, calcium carbonate, calcium phosphate, barium sulfate, kaolin, glass powder, talc, and the polymer fine particles are silicone resin, acrylic resin, polyamide It is preferable that it is 1 or more types selected from the polymer resin particle group which consists of resin based, polyester based resin, polyethylene based resin, polypropylene based resin, polystyrene based resin and epoxy based resin.

また、前記基材フィルムがポリエステルフィルムであることが好ましい。   Moreover, it is preferable that the said base film is a polyester film.

また、本発明は、少なくとも樹脂フィルムの片面に粘着剤層が積層された、１つ以上の粘着剤層の表面を有する積層体と、請求項１から３のいずれかに記載の離型フィルムとを備え、前記積層体の粘着剤層の表面に、前記離型フィルムの離型剤層を貼り合わせてなる積層フィルムを提供する。   In addition, the present invention provides a laminate having the surface of one or more pressure-sensitive adhesive layers in which a pressure-sensitive adhesive layer is laminated on at least one surface of the resin film, and the release film according to any one of claims 1 to 3 And a laminated film obtained by bonding the release agent layer of the release film to the surface of the pressure-sensitive adhesive layer of the laminate.

本発明によれば、セラミックグリーンシートの成形用離型フィルム、各種の粘着剤層を有する光学部材用の剥離性に優れた離型フィルムを提供できる。本発明の離型フィルムは、剥離力が小さく、粘着剤層に貼合した状態で時間が経過しても、剥離力が大きくなり難く、かつ、粘着剤層へのシリコーン成分の移行が少ないため、貼合した粘着剤層の粘着力を低下させない、剥離性に優れた離型フィルムを提供することができる。   ADVANTAGE OF THE INVENTION According to this invention, the mold release film for shaping | molding of a ceramic green sheet and the mold release film excellent in the peelability for optical members which have various adhesive layers can be provided. The release film of the present invention has a small peel force, and even when time passes in the state of being bonded to the pressure-sensitive adhesive layer, the peel force is hardly increased, and the silicone component does not migrate to the pressure-sensitive adhesive layer. It is possible to provide a release film excellent in releasability that does not reduce the adhesive strength of the bonded pressure-sensitive adhesive layer.

本発明の離型フィルムの一例を、模式的に示す断面図である。It is sectional drawing which shows an example of the release film of this invention typically. 本発明の積層フィルムの第１形態例を、模式的に示す断面図である。It is sectional drawing which shows typically the 1st form example of the laminated | multilayer film of this invention. 本発明の積層フィルムの第２形態例を、模式的に示す断面図である。It is sectional drawing which shows typically the 2nd form example of the laminated | multilayer film of this invention.

以下、本発明の好適な実施の形態について説明する。
図１は、本発明の離型フィルムの一例を、模式的に示す断面図であって、基材フィルム１の片面に、微粒子を含有しない第１の離型剤層２と、無機微粒子および／またはポリマー微粒子からなる微粒子３を含有する第２の離型剤層４とが、この順に積層されている。 Hereinafter, preferred embodiments of the present invention will be described.
FIG. 1 is a cross-sectional view schematically showing an example of a release film of the present invention, and includes a first release agent layer 2 containing no fine particles, inorganic fine particles, and / or one side of a base film 1. Alternatively, a second release agent layer 4 containing fine particles 3 made of polymer fine particles is laminated in this order.

本発明の離型フィルム５において、基材フィルム１として用いる樹脂フィルムは、用途に合わせて選定すればよいが、ポリエステル樹脂フィルム、ポリアミド樹脂フィルム、ポリイミド樹脂フィルム、ポリオレフィン樹脂フィルム、ポリ塩化ビニル樹脂フィルム、ポリスチレン樹脂フィルム、アクリル樹脂フィルム、アセテート樹脂フィルム、ポリフェニレンサルファイド樹脂フィルムなどが挙げられる。
中でも、光学特性や耐熱特性などの特性面や価格面、外観の品位などの面から、ポリエステル樹脂フィルムが好適である。ポリエステル樹脂としては、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、ポリエチレンイソフタレートとポリエチレンテレフタレートの共重合体、ポリブチレンテレフタレートなどが挙げられる。これらの中でも、コストや光学特性の観点から、ポリエチレンテレフタレート（ＰＥＴ）が特に好ましい。また、光学特性の点からすると、１軸延伸または２軸延伸品の光学用のポリエチレンテレフタレートが好ましい。
また、必要に応じて、基材フィルム１の表面に、プラズマ放電やコロナ放電による表面改質、アンカーコート剤の塗付などの易接着処理を施してもよい。 In the release film 5 of the present invention, the resin film used as the base film 1 may be selected according to the use, but the polyester resin film, polyamide resin film, polyimide resin film, polyolefin resin film, polyvinyl chloride resin film. , Polystyrene resin film, acrylic resin film, acetate resin film, polyphenylene sulfide resin film, and the like.
Among these, a polyester resin film is preferable from the viewpoints of characteristics such as optical characteristics and heat resistance, price, and appearance. Examples of the polyester resin include polyethylene terephthalate, polyethylene naphthalate, a copolymer of polyethylene isophthalate and polyethylene terephthalate, and polybutylene terephthalate. Among these, polyethylene terephthalate (PET) is particularly preferable from the viewpoint of cost and optical properties. Also, from the viewpoint of optical characteristics, monoaxially stretched or biaxially stretched polyethylene terephthalate for optics is preferable.
Further, if necessary, the surface of the base film 1 may be subjected to easy adhesion treatment such as surface modification by plasma discharge or corona discharge, application of an anchor coating agent, and the like.

基材フィルム１の厚さは、特に制限はないが、離型フィルム５としての取扱いの容易さや、離型フィルム５をロール状に巻き取ることを想定すると、基材フィルム１の厚さは、１０〜２００μｍ程度が好ましい。   The thickness of the base film 1 is not particularly limited, but assuming the ease of handling as the release film 5 and winding the release film 5 in a roll shape, the thickness of the base film 1 is About 10-200 micrometers is preferable.

本発明の離型フィルムでは、基材フィルムの少なくとも一方の面に、微粒子を含有しない第１の離型剤層２と、無機微粒子および／またはポリマー微粒子からなる微粒子３を含有する第２の離型剤層４とが、この順に積層されている。
第１の離型剤層２は、離型フィルムの離型剤処理面の耐溶剤性を向上させるため、基材フィルム１と、微粒子３を含有する第２の離型剤層４とを接着する機能を果たすとともに、離型剤としての機能（粘着剤層等から離型フィルムを剥離する際に、剥離時の応力により、離型剤層の被膜がエラストマーとして微小変形し、粘着剤層と離型剤層の界面に応力が集中するようにする機能）も有した層である。 In the release film of the present invention, the second release agent containing the first release agent layer 2 containing no fine particles and the fine particles 3 composed of inorganic fine particles and / or polymer fine particles on at least one surface of the base film. The mold material layer 4 is laminated in this order.
The first release agent layer 2 bonds the base film 1 and the second release agent layer 4 containing the fine particles 3 in order to improve the solvent resistance of the release agent-treated surface of the release film. Function as a release agent (when releasing a release film from an adhesive layer or the like, the release layer is slightly deformed as an elastomer by the stress at the time of release, and the adhesive layer and This layer also has a function of concentrating stress on the interface of the release agent layer.

第１の離型剤層２に使用する離型剤としては、シリコーン系離型剤が挙げられる。シリコーン系離型剤には、付加反応型、縮合反応型、カチオン重合型、ラジカル重合型などの、公知のシリコーン系離型剤が挙げられる。付加反応型シリコーン系離型剤として市販されている製品には、例えば、ＫＳ−７７６Ａ、ＫＳ−７７６Ｌ、ＫＳ−８４７、ＫＳ−８４７Ｔ、ＫＳ−７７９Ｈ、ＫＳ−８３７、ＫＳ−７７８、ＫＳ−８３０、ＫＳ−７７４、ＫＳ−３５６５、Ｘ−６２−２８２９、ＫＳ−３６５０、ＫＮＳ−３０５１、ＫＮＳ−３２０Ａ、ＫＮＳ−３１６、ＫＮＳ−３００２、Ｘ−６２−１３８７（信越化学工業(株)製）、ＳＲＸ−２１１、ＳＲＸ−３４５、ＳＲＸ−３５７、ＳＤ７３３３、ＳＤ７２２０、ＳＤ７２２３、ＬＴＣ−３００Ｂ、ＬＴＣ−３５０Ｇ、ＬＴＣ−３１０、ＬＴＣ−７５０Ａ、ＳＰ−７０２５、ＳＰ−７２４８Ｓ、ＳＰ−７０１５、ＳＰ−７２５９、ＬＴＣ−１００６Ｌ、ＬＴＣ−１０５６Ｌ（東レダウコーニング(株)製）、ＴＰＲ−６７２２、ＴＰＲ−６７２１、ＴＰＲ−６７０２、ＴＰＲ−６７００、ＴＰＲ−６６００、ＳＬ６６２５（モメンティブ・パーフォーマンス・マテリアルズ社製）などが挙げられる。縮合反応型として市販されている製品には、例えば、ＳＲＸ−２９０、ＳＹＬＯＦＦ−２３（東レダウコーニング(株)製）、ＹＳＲ−３０２２（モメンティブ・パーフォーマンス・マテリアルズ社製）などが挙げられる。カチオン重合型として市販されている製品には、例えば、ＴＰＲ−６５０１、ＴＰＲ−６５０２、ＴＰＲ−６５００、ＵＶ９３００、ＶＵ９３１５、ＵＶ９４３０（モメンティブ・パーフォーマンス・マテリアルズ社製）、Ｘ６２−７６２２、Ｘ−６２−７６６０、Ｘ−６２−７６５５（信越化学工業(株)製）などが挙げられる。ラジカル重合型として市販されている製品には、例えば、ＫＦ−２００５、Ｘ６２−７２０５（信越化学工業(株)製）などが挙げられる。粘着剤層へのシリコーン成分の移行の少ない離型剤としては、軽剥離添加成分（付加反応に関与する有機官能基を有しないシリコーン、例えば、ポリジメチルシロキサン等）を含有しないシリコーン系離型剤が挙げられる。   Examples of the release agent used for the first release agent layer 2 include silicone release agents. Examples of the silicone release agent include known silicone release agents such as an addition reaction type, a condensation reaction type, a cationic polymerization type, and a radical polymerization type. Examples of products that are commercially available as addition reaction type silicone release agents include KS-776A, KS-776L, KS-847, KS-847T, KS-779H, KS-837, KS-778, and KS-830. , KS-774, KS-3565, X-62-2829, KS-3650, KNS-3051, KNS-320A, KNS-316, KNS-3002, X-62-1387 (manufactured by Shin-Etsu Chemical Co., Ltd.), SRX-211, SRX-345, SRX-357, SD7333, SD7220, SD7223, LTC-300B, LTC-350G, LTC-310, LTC-750A, SP-7025, SP-7248S, SP-7015, SP-7259, LTC-1006L, LTC-1056L (manufactured by Toray Dow Corning Co., Ltd.), TPR-6 722, TPR-6721, TPR-6702, TPR-6700, TPR-6600, SL6625 (manufactured by Momentive Performance Materials). Examples of the products marketed as the condensation reaction type include SRX-290, SYLOFF-23 (manufactured by Toray Dow Corning), YSR-3022 (manufactured by Momentive Performance Materials). Examples of products marketed as a cationic polymerization type include TPR-6501, TPR-6502, TPR-6500, UV9300, VU9315, UV9430 (manufactured by Momentive Performance Materials), X62-7622, X-62. -7660, X-62-7655 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. Examples of products marketed as radical polymerization types include KF-2005, X62-7205 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. Silicone mold release agent that does not contain a light release additive component (silicone that does not have an organic functional group involved in an addition reaction, such as polydimethylsiloxane) as a mold release agent with little migration of the silicone component to the adhesive layer Is mentioned.

シリコーン系離型剤は、１種類を単独で使用しても良いし、複数の品種を混合して使用しても良い。また、シランカップリング剤や帯電防止剤、濡れ性改良剤などシリコーン系離型剤以外の成分を添加しても良く、剥離性、塗工性、硬化性などを考慮して決めればよい。離型剤の塗布は、公知の方法で行えばよく、特に限定されるものではないが、メイヤーバー工法、グラビア工法、リバースロール工法、エアーナイフ工法、多段ロール工法などが挙げられる。シリコーン系離型剤の硬化方法は、加熱硬化、紫外線硬化、電子線硬化、加熱と紫外線照射の併用などの方法が挙げられるが、シリコーン系離型剤の種類に合わせて、適した方法を選択して採用すればよい。第１の離型剤層２の厚さは、特に限定されないが、耐溶剤性を十分に確保するためには、０．１μｍ以上であることが好ましい。
微粒子を含有しない第１の離型剤層２の厚さと、微粒子３を含有する第２の離型剤層４の厚さ（微粒子３のない部分の平均的な厚さ）とを合計した総厚さ（離型剤層の総厚さ）が０．４〜２．０μｍの範囲に入る範囲で、調整すればよい。 One type of silicone release agent may be used alone, or a plurality of types may be mixed and used. In addition, components other than silicone release agents such as a silane coupling agent, an antistatic agent, and a wettability improver may be added, and may be determined in consideration of releasability, coatability, curability, and the like. The release agent may be applied by a known method and is not particularly limited, and examples thereof include a Mayer bar method, a gravure method, a reverse roll method, an air knife method, and a multistage roll method. Examples of curing methods for silicone mold release agents include methods such as heat curing, ultraviolet curing, electron beam curing, and combined use of heating and ultraviolet irradiation. Select a suitable method according to the type of silicone mold release agent. And adopt it. Although the thickness of the 1st mold release agent layer 2 is not specifically limited, In order to ensure sufficient solvent resistance, it is preferable that it is 0.1 micrometer or more.
The total sum of the thickness of the first release agent layer 2 containing no fine particles and the thickness of the second release agent layer 4 containing the fine particles 3 (average thickness of the portion without the fine particles 3) The thickness (total thickness of the release agent layer) may be adjusted within a range of 0.4 to 2.0 μm.

本発明では、基材フィルムの少なくとも一方の面に、微粒子を含有しない第１の離型剤層２と、微粒子３を含有する第２の離型剤層４とが、この順に積層されている。微粒子３は、シリコーン系離型剤を含む離型剤層の厚さを厚くしても、離型剤層が、離型フィルムの背面に合わさった際にブロッキングを起こさないように、第２の離型剤層４の表面に凹凸形状を形成させるために用いるものである。
ブロッキング防止用の微粒子３である無機微粒子および／またはポリマー微粒子としては、無機化合物の微粒子である無機微粒子や、高分子樹脂の微粒子であるポリマー微粒子が挙げられる。無機微粒子とポリマー微粒子とは、いずれか一方を用いてもよく、また両者を併用してもよい。無機微粒子が、シリカ、炭酸カルシウム、リン酸カルシウム、硫酸バリウム、カオリン、ガラス粉末、タルクからなる無機粒子群から選択された１種以上であることが好ましい。また、ポリマー微粒子が、シリコーン系樹脂、アクリル系樹脂、ポリアミド系樹脂、ポリエステル系樹脂、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリスチレン系樹脂、エポキシ系樹脂からなる高分子樹脂粒子群から選択された１種以上であることが好ましい。
微粒子３の形状は、特に限定されるものではなく、球状、棒状、鱗片状、半球状、凸レンズ状、マッシュルーム状、不定形などいずれでも良いが、球形や球形に近い形状の方が、ブロッキング防止性能が高まるため、より好適である。
微粒子の体積基準平均粒子径は、第２の離型剤層４の厚さよりも大きいものが良く、第２の離型剤層４の表面から突出する微粒子３の頂点までの高さ（微粒子３の突出高さ）が、第１の離型剤層２と第２の離型剤層４との総厚さ以上になるような体積基準平均粒子径の微粒子を選定すれば良い。微粒子３の頂点は、第２の離型剤層４の表面から最も離れた点であればよく、頂点が尖っているか、丸みを帯びているかは、問わない。 In the present invention, the first release agent layer 2 not containing fine particles and the second release agent layer 4 containing fine particles 3 are laminated in this order on at least one surface of the base film. . In order to prevent the fine particles 3 from blocking when the release agent layer is combined with the back surface of the release film, even if the release agent layer containing the silicone release agent is increased in thickness, It is used for forming an uneven shape on the surface of the release agent layer 4.
Examples of the inorganic fine particles and / or polymer fine particles that are the fine particles 3 for blocking prevention include inorganic fine particles that are fine particles of an inorganic compound and polymer fine particles that are fine particles of a polymer resin. Either inorganic fine particles or polymer fine particles may be used, or both may be used in combination. The inorganic fine particles are preferably at least one selected from the group of inorganic particles consisting of silica, calcium carbonate, calcium phosphate, barium sulfate, kaolin, glass powder, and talc. In addition, the polymer fine particles are selected from a group of polymer resin particles composed of silicone resin, acrylic resin, polyamide resin, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, and epoxy resin. The above is preferable.
The shape of the fine particles 3 is not particularly limited, and may be any of spherical, rod-like, scale-like, hemispherical, convex lens-like, mushroom-like, and indeterminate shapes. Since the performance is increased, it is more preferable.
The volume-based average particle diameter of the fine particles is preferably larger than the thickness of the second release agent layer 4, and the height to the top of the fine particles 3 protruding from the surface of the second release agent layer 4 (fine particles 3 Of the volume-based average particle diameter may be selected so that the height of the protrusion is equal to or greater than the total thickness of the first release agent layer 2 and the second release agent layer 4. The vertex of the fine particles 3 may be a point farthest from the surface of the second release agent layer 4, and it does not matter whether the vertex is pointed or rounded.

微粒子３のバインダー樹脂としても機能する、第２の離型剤層４を形成する離型剤としては、シリコーン系離型剤が挙げられる。シリコーン系離型剤には、付加反応型、縮合反応型、カチオン重合型、ラジカル重合型などの、公知のシリコーン系離型剤が挙げられる。
シリコーン系離型剤は、１種類を単独で使用しても良いし、複数の品種を混合して使用しても良い。また、シランカップリング剤や帯電防止剤、濡れ性改良剤などシリコーン系離型剤以外の成分を添加しても良く、剥離性、塗工性、硬化性などを考慮して決めればよい。第２の離型剤層４を形成するシリコーン系離型剤は、第１の離型剤層２を形成する離型剤と同じシリコーン系離型剤でもよく、異なるものでもよい。 Examples of the release agent that functions as a binder resin for the fine particles 3 and forms the second release agent layer 4 include silicone-based release agents. Examples of the silicone release agent include known silicone release agents such as an addition reaction type, a condensation reaction type, a cationic polymerization type, and a radical polymerization type.
One type of silicone release agent may be used alone, or a plurality of types may be mixed and used. In addition, components other than silicone release agents such as a silane coupling agent, an antistatic agent, and a wettability improver may be added, and may be determined in consideration of releasability, coatability, curability, and the like. The silicone release agent that forms the second release agent layer 4 may be the same silicone release agent as the release agent that forms the first release agent layer 2, or may be different.

微粒子３は、第２の離型剤層４を形成するシリコーン系離型剤を含有する離型剤に混合されて、第１の離型剤層２の上に塗布される。微粒子３の一部（上部）は、第２の離型剤層４の厚さ（微粒子３のない部分の平均的な厚さ）より突出する。微粒子３の上部表面に第２の離型剤層４の離型剤が薄く付着しても良いし、或いは付着しなくても、構わない。微粒子３の下部は、第２の離型剤層４に埋め込まれているが、基材フィルム１には接していない。これは、微粒子を含有しない第１の離型剤層２が介在するためである。   The fine particles 3 are mixed with a release agent containing a silicone release agent that forms the second release agent layer 4, and are applied onto the first release agent layer 2. A part (upper part) of the fine particles 3 protrudes from the thickness of the second release agent layer 4 (an average thickness of a part without the fine particles 3). The release agent of the second release agent layer 4 may be thinly attached to the upper surface of the fine particles 3 or may not be attached. The lower part of the fine particles 3 is embedded in the second release agent layer 4 but is not in contact with the base film 1. This is because the first release agent layer 2 containing no fine particles is interposed.

微粒子３の、第２の離型剤層４の離型剤への混合・分散方法については、離型剤および微粒子の種類に合わせて既知の方法で行えばよい。離型剤に微粒子が分散し易い系であれば、スパチュラなどの手動の器具で撹拌混合すればよい。離型剤に微粒子が分散しにくい組み合わせや、分散し易い系であっても、離型剤および微粒子が多量の場合には、ホモジナイザーやホモミキサーなどの分散機を使用して分散混合させても良い。また、微粒子および離型剤のほかに、必要に応じて着色剤、帯電防止剤、レベリング剤、密着性向上剤などを添加しても良い。   The mixing / dispersing method of the fine particles 3 in the release agent of the second release agent layer 4 may be performed by a known method according to the type of the release agent and the fine particles. What is necessary is just to stir and mix with manual tools, such as a spatula, if it is a system in which microparticles | fine-particles are easy to disperse | distribute to a mold release agent. Even if the release agent is a combination in which fine particles are difficult to disperse or a system that is easy to disperse, or if the release agent and fine particles are in large quantities, they can be dispersed and mixed using a disperser such as a homogenizer or homomixer. good. In addition to the fine particles and the release agent, a colorant, an antistatic agent, a leveling agent, an adhesion improver, and the like may be added as necessary.

微粒子３を含有した第２の離型剤層４の形成方法は、微粒子３を含有した離型剤を、基材フィルム１に形成された第１の離型剤層２の上にコーティングして設ければよい。塗工方法は、特に限定されるものではなく、微粒子３を含有した離型剤の粘度、塗布量に合わせて公知の塗工方法から選定すれば良い。一例としては、メイヤーバー工法、グラビア工法、リバースロール工法、エアーナイフ工法、多段ロール工法などが挙げられる。   The method for forming the second release agent layer 4 containing the fine particles 3 includes coating the release agent containing the fine particles 3 on the first release agent layer 2 formed on the base film 1. What is necessary is just to provide. The coating method is not particularly limited, and may be selected from known coating methods according to the viscosity and the coating amount of the release agent containing fine particles 3. Examples include the Mayer bar method, the gravure method, the reverse roll method, the air knife method, and the multi-stage roll method.

微粒子３を含有した第２の離型剤層４の硬化または固化は、離型剤の種類に合わせて行えばよい。例えば、加熱乾燥による溶剤または水などの除去や、紫外線照射や電子線照射などによる離型剤層の硬化などを行えばよい。   The second release agent layer 4 containing the fine particles 3 may be cured or solidified according to the type of the release agent. For example, the solvent or water may be removed by heat drying, or the release agent layer may be cured by ultraviolet irradiation or electron beam irradiation.

第２の離型剤層４の厚さは、特に限定されないが、微粒子３のバインダー樹脂としての機能を十分確保するためには、微粒子３の体積基準平均粒子径の２５％以上であることが好ましい。第１の離型剤層２の厚さと、第２の離型剤層４の厚さとを合わせた総厚さが０．４μｍより小さいと、剥離力が大きくなり易い。また、第１の離型剤層２の厚さと、第２の離型剤層４の厚さとを合わせた総厚さの上限は、特に問題とならないが、第１の離型剤層２の厚さと、第２の離型剤層４の厚さとを合わせた総厚さを大きくした場合には、コストが高くなる問題や、微粒子３の体積基準平均粒子径を大きくすることにより離型フィルムの外観が白っぽくなってしまう問題があるため、２μｍ程度までに抑えるのが好ましい。   The thickness of the second release agent layer 4 is not particularly limited, but may be 25% or more of the volume-based average particle diameter of the fine particles 3 in order to sufficiently ensure the function of the fine particles 3 as a binder resin. preferable. If the total thickness of the thickness of the first release agent layer 2 and the thickness of the second release agent layer 4 is less than 0.4 μm, the peeling force tends to increase. Further, the upper limit of the total thickness of the first release agent layer 2 and the second release agent layer 4 combined is not particularly problematic, but the first release agent layer 2 has When the total thickness of the thickness and the thickness of the second release agent layer 4 is increased, there is a problem that the cost is increased, or the release film is increased by increasing the volume-based average particle diameter of the fine particles 3. It is preferable to suppress the thickness to about 2 μm.

本発明の離型フィルム５を、各種セラミック製電子部品の製造時に使用されるグリーンシートの成形用離型シートに使用する場合、グリーンシートは、セラミック粒子を有機溶剤に分散したスラリーの塗布、乾燥により形成される。このような、グリーンシートを保護する用途に使用される離型フィルム５では、耐溶剤性が要求される。本発明の離型フィルム５は、基材フィルム１と、微粒子３を含有する第２の離型剤層４との間に、微粒子を含有しない第１の離型剤層２を設けている。このため、溶剤が、第２の離型剤層４の離型剤と微粒子３との隙間から第２の離型剤層４と第１の離型剤層２との界面に浸透しても、第１の離型剤層２と基材フィルム１との界面には溶剤は達しないため、第１の離型剤層２が基材フィルム１から剥離することがなく、耐溶剤性も良好である。また、本発明の離型フィルム５は、グリーンシートに限らず、導体ペースト、絶縁体ペースト等、各種粉体を分散した塗膜や、溶剤を含む塗膜の表面を保護する用途に好適に使用できる。   When the release film 5 of the present invention is used as a release sheet for forming a green sheet used in the production of various ceramic electronic parts, the green sheet is coated with a slurry in which ceramic particles are dispersed in an organic solvent, and dried. It is formed by. Such a release film 5 used for protecting the green sheet is required to have solvent resistance. In the release film 5 of the present invention, the first release agent layer 2 containing no fine particles is provided between the base film 1 and the second release agent layer 4 containing the fine particles 3. Therefore, even if the solvent penetrates into the interface between the second release agent layer 4 and the first release agent layer 2 through the gap between the release agent of the second release agent layer 4 and the fine particles 3. Since the solvent does not reach the interface between the first release agent layer 2 and the substrate film 1, the first release agent layer 2 is not peeled off from the substrate film 1, and the solvent resistance is also good. It is. In addition, the release film 5 of the present invention is not limited to a green sheet, and is suitably used for the purpose of protecting the surface of a coating film in which various powders such as a conductor paste and an insulator paste are dispersed and a coating film containing a solvent it can.

図２は、本発明の積層フィルムの第１形態例を、模式的に示す断面図である。図２の粘着付き光学フィルム８は、本発明の離型フィルム５を、光学フィルム７に積層した粘着剤層６を保護する用途に使用したものである。図１の本発明の離型フィルム５に、粘着剤層６を介して光学フィルム７が貼合されている。このような粘着付き光学フィルム８の製造方法は、離型フィルム５に溶剤型粘着剤を塗布、乾燥した後、光学フィルム７を貼合してもよい。このような、粘着剤層６を保護する用途に使用される離型フィルム５では、耐溶剤性が要求される。本発明の離型フィルム５は、基材フィルム１と、微粒子３を含有する第２の離型剤層４との間に、微粒子を含有しない第１の離型剤層２を設けている。このため、溶剤が、第２の離型剤層４の離型剤と微粒子３との隙間から第２の離型剤層４と第１の離型剤層２との界面に浸透しても、第１の離型剤層２と基材フィルム１との界面には溶剤は達しないため、第１の離型剤層２が基材フィルム１から剥離することがなく、耐溶剤性も良好である。粘着剤層６を含む積層体は、１又は２以上の樹脂フィルムと、１又は２以上の粘着剤層とを含むことができる。例えば、光学フィルム７の両面に粘着剤層６を設け、それぞれの粘着剤層６に、離型フィルム５を貼合してもよい。他の製造方法としては、光学フィルム７の片面に粘着剤層６を設けた積層体１０に、離型フィルム５を貼合してもよい。あるいは、無溶剤型粘着剤を塗布した後、離型フィルム５と光学フィルム７との間で、光や熱等により粘着剤層６を硬化させることもできる。使用時には、粘着付き光学フィルム８から離型フィルム５を剥離することにより、離型フィルム５から積層体１０を分離し、粘着剤層６の表面を露出することができる。一般に、光学フィルム７と粘着剤層６との間の密着力は、粘着剤層６から離型フィルム５を剥離する時の剥離力より大きい。   FIG. 2 is a cross-sectional view schematically showing a first embodiment of the laminated film of the present invention. 2 is used for the purpose of protecting the pressure-sensitive adhesive layer 6 laminated on the optical film 7 with the release film 5 of the present invention. An optical film 7 is bonded to the release film 5 of the present invention shown in FIG. In such a method for producing the optical film 8 with pressure-sensitive adhesive, the optical film 7 may be bonded after the solvent-type pressure-sensitive adhesive is applied to the release film 5 and dried. Such a release film 5 used for protecting the pressure-sensitive adhesive layer 6 requires solvent resistance. In the release film 5 of the present invention, the first release agent layer 2 containing no fine particles is provided between the base film 1 and the second release agent layer 4 containing the fine particles 3. Therefore, even if the solvent penetrates into the interface between the second release agent layer 4 and the first release agent layer 2 through the gap between the release agent of the second release agent layer 4 and the fine particles 3. Since the solvent does not reach the interface between the first release agent layer 2 and the substrate film 1, the first release agent layer 2 is not peeled off from the substrate film 1, and the solvent resistance is also good. It is. The laminate including the pressure-sensitive adhesive layer 6 can include one or more resin films and one or more pressure-sensitive adhesive layers. For example, the adhesive layer 6 may be provided on both surfaces of the optical film 7, and the release film 5 may be bonded to each adhesive layer 6. As another manufacturing method, you may bond the release film 5 to the laminated body 10 which provided the adhesive layer 6 in the single side | surface of the optical film 7. FIG. Alternatively, the adhesive layer 6 can be cured between the release film 5 and the optical film 7 by light, heat, or the like after applying the solventless adhesive. At the time of use, by peeling the release film 5 from the adhesive optical film 8, the laminate 10 can be separated from the release film 5 and the surface of the pressure-sensitive adhesive layer 6 can be exposed. In general, the adhesive force between the optical film 7 and the pressure-sensitive adhesive layer 6 is larger than the peeling force when peeling the release film 5 from the pressure-sensitive adhesive layer 6.

また、図３は、本発明の積層フィルムの第２形態例を、模式的に示す断面図である。図３の光学粘着シート９は、タッチパネル部材や光学部材の貼合に用いられる粘着剤層６に、本発明の離型フィルム５を、該粘着剤層６を保護するために貼り合わせたものである。光学粘着シート９は、２枚の離型フィルム５で粘着剤層６を挟んだ形態になっている。このような光学粘着シート９の製造方法では、一方の離型フィルム５に溶剤型粘着剤を塗布、乾燥した後、もう一方の離型フィルム５を貼合するのが一般的である。このような、粘着剤層６を保護する用途に使用される離型フィルム５では、耐溶剤性が要求される。本発明の離型フィルム５は、耐溶剤性も良好なため、粘着剤層６を保護する用途に好適に使用できる。   Moreover, FIG. 3 is sectional drawing which shows typically the 2nd form example of the laminated | multilayer film of this invention. The optical pressure-sensitive adhesive sheet 9 in FIG. 3 is obtained by bonding the release film 5 of the present invention to the pressure-sensitive adhesive layer 6 used for bonding a touch panel member or an optical member in order to protect the pressure-sensitive adhesive layer 6. is there. The optical adhesive sheet 9 has a form in which the adhesive layer 6 is sandwiched between two release films 5. In such a method for producing the optical pressure-sensitive adhesive sheet 9, a solvent-type pressure-sensitive adhesive is applied to one release film 5 and dried, and then the other release film 5 is bonded. Such a release film 5 used for protecting the pressure-sensitive adhesive layer 6 requires solvent resistance. Since the release film 5 of the present invention has good solvent resistance, it can be suitably used for the purpose of protecting the pressure-sensitive adhesive layer 6.

本発明の積層フィルムの粘着剤層６に使用される粘着剤は、水系、非水系（溶剤系）でも無溶剤タイプでも良い。粘着剤としては、アクリル系粘着剤、シリコーン系粘着剤、ゴム系粘着剤、ウレタン系粘着剤等、いずれでもよい。アクリル系粘着剤は、透明性、耐候性に優れるため、好ましい。
積層フィルムに用いられる樹脂フィルムは、光学フィルム７に限らず、不透明の樹脂フィルムであってもよい。光学フィルムとしては、偏光フィルム、位相差フィルム、反射防止フィルム、防眩（アンチグレア）フィルム、紫外線吸収フィルム、赤外線吸収フィルム、光学補償フィルム、輝度向上フィルム、高透明フィルム等が挙げられる。
本発明の積層フィルムは、離型フィルムの離型剤層が粘着剤層の表面に貼り合わせてなる積層フィルムであり、図３に示すように、離型フィルム５と粘着剤層６とのみからなる積層フィルムでもよく、図２に示すように、光学フィルム７のような樹脂フィルム（粘着剤層６の支持体）などを含む積層フィルムでもよい。 The pressure-sensitive adhesive used for the pressure-sensitive adhesive layer 6 of the laminated film of the present invention may be water-based, non-aqueous (solvent-based) or solvent-free type. As the pressure-sensitive adhesive, any of an acrylic pressure-sensitive adhesive, a silicone pressure-sensitive adhesive, a rubber pressure-sensitive adhesive, a urethane pressure-sensitive adhesive, and the like may be used. An acrylic pressure-sensitive adhesive is preferable because it is excellent in transparency and weather resistance.
The resin film used for the laminated film is not limited to the optical film 7 and may be an opaque resin film. Examples of the optical film include a polarizing film, a retardation film, an antireflection film, an antiglare (antiglare) film, an ultraviolet absorption film, an infrared absorption film, an optical compensation film, a brightness enhancement film, and a highly transparent film.
The laminated film of the present invention is a laminated film in which the release agent layer of the release film is bonded to the surface of the pressure-sensitive adhesive layer, and only from the release film 5 and the pressure-sensitive adhesive layer 6 as shown in FIG. The laminated film may be a laminated film including a resin film (support for the pressure-sensitive adhesive layer 6) such as the optical film 7 as shown in FIG.

以下、実施例をもって本発明を具体的に説明する。   Hereinafter, the present invention will be specifically described with reference to examples.

（実施例１の離型フィルム）
厚さ３８μｍのポリエステルフィルムからなる基材フィルムの片面に、コロナ処理が施され、該コロナ処理面に、付加反応型シリコーン系離型剤Ａ（東レ・ダウコーニング社製、ＳＲＸ−２１１の１０重量部に対して白金触媒のＳＲＸ２１２を０．１重量部、トルエン／酢酸エチルの５０／５０混合溶剤９０重量部を混ぜ、混合したもの）を乾燥後の厚さが０．１μｍになるように、メイヤーバーにて塗工し、１２０℃の熱風循環式乾燥器にて１分間加熱した。その後、シリコーン系離型剤塗布面に、付加反応型シリコーン系離型剤Ｂ（東レ・ダウコーニング社製、ＬＴＣ−１０５６Ｌの３０重量部に対して白金触媒のＳＲＸ２１２を１重量部、トルエン／酢酸エチルの５０／５０混合溶剤７０重量部を混ぜ、混合したもの）と、平均粒子径（体積基準平均粒子径）が２μｍのシリコーン系樹脂ポリマー微粒子（モメンティブ・パーフォーマンス・マテリアルズ社製、品名：トスパール（登録商標）１２０）の０．０１６６重量部とを混ぜたものを、付加反応型シリコーン系離型剤Ｂの乾燥後の厚さが０．９μｍになるように、メイヤーバーにて塗工し、１２０℃の熱風循環式乾燥器にて１分間加熱し、実施例１の離型フィルムを得た。 (Release film of Example 1)
One side of a base film made of a polyester film having a thickness of 38 μm is subjected to corona treatment, and an addition reaction type silicone release agent A (manufactured by Toray Dow Corning, SRX-211, 10 weight) is applied to the corona treatment surface. So that 0.1 parts by weight of platinum catalyst SRX212 and 90 parts by weight of 50/50 mixed solvent of toluene / ethyl acetate were mixed with each other) and the thickness after drying was 0.1 μm. The coating was performed with a Mayer bar, and the mixture was heated for 1 minute in a 120 ° C. hot air circulation dryer. Thereafter, 1 part by weight of platinum catalyst SRX212 was added to 30 parts by weight of addition reaction type silicone release agent B (manufactured by Toray Dow Corning, LTC-1056L, toluene / acetic acid on the silicone release agent application surface. 70 parts by weight of 50/50 mixed solvent of ethyl and mixed) and silicone resin polymer fine particles having an average particle diameter (volume-based average particle diameter) of 2 μm (made by Momentive Performance Materials, product name: Coated with 0.0166 parts by weight of Tospearl (registered trademark) 120) with a Mayer bar so that the thickness after drying of the addition reaction type silicone release agent B becomes 0.9 μm. And it heated for 1 minute with a 120 degreeC hot-air circulation type dryer, and the release film of Example 1 was obtained.

（実施例２の離型フィルム）
付加反応型シリコーン系離型剤Ａの乾燥後の厚さを０．３μｍにし、付加反応型シリコーン系離型剤Ｂの乾燥後の厚さを０．７μｍにし、シリコーン系樹脂ポリマー微粒子（モメンティブ・パーフォーマンス・マテリアルズ社製、品名：トスパール（登録商標）１２０）の代わりに、体積基準平均粒子径２．７μｍの無定形シリカ（富士シンシア社製、品名：サイリシア（登録商標）３１０Ｐ）にした以外は、実施例１と同様にして実施例２の離型フィルムを得た。 (Release film of Example 2)
The thickness of the addition reaction type silicone release agent A after drying is 0.3 μm, the thickness of the addition reaction type silicone release agent B after drying is 0.7 μm, and the silicone resin polymer fine particles (momentive Instead of Performance Materials, product name: Tospearl (registered trademark) 120), amorphous silica with a volume-based average particle size of 2.7 μm (manufactured by Fuji Cynthia, product name: Cylicia (registered trademark) 310P) was used. Except for the above, a release film of Example 2 was obtained in the same manner as Example 1.

（実施例３の離型フィルム）
付加反応型シリコーン系離型剤Ｂの乾燥後の厚さを０．４μｍにした以外は、実施例１と同様にして実施例３の離型フィルムを得た。 (Release film of Example 3)
A release film of Example 3 was obtained in the same manner as in Example 1 except that the thickness of the addition reaction type silicone release agent B after drying was 0.4 μm.

（実施例４の離型フィルム）
付加反応型シリコーン系離型剤Ａの乾燥後の厚さを０．３μｍにし、付加反応型シリコーン系離型剤Ｂの乾燥後の厚さを１．７μｍにし、シリコーン系樹脂ポリマー微粒子（モメンティブ・パーフォーマンス・マテリアルズ社製、品名：トスパール（登録商標）１２０）の代わりに、体積基準平均粒子径４．５μｍのシリコーン系樹脂ポリマー微粒子（モメンティブ・パーフォーマンス・マテリアルズ社製、品名：トスパール（登録商標）１４５）にした以外は、実施例１と同様にして実施例４の離型フィルムを得た。 (Release film of Example 4)
The thickness of the addition reaction type silicone release agent A after drying is 0.3 μm, the thickness of the addition reaction type silicone release agent B after drying is 1.7 μm, and the silicone resin polymer fine particles (momentive Instead of Performance Materials Co., Ltd., product name: Tospearl (registered trademark) 120), a silicone resin polymer fine particle having a volume-based average particle diameter of 4.5 μm (Momentive Performance Materials Co., Ltd., product name: Tospearl ( A release film of Example 4 was obtained in the same manner as in Example 1 except that (registered trademark) 145) was used.

（比較例１の離型フィルム）
付加反応型シリコーン系離型剤Ａを設けなかった以外は、実施例１と同様にして比較例１の離型フィルムを作成した。 (Release film of Comparative Example 1)
A release film of Comparative Example 1 was prepared in the same manner as in Example 1 except that the addition reaction type silicone release agent A was not provided.

（比較例２の離型フィルム）
付加反応型シリコーン系離型剤Ｂの乾燥後の厚さを１．２μｍにした以外は、実施例１と同様にして比較例２の離型フィルムを得た。 (Release film of Comparative Example 2)
A release film of Comparative Example 2 was obtained in the same manner as in Example 1 except that the thickness of the addition reaction type silicone release agent B after drying was 1.2 μm.

（比較例３の離型フィルム）
厚さ３８μｍのポリエステルフィルムからなる基材フィルムの片面に、コロナ処理が施され、該コロナ処理面に、付加反応型シリコーン系離型剤Ｂのみを、乾燥後の厚さが０．２μｍとなるように、メイヤーバーにて塗工し、１２０℃の熱風循環式乾燥器にて１分間加熱し、比較例３の離型フィルムを得た。 (Release film of Comparative Example 3)
One side of a base film made of a polyester film having a thickness of 38 μm is subjected to corona treatment, and only the addition-reactive silicone release agent B is applied to the corona-treated surface, resulting in a thickness after drying of 0.2 μm. As described above, coating was performed using a Mayer bar, and heating was performed for 1 minute using a 120 ° C. hot-air circulating drier to obtain a release film of Comparative Example 3.

（ブロッキングの有無の確認）
離型フィルムを３枚重ねたサンプルを作成し、ステンレス板（ＳＵＳ３０４）２枚の間に挟む。このサンプルに２０ｇ／ｃｍ２｛０．１９６Ｎ／ｃｍ２｝の荷重を掛けた状態で、２３℃、５０％ＲＨの環境で２４時間放置する。その後、３枚重なった離型フィルムを取り出し、離型フィルムを１枚ずつ手で剥がすことによりブロッキング状態を確認した。ブロッキングがなく、離型フィルムが軽く剥がれたものをブロッキング性良好（○）、離型フィルムの剥離時に抵抗があったものをブロッキング性不良（×）とした。 (Check for blocking)
A sample in which three release films are stacked is prepared and sandwiched between two stainless plates (SUS304). The sample is allowed to stand in an environment of 23 ° C. and 50% RH for 24 hours under a load of 20 g / cm 2 {0.196 N / cm 2 }. Then, the release film which overlapped 3 sheets was taken out, and the blocking state was confirmed by peeling a release film one sheet at a time. No blocking was observed, and the release film was peeled off lightly, and the blocking property was good (O), and the one having resistance when the release film was peeled was determined as poor blocking property (X).

（剥離力の測定）
離型フィルムの離型剤層の表面に、ポリエステル粘着テープ（日東電工株式会社製、商品名：ポリエステルテープＮｏ．３１Ｂ）を貼り合わせ、２０ｇ／ｃｍ２の荷重下、７０℃で２０時間エージングした後、卓上型精密万能試験機（島津製作所社製、オートグラフ（登録商標））にて、剥離速度３００ｍｍ／分、剥離角度１８０°にて引き剥がした際の剥離強度を、剥離力（ｍＮ／５０ｍｍ）として測定した。 (Measurement of peel force)
A polyester adhesive tape (manufactured by Nitto Denko Corporation, trade name: polyester tape No. 31B) was bonded to the surface of the release agent layer of the release film, and aged at 70 ° C. for 20 hours under a load of 20 g / cm 2 . Thereafter, the peel strength when peeled at a peeling speed of 300 mm / min and a peeling angle of 180 ° with a desktop precision universal testing machine (manufactured by Shimadzu Corporation, Autograph (registered trademark)) 50 mm).

（残留接着率の測定）
上記（剥離力の測定）による試験後の、離型フィルムから引き剥がした粘着テープを被着体（ステンレス板）に対してローラで圧着し、２３℃、５５％ＲＨの環境下で１時間放置した後、卓上型精密万能試験機（島津製作所社製、オートグラフ（登録商標））にて、剥離速度３００ｍｍ／分、剥離角度１８０°にて当該被着体から剥離するときの剥離力を測定して残留接着力とした。
これとは別に、未使用の粘着テープを同一材質の被着体に圧着して剥離するときの剥離力を、同様に測定して基準粘着力とした。
残留接着率は、残留接着率＝（残留粘着力）／（基準粘着力）×１００（％）により算出した。 (Measurement of residual adhesion rate)
After the test according to the above (measurement of peel force), the adhesive tape peeled off from the release film is pressure-bonded to the adherend (stainless steel plate) with a roller and left in an environment of 23 ° C. and 55% RH for 1 hour. Then, using a desktop precision universal testing machine (manufactured by Shimadzu Corp., Autograph (registered trademark)), the peeling force when peeling from the adherend at a peeling speed of 300 mm / min and a peeling angle of 180 ° is measured. The residual adhesive strength was obtained.
Separately from this, the peeling force when an unused pressure-sensitive adhesive tape was pressure-bonded to an adherend of the same material and peeled was measured in the same manner as a reference pressure-sensitive adhesive force.
The residual adhesive rate was calculated by the residual adhesive rate = (residual adhesive force) / (reference adhesive force) × 100 (%).

（離型剤層の密着性の確認）
上記（剥離力の測定）による試験後の、離型フィルムの離型剤層の表面を、指の腹で強く３回擦った後、擦った部分を目視で観察した。基材フィルムから、離型剤層が脱落していることの有無を目視にて確認し、離型剤層の脱落がほとんどなかったものを（○）、離型剤層の脱落が著しかったものを（×）として評価した。 (Confirmation of adhesion of release agent layer)
After the test according to the above (measurement of peel force), the surface of the release agent layer of the release film was strongly rubbed with the belly of the finger three times, and then the rubbed portion was visually observed. Visually confirmed that the release agent layer had fallen off from the base film. (○), where the release agent layer was almost free. Was evaluated as (×).

（離型剤層の耐溶剤性の確認）
離型フィルムの離型剤層の表面を、酢酸エチルを染み込ませた不織布（旭化成せんい社製ベンコット（登録商標）Ｍ−１）を用いて、２００ｇの分銅で荷重を掛けた状態で一往復擦る。その後、離型フィルムの離型剤層の表面を目視で観察することにより、離型フィルムの離型剤層の耐溶剤性を確認した。離型剤層の表面を目視にて確認し、外観に変化の無かったものを（○）、離型剤層が脱落したものを（×）と判定した。 (Confirmation of solvent resistance of release agent layer)
The surface of the release agent layer of the release film is rubbed once in a state where a load is applied with a weight of 200 g using a non-woven fabric impregnated with ethyl acetate (Bencot (registered trademark) M-1 manufactured by Asahi Kasei Corporation). . Then, the solvent resistance of the release agent layer of the release film was confirmed by visually observing the surface of the release agent layer of the release film. The surface of the release agent layer was confirmed by visual observation, and it was determined that the appearance did not change (O) and that the release agent layer dropped off (X).

（測定、確認試験の結果）
実施例１〜４および比較例１〜３で得られた離型フィルムの、各種測定、確認試験の結果を表１に示す。 (Measurement and confirmation test results)
Table 1 shows the results of various measurements and confirmation tests of the release films obtained in Examples 1 to 4 and Comparative Examples 1 to 3.

Figure 0006480295
Figure 0006480295

（まとめ）
本発明に係わる実施例１〜４の離型フィルムは、剥離力が非常に小さく、かつ、残留接着率が非常に高い数値を示した。また、実施例１〜４の離型フィルムは、ブロッキングの有無の確認試験において、第２の離型剤層と離型フィルムの背面とがブロッキングを起こしておらず、微粒子を含有する第２の離型剤層の密着性、耐溶剤性も良好であった。
これに対して、比較例１の離型フィルムは、微粒子を含有しない第１の離型剤層を設けなかったために、微粒子を含有する離型剤層が、基材フィルムに接した構造となっていて、耐溶剤性が悪い結果となった。
また、比較例２の離型フィルムは、微粒子を含有する第２の離型剤層の凹凸が小さく、離型フィルムがブロッキングしてしまい、剥離力も重くなった。
また、比較例３の離型フィルムは、微粒子を含有しないシリコーン系離型剤のみを、一般的な塗布量で塗工して離型剤層が形成されており、本発明に係わる実施例１〜４の離型フィルムよりも剥離力が大きい結果となった。 (Summary)
The release films of Examples 1 to 4 according to the present invention exhibited a numerical value with a very small peel force and a very high residual adhesion rate. Moreover, the release film of Examples 1-4 WHEREIN: In the confirmation test of the presence or absence of blocking, the 2nd mold release agent layer and the back surface of a release film are not raising blocking, but 2nd containing fine particles. The adhesion and solvent resistance of the release agent layer were also good.
On the other hand, since the release film of Comparative Example 1 was not provided with the first release agent layer containing no fine particles, the release agent layer containing fine particles was in contact with the base film. As a result, the solvent resistance was poor.
Further, in the release film of Comparative Example 2, the unevenness of the second release agent layer containing fine particles was small, the release film blocked, and the peeling force became heavy.
In addition, the release film of Comparative Example 3 is formed with a release agent layer formed by coating only a silicone release agent containing no fine particles with a general coating amount. Example 1 according to the present invention As a result, the release force was larger than that of the release film of ~ 4.

１…基材フィルム、２…第１の離型剤層、３…微粒子、４…第２の離型剤層、５…離型フィルム、６…粘着剤層、７…光学フィルム、８…粘着付き光学フィルム、９…光学粘着シート、１０…積層体。 DESCRIPTION OF SYMBOLS 1 ... Base film, 2 ... 1st mold release agent layer, 3 ... Fine particle, 4 ... 2nd mold release agent layer, 5 ... Release film, 6 ... Adhesive layer, 7 ... Optical film, 8 ... Adhesion Attached optical film, 9 ... optical adhesive sheet, 10 ... laminate.

Claims (4)

基材フィルムの少なくとも一方の面に、微粒子を含有しない第１の離型剤層と、微粒子として、無機微粒子および／またはポリマー微粒子を含有する第２の離型剤層とが、この順に積層された離型フィルムであって、
前記第１の離型剤層の厚さと、前記第２の離型剤層の厚さと、を合わせた総厚さが、０．４〜２．０μｍであり、
前記微粒子の頂点が、前記第２の離型剤層の表面から突出してなり、
前記第２の離型剤層の表面から前記微粒子の頂点までの平均の突出高さが、前記総厚さ以上であり、かつ、前記第２の離型剤層が、シリコーン系離型剤を含むことを特徴とする離型フィルム。 A first release agent layer not containing fine particles and a second release agent layer containing inorganic fine particles and / or polymer fine particles as fine particles are laminated in this order on at least one surface of the base film. Release film,
The total thickness of the thickness of the first release agent layer and the thickness of the second release agent layer is 0.4 to 2.0 μm;
The tops of the fine particles protrude from the surface of the second release agent layer ,
The average protrusion height from the surface of the second release agent layer to the top of the fine particles is not less than the total thickness, and the second release agent layer is made of a silicone release agent. A release film characterized by containing. 前記無機微粒子が、シリカ、炭酸カルシウム、リン酸カルシウム、硫酸バリウム、カオリン、ガラス粉末、タルクからなる無機粒子群から選択された１種以上であり、前記ポリマー微粒子が、シリコーン系樹脂、アクリル系樹脂、ポリアミド系樹脂、ポリエステル系樹脂、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリスチレン系樹脂、エポキシ系樹脂からなる高分子樹脂粒子群から選択された１種以上であることを特徴とする請求項１に記載の離型フィルム。   The inorganic fine particles are at least one selected from the group of inorganic particles consisting of silica, calcium carbonate, calcium phosphate, barium sulfate, kaolin, glass powder, talc, and the polymer fine particles are silicone resin, acrylic resin, polyamide 2. The separation according to claim 1, which is at least one selected from the group consisting of polymer resin particles consisting of a resin, a polyester resin, a polyethylene resin, a polypropylene resin, a polystyrene resin, and an epoxy resin. Mold film. 前記基材フィルムがポリエステルフィルムである請求項１又は２に記載の離型フィルム。   The release film according to claim 1 or 2, wherein the base film is a polyester film. 少なくとも樹脂フィルムの片面に粘着剤層が積層された、１つ以上の粘着剤層の表面を有する積層体と、請求項１から３のいずれかに記載の離型フィルムとを備え、前記積層体の粘着剤層の表面に、前記離型フィルムの離型剤層を貼り合わせてなる積層フィルム。   A laminate comprising at least one pressure-sensitive adhesive layer having a pressure-sensitive adhesive layer laminated on at least one surface of the resin film, and the release film according to any one of claims 1 to 3, wherein the laminate is provided. A laminated film obtained by laminating the release agent layer of the release film on the surface of the pressure-sensitive adhesive layer.
JP2015187549A 2015-09-25 2015-09-25 Release film with excellent releasability Active JP6480295B2 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
JP2015187549A JP6480295B2 (en) 2015-09-25 2015-09-25 Release film with excellent releasability
KR1020160095209A KR101876195B1 (en) 2015-09-25 2016-07-27 Release film having excellent peelability
CN201610602186.7A CN106553395B (en) 2015-09-25 2016-07-27 Release film having excellent releasability
TW109114124A TWI725831B (en) 2015-09-25 2016-08-08 Release film having excellent peelability
TW105125127A TWI694929B (en) 2015-09-25 2016-08-08 Release film having excellent peelability
KR1020180076804A KR101968935B1 (en) 2015-09-25 2018-07-03 Release film having excellent peelability
KR1020190041141A KR102053851B1 (en) 2015-09-25 2019-04-09 Release film having excellent peelability

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2015187549A JP6480295B2 (en) 2015-09-25 2015-09-25 Release film with excellent releasability

Related Child Applications (1)

Application Number Title Priority Date Filing Date
JP2019020609A Division JP6694981B2 (en) 2019-02-07 2019-02-07 Release film with excellent releasability

Publications (2)

Publication Number Publication Date
JP2017061081A JP2017061081A (en) 2017-03-30
JP6480295B2 true JP6480295B2 (en) 2019-03-06

Family

ID=58418357

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2015187549A Active JP6480295B2 (en) 2015-09-25 2015-09-25 Release film with excellent releasability

Country Status (4)

Country Link
JP (1) JP6480295B2 (en)
KR (3) KR101876195B1 (en)
CN (1) CN106553395B (en)
TW (2) TWI725831B (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6434437B2 (en) * 2016-03-24 2018-12-05 藤森工業株式会社 Release film with excellent releasability
CN107020775B (en) * 2017-03-01 2020-03-03 张家港康得新光电材料有限公司 Release film, protective film and display device
WO2018181134A1 (en) 2017-03-27 2018-10-04 グローリー株式会社 Optical sensor, light detecting device, paper sheet processing device, light detecting method, and phosphorescence detecting device
JP6655695B2 (en) * 2018-11-07 2020-02-26 藤森工業株式会社 Laminated film
KR102277357B1 (en) * 2018-11-16 2021-07-14 주식회사 엘지화학 Adhesive film comprising release liner with concave-convex pattern and method for manufacturing the same
CN111073548A (en) * 2019-12-30 2020-04-28 苏州赛伍应用技术股份有限公司 Matte adhesive tape release film for flexible OLED module, matte double-sided adhesive tape and preparation method
JP7038430B2 (en) * 2020-07-08 2022-03-18 株式会社東京セロレーベル Release film
KR102254658B1 (en) * 2020-09-09 2021-05-21 주식회사 진양엠티에스 Release film with embossed shape and method of fabricating of the same
KR102706835B1 (en) 2022-08-05 2024-09-20 미쯔비시 케미컬 주식회사 Heteromorphic film
CN115536890B (en) * 2022-11-04 2023-07-07 惠州市鑫亚凯立科技有限公司 Optical fluorine release film with three-dimensional micro-nano structure and manufacturing method thereof

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3095978B2 (en) * 1995-08-17 2000-10-10 帝人株式会社 Release film
JPH09248890A (en) * 1996-03-18 1997-09-22 Teijin Ltd Release film
JP2004142179A (en) * 2002-10-23 2004-05-20 Teijin Dupont Films Japan Ltd Biaxially oriented polyester film for mold releasing
JP2006007689A (en) 2004-06-29 2006-01-12 Toray Advanced Film Co Ltd Mold releasing film
JP2008265227A (en) 2007-04-24 2008-11-06 Mitsubishi Plastics Ind Ltd Release film
JP5432459B2 (en) * 2008-02-22 2014-03-05 リンテック株式会社 Substrate-less double-sided adhesive sheet and release sheet
JP5351432B2 (en) * 2008-04-10 2013-11-27 リンテック株式会社 Double-sided pressure-sensitive adhesive sheet and method for producing the same
JP5412321B2 (en) * 2010-02-25 2014-02-12 藤森工業株式会社 Release film with excellent transparency
JP6164791B2 (en) 2010-12-27 2017-07-19 三菱ケミカル株式会社 Polyester film for double-sided pressure-sensitive adhesive sheets
JP6081123B2 (en) * 2011-10-08 2017-02-15 三菱樹脂株式会社 Substrate-less double-sided adhesive sheet
SG11201402989WA (en) * 2011-12-09 2014-10-30 Cpfilms Inc Modified release coatings for optically clear film
KR20130091808A (en) * 2012-02-09 2013-08-20 에스케이씨하스디스플레이필름(유) Silicone release film for release with superior release and anti-blocking properties
KR102046146B1 (en) * 2012-09-10 2019-11-18 도레이첨단소재 주식회사 Silicone release film with excellent stability in peeling force over time and optical display using the same
KR101971649B1 (en) * 2012-12-17 2019-04-23 미쯔비시 케미컬 주식회사 Base-less double-sided adhesive sheet
KR101460553B1 (en) * 2013-08-27 2014-11-12 도레이첨단소재 주식회사 Release film with laminated release layers with crosslink density gradient

Also Published As

Publication number Publication date
CN106553395B (en) 2020-06-05
KR101876195B1 (en) 2018-07-09
KR20180080707A (en) 2018-07-12
CN106553395A (en) 2017-04-05
KR20170037498A (en) 2017-04-04
KR101968935B1 (en) 2019-04-15
JP2017061081A (en) 2017-03-30
TWI694929B (en) 2020-06-01
KR102053851B1 (en) 2019-12-09
KR20190039916A (en) 2019-04-16
TWI725831B (en) 2021-04-21
TW202030080A (en) 2020-08-16
TW201714739A (en) 2017-05-01

Similar Documents

Publication Publication Date Title
JP6480295B2 (en) Release film with excellent releasability
KR101987643B1 (en) Release film having excellent peelability
JP6434437B2 (en) Release film with excellent releasability
JP6251111B2 (en) Double-sided adhesive film and protective member for information display screen using the same
JP6694981B2 (en) Release film with excellent releasability
KR20140142240A (en) Re-peelable protective adhesive film and manufacturing method therefor
JP6427777B2 (en) Double-sided adhesive film and protective member for information display screen using the same
JP6472044B2 (en) Double-sided adhesive film and protective member for information display screen using the same
JP2017115077A (en) Laminate structure of double side adhesive film
JP6407351B2 (en) Laminated film
JP6383968B2 (en) Double-sided adhesive film and protective member for information display screen using the same
JP6207087B2 (en) Surface protective film for transparent conductive film and transparent conductive film using the same
JP2019018583A (en) Laminated film
JP2016102136A5 (en)

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20171025

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20180529

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20180605

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20180730

RD03 Notification of appointment of power of attorney

Free format text: JAPANESE INTERMEDIATE CODE: A7423

Effective date: 20181026

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: 20190108

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20190207

R150 Certificate of patent or registration of utility model

Ref document number: 6480295

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250