JP4183962B2 - Release film - Google Patents
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- JP4183962B2 JP4183962B2 JP2002106206A JP2002106206A JP4183962B2 JP 4183962 B2 JP4183962 B2 JP 4183962B2 JP 2002106206 A JP2002106206 A JP 2002106206A JP 2002106206 A JP2002106206 A JP 2002106206A JP 4183962 B2 JP4183962 B2 JP 4183962B2
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Description
【0001】
【発明の属する技術分野】
本発明は、離型フィルムに関し、詳しくは、グリーンシート成形用などで好適に使用される離型フィルムに関する。
【0002】
【従来の技術】
従来、セラミック積層コンデンサのグリーンシート成形用キャリアフィルムとして、ポリエステルフィルムを基材とし、ポリシロキサンなどのシリコーン系化合物などが積層された離型フィルムが使用されている。近年、電子機器の小型化に伴うコンデンサの小型化に伴い、セラミックグリーンシート自体が薄膜化されている。
かかる状況の中、セラミックスラリー塗工時のスラリーのはじき、ピンホールの発生、グリーンシート剥離時には、グリーンシートの破断等の不具合が頻発するようになり、改良が求められている。
また、離型層を設置して巻き取る際にブロッキング発生や離型フィルムの搬送性悪化等の問題が生じる場合があり、セラミック層の両面に電極を設けてコンデンサとした際の誘電率のバラツキが大きくなる等、これらを改良できる離型フィルムが求められている。
さらに、用途によってはシロキサン系低分子量物を嫌うため、離型層はシリコーン化合物以外とすることが望まれている。
【0003】
【発明が解決しようとする課題】
本発明は、上記実情に鑑みなされたものであって、その解決課題は、例えばセラミック積層コンデンサのグリーンシート成形用キャリアフィルムとして用いた際、セラミックスラリー塗工時のスラリーのはじき、ピンホールの発生、グリーンシート剥離時のグリーンシートの破断等の不具合を解消し、シリコーン化合物以外の離型層を用いた離型フィルムを提供することにある。
【0004】
【課題を解決するための手段】
本発明者らは、上記課題に鑑み鋭意検討した結果、特定の構成を有する離型フィルムによれば、上記課題を容易に解決できることを見いだし、本発明を完成するに至った。
【0005】
すなわち、本発明の要旨は、長鎖アルキル基含有ポリマーからなる離型層で構成された表面(A面)の中心面平均粗さ(SRa(A))が20nm以下、常態剥離力が150mN/cm以下であり、もう一方のフィルム表面(B面)の中心面平均粗さSRa(B)が10〜50nmであることを特徴とする離型フィルムに存する。
【0006】
【発明の実施の形態】
以下、本発明を詳細に説明する。
本発明でいうポリエステルとは、カルボキシル基および水酸基を複数個有する化合物、例えばテレフタル酸、2,6−ナフタレンジカルボン酸、ピロメリット酸などの多価カルボン酸や、エチレングリコール、テトラメチレングリコールなどの多価アルコールや、あるいはp−ヒドロキシ安息香酸などのヒドロキシカルボン酸などを重縮合して得られるポリマーである。フィルム素材として広く用いられるポリエチレンテレフタレートもポリエステルの典型例の1つである。
ポリエステルを重縮合するための触媒としては、三酸化アンチモンなどが通常使用されるが、イオン性不純物を副生成する場合があり、被着物への転着を低減する観点から、二酸化ゲルマニウムなどのゲルマニウム化合物、テトラブチルチタネートなどのチタン化合物あるいはこれらの複合系などの触媒系によって重合することが推奨される。
【0007】
本発明に使用されるフィルムは、押出成形法、流延法などの常法によって得ることができるが、耐熱性の観点から、シートに成形後、必要に応じて延伸・熱固定を施すことが好ましい。
本発明の離型フィルムは、離型層の表面(A面)の中心面平均粗さSRa(A)が20nm以下、好ましくは10nm以下である。SRa(A)が20nmを超えると、グリーンシート成形時に、ハジキ、抜けを生じるなどスラリー塗工性が不十分となるため好ましくない。
本発明の離型フィルムは、A面の反対面(B面)の中心面平均粗さSRa(B)が10〜50nm、好ましくは15〜30nmである。SRa(B)が10nmに満たない場合、ブロッキングの発生や搬送性悪化等の問題を生じる場合があるので好ましくない。SRa(B)が50nmを超えると、A面へのC面表面突起の転写、いわゆる裏写りが生じ、SRa(A)を10nm以上としてしまうため好ましくない。
【0008】
SRa(A)、SRa(B)をかかる範囲とする方法として、基材となるポリエステルフィルムを2層構成とし、それぞれの層に不活性微粒子、例えばシリカ、炭酸カルシウム、カオリン、酸化チタン、酸化アルミニウム、硫酸バリウム、ゼオライト等の無機粒子、または架橋ポリスチレン、アクリル樹脂等の有機粒子を単独または混合体で適当量配合することで、それぞれの表面粗さを設計したものを利用するなどの方法が挙げられる。この場合、使用する粒子の平均粒径、添加量、さらに粒径分布は、本発明の要旨を逸脱しない限り、特に限定されるものではないが、平均粒径は0.1〜4.0μmの範囲、添加量は0.01〜3.0重量%の範囲、粒径分布はその分散が小さいことがそれぞれ好ましい。
また、それぞれの面を構成する層のほかに、中間的な層を1つないしは複数設けることもできる。この場合、中間層には特定表面粗さの形成などの制約がないため、実質的に各種フィラーを含まず、添加フィラーに起因する異物の削減や生産コスト低減等を図ることも工業的観点から望ましい。
【0009】
本発明の離型フィルムのA面は、長鎖アルキル基含有ポリマーで構成される層からなる。長鎖アルキル基含有ポリマーの例としては、ポリオレフィンやメチレン構造を主体とする主鎖に長鎖アルキル基側鎖が結合されたポリマーなどが挙げられる。基材フィルムへの密着性の観点からは、特に長鎖アルキル基側鎖を有するポリマーであって、長鎖アルキル基側鎖がエステル結合で主鎖に結合されているものが特に推奨される。エステル結合を有することで基材ポリエステルフィルムへの密着性が良好となる。エステル結合としては、カルボン酸エステル、カルバミン酸エステルなどが挙げられる。すなわち、ポリアルキル(メタ)アクリレートやポリビニルアルキルカルバメート、および他重合単位がこれらに共重合されたものなどが好適である。側鎖となる長鎖アルキル基としては炭素数が10〜22のポリメチレン基が、表面エネルギーが低く離型性も良いので好適である。これらポリマーには必要に応じてUV硬化、熱硬化などの架橋処理を可能ならしめるように化学修飾し、耐溶剤性を付与してもよい。
【0010】
本発明の離型フィルムは、離型面における剥離力が150mN/cm以下、好ましくは100mN/cm以下である。剥離力が150mN/cmを超えると、軽剥離用途に適さないため好ましくない。剥離力の下限は、通常5mN/cmとされる。
なお、離型層が凝集破壊を生じやすく、剥落するために剥離力が小さくなるのでは、本発明の主旨にそぐわないので、前述の常態剥離力は、残留接着率が80%以上、好ましくは90%以上である上で実現されることが望まれる。
基材フィルムの表面に長鎖アルキル基含有ポリマー離型層を形成する方法としては、例えば、ホットメルト法、塗布法、共押出法などの方法が挙げられる。塗布法の場合には、原崎勇次著、槇書店、1979年発行、「コーティング方式」に示されるリバースロールコーター、グラビアコーター、ロッドコーター、エアドクターコーターまたはこれら以外の塗布装置を使用し、基材フィルム製造工程外で塗布液を塗布する方法、フィルム製造工程内で塗布する方法が挙げられる。
【0011】
離型層は基材フィルムの片面にのみに形成してもよいし、両面に形成してもよい。片面のみに形成した場合は、その反対面に、必要に応じ、易滑層、帯電防止層などの層を形成してもよい。また、基材フィルムと離型層との間には、易接着層、帯電防止層などの中間層を設けてもよい。さらに、必要に応じ、基材フィルムの表面には、コロナ放電処理などの易接着処理を行ってもよい。
離型層の厚さは、通常10nm以上、好ましくは50nm以上である。離型層の厚さが10nm未満の場合には、均一な層が得難いために剥離性が劣るようになることがある。一方、上限は、特に限定はないが、厚過ぎる場合はコストアップ要因となること、場合によっては10μm以上で滑り性が低下すること等から、10μm以下にすることが推奨される。
本発明の離型フィルムには、発明の主旨を損ねない範囲内で必要に応じ、各種安定剤、紫外線吸収剤、酸化防止剤、可塑剤、消包剤、塗布性改良剤、増粘剤、界面活性剤、潤滑剤、染料、顔料、高分子化合物などを添加してもよい。
【0012】
【実施例】
以下、本発明を実施例によりさらに詳細に説明するが、本発明は、その要旨を越えない限り、以下の実施例に限定されるものではない。なお、実施例および比較例中「部」とあるのは固形分としての「重量部」を示す。
【0013】
(1)中心面平均粗さの測定
3cm角のフィルム試料の表面にAl蒸着を行い、直接位相検出干渉法、いわゆる2光束干渉法を用いた非接触式3次元粗さ計(マイクロマップ社製512)で、測定波長:554nm、対物レンズ倍率:20倍の条件にて、突起高さ分布曲線より、232μm×177μmの測定領域におけるフィルム表面の中心面平均粗さSRaを50点にわたり測定し、50点のSRa値を平均して、フィルムのSRaを算出した。
【0014】
(2)スラリー塗工性の評価
下記組成よりなるセラミックスラリーを湿潤状態で5μmとなるようにフィルム面上に塗布し、その際のスラリー塗工性を下記判定基準にて判定を行った。
<セラミックスラリー組成>
セラミック粉体(チタン酸バリウム) 100部
結合剤(ポリビニルブチラール樹脂) 5部
可塑剤(フタル酸ジオクチル) 1部
トルエン/MEK混合溶媒(1:1の配合比率) 10部
<スラリー塗工性 判定基準>
◎:スラリーの塗工性が極めて良好
○:スラリーの塗工性が良好
△:微小なスラリーのはじきが見られる
×:スラリーをはじく
◎、○は実用上問題ないレベルである。
【0015】
(3)離型フィルムのブロッキング性の評価
フィルムを10cm角に裁断し、A面とB面が合わさるように10枚重ね、100℃、1時間、10kg/cm2の条件下でプレスした後、剥離時のブロッキング発生の程度を、下記判定基準にて判定した。
<判定基準>
◎:ブロッキングの発生が全く認められない。
○:ブロッキングの発生が殆どない。
△:ブロッキングの発生が認められる。
×:ブロッキングの発生が顕著に認められる。
◎、○、△は、実用上問題ないレベルである。
【0016】
(4)剥離力[mN/cm]
離型層表面に、粘着テープ「No.502」(日東電工(株)製)を貼り付けて、室温にて1時間放置後、引張試験機にて引張速度300mm/分で180°剥離を行い、剥離が安定した領域における平均剥離荷重を粘着テープ幅で除した値を剥離力とした。
【0017】
実施例および比較例において用いたフィルムの製造方法は、以下のとおりである。
(ポリエステルの製造)
テレフタル酸86部、エチレングリコール70部を反応器に採り、約250℃で4時間エステル化反応を行った。次いで、二酸化ゲルマニウム0.012部、リン酸0.01部(ポリマ−に対してリン元素として32ppm)を加え、250℃から285℃まで徐々に昇温すると共に圧力を徐々に減じて0.5mmHgとした。4時間後、重合反応を停止し、極限粘度0.68のポリエチレンテレフタレート(ポリエステルAとする)を得た。得られたポリエステル中に残存するGe、Pそれぞれの元素量は、各々ポリマーに対し、45ppm,25ppmであった。
ポリエステルAの製造に際して、平均粒径0.7μmの炭酸カルシウムを20000ppm添加したものをポリエステルBとした。
ポリエステルAの製造に際して、平均粒径2.4μmの非晶質シリカを20000ppm添加したものをポリエステルCとした。
ポリエステルAの製造に際して、平均粒径0.2μmの酸化アルミニウムを20000ppm添加したものをポリエステルDとした。
【0018】
(ポリエステルフィルムの製造)
各種混合比のポリエチレンテレフタレートを1台乃至3台のベント式2軸押出機にて溶融し、Tダイよりキャストドラム上に共押出し、ガラス転移点未満まで急冷し、実質的に非晶質の多層シートを得た。但し、キャストに際しては、A面となるべき側がキャストドラムに設置するように共押出の層序を決定した。得られた非晶質シートをロール延伸機にて90℃で3倍長手方向に延伸し、さらに、テンター延伸機にて100℃で4倍横方向に延伸した。引き続き、定幅のまま230℃で10秒間熱固定を施し、さらに、180℃で幅方向に5%の弛緩を施し、厚さ50μmのポリエステルフィルムを得た。
【0019】
(離型フィルムの製造)
2%濃度となるように適宜溶解・希釈して得た下記表1のコート液をウェット厚みが12μmとなるようにメイヤバーにてポリエステルフィルム上に塗布し、引き続き120℃2分間の熱処理を行い、離型フィルムを得た。
【0020】
実施例1〜2、比較例1〜2
基材ポリエステルフィルムの共押出に際して、P層(A面側の表層)、Q層(中間層)、R層(B面を構成する表層)それぞれに、表1の配合比で各種ポリエステルを混合したものを積層し、得られた2軸配向ポリエステルフィルムに、同じく表1に掲げたコート剤を塗設して離型フィルムを得た。
【0021】
【表1】
上記表中、RA80はアシオレジンRA−80(アシオ産業(株)製)、RA95はアシオレジンRA−95H(アシオ産業(株)製)である。
【0022】
【発明の効果】
本発明の離型フィルムは、薄層グリーンシートの工程フィルムとして好適であり、その工業的価値は非常に高い。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a release film, and in particular, relates to a release film that is suitably used for forming a green sheet.
[0002]
[Prior art]
Conventionally, as a carrier film for forming a green sheet of a ceramic multilayer capacitor, a release film in which a polyester film is used as a base material and a silicone compound such as polysiloxane is laminated is used. In recent years, ceramic green sheets themselves have been made thinner with the miniaturization of capacitors accompanying the miniaturization of electronic devices.
Under such circumstances, problems such as breakage of the green sheet frequently occur at the time of slurry repelling, pinhole generation, and green sheet peeling at the time of ceramic slurry coating, and improvement is required.
In addition, when a release layer is installed and wound, problems such as blocking and deterioration in the transportability of the release film may occur, and variations in dielectric constant when electrodes are provided on both sides of the ceramic layer to form a capacitor. There is a need for a release film that can improve these properties, such as increasing the thickness.
Furthermore, since the siloxane-based low molecular weight substance is disliked depending on the use, it is desired that the release layer is other than the silicone compound.
[0003]
[Problems to be solved by the invention]
The present invention has been made in view of the above circumstances, and the problem to be solved is, for example, when it is used as a carrier film for forming a green sheet of a ceramic multilayer capacitor, the repelling of the slurry during the coating of the ceramic slurry and the occurrence of pinholes An object of the present invention is to provide a release film using a release layer other than the silicone compound by eliminating problems such as breakage of the green sheet when the green sheet is peeled off.
[0004]
[Means for Solving the Problems]
As a result of intensive studies in view of the above problems, the present inventors have found that the above problems can be easily solved by a release film having a specific configuration, and have completed the present invention.
[0005]
That is, the gist of the present invention is that the center plane average roughness (SRa (A)) of a surface (A surface) composed of a release layer composed of a long-chain alkyl group-containing polymer is 20 nm or less, and the normal state peeling force is 150 mN / The release film is characterized by having a center plane average roughness SRa (B) of 10 to 50 nm on the other film surface (B surface).
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The polyester referred to in the present invention is a compound having a plurality of carboxyl groups and hydroxyl groups, for example, polyvalent carboxylic acids such as terephthalic acid, 2,6-naphthalenedicarboxylic acid and pyromellitic acid, and many compounds such as ethylene glycol and tetramethylene glycol. It is a polymer obtained by polycondensation of a monohydric alcohol or a hydroxycarboxylic acid such as p-hydroxybenzoic acid. Polyethylene terephthalate, which is widely used as a film material, is also a typical example of polyester.
As a catalyst for polycondensation of polyester, antimony trioxide is usually used, but ionic impurities may be by-produced, and germanium such as germanium dioxide is used from the viewpoint of reducing transfer to the adherend. It is recommended to polymerize with a catalyst system such as a compound, a titanium compound such as tetrabutyl titanate, or a composite system thereof.
[0007]
The film used in the present invention can be obtained by conventional methods such as extrusion molding and casting, but from the viewpoint of heat resistance, it may be stretched and heat-set as necessary after being formed into a sheet. preferable.
In the release film of the present invention, the center plane average roughness SRa (A) of the surface (A surface) of the release layer is 20 nm or less, preferably 10 nm or less. When SRa (A) exceeds 20 nm, slurry coating properties such as repellency and dropout are insufficient at the time of forming a green sheet, which is not preferable.
In the release film of the present invention, the center surface average roughness SRa (B) of the surface opposite to the A surface (B surface) is 10 to 50 nm, preferably 15 to 30 nm. When SRa (B) is less than 10 nm, problems such as blocking and deterioration of transportability may occur, which is not preferable. If SRa (B) exceeds 50 nm, transfer of the C-plane surface protrusion to the A-plane, so-called show-through occurs, and SRa (A) is set to 10 nm or more, which is not preferable.
[0008]
As a method for setting SRa (A) and SRa (B) in such a range, a polyester film as a base material has a two-layer structure, and each layer has inert fine particles such as silica, calcium carbonate, kaolin, titanium oxide, and aluminum oxide. In addition, inorganic particles such as barium sulfate and zeolite, or organic particles such as crosslinked polystyrene and acrylic resin may be used alone or in a mixture to blend them in an appropriate amount to use a method for designing each surface roughness. It is done. In this case, the average particle size, the amount added, and the particle size distribution of the particles used are not particularly limited as long as they do not depart from the gist of the present invention, but the average particle size is 0.1 to 4.0 μm. It is preferable that the range and addition amount are in the range of 0.01 to 3.0% by weight, and that the particle size distribution has a small dispersion.
In addition to the layers constituting each surface, one or a plurality of intermediate layers can be provided. In this case, since there is no restriction such as the formation of specific surface roughness in the intermediate layer, it does not contain various fillers substantially, and it is also possible from the industrial point of view to reduce foreign matter and production costs caused by the added filler. desirable.
[0009]
The A surface of the release film of the present invention comprises a layer composed of a long chain alkyl group-containing polymer. Examples of the long-chain alkyl group-containing polymer include polyolefins and polymers in which a long-chain alkyl group side chain is bonded to a main chain mainly composed of a methylene structure. From the viewpoint of adhesion to the base film, a polymer having a long-chain alkyl group side chain, in which the long-chain alkyl group side chain is bonded to the main chain by an ester bond is particularly recommended. By having an ester bond, the adhesion to the base polyester film is improved. Examples of the ester bond include carboxylic acid esters and carbamic acid esters. That is, polyalkyl (meth) acrylate, polyvinyl alkyl carbamate, and those obtained by copolymerizing other polymerized units are suitable. As the long-chain alkyl group serving as the side chain, a polymethylene group having 10 to 22 carbon atoms is preferable because of its low surface energy and good releasability. If necessary, these polymers may be chemically modified so that crosslinking treatment such as UV curing and heat curing is possible, and solvent resistance may be imparted.
[0010]
The release film of the present invention has a peel force on the release surface of 150 mN / cm or less, preferably 100 mN / cm or less. A peeling force exceeding 150 mN / cm is not preferable because it is not suitable for light peeling applications. The lower limit of the peeling force is usually 5 mN / cm.
Note that the release layer is likely to cause cohesive failure, and the peeling force is small because it peels off. This does not meet the gist of the present invention. Therefore, the above-mentioned normal peeling force has a residual adhesion rate of 80% or more, preferably 90%. It is desired to be realized on the basis of% or more.
Examples of the method for forming the long-chain alkyl group-containing polymer release layer on the surface of the base film include a hot melt method, a coating method, and a coextrusion method. In the case of the coating method, use the reverse roll coater, gravure coater, rod coater, air doctor coater or other coating device shown in “Coating Method” by Yuji Harasaki, Tsuji Shoten, 1979, The method of apply | coating a coating liquid outside a film manufacturing process and the method of apply | coating within a film manufacturing process are mentioned.
[0011]
The release layer may be formed only on one side of the base film, or may be formed on both sides. When it is formed on only one side, a layer such as a slippery layer or an antistatic layer may be formed on the opposite side as necessary. Moreover, you may provide intermediate | middle layers, such as an easily bonding layer and an antistatic layer, between a base film and a mold release layer. Furthermore, if necessary, the surface of the base film may be subjected to easy adhesion treatment such as corona discharge treatment.
The thickness of the release layer is usually 10 nm or more, preferably 50 nm or more. When the thickness of the release layer is less than 10 nm, it may be difficult to obtain a uniform layer, and the peelability may be deteriorated. On the other hand, the upper limit is not particularly limited, but it is recommended that the upper limit is 10 μm or less because it is a cause of cost increase if it is too thick, and in some cases slipperiness is lowered at 10 μm or more.
In the release film of the present invention, various stabilizers, ultraviolet absorbers, antioxidants, plasticizers, anti-packaging agents, coatability improvers, thickeners, as necessary, within a range that does not impair the gist of the invention. Surfactants, lubricants, dyes, pigments, polymer compounds and the like may be added.
[0012]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded. In the examples and comparative examples, “parts” means “parts by weight” as a solid content.
[0013]
(1) Measurement of center plane average roughness Non-contact type three-dimensional roughness meter (manufactured by Micromap Co., Ltd.) by depositing Al on the surface of a 3 cm square film sample and using direct phase detection interferometry, so-called two-beam interferometry. 512), measuring the center plane average roughness SRa of the film surface in a measurement region of 232 μm × 177 μm over 50 points under the conditions of the measurement wavelength: 554 nm and the objective lens magnification: 20 times, The SRa of the film was calculated by averaging the SRa values at 50 points.
[0014]
(2) Evaluation of slurry coatability A ceramic slurry having the following composition was applied on the film surface so as to be 5 μm in a wet state, and the slurry coatability at that time was determined according to the following criteria.
<Ceramic slurry composition>
Ceramic powder (barium titanate) 100 parts Binder (polyvinyl butyral resin) 5 parts Plasticizer (dioctyl phthalate) 1 part Toluene / MEK mixed solvent (1: 1 mixing ratio) 10 parts <Slurry coating property Criteria >
A: Extremely good coating property of slurry O: Good coating property of slurry Δ: Repelling of minute slurry is observed X: Repelling slurry A, ○ is a level that is not problematic in practical use.
[0015]
(3) Evaluation of the blocking property of the release film The film was cut into 10 cm square, 10 sheets were stacked so that the A side and the B side were combined, and pressed at 100 ° C. for 1 hour under the conditions of 10 kg / cm 2 . The degree of occurrence of blocking during peeling was determined according to the following criteria.
<Criteria>
(Double-circle): Generation | occurrence | production of blocking is not recognized at all.
○: Almost no blocking occurred.
Δ: Generation of blocking is observed.
X: Generation | occurrence | production of blocking is recognized notably.
“◎”, “◯”, and “Δ” are levels that have no practical problem.
[0016]
(4) Peeling force [mN / cm]
Adhesive tape “No. 502” (manufactured by Nitto Denko Co., Ltd.) is applied to the surface of the release layer, left at room temperature for 1 hour, and then peeled 180 ° at a tensile speed of 300 mm / min with a tensile tester. The value obtained by dividing the average peeling load in the region where the peeling was stable by the width of the adhesive tape was defined as the peeling force.
[0017]
The manufacturing method of the film used in the Example and the comparative example is as follows.
(Manufacture of polyester)
86 parts of terephthalic acid and 70 parts of ethylene glycol were placed in a reactor and subjected to esterification at about 250 ° C. for 4 hours. Next, 0.012 part of germanium dioxide and 0.01 part of phosphoric acid (32 ppm as phosphorus element with respect to the polymer) were added, the temperature was gradually raised from 250 ° C. to 285 ° C., and the pressure was gradually reduced to 0.5 mmHg. It was. After 4 hours, the polymerization reaction was stopped to obtain polyethylene terephthalate (referred to as polyester A) having an intrinsic viscosity of 0.68. The respective element amounts of Ge and P remaining in the obtained polyester were 45 ppm and 25 ppm with respect to the polymer, respectively.
Polyester B was prepared by adding 20000 ppm of calcium carbonate having an average particle size of 0.7 μm during the production of polyester A.
Polyester C was prepared by adding 20000 ppm of amorphous silica having an average particle size of 2.4 μm during the production of polyester A.
Polyester D was prepared by adding 20000 ppm of aluminum oxide having an average particle size of 0.2 μm during the production of polyester A.
[0018]
(Manufacture of polyester film)
Polyethylene terephthalate with various mixing ratios is melted in one to three bent type twin screw extruders, co-extruded from a T-die onto a cast drum, rapidly cooled to below the glass transition point, and substantially amorphous multilayer A sheet was obtained. However, when casting, the co-extrusion stratigraphy was determined so that the side to be the A side was installed on the cast drum. The obtained amorphous sheet was stretched 3 times in the longitudinal direction at 90 ° C. with a roll stretching machine, and further stretched 4 times in the transverse direction at 100 ° C. with a tenter stretching machine. Subsequently, the film was heat-set at 230 ° C. for 10 seconds while maintaining the constant width, and further relaxed by 5% in the width direction at 180 ° C. to obtain a polyester film having a thickness of 50 μm.
[0019]
(Manufacture of release film)
The coating solution shown in Table 1 below, which was obtained by appropriately dissolving and diluting to a 2% concentration, was applied on a polyester film with a Mayer bar so that the wet thickness was 12 μm, followed by heat treatment at 120 ° C. for 2 minutes, A release film was obtained.
[0020]
Examples 1-2 and Comparative Examples 1-2
Upon co-extrusion of the base polyester film, various polyesters were mixed in the blending ratios shown in Table 1 to each of the P layer (surface on the A side), Q layer (intermediate layer), and R layer (surface layer constituting the B surface). The layers were laminated, and the obtained biaxially oriented polyester film was coated with the coating agents listed in Table 1 to obtain a release film.
[0021]
[Table 1]
In the above table, RA80 is ashioresin RA-80 (manufactured by Ashio Sangyo Co., Ltd.), and RA95 is ashioresin RA-95H (manufactured by Ashio Sangyo Co., Ltd.).
[0022]
【The invention's effect】
The release film of the present invention is suitable as a process film for thin-layer green sheets, and its industrial value is very high.
Claims (1)
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JP2006181993A (en) * | 2004-12-28 | 2006-07-13 | Toyobo Co Ltd | Manufacturing method of mold release film roll for manufacturing thin ceramic sheet |
JP4961667B2 (en) * | 2004-12-28 | 2012-06-27 | 東洋紡績株式会社 | Method for producing release film roll for producing thin ceramic sheet |
JP4923484B2 (en) * | 2005-08-31 | 2012-04-25 | 東洋紡績株式会社 | Laminated polyethylene terephthalate film roll for mold release |
JP2013252634A (en) * | 2012-06-06 | 2013-12-19 | Mitsubishi Plastics Inc | Laminated polyester film |
JP5907640B2 (en) * | 2012-07-02 | 2016-04-26 | 三菱樹脂株式会社 | Release film |
JP6105366B2 (en) * | 2013-04-24 | 2017-03-29 | 信越ポリマー株式会社 | Release film |
WO2016098779A1 (en) * | 2014-12-18 | 2016-06-23 | 東洋紡株式会社 | Mold release layer, molded article comprising mold release layer, and mold release agent |
JP6172338B2 (en) * | 2016-05-27 | 2017-08-02 | 三菱ケミカル株式会社 | Laminated polyester film |
JP6366029B2 (en) | 2016-08-25 | 2018-08-01 | 東レフィルム加工株式会社 | Release film |
JP6970400B2 (en) * | 2017-09-28 | 2021-11-24 | 東レフィルム加工株式会社 | Release film and laminate using it |
KR20210039460A (en) | 2018-08-09 | 2021-04-09 | 도레이 필름 카코우 가부시키가이샤 | Release film |
KR20210148084A (en) | 2019-03-25 | 2021-12-07 | 니치유 가부시키가이샤 | Block copolymer, release agent composition, release layer, and release sheet |
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