JPH11300894A - Release film for process - Google Patents
Release film for processInfo
- Publication number
- JPH11300894A JPH11300894A JP10122807A JP12280798A JPH11300894A JP H11300894 A JPH11300894 A JP H11300894A JP 10122807 A JP10122807 A JP 10122807A JP 12280798 A JP12280798 A JP 12280798A JP H11300894 A JPH11300894 A JP H11300894A
- Authority
- JP
- Japan
- Prior art keywords
- film
- release
- weight
- parts
- resin
- 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.)
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Links
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- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、セラミックスシー
トや樹脂シート、例えばセラミックスグリーンシートや
マーキングフィルム等の製造に有用な工程用離型フィル
ムに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process release film useful for producing ceramic sheets and resin sheets, for example, ceramic green sheets and marking films.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】多層セ
ラミックス基板、積層セラミックスコンデンサー等の製
造に使用されるグリーンシートは、一般にプラスチック
フィルム（例えばポリエステルフィルム、ポリイミドフ
ィルム、ポリメチルペンテンフィルム等）単体又はこれ
らフィルムの片面にシリコーン等の離型剤をコーティン
グした離型フィルム上に適宜な厚みでセラミックススラ
リーを塗布し、これを熱乾燥して生産される。2. Description of the Related Art Green sheets used in the production of multilayer ceramic substrates, multilayer ceramic capacitors and the like are generally made of a plastic film (eg, polyester film, polyimide film, polymethylpentene film, etc.) alone or A ceramic slurry is applied at an appropriate thickness onto a release film in which one side of these films is coated with a release agent such as silicone, and the slurry is dried by heating to produce a ceramic slurry.
【０００３】このセラミックススラリーは、セラミック
ス粉末、可塑剤、バインダー等からなり、多くの組み合
わせが可能であるが、バインダーの種類とその溶解性能
から有機溶剤系と水系に大別される。[0003] The ceramic slurry is composed of ceramic powder, a plasticizer, a binder, and the like, and many combinations are possible. However, the slurry is roughly classified into an organic solvent type and an aqueous type depending on the type of the binder and its dissolving performance.
【０００４】この場合、有機溶剤系スラリーは、例えば
バインダーとしてポリビニルブチラールやエチルセルロ
ースを用い、トルエン、エタノール等の溶剤を使用した
ものである。この有機溶剤系スラリーは、スラリーの粘
度特性などから薄膜で強靱なグリーンシートを得ること
が可能であるが、安全性、作業性に難があり、また環境
衛生面からも問題があった。In this case, the organic solvent-based slurry uses, for example, polyvinyl butyral or ethyl cellulose as a binder and uses a solvent such as toluene or ethanol. This organic solvent-based slurry makes it possible to obtain a thin and tough green sheet due to the viscosity characteristics of the slurry and the like, but has problems in safety and workability, and also has problems in terms of environmental hygiene.
【０００５】一方、水系スラリーは、一般的にバインダ
ーとしてポリビニルアルコール及びアクリル系樹脂を用
い、可塑剤にはポリエチレングリコールが用いられるも
のである。この水系スラリーは、安全面などの問題はな
いものの、塗工性、品質面に劣るため、溶剤系に比べて
高品質のセラミックスグリーンシートを得難いという欠
点があった。このことは、同様に水系樹脂から樹脂シー
トを成形する場合にも生ずる問題であった。On the other hand, an aqueous slurry generally uses polyvinyl alcohol and an acrylic resin as a binder, and uses polyethylene glycol as a plasticizer. Although this aqueous slurry has no problem in terms of safety and the like, it is inferior in coatability and quality, and thus has a drawback that it is difficult to obtain a high-quality ceramic green sheet as compared with a solvent-based slurry. This is a problem that also occurs when a resin sheet is formed from an aqueous resin.
【０００６】このような水系スラリーを用いた場合に生
じる問題の原因は、表面に熱硬化性シリコーンを離型層
として設けた離型フィルムが、水系塗液を塗工時にはじ
き易く、凝集などが生じ、使用できないためと考えられ
る。同様に長鎖アルキル基を含有したポリビニルカーバ
メート、ポリエチレンイミン等もはじきが発生し、均一
な塗膜が形成できない。[0006] The cause of the problem that occurs when such an aqueous slurry is used is that a release film having a thermosetting silicone as a release layer on its surface is easily repelled when an aqueous coating liquid is applied, and agglomeration and the like occur. Probably because it occurred and could not be used. Similarly, polyvinyl carbamate, polyethyleneimine and the like containing a long-chain alkyl group are repelled, and a uniform coating film cannot be formed.
【０００７】これらの問題の解決策としては、塗液を高
粘度化する方法や塗液の表面張力を低減するために界面
活性剤を添加する方法が提案されている。As a solution to these problems, there have been proposed a method of increasing the viscosity of the coating liquid and a method of adding a surfactant to reduce the surface tension of the coating liquid.
【０００８】しかしながら、高粘度の塗液は塗工に際し
レベリングが難しく、均一な塗膜が形成され難い。ま
た、界面活性剤を添加する方法では、塗膜から界面活性
剤がブリードし、塗膜の特性に悪影響を及ぼす等の欠点
があった。従って、いずれの方法も満足な塗工性改善策
とは言い難いものであった。However, a high-viscosity coating liquid is difficult to level at the time of coating, and it is difficult to form a uniform coating film. In addition, the method of adding a surfactant has a drawback that the surfactant bleeds from the coating film and adversely affects the properties of the coating film. Therefore, none of these methods can be said to be satisfactory measures for improving coatability.
【０００９】本発明は、上記事情に鑑みなされたもの
で、水系セラミックススラリーを均一に塗工でき、かつ
乾燥後のグリーンシートの剥離性にも優れ、セラミック
ススラリーを用いて高品質のグリーンシートを生産可能
であり、また樹脂シートの製造などにも有用な工程用離
型フィルムを提供することを目的とする。The present invention has been made in view of the above circumstances, and it is possible to apply a water-based ceramic slurry uniformly and to have excellent releasability of a green sheet after drying. An object of the present invention is to provide a release film for a process that can be produced and is also useful for producing a resin sheet.
【００１０】[0010]
【課題を解決するための手段及び発明の実施の形態】本
発明者は、上記目的を達成するため鋭意検討を行った結
果、プラスチックフィルムの片面又は両面に離型層が形
成された工程用離型フィルムにおいてその離型層を、
（Ａ）アルキッド樹脂、アミノ樹脂及びアクリル樹脂か
ら選ばれる少なくとも２種以上の樹脂と、必要により
（Ｂ）芳香族性有機基を１０〜４０モル％含有するカル
ビトール変性シリコーンと、（Ｃ）縮合触媒と、（Ｄ）
溶剤とを配合した離型剤組成物によって形成することに
より、水系の塗工液、特に水系セラミックススラリーに
対してもはじき、凝集などを発生させず、優れた塗工性
と離型性を奏する工程用離型フィルムが得られることを
見出した。Means for Solving the Problems and Embodiments of the Invention The present inventors have made intensive studies to achieve the above object, and as a result, have found that a release film for a process in which a release layer is formed on one or both surfaces of a plastic film. The release layer in the mold film,
(A) at least two or more resins selected from alkyd resins, amino resins and acrylic resins, and if necessary (B) carbitol-modified silicone containing 10 to 40 mol% of aromatic organic groups, and (C) condensation A catalyst and (D)
By forming with a release agent composition blended with a solvent, it does not repel water-based coating liquids, especially water-based ceramic slurries, does not generate aggregation, etc., and exhibits excellent coating properties and release properties. It has been found that a release film for a process can be obtained.
【００１１】即ち、従来のシリコーン系離型剤を使用し
た離型フィルムは、離型層の表面張力が低いため、水系
セラミックススラリーを使用すると塗液をはじき易く均
一なセラミックスグリーンシートが製造できないもので
あったが、本発明の工程用離型フィルムは、上記樹脂成
分からなる離型剤組成物で離型層を形成することによ
り、この離型層は、プラスチックフィルムとの密着性に
優れ、良好に塗布し得る上、この離型層上に水系の塗工
液を塗布しても濡れ性が良好であり、はじきによる欠陥
のない塗膜が得られ、塗膜の剥離性能にも優れたもので
ある。それ故、本発明の工程用離型フィルムは、セラミ
ックスシートや樹脂シート、例えばセラミックスグリー
ンシートやマーキングフィルム等の製造に使用し得、ま
た粘着剤層の保護材などとしても好適に使用し得ること
を知見し、本発明をなすに至った。That is, a conventional release film using a silicone release agent has a low surface tension of a release layer. Therefore, when an aqueous ceramic slurry is used, a coating liquid is easily repelled and a uniform ceramic green sheet cannot be produced. However, the release film for the process of the present invention, by forming a release layer with a release agent composition comprising the resin component, the release layer has excellent adhesion to the plastic film, In addition to being able to be applied well, even when an aqueous coating liquid is applied on this release layer, the wettability is good, a coating film without defects due to repelling is obtained, and the coating film has excellent peeling performance. Things. Therefore, the process release film of the present invention can be used for manufacturing a ceramic sheet or a resin sheet, for example, a ceramic green sheet or a marking film, and can also be suitably used as a protective material for an adhesive layer. And found the present invention.
【００１２】従って、本発明は、プラスチックフィルム
の片面又は両面に離型層が形成された工程用離型フィル
ムであって、該離型層が、 （Ａ）アルキッド樹脂、アミノ樹脂及びアクリル樹脂から選ばれる少なくとも２ 種以上の樹脂 １００重量部 （Ｂ）芳香族性有機基を１０〜４０モル％含有するカルビトール変性シリコーン ０〜６重量部 （Ｃ）縮合触媒 １〜１０重量部 （Ｄ）溶剤 各成分を均一に溶解し得る量 を含有してなる離型剤組成物により形成されたものであることを特徴とする工程 用離型フィルムを提供する。Accordingly, the present invention is a process release film in which a release layer is formed on one or both sides of a plastic film, wherein the release layer comprises (A) an alkyd resin, an amino resin, and an acrylic resin. 100 parts by weight of at least two or more selected resins (B) Carbitol-modified silicone containing 10 to 40 mol% of aromatic organic groups 0 to 6 parts by weight (C) Condensation catalyst 1 to 10 parts by weight (D) Solvent Provided is a process release film characterized by being formed from a release agent composition containing an amount capable of uniformly dissolving each component.
【００１３】以下、本発明につき更に詳細に説明する
と、本発明の工程用離型フィルムは、プラスチックフィ
ルムの片面又は両面に離型層が形成されたものである。Now, the present invention will be described in further detail. The process release film of the present invention is a plastic film having a release layer formed on one or both sides of a plastic film.
【００１４】ここで、プラスチックフィルムとしては、
例えばポリエステル系フィルム、ポリイミドフィルム、
ポリイミドエーテルフィルム等のポリイミド系フィル
ム、ポリアミド系フィルムなどを挙げることができる。
これらの中では、特にポリエステル系フィルムがコスト
パーフォーマンスの点で好ましく使用される。Here, as the plastic film,
For example, polyester film, polyimide film,
Examples thereof include a polyimide film such as a polyimide ether film and a polyamide film.
Among these, a polyester film is particularly preferably used in terms of cost performance.
【００１５】ポリエステル系フィルムとしては、芳香族
二塩基酸又はそのエステル形成性誘導体とジオールから
合成される結晶性の線状飽和ポリエステルが好適であ
り、具体的には、ポリエチレンテレフタレート、ポリプ
ロピレンテレフタレート、ポリブチレンテレフタレー
ト、ポリエチレン−２，６−ナフタレート等が例示され
る。As the polyester film, a crystalline linear saturated polyester synthesized from an aromatic dibasic acid or an ester-forming derivative thereof and a diol is preferable, and specifically, polyethylene terephthalate, polypropylene terephthalate, and poly (ethylene terephthalate). Butylene terephthalate, polyethylene-2,6-naphthalate and the like are exemplified.
【００１６】なお、これらフィルムは、従来から知られ
ている方法で製造でき、フィルム特性の改良を目的に種
々の改良剤を添加することもできる。These films can be produced by a conventionally known method, and various improving agents can be added for the purpose of improving film characteristics.
【００１７】使用されるプラスチックフィルムの厚みは
特に限定されるものではないが、耐熱性、作業性等から
２０〜２００μｍが好ましい。The thickness of the plastic film used is not particularly limited, but is preferably 20 to 200 μm from the viewpoint of heat resistance and workability.
【００１８】本発明において、上記フイルムの片面又は
両面に形成される離型層は、 （Ａ）アルキッド樹脂、アミノ樹脂及びアクリル樹脂か
ら選ばれる少なくとも２種以上の樹脂を主成分とし、こ
れに好ましくは（Ｂ）芳香族性有機基を１０〜４０モル
％含有するカルビトール変性シリコーンを配合し、
（Ｃ）縮合触媒を配合すると共に、これら成分を（Ｄ）
溶剤に溶解した離型剤組成物から形成される。In the present invention, the release layer formed on one side or both sides of the above-mentioned film preferably comprises (A) at least two or more resins selected from alkyd resins, amino resins and acrylic resins as main components, and Blends (B) a carbitol-modified silicone containing 10 to 40 mol% of an aromatic organic group,
(C) A condensation catalyst is blended and these components are added to (D)
It is formed from a release agent composition dissolved in a solvent.
【００１９】ここで、（Ａ）成分として使用されるアル
キッド樹脂としては、中性油にグリセリンと無水フタル
酸を反応させたものが好ましく、例えばやし油変性アル
キッド樹脂、ひまし油変性アルキッド樹脂やそれらにア
クリル基を導入したものなどが挙げられる。As the alkyd resin used as the component (A), those obtained by reacting glycerin and phthalic anhydride with a neutral oil are preferable. For example, coconut oil-modified alkyd resins, castor oil-modified alkyd resins, and the like. And an acrylic group.
【００２０】アミノ樹脂としては、例えばメチル化メラ
ミン樹脂、ブチル化メラミン樹脂、ブチル化尿素メラミ
ン樹脂等が挙げられる。Examples of the amino resin include a methylated melamine resin, a butylated melamine resin, and a butylated urea melamine resin.
【００２１】アクリル樹脂としては、メチルメタクリレ
ート、ブチルアクリレート、２−エチルヘキシルアクリ
レート等のモノマーを単独或いは数種類共重合したもの
が用いられる。As the acrylic resin, those obtained by copolymerizing monomers such as methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate or the like alone or in combination of several types are used.
【００２２】本発明では、上記樹脂から選ばれる少なく
とも２種以上の樹脂を組み合わせて使用する。この場
合、樹脂の組み合わせに特に制限はないが、アルキッド
樹脂とアミノ樹脂とを組み合わせ、更に必要に応じてア
クリル樹脂を使用することが好適である。この場合、各
樹脂の配合比率は、アルキッド樹脂：アミノ樹脂は重量
比で９０：１０〜５０：５０の範囲で使用することが好
適であり、アクリル樹脂を使用する場合は、前記混合物
に対し０〜２００重量％、特に０〜１００重量％の範囲
で配合することが好ましい。In the present invention, at least two or more resins selected from the above resins are used in combination. In this case, the combination of the resins is not particularly limited, but it is preferable to combine the alkyd resin and the amino resin, and further use an acrylic resin as needed. In this case, the compounding ratio of each resin is preferably such that the weight ratio of alkyd resin: amino resin is in the range of 90:10 to 50:50, and when acrylic resin is used, the mixing ratio of alkyd resin to amino resin is 0 to 50%. It is preferable to mix in the range of 200 to 200% by weight, particularly 0 to 100% by weight.
【００２３】次に、（Ｂ）成分であるカルビトール変性
シリコーンは、分子中に芳香族性有機基を１０〜４０モ
ル％含有する。このカルビトール変性シリコーンは、反
応基であるヒドロキシル基含有アルキル基が（Ａ）成分
と反応するもので、このヒドロキシル基含有アルキル基
は、分子鎖末端及び側鎖のいずれにあってもよい。Next, the carbitol-modified silicone as the component (B) contains an aromatic organic group in the molecule in an amount of 10 to 40 mol%. In the carbitol-modified silicone, a hydroxyl group-containing alkyl group, which is a reactive group, reacts with the component (A), and the hydroxyl group-containing alkyl group may be located at either a molecular chain terminal or a side chain.
【００２４】芳香族性有機基は、（Ａ）成分と親和する
ために必要な基であり、例えばフェニル基、トリル基、
フェネチル基等が挙げられる。芳香族性有機基の含有量
は、１０〜４０モル％、好ましくは１５〜３５モル％と
するもので、１０モル％未満では相溶性が不足し、４０
モル％を超えると粘度が高くなり、不適当となる。The aromatic organic group is a group necessary for affinity with the component (A), and includes, for example, a phenyl group, a tolyl group,
And a phenethyl group. The content of the aromatic organic group is from 10 to 40 mol%, preferably from 15 to 35 mol%.
If it exceeds mol%, the viscosity will be high, and it will be unsuitable.
【００２５】カルビトール変性シリコーンの粘度は、
１，０００〜１０，０００ｃｐ（２５℃）が好ましい。
（Ｂ）成分の配合量は、（Ａ）成分に対して６重量部以
下、好ましくは３重量部以下であり、６重量部を超える
と分散性が低下し、硬化皮膜の特性もばらついてしま
う。The viscosity of the carbitol-modified silicone is
1,000 to 10,000 cp (25 ° C.) is preferred.
The amount of the component (B) is at most 6 parts by weight, preferably at most 3 parts by weight, based on the amount of the component (A). If the amount exceeds 6 parts by weight, the dispersibility is reduced and the properties of the cured film vary. .
【００２６】本発明では、（Ｂ）成分を配合するに際し
て、（Ａ）及び（Ｂ）成分を単に混合しても目的を達成
することができるが、予め（Ａ）成分に（Ｂ）成分を加
熱反応させたものを配合してもよい。なお、反応条件は
１００〜１６０℃で４〜８時間加熱する条件を採用し得
る。In the present invention, when the component (B) is blended, the object can be achieved by simply mixing the components (A) and (B), but the component (B) is added to the component (A) in advance. Those reacted by heating may be blended. The reaction may be carried out at 100 to 160 ° C. for 4 to 8 hours.
【００２７】（Ｃ）成分の縮合触媒は、有機酸、スズ
系、亜鉛系等の公知のものでよく、その使用量は硬化条
件によって異なるものであるが、通常、（Ａ）成分に対
し１〜１０重量部が適当である。The condensation catalyst for the component (C) may be a known one such as an organic acid, tin-based or zinc-based catalyst. The amount of the catalyst varies depending on the curing conditions. 10 to 10 parts by weight is suitable.
【００２８】次いで、（Ｄ）成分である溶剤としては、
上記各成分を均一に溶解できればよく、種々の溶剤を使
用することができるが、例えばトルエン、メチルエチル
ケトン、酢酸エチル等が好適であり、これら溶剤の１種
を単独で使用しても２種以上を混合して用いることも可
能である。Next, as the solvent as the component (D),
Various solvents can be used as long as the above components can be uniformly dissolved, and for example, toluene, methyl ethyl ketone, ethyl acetate and the like are suitable. Even if one of these solvents is used alone, two or more of them can be used. It is also possible to use a mixture.
【００２９】溶剤の使用量は、各成分を均一に溶解でき
る量であればよく、（Ａ）〜（Ｃ）成分の合計量１００
重量部に対して１００〜４００重量部とすることができ
る。The amount of the solvent used is not particularly limited as long as the components can be uniformly dissolved, and the total amount of the components (A) to (C) is 100.
It can be 100 to 400 parts by weight with respect to parts by weight.
【００３０】本発明では、上記成分を単に混合すること
により離型剤組成物を得ることができる。また、上記の
離型剤組成物をプラスチックフィルムの表面に塗布する
方法としては、一般によく知られた塗布方法でよく、バ
ーコーター、グラビアコーター、リバースコーター、ワ
イヤーバー等を用いて塗布することができ、これを熱風
循環式乾燥機等を使用して１２０〜１８０℃で１２０〜
３０秒間乾燥硬化させることにより硬化被膜を得ること
ができる。なお、乾燥後の離型層膜厚は、０．０５〜
２．０μｍになるようにするのが好ましい。In the present invention, a release agent composition can be obtained by simply mixing the above components. Further, as a method of applying the release agent composition to the surface of the plastic film, a generally well-known application method may be used, and a bar coater, a gravure coater, a reverse coater, a wire bar, or the like may be used. It can be dried at 120-180 ° C. using a hot air circulating dryer or the like.
A cured film can be obtained by drying and curing for 30 seconds. The release layer thickness after drying is 0.05 to
Preferably, the thickness is 2.0 μm.
【００３１】[0031]
【発明の効果】本発明の工程用剥離フィルムは、剥離層
がプラスチックフィルムに密着性良く塗工され、安定し
た性能及び耐久性に優れた剥離被膜を有し、かつ水系塗
工液、特に水系セラミックススラリーを塗工した場合に
おける濡れ性が良好であり、はじきによる欠陥のない塗
工膜が得られる。従って、本発明の工程用剥離フィルム
は、セラミックスシートや樹脂シートなどの製造に好適
に用いられる。The process release film of the present invention has a release layer coated on a plastic film with good adhesion, has a stable release film with excellent performance and durability, and is an aqueous coating solution, especially an aqueous coating solution. The wettability when the ceramic slurry is applied is good, and a coating film free from defects due to repelling can be obtained. Therefore, the process release film of the present invention is suitably used for producing ceramic sheets, resin sheets, and the like.
【００３２】[0032]
【実施例】以下、実施例及び比較例を示し、本発明を具
体的に説明するが、本発明は下記の実施例に制限される
ものではない。EXAMPLES The present invention will be described below in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
【００３３】［実施例１］やし油変性アルキッド樹脂６
５重量部、メチル化メラミン樹脂１５重量部、ブチル化
尿素メラミン樹脂２０重量部をトルエン−メチルエチル
ケトン混合溶剤（重量比１：１）で２重量％（固形分）
になるように溶解し、組成物を得た。この組成物１００
重量部にｐ−トルエンスルホン酸５０％メタノール溶液
０．１重量部を添加した。これを塗工液として使用し、
ポリエステルフィルム上を乾燥後、厚み０．３μｍにな
るようワイヤーバーで上記塗工液を均一に塗布し、熱風
循環式乾燥機にて１４０℃で３０秒間乾燥硬化し、離型
フィルムを作成した。この表面の濡れ指数は３４ｄｙｎ
ｅ／ｃｍであった。Example 1 Palm oil-modified alkyd resin 6
5 parts by weight, 15 parts by weight of a methylated melamine resin, and 20 parts by weight of a butylated urea melamine resin are 2% by weight (solid content) in a mixed solvent of toluene and methyl ethyl ketone (weight ratio: 1: 1).
To give a composition. This composition 100
0.1 parts by weight of a 50% methanol solution of p-toluenesulfonic acid was added to parts by weight. Use this as a coating liquid,
After drying on a polyester film, the above coating liquid was uniformly applied with a wire bar so as to have a thickness of 0.3 μm, and dried and cured at 140 ° C. for 30 seconds with a hot-air circulating drier to prepare a release film. The surface wetting index is 34 dyn
e / cm.
【００３４】［実施例２］やし油変性アルキッド樹脂６
５重量部、メチル化メラミン樹脂１５重量部、ブチル化
尿素メラミン樹脂２０重量部に対し、両末端カルビトー
ル変性シロキサン（フェニル基３０モル％含有、粘度４
５００ｃｐ）を３重量部添加し、実施例１と同様にトル
エン−メチルエチルケトン混合溶剤（重量比１：１）で
２重量％（固形分）になるように溶解させた。これを塗
工液として使用し、ポリエステルフィルムに塗布処理
し、離型フィルムを得た。この表面の濡れ指数は３２ｄ
ｙｎｅ／ｃｍであった。[Example 2] Palm oil-modified alkyd resin 6
5 parts by weight, 15 parts by weight of methylated melamine resin and 20 parts by weight of butylated urea melamine resin, carbitol-modified siloxane at both ends (containing 30 mol% of phenyl groups, viscosity of 4)
Then, 3 parts by weight of 500 cp) were added and dissolved in a mixed solvent of toluene and methyl ethyl ketone (1: 1 by weight) to 2% by weight (solid content) in the same manner as in Example 1. This was used as a coating solution and applied to a polyester film to obtain a release film. The wetting index of this surface is 32d
yne / cm.
【００３５】［実施例３］トルエン−メチルエチルケト
ン混合溶剤（重量比１：１）で２重量％（固形分）にな
るように溶解させる代わりにトルエン−メチルエチルケ
トンで５０重量％になるように溶解させた後、１００℃
で６時間加熱反応させる以外は実施例２と同様にして塗
工液を得た。この塗工液を使用して、実施例１と同様に
して離型フィルムを得た。この表面の濡れ指数は３２ｄ
ｙｎｅ／ｃｍであった。Example 3 Instead of dissolving 2% by weight (solid content) with a mixed solvent of toluene and methyl ethyl ketone (weight ratio 1: 1), dissolving it with 50% by weight of toluene and methyl ethyl ketone. After, 100 ℃
, And a coating solution was obtained in the same manner as in Example 2 except that the reaction was carried out for 6 hours. Using this coating liquid, a release film was obtained in the same manner as in Example 1. The wetting index of this surface is 32d
yne / cm.
【００３６】［実施例４］メチル化メラミン樹脂５０重
量部、アクリル変性アルキッド樹脂５０重量部、をトル
エン−メチルエチルケトン混合溶剤（重量比１：１）で
２重量％（固形分）になるように溶解させて得た組成物
１００重量部に、ｐ−トルエンスルホン酸５０％メタノ
ール溶液０．１重量部を添加し、塗工液を得た。この塗
工液を使用してポリエステルフィルム上に実施例１と同
様に処理し、離型フィルムを得た。この表面の濡れ指数
は３５ｄｙｎｅ／ｃｍであった。Example 4 50 parts by weight of a methylated melamine resin and 50 parts by weight of an acryl-modified alkyd resin were dissolved in a mixed solvent of toluene and methyl ethyl ketone (weight ratio 1: 1) so as to be 2% by weight (solid content). To 100 parts by weight of the composition thus obtained, 0.1 part by weight of a 50% methanol solution of p-toluenesulfonic acid was added to obtain a coating liquid. Using this coating solution, a polyester film was treated in the same manner as in Example 1 to obtain a release film. The wetting index of this surface was 35 dyne / cm.
【００３７】［実施例５］やし油変性アルキッド樹脂５
０重量部、メチル化メラミン樹脂２０重量部、ブチル化
メラミン樹脂１５重量部、アクリル樹脂１５重量部をト
ルエン−メチルエチルケトン混合溶剤（重量比１：１）
で２重量％（固形分）になるように溶解した組成物１０
０重量部にメタンスルホン酸０．１重量部を添加し、塗
工液を得た。この塗工液を使用して、ポリエステルフィ
ルム上に実施例１と同様に塗布して処理し、離型フィル
ムを得た。この表面の濡れ指数は３４ｄｙｎｅ／ｃｍで
あった。Example 5 Palm oil-modified alkyd resin 5
0 parts by weight, methylated melamine resin 20 parts by weight, butylated melamine resin 15 parts by weight, acrylic resin 15 parts by weight in a mixed solvent of toluene and methyl ethyl ketone (weight ratio 1: 1)
Composition 10 dissolved to 2% by weight (solid content)
0.1 parts by weight of methanesulfonic acid was added to 0 parts by weight to obtain a coating liquid. Using this coating solution, it was applied and treated on a polyester film in the same manner as in Example 1 to obtain a release film. The wetting index of this surface was 34 dyne / cm.
【００３８】［比較例１］ポリエステルフィルム上に剥
離紙用シリコーンＫＳ−７７４（信越化学工業（株）
製）を乾燥後０．２μｍになるように塗工乾燥し、離型
フィルムを得た。この離型フィルムの表面濡れ指数は３
０未満であり、このフィルム上には水系塗料を均一に塗
工できず、グリーンシートを作成することができなかっ
た。Comparative Example 1 Silicone KS-774 for release paper on a polyester film (Shin-Etsu Chemical Co., Ltd.)
Was dried and coated to a thickness of 0.2 μm to obtain a release film. The surface wetting index of this release film is 3
It was less than 0, and a water-based paint could not be uniformly applied on this film, and a green sheet could not be formed.
【００３９】［比較例２］両末端カルビトール変性シロ
キサンとしてＫＦ６００１（フェニル基０モル％、４０
ｃｐ、信越化学工業（株）製）を添加する以外は実施例
２と同様にして塗工液を得た。この塗工液を使用して、
実施例１と同様にポリエステルフィルム上に処理し、離
型フィルムを得た。得られた離型フィルムの表面の濡れ
指数は３０ｄｙｎｅ／ｃｍであった。このフィルムにス
ラリーを塗布すると、ピンホールが多数できてしまっ
た。Comparative Example 2 KF6001 (0 mol% of phenyl group, 40
cp, Shin-Etsu Chemical Co., Ltd.), and a coating liquid was obtained in the same manner as in Example 2. Using this coating liquid,
Processing was performed on a polyester film in the same manner as in Example 1 to obtain a release film. The surface of the obtained release film had a wetting index of 30 dyne / cm. When slurry was applied to this film, many pinholes were formed.
【００４０】上記実施例及び比較例で得られた離型フィ
ルムの特性を下記方法で評価した。結果を表１に示す。The properties of the release films obtained in the above Examples and Comparative Examples were evaluated by the following methods. Table 1 shows the results.
【００４１】水系塗料の濡れ性：下記に示す成分をボー
ルミルで十分混合し、セラミックススラリーを調製し
た。 （ａ）チタン酸バリウム １００重量部 （ｂ）アクリルエマルジョン １０重量部 （ｃ）ポリウレタンエマルジョン １重量部 （ｄ）ポリカルボン酸アンモニウム １重量部 （ｅ）水 １５重量部 （ｆ）アンモニア水 １重量部 このスラリーをアプリケーターを用いて作成した離型フ
ィルム上に塗工し、１４０℃にて１分間乾燥後、はじき
の程度を観察し、下記基準にて濡れ性を評価した。 ○：はじきなし（濡れ性良好） △：はじき若干あり（濡れ性やや良好） ×：はじきあり（濡れ性不良）Water-based paint wettability: The following components were sufficiently mixed in a ball mill to prepare a ceramic slurry. (A) barium titanate 100 parts by weight (b) acrylic emulsion 10 parts by weight (c) polyurethane emulsion 1 part by weight (d) ammonium polycarboxylate 1 part by weight (e) water 15 parts by weight (f) ammonia water 1 part by weight The slurry was applied on a release film prepared using an applicator, dried at 140 ° C. for 1 minute, observed for repellency, and evaluated for wettability according to the following criteria. ：: No repellency (good wettability) △: Slight repellency (slightly good wettability) ×: Repelled (poor wettability)
【００４２】剥離強度：ポリエステルフィルムに形成し
た離型面にニットーポリエステルテープＮｏ．３１Ｂ
（日東電工（株）製品名）を貼り合わせ、２ｋｇの圧着
ローラーで１往復圧着し、室温で２０時間放置後、粘着
テープを１８０°の角度、０．３ｍ／分の速度で引っ張
り試験機にて剥離強度を測定した。好ましい剥離強度は
５０〜４００ｇ／２５ｍｍであり、５０ｇ／２５ｍｍ未
満では巻き取り時に作成したシートが離型面からずれし
わ等を生じ、４００ｇ／２５ｍｍを超えるとシートを剥
離しずらくなり、破損してしまう。Peel strength: Nitto polyester tape No. was applied to the release surface formed on the polyester film. 31B
(Nitto Denko Co., Ltd. product name), and reciprocated with a 2 kg pressure roller once and left at room temperature for 20 hours. Then, the adhesive tape was applied to a tensile tester at an angle of 180 ° at a speed of 0.3 m / min. The peel strength was measured. A preferable peel strength is 50 to 400 g / 25 mm. If the peel strength is less than 50 g / 25 mm, the sheet produced at the time of winding will be displaced from the release surface, and if it exceeds 400 g / 25 mm, the sheet will be difficult to peel and break. Would.
【００４３】残存接着率：硬化皮膜を形成させた離型フ
ィルムを２５℃の室温に２４時間放置した後、この皮膜
面にニットーポリエステルテープＮｏ．３１Ｂ［日東電
工（株）製品名］を貼着し、室温で２０時間放置してか
ら粘着テープを剥離して、これをステンレス板に貼り、
ここに２ｋｇの圧着ローラーを１往復させた後、これに
ついて上記剥離強度と同じ方法で剥離強度を測定した
（ｆ）。また、テフロン板に上記と同じポリエステルテ
ープＮｏ．３１Ｂを貼着し、これを上記と同様に処理し
てこのものの剥離力を測定し、これをブランク（ｆ0）
とした。Residual adhesion: The release film on which the cured film was formed was allowed to stand at room temperature of 25 ° C. for 24 hours. 31B [product name of Nitto Denko Corporation] was stuck, left at room temperature for 20 hours, the adhesive tape was peeled off, and this was stuck on a stainless steel plate.
After reciprocating a 2 kg pressure roller one time, the peel strength was measured by the same method as the peel strength described above (f). In addition, the same polyester tape No. 31B was adhered thereto, treated in the same manner as above, and the peeling force of this was measured, and this was blank (f 0 )
And
【００４４】これら測定値に基づき、下記の式により残
留接着率を求めた。なお、残留接着率は９５％以上が好
ましく、それ未満であると形成されたシートの表面を汚
染し、接着性等の特性が低下する。 残留接着率（％）＝ｆ／ｆ0×１００Based on these measured values, the residual adhesion rate was determined by the following equation. The residual adhesion rate is preferably 95% or more, and if it is less than 95%, the surface of the formed sheet is contaminated, and properties such as adhesiveness are reduced. Residual adhesion rate (%) = f / f 0 × 100
【００４５】[0045]
【表１】 [Table 1]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ // Ｃ０８Ｊ 7/04 ＣＦＤ Ｃ０８Ｊ 7/04 ＣＦＤＺ ＣＦＧ ＣＦＧＺ Ｃ０８Ｌ 33/00 Ｃ０８Ｌ 33/00 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification symbol FI // C08J 7/04 CFD C08J 7/04 CFDZ CFG CFGZ C08L 33/00 C08L 33/00
Claims (4)
離型層が形成された工程用離型フィルムであって、該離
型層が、 （Ａ）アルキッド樹脂、アミノ樹脂及びアクリル樹脂から選ばれる少なくとも２ 種以上の樹脂 １００重量部 （Ｃ）縮合触媒 １〜１０重量部 （Ｄ）溶剤 各成分を均一に溶解し得る量 を含有してなる離型剤組成物により形成されたものであることを特徴とする工程 用離型フィルム。1. A process release film in which a release layer is formed on one or both surfaces of a plastic film, wherein the release layer comprises: (A) at least two resins selected from alkyd resins, amino resins and acrylic resins. 100 parts by weight of resin of at least one kind (C) Condensation catalyst 1 to 10 parts by weight (D) Solvent It is characterized by being formed from a release agent composition containing an amount capable of uniformly dissolving each component. Release film for the process.
％含有するカルビトール変性シリコーンを（Ａ）成分１
００重量部に対し６重量部以下の割合で離型剤組成物に
配合した請求項１記載の工程用離型フィルム。2. A carbitol-modified silicone containing (B) 10 to 40 mol% of an aromatic organic group as component (A)
The release film for a process according to claim 1, wherein the release film is blended in an amount of 6 parts by weight or less with respect to 00 parts by weight in the release agent composition.
たものを配合する請求項２記載の工程用離型フィルム。3. The process release film according to claim 2, wherein a component obtained by previously reacting the component (B) with the component (A) is blended.
系フィルム、ポリイミド系フィルム又はポリアミド系フ
ィルムである請求項１、２又は３記載の工程用離型フィ
ルム。4. The release film for a process according to claim 1, wherein the plastic film is a polyester film, a polyimide film or a polyamide film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10122807A JPH11300894A (en) | 1998-04-16 | 1998-04-16 | Release film for process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10122807A JPH11300894A (en) | 1998-04-16 | 1998-04-16 | Release film for process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11300894A true JPH11300894A (en) | 1999-11-02 |
Family
ID=14845132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10122807A Pending JPH11300894A (en) | 1998-04-16 | 1998-04-16 | Release film for process |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11300894A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001287316A (en) * | 2000-04-06 | 2001-10-16 | Mitsubishi Plastics Ind Ltd | Laminated film |
| JP2002019037A (en) * | 2000-07-06 | 2002-01-22 | Lintec Corp | Process film for manufacturing ceramic green sheet |
| JP2004250681A (en) * | 2003-01-30 | 2004-09-09 | Mitsubishi Chemicals Corp | Release agent solution and release film |
| JP2004277614A (en) * | 2003-03-18 | 2004-10-07 | Lintec Corp | Releasing agent composition, release sheet and adhesive laminate |
| JP2008156499A (en) * | 2006-12-25 | 2008-07-10 | Hitachi Kasei Polymer Co Ltd | Releasant composition for adhesive tape and release liner |
| JP2011206994A (en) * | 2010-03-29 | 2011-10-20 | Tdk Corp | Peeling film, ceramic component sheet, methods for manufacturing these, and method for manufacturing ceramic component |
| JP2014017503A (en) * | 2007-09-11 | 2014-01-30 | Ajinomoto Co Inc | Multilayer printed wiring board manufacturing method |
| KR101459414B1 (en) * | 2013-07-22 | 2014-11-07 | 도레이첨단소재 주식회사 | Release film for carrrier and manufacturing method thereof |
| WO2015087884A1 (en) * | 2013-12-09 | 2015-06-18 | 日立化成株式会社 | Mold-release polyimide film, laminated board having mold-release polyimide film having adhesive layer, laminated board, monolayer or multilayer wiring board having mold-release polyimide film having adhesive layer, and method for manufacturing multilayer wiring board |
| KR20170073619A (en) | 2014-10-17 | 2017-06-28 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Heavy release additive for release sheet, organopolysiloxane composition for release sheet, and release sheet |
| KR20170130446A (en) * | 2015-03-27 | 2017-11-28 | 린텍 가부시키가이샤 | Releasing film for ceramic green sheet production step |
| JP2018168303A (en) * | 2017-03-30 | 2018-11-01 | リンテック株式会社 | Peeling film for adhesive sheet |
| JP2019130889A (en) * | 2018-01-29 | 2019-08-08 | 東レ株式会社 | Laminate and resin film |
| JP2019130888A (en) * | 2018-01-29 | 2019-08-08 | 東レ株式会社 | Release film |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60167995A (en) * | 1984-02-07 | 1985-08-31 | 信越化学工業株式会社 | Production of process release paper |
| JPH0317146A (en) * | 1989-06-14 | 1991-01-25 | Shin Etsu Chem Co Ltd | Resin composition for industrial release paper |
| JPH0999439A (en) * | 1995-10-05 | 1997-04-15 | Yokohama Rubber Co Ltd:The | Mandrel release agent for producing hose |
| JPH09239913A (en) * | 1996-03-04 | 1997-09-16 | Teijin Ltd | Mold releasing film |
| JPH09262936A (en) * | 1996-03-28 | 1997-10-07 | Teijin Ltd | Mold releasing film |
| JPH10138431A (en) * | 1996-11-13 | 1998-05-26 | Teijin Ltd | Release film |
-
1998
- 1998-04-16 JP JP10122807A patent/JPH11300894A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60167995A (en) * | 1984-02-07 | 1985-08-31 | 信越化学工業株式会社 | Production of process release paper |
| JPH0317146A (en) * | 1989-06-14 | 1991-01-25 | Shin Etsu Chem Co Ltd | Resin composition for industrial release paper |
| JPH0999439A (en) * | 1995-10-05 | 1997-04-15 | Yokohama Rubber Co Ltd:The | Mandrel release agent for producing hose |
| JPH09239913A (en) * | 1996-03-04 | 1997-09-16 | Teijin Ltd | Mold releasing film |
| JPH09262936A (en) * | 1996-03-28 | 1997-10-07 | Teijin Ltd | Mold releasing film |
| JPH10138431A (en) * | 1996-11-13 | 1998-05-26 | Teijin Ltd | Release film |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001287316A (en) * | 2000-04-06 | 2001-10-16 | Mitsubishi Plastics Ind Ltd | Laminated film |
| JP2002019037A (en) * | 2000-07-06 | 2002-01-22 | Lintec Corp | Process film for manufacturing ceramic green sheet |
| KR100766669B1 (en) * | 2000-07-06 | 2007-10-11 | 린텍 가부시키가이샤 | Casting film for producing ceramic green sheet |
| JP2004250681A (en) * | 2003-01-30 | 2004-09-09 | Mitsubishi Chemicals Corp | Release agent solution and release film |
| JP2004277614A (en) * | 2003-03-18 | 2004-10-07 | Lintec Corp | Releasing agent composition, release sheet and adhesive laminate |
| JP2008156499A (en) * | 2006-12-25 | 2008-07-10 | Hitachi Kasei Polymer Co Ltd | Releasant composition for adhesive tape and release liner |
| JP2014017503A (en) * | 2007-09-11 | 2014-01-30 | Ajinomoto Co Inc | Multilayer printed wiring board manufacturing method |
| JP2015005758A (en) * | 2007-09-11 | 2015-01-08 | 味の素株式会社 | Multilayer printed wiring board manufacturing method |
| JP2011206994A (en) * | 2010-03-29 | 2011-10-20 | Tdk Corp | Peeling film, ceramic component sheet, methods for manufacturing these, and method for manufacturing ceramic component |
| KR101459414B1 (en) * | 2013-07-22 | 2014-11-07 | 도레이첨단소재 주식회사 | Release film for carrrier and manufacturing method thereof |
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| US10570234B2 (en) | 2014-10-17 | 2020-02-25 | Shin-Etsu Chemical Co., Ltd. | Heavy release additive for release sheet, organopolysiloxane composition for release sheet, and release sheet |
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