JP7493740B2 - Release film and method for producing same - Google Patents
Release film and method for producing same Download PDFInfo
- Publication number
- JP7493740B2 JP7493740B2 JP2019048572A JP2019048572A JP7493740B2 JP 7493740 B2 JP7493740 B2 JP 7493740B2 JP 2019048572 A JP2019048572 A JP 2019048572A JP 2019048572 A JP2019048572 A JP 2019048572A JP 7493740 B2 JP7493740 B2 JP 7493740B2
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- Prior art keywords
- resin layer
- acid
- film
- resin
- release film
- Prior art date
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- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesive Tapes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、離型フィルムに関する。 The present invention relates to a release film.
離型フィルムは、医療分野、工業分野に広く使用されている。その具体例としては、医療用テープやハップ剤の保護フィルム、プリント配線板、フレキシブルプリント配線板、多層プリント配線板などの製造のための工程材料、粘着材料、液晶ディスプレイ用部品などの保護材料などが挙げられる。 Release films are widely used in the medical and industrial fields. Specific examples include protective films for medical tapes and poultices, process materials for the manufacture of printed wiring boards, flexible printed wiring boards, and multilayer printed wiring boards, adhesive materials, and protective materials for liquid crystal display parts.
離型層としてシリコーン樹脂が用いられた離型フィルムは、剥離性能が高く軽剥離であり安価であることから、一般的に広く使用されている。ただし、離型層にシリコーン樹脂を用いた場合には、離型フィルムから被着体側にシリコーン樹脂の一部が転写してしまい、被着体を汚染してしまう問題があった。 Release films that use silicone resin as the release layer are widely used because they have high release performance, are easy to release, and are inexpensive. However, when silicone resin is used for the release layer, there is a problem that part of the silicone resin is transferred from the release film to the adherend, contaminating the adherend.
非シリコーン系の離型フィルムとしては、各社開発が行われており、例えば特許文献１、２に開示されているように、樹脂層が酸変性ポリオレフィン樹脂である離型フィルムが挙げられる。
近年、電子部品等には小型化、軽量化が求められており、より形状の自由度が求められている。例えば、離型フィルムの離型層上の一部にアクリル粘着剤シートとエポキシプリプレグという異なる被着体をそれぞれ一面上に積層し、その後、アクリル粘着剤とエポキシ被着体とから剥離する場合があった。
Non-silicone release films have been developed by various companies, and examples thereof include release films having a resin layer made of an acid-modified polyolefin resin, as disclosed in Patent Documents 1 and 2.
In recent years, electronic components and the like have been required to be smaller and lighter, and greater freedom in shape has been required. For example, there have been cases where different adherends, namely, an acrylic adhesive sheet and an epoxy prepreg, are laminated on one side of a part of the release layer of a release film, and then the acrylic adhesive is peeled off from the epoxy adherend.
しかしながら、特許文献１、２に開示された離型フィルムは、特定種類の被着体に対しての離型性は良好であるが、アクリル系被着体とエポキシ系被着体の両方に対しての離型性は有しておらず、両被着体に対して良好な離型性を示す非シリコーン系の離型フィルムはなかった。 However, while the release films disclosed in Patent Documents 1 and 2 have good releasability from certain types of adherends, they do not have releasability from both acrylic and epoxy adherends, and there are no non-silicone release films that exhibit good releasability from both types of adherends.
本発明の課題は、上記のようにアクリル系被着体とエポキシ系被着体という異なる種類の被着体に対して離型性に優れており、同時に剥離できるような非シリコーン系の離型フィルムを提供することである。 The object of the present invention is to provide a non-silicone release film that has excellent releasability from different types of adherends, such as acrylic-based and epoxy-based adherends, and that can be simultaneously peeled off.
本発明者らは、上記課題を解決するために鋭意検討を行った結果、あらかじめ酸変性ポリオレフィン樹脂水性分散体にγ線を照射し、γ線照射後の酸変性ポリオレフィン樹脂水性分散体を用いて樹脂層を形成することで、アクリル系被着体、エポキシ系被着体という種類の異なる被着体に対して、離型性に優れた非シリコーン系の離型フィルムが得られることを見出し、本発明に到達した。 As a result of intensive research conducted by the present inventors to solve the above problems, they discovered that by irradiating an acid-modified polyolefin resin aqueous dispersion with gamma rays in advance and then forming a resin layer using the acid-modified polyolefin resin aqueous dispersion after gamma ray irradiation, a non-silicone release film with excellent releasability can be obtained for different types of adherends, such as acrylic adherends and epoxy adherends, and thus arrived at the present invention.
すなわち、本発明の要旨は下記のとおりである。
（１）基材フィルムであるポリエステルフィルムの少なくとも片面に樹脂層が設けられた離型フィルムであって、樹脂層が酸変性ポリオレフィン樹脂および架橋剤を含有し、以下の（イ）、（ロ）の要件を満たす離型フィルム。
（イ）アクリル系被着体を樹脂層に貼り付けて７０℃で熱処理後測定したときの剥離力が１．５Ｎ／ｃｍ以下であること
（ロ）エポキシ系被着体を樹脂層に貼り付けて１９０℃で熱処理後測定したときの剥離力が０．２Ｎ／ｃｍ以下であること
（２）酸変性ポリオレフィン樹脂のオレフィン成分が、プロピレンを含む（１）に記載の離型フィルム。
（３）ゴム系被着体を樹脂層に貼り付けて測定したときの剥離力が０．３Ｎ／ｃｍ以下である（１）または（２）に記載の離型フィルム。
（４）樹脂層に、さらにポリビニルアルコールを含有する（１）～（３）のいずれかに記載の離型フィルム。
（５）基材フィルムの少なくとも片面に、酸変性ポリオレフィン樹脂および架橋剤を含有する樹脂層が設けられ、以下の（イ）、（ロ）の要件を満たす離型フィルムの製造方法であって、γ線を照射した酸変性ポリオレフィン樹脂水性分散体を基材フィルムに塗工することで樹脂層を形成する離型フィルムの製造方法。
（イ）アクリル系被着体を樹脂層に貼り付けて測定したときの剥離力が１．５Ｎ／ｃｍ以下であること
（ロ）エポキシ系被着体を樹脂層に貼り付けて測定したときの剥離力が０．２Ｎ／ｃｍ以下であること
（６）γ線照射量が１０～４００ｋＧｙである（５）記載の離型フィルムの製造方法。
That is, the gist of the present invention is as follows.
(1) A release film comprising a polyester film as a base film and a resin layer provided on at least one side thereof, the resin layer containing an acid-modified polyolefin resin and a crosslinking agent, and satisfying the following requirements (a) and (b).
(a) The peel strength is 1.5 N/cm or less when an acrylic adherend is attached to the resin layer and heat-treated at 70°C and then measured. (b) The peel strength is 0.2 N/cm or less when an epoxy adherend is attached to the resin layer and heat-treated at 190°C and then measured. (2) The release film according to (1), wherein the olefin component of the acid-modified polyolefin resin contains propylene.
(3) The release film according to (1) or (2), which has a peel strength of 0.3 N/cm or less when a rubber-based adherend is attached to the resin layer and measured.
(4) The release film according to any one of (1) to (3), wherein the resin layer further contains polyvinyl alcohol.
(5) A method for producing a release film in which a resin layer containing an acid-modified polyolefin resin and a crosslinking agent is provided on at least one surface of a base film and the method satisfies the following requirements (i) and (ii), in which the resin layer is formed by applying an aqueous dispersion of acid-modified polyolefin resin that has been irradiated with gamma rays to the base film.
(a) The peel strength when an acrylic adherend is attached to a resin layer and measured is 1.5 N/cm or less.
(b) The peel strength when an epoxy-based adherend is attached to a resin layer and measured is 0.2 N/cm or less.
(6) The method for producing a release film according to (5), wherein the amount of gamma ray irradiation is 10 to 400 kGy.
本発明の離型フィルムは、アクリル系被着体、エポキシ系被着体という種類の異なる被着体に対して、離型性に優れており、両面テープや粘着材料の保護フィルムや液晶ディスプレイ用部品、プリント配線板などを製造する際の保護材料や工程材料、イオン交換膜やセラミックグリーンシート、放熱シートなどのシート状構造体成形用途など様々な用途に用いることができる。 The release film of the present invention has excellent releasability for different types of adherends, such as acrylic and epoxy adherends, and can be used for a variety of applications, such as protective films for double-sided tapes and adhesive materials, protective materials and process materials when manufacturing liquid crystal display parts and printed wiring boards, and for forming sheet-like structures such as ion exchange membranes, ceramic green sheets, and heat dissipation sheets.
以下、本発明を詳細に説明する。
本発明の離型フィルムは、基材フィルムの少なくとも一方の面に、酸変性ポリオレフィン樹脂と架橋剤とを含有する樹脂層が設けられたものである。
The present invention will be described in detail below.
The release film of the present invention comprises a base film and a resin layer containing an acid-modified polyolefin resin and a crosslinking agent provided on at least one surface of the base film.
本発明の離型フィルムは、粘着材料としてのアクリル系被着体を樹脂層に貼り付けて測定したときの被着体との剥離力を１．５Ｎ／ｃｍ以下とすることができ、好ましくは１．２Ｎ／ｃｍ以下、より好ましくは１．０Ｎ／ｃｍ以下とすることができる。剥離力が１．５Ｎ／ｃｍを超えると、アクリル系被着体以外の被着体との剥離の際にハンドリング性が悪くなる場合がある。
また、本発明の離型フィルムは、エポキシ系被着体としてエポキシプリプレグを樹脂層に貼り付けて測定したときの、樹脂層とエポキシプリプレグとの剥離力を０．２Ｎ／ｃｍ以下とすることができ、好ましくは０．００５～０．１Ｎ／ｃｍ、より好ましくは０．０１～０．０５Ｎ／ｃｍとすることができる。剥離力が０．２Ｎ／ｃｍを超える場合、エポキシプリプレグとの剥離力が大きくなりハンドリング性が悪くなる場合がある。
The release film of the present invention can have a peel strength from the adherend of 1.5 N/cm or less, preferably 1.2 N/cm or less, more preferably 1.0 N/cm or less, when the release film is measured by attaching an acrylic adherend as a pressure-sensitive adhesive material to the resin layer. If the peel strength exceeds 1.5 N/cm, the handling property may be deteriorated when the release film is peeled from an adherend other than an acrylic adherend.
Furthermore, the release film of the present invention can have a peel strength between the resin layer and the epoxy prepreg of 0.2 N/cm or less, preferably 0.005 to 0.1 N/cm, and more preferably 0.01 to 0.05 N/cm, when measured by attaching an epoxy prepreg as an epoxy-based adherend to the resin layer. If the peel strength exceeds 0.2 N/cm, the peel strength from the epoxy prepreg becomes large, and handling properties may become poor.
前記剥離力は、あらかじめγ線を照射した酸変性ポリオレフィン樹脂水性分散体から媒体を除去した樹脂生成物を樹脂層に用いることにより達成される。 The above peel strength is achieved by using a resin product obtained by removing the medium from an aqueous dispersion of acid-modified polyolefin resin that has been irradiated with gamma rays in advance for the resin layer.
また、本発明の離型フィルムは、アクリル系被着体とエポキシ系被着体との離型性に優れた離型フィルムであるが、粘着材料としてのゴム系被着体との離型性にも優れている。ゴム系被着体を樹脂層に貼り付けて測定したときの被着体との剥離力を、好ましくは０．３Ｎ／ｃｍ以下、より好ましくは０．２Ｎ／ｃｍ以下、さらに好ましくは０．１Ｎ／ｃｍ以下とすることができる。 The release film of the present invention is a release film that has excellent releasability from acrylic and epoxy adherends, but also has excellent releasability from rubber adherends as adhesive materials. The peel force from the adherend, measured by attaching the rubber adherend to the resin layer, can be preferably 0.3 N/cm or less, more preferably 0.2 N/cm or less, and even more preferably 0.1 N/cm or less.
本発明の離型フィルムにおける樹脂層について説明する。
樹脂層に含まれる酸変性ポリオレフィン樹脂は、オレフィン成分を主成分とし、酸変性成分により変性された樹脂である。
酸変性ポリオレフィン樹脂を構成するオレフィン成分は、エチレン、プロピレン、ブテンから選ばれる少なくとも１種を含むことが好ましく、エポキシプリプレグに対する離型性の観点で、プロピレンを含むことがより好ましく、オレフィン成分の主成分がプロピレン成分であることがより好ましい。
The resin layer in the release film of the present invention will be described.
The acid-modified polyolefin resin contained in the resin layer is a resin containing an olefin component as a main component and modified with an acid-modifying component.
The olefin component constituting the acid-modified polyolefin resin preferably contains at least one selected from ethylene, propylene and butene, and from the viewpoint of releasability from the epoxy prepreg, it is more preferable that it contains propylene, and it is more preferable that the main component of the olefin component is a propylene component.
酸変性ポリオレフィン樹脂を構成する酸変性成分としては、不飽和カルボン酸成分が好ましく、具体的には、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、イタコン酸、無水イタコン酸、フマル酸、クロトン酸等のほか、不飽和ジカルボン酸のハーフエステル、ハーフアミド等が挙げられる。中でも、後述する樹脂の水性分散化において、樹脂を安定的に分散するために、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸が好ましく、アクリル酸、メタクリル酸、無水マレイン酸が特に好ましい。これらの酸変性成分は酸変性ポリオレフィン樹脂中に２種類以上含まれていてもよい。 As the acid-modified component constituting the acid-modified polyolefin resin, an unsaturated carboxylic acid component is preferable, and specifically, in addition to acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, etc., half esters and half amides of unsaturated dicarboxylic acids can be mentioned. Among them, in order to stably disperse the resin in the aqueous dispersion of the resin described later, acrylic acid, methacrylic acid, maleic acid anhydride are preferable, and acrylic acid, methacrylic acid, and maleic anhydride are particularly preferable. Two or more of these acid-modified components may be contained in the acid-modified polyolefin resin.
酸変性ポリオレフィン樹脂における酸変性成分の割合は、１～１０質量％であることが好ましく、２～９質量％であることがより好ましい。酸変性成分が１％未満の場合は、樹脂層に含まれる酸変性ポリオレフィン樹脂中の極性基の割合が少なくなるため、樹脂層は、基材フィルムとの十分な密着性が得られず、樹脂層から離型した被着体を汚染することがある。さらに後述する樹脂の水性分散化において、樹脂を安定的に分散するのが困難になる傾向がある。一方、酸変性成分の割合が１０質量％を超える場合は、極性基の割合が多くなるため、樹脂層と基材フィルムとの密着性が十分にはなるが、樹脂層と被着体との密着性も同時に高くなるため、被着体との離型性が低下する傾向がある。 The proportion of the acid-modified component in the acid-modified polyolefin resin is preferably 1 to 10% by mass, and more preferably 2 to 9% by mass. If the proportion of the acid-modified component is less than 1%, the proportion of polar groups in the acid-modified polyolefin resin contained in the resin layer is reduced, so that the resin layer does not obtain sufficient adhesion to the substrate film, and may contaminate the adherend released from the resin layer. Furthermore, in the aqueous dispersion of the resin described below, it tends to be difficult to stably disperse the resin. On the other hand, if the proportion of the acid-modified component exceeds 10% by mass, the proportion of polar groups increases, so that the adhesion between the resin layer and the substrate film is sufficient, but the adhesion between the resin layer and the adherend also increases at the same time, so that the releasability from the adherend tends to decrease.
酸変性ポリオレフィン樹脂には、その他のモノマーが、少量、共重合されていてもよい。その他のモノマーとして、例えば、ジエン類、（メタ）アクリロニトリル、ハロゲン化ビニル類、ハロゲン化ビニリデン類、一酸化炭素、二酸化硫黄等が挙げられる。 The acid-modified polyolefin resin may be copolymerized with a small amount of other monomers. Examples of other monomers include dienes, (meth)acrylonitrile, vinyl halides, vinylidene halides, carbon monoxide, and sulfur dioxide.
酸変性ポリオレフィン樹脂を構成する各成分は、酸変性ポリオレフィン樹脂中に共重合されていればよく、その形態は限定されない。共重合の状態としては、例えば、ランダム共重合、ブロック共重合、グラフト共重合（グラフト変性）などが挙げられる。 The components constituting the acid-modified polyolefin resin may be copolymerized in the acid-modified polyolefin resin, and there are no limitations on the form. Examples of the copolymerization state include random copolymerization, block copolymerization, and graft copolymerization (graft modification).
本発明において酸変性ポリオレフィン樹脂として市販のものを使用することができ、例えば、三井・デュポンポリケミカル社製「ニュクレル」の「ＡＮ４２１１５Ｃ」、「Ｎ１０５０Ｈ」、「Ｎ１１１０Ｈ」；日本ポリエチレン社製「レクスパール」の「Ａ２１０Ｋ」；三洋化成社製「ユーメックス」の「１００１」；アルケマ社製「ボンダイン」の「ＬＸ－４１１０」、「ＨＸ－８２１０」、「ＨＸ－８２９０」、「ＴＸ－８０３０」などが挙げられる。 In the present invention, commercially available acid-modified polyolefin resins can be used, such as "AN42115C", "N1050H", and "N1110H" from "Nucrel" manufactured by DuPont-Mitsui Polychemicals; "A210K" from "Rexpearl" manufactured by Japan Polyethylene Corporation; "1001" from "UMEX" manufactured by Sanyo Chemical Industries; and "LX-4110", "HX-8210", "HX-8290", and "TX-8030" from "Bondine" manufactured by Arkema.
本発明において、樹脂層は、架橋剤を含有することが必要である。
架橋剤の含有量は、酸変性ポリオレフィン樹脂１００質量部に対して１～２０質量部であることが好ましく、２～１５質量部であることがより好ましく、２～１０質量部であることがさらに好ましい。架橋剤の含有量が１質量部未満であると、樹脂層の凝集力が弱くなり、樹脂層が被着体に移行しやすく、被着体が粘着材料であると残存接着率が低下する傾向にある。一方、２０質量部を超えると、樹脂層と被着体との間で反応を生じ、剥離強度が大きくなることがある。
In the present invention, the resin layer must contain a crosslinking agent.
The content of the crosslinking agent is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, and even more preferably 2 to 10 parts by mass, relative to 100 parts by mass of the acid-modified polyolefin resin. If the content of the crosslinking agent is less than 1 part by mass, the cohesive force of the resin layer is weakened, the resin layer is easily transferred to the adherend, and if the adherend is an adhesive material, the residual adhesion rate tends to decrease. On the other hand, if the content exceeds 20 parts by mass, a reaction occurs between the resin layer and the adherend, and the peel strength may increase.
架橋剤としては、カルボキシル基と反応する官能基を分子内に複数個有する化合物等を用いることができ、このうちイソシアネート化合物、メラミン化合物、尿素化合物、エポキシ化合物、カルボジイミド化合物、オキサゾリン化合物等が好ましく、特に、カルボジイミド化合物、オキサゾリン化合物が効果的である。これらの架橋剤は組み合わせて使用してもよい。 As the crosslinking agent, a compound having multiple functional groups in the molecule that react with carboxyl groups can be used. Among these, isocyanate compounds, melamine compounds, urea compounds, epoxy compounds, carbodiimide compounds, oxazoline compounds, etc. are preferred, and carbodiimide compounds and oxazoline compounds are particularly effective. These crosslinking agents may be used in combination.
架橋剤として用いるカルボジイミド化合物は、分子中に１つ以上のカルボジイミド基を有しているものであれば特に限定されるものではない。カルボジイミド化合物は、１つのカルボジイミド部分において、酸変性ポリオレフィン樹脂の酸変性部分における２つのカルボキシル基とエステルを形成し、架橋を達成する。 The carbodiimide compound used as the crosslinking agent is not particularly limited as long as it has one or more carbodiimide groups in the molecule. The carbodiimide compound forms an ester with two carboxyl groups in the acid-modified portion of the acid-modified polyolefin resin at one carbodiimide portion, thereby achieving crosslinking.
カルボジイミド化合物の具体例として、例えば、ｐ－フェニレン－ビス（２，６－キシリルカルボジイミド）、テトラメチレン－ビス（ｔ－ブチルカルボジイミド）、シクロヘキサン－１，４－ビス（メチレン－ｔ－ブチルカルボジイミド）などのカルボジイミド基を有する化合物や、カルボジイミド基を有する重合体であるポリカルボジイミドが挙げられる。これらの１種又は２種以上を用いることができる。これらの中でも、取り扱いやすさから、ポリカルボジイミドが好ましい。 Specific examples of carbodiimide compounds include compounds having a carbodiimide group, such as p-phenylene-bis(2,6-xylylcarbodiimide), tetramethylene-bis(t-butylcarbodiimide), and cyclohexane-1,4-bis(methylene-t-butylcarbodiimide), as well as polycarbodiimide, which is a polymer having a carbodiimide group. One or more of these may be used. Among these, polycarbodiimide is preferred because of its ease of handling.
ポリカルボジイミドの市販品としては、日清紡社製のカルボジライトシリーズが挙げられ、具体的には、水溶性タイプの「ＳＶ－０２」、「Ｖ－０２」、「Ｖ－０２－Ｌ２」、「Ｖ－０４」；エマルションタイプの「Ｅ－０１」、「Ｅ－０２」；有機溶液タイプの「Ｖ－０１」、「Ｖ－０３」、「Ｖ－０７」、「Ｖ－０９」；無溶剤タイプの「Ｖ－０５」が挙げられる。 Commercially available polycarbodiimide products include the Carbodilite series manufactured by Nisshinbo Corporation, which specifically includes the water-soluble types "SV-02", "V-02", "V-02-L2", and "V-04", the emulsion types "E-01" and "E-02", the organic solution types "V-01", "V-03", "V-07", and "V-09", and the solventless type "V-05".
架橋剤として用いるオキサゾリン化合物は、分子中にオキサゾリン基を２つ以上有しているものであれば、特に限定されるものではない。オキサゾリン化合物は、２つのオキサゾリン部分のそれぞれにおいて、酸変性ポリオレフィン樹脂の酸変性部分における１つのカルボキシル基とアミドエステルを形成し、架橋を達成する。オキサゾリン化合物の具体例として、例えば、２，２′－ビス（２－オキサゾリン）、２，２′－エチレン－ビス（４，４′－ジメチル－２－オキサゾリン）、２，２′－ｐ－フェニレン－ビス（２－オキサゾリン）、ビス（２－オキサゾリニルシクロヘキサン）スルフィドなどのオキサゾリン基を有する化合物や、オキサゾリン基含有ポリマーが挙げられる。これらの１種又は２種以上を用いることができる。これらの中でも、取り扱いやすさからオキサゾリン基含有ポリマーが好ましい。 The oxazoline compound used as the crosslinking agent is not particularly limited as long as it has two or more oxazoline groups in the molecule. The oxazoline compound forms an amide ester with one carboxyl group in the acid-modified portion of the acid-modified polyolefin resin in each of the two oxazoline portions to achieve crosslinking. Specific examples of the oxazoline compound include compounds having an oxazoline group such as 2,2'-bis(2-oxazoline), 2,2'-ethylene-bis(4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene-bis(2-oxazoline), and bis(2-oxazolinylcyclohexane)sulfide, and oxazoline group-containing polymers. One or more of these can be used. Among these, oxazoline group-containing polymers are preferred because of their ease of handling.
オキサゾリン基含有ポリマーの市販品としては、日本触媒社製のエポクロスシリーズが挙げられ、具体的には、水溶性タイプの「ＷＳ－５００」、「ＷＳ－７００」；エマルションタイプの「Ｋ－１０１０Ｅ」、「Ｋ－１０２０Ｅ」、「Ｋ－１０３０Ｅ」、「Ｋ－２０１０Ｅ」、「Ｋ－２０２０Ｅ」、「Ｋ－２０３０Ｅ」などが挙げられる。 Commercially available oxazoline group-containing polymers include the Epocross series manufactured by Nippon Shokubai Co., Ltd., including the water-soluble types "WS-500" and "WS-700" and the emulsion types "K-1010E", "K-1020E", "K-1030E", "K-2010E", "K-2020E", and "K-2030E".
本発明において、樹脂層は、ポリビニルアルコールを含有してもよい。
ポリビニルアルコールの種類は、特に限定されないが、ビニルエステルの重合体を完全または部分ケン化したものなどが挙げられる。
後述のように、樹脂層の形成に水性分散体を用いるため、ポリビニルアルコールは水溶性であることが好ましい。
In the present invention, the resin layer may contain polyvinyl alcohol.
The type of polyvinyl alcohol is not particularly limited, but examples include those obtained by completely or partially saponifying a vinyl ester polymer.
As described later, since an aqueous dispersion is used to form the resin layer, the polyvinyl alcohol is preferably water-soluble.
ポリビニルアルコールの平均重合度は、特に限定されるものではなく、例えば、３００～５０００であるものを使用することができるが、樹脂層を形成するための液状物の安定性向上の観点からは、３００～２０００であることが好ましい。 The average degree of polymerization of polyvinyl alcohol is not particularly limited, and for example, one having a degree of polymerization of 300 to 5000 can be used. From the viewpoint of improving the stability of the liquid material used to form the resin layer, however, a degree of polymerization of 300 to 2000 is preferable.
ポリビニルアルコールの含有量は、酸変性ポリオレフィン樹脂１００質量部に対して１０００質量部以下であることが好ましい。１０００質量部を超えると、樹脂層を形成するための液状物の粘度が高くなり塗工ムラを生じやすくなるとともに、ゲルが生じることがあり、樹脂層表面粗さが劣る傾向にある。ポリビニルアルコールの含有量は、５００質量部以下であることが好ましく、３００質量部以下であることがより好ましい。 The content of polyvinyl alcohol is preferably 1000 parts by mass or less per 100 parts by mass of acid-modified polyolefin resin. If it exceeds 1000 parts by mass, the viscosity of the liquid material for forming the resin layer increases, which makes it easier for uneven coating to occur, and gel may occur, tending to deteriorate the surface roughness of the resin layer. The content of polyvinyl alcohol is preferably 500 parts by mass or less, and more preferably 300 parts by mass or less.
本発明においてポリビニルアルコールとして市販のものを使用することができ、例えば、日本酢ビ・ポバール社製「Ｊ－ポバール」の「ＪＦ－０３」、「ＪＦ－０５」、「ＪＴ－０５」、「ＶＣ－１０」、「ＪＰ－１８」、「ＡＳＣ－０５Ｘ」、「ＵＭＲ－１０ＨＨ」；クラレ社製「クラレポバール」の「ＰＶＡ－１０３」、「ＰＶＡ－１０５」や、「エクセバール」の「ＡＱ４１０４」、「ＨＲ３０１０」；電気化学工業社製「デンカポバール」の「ＰＣ－１０００」、「ＰＣ－２０００」などが挙げられる。 In the present invention, commercially available polyvinyl alcohols can be used, such as "J-Poval" JF-03, "JF-05", "JT-05", "VC-10", "JP-18", "ASC-05X", and "UMR-10HH" manufactured by Nippon Vinyl Acetate & Poval Co., Ltd.; "Kuraray Poval" PVA-103, "PVA-105", "Exceval" AQ4104, and "HR3010" manufactured by Kuraray Co., Ltd.; and "Denka Poval" PC-1000 and PC-2000 manufactured by Denki Kagaku Kogyo Co., Ltd.
また、樹脂層は、本発明の効果を損なわない範囲で、滑剤を含有してもよい。滑剤として、例えば、炭酸カルシウム、炭酸マグネシウム、酸化カルシウム、酸化亜鉛、酸化マグネシウム、酸化ケイ素、ケイ酸ソーダ、水酸化アルミニウム、酸化鉄、酸化ジルコニウム、硫酸バリウム、酸化チタン、酸化錫、三酸化アンチモン、カーボンブラック、二硫化モリブデン等の無機粒子や、アクリル系架橋重合体、スチレン系架橋重合体、シリコーン樹脂、フッ素樹脂、ベンゾグアナミン樹脂、フェノール樹脂、ナイロン樹脂、ポリエチレンワックス等の有機粒子、界面活性剤等が挙げられる。 The resin layer may also contain a lubricant to the extent that the effect of the present invention is not impaired. Examples of lubricants include inorganic particles such as calcium carbonate, magnesium carbonate, calcium oxide, zinc oxide, magnesium oxide, silicon oxide, sodium silicate, aluminum hydroxide, iron oxide, zirconium oxide, barium sulfate, titanium oxide, tin oxide, antimony trioxide, carbon black, and molybdenum disulfide; organic particles such as acrylic crosslinked polymers, styrene crosslinked polymers, silicone resins, fluororesins, benzoguanamine resins, phenolic resins, nylon resins, and polyethylene wax; and surfactants.
本発明において樹脂層の厚みは、０．０１～１μｍであることが好ましく、０．０３～０．７μｍであることがより好ましく、０．０５～０．５μｍであることがさらに好ましい。樹脂層の厚みが０．０１μｍ未満であると、十分な離型性が得られず、１μｍを超えると、離型性は飽和して改善しないばかりか、凝集力を低下させ、被着体に移行しやすくなる。 In the present invention, the thickness of the resin layer is preferably 0.01 to 1 μm, more preferably 0.03 to 0.7 μm, and even more preferably 0.05 to 0.5 μm. If the thickness of the resin layer is less than 0.01 μm, sufficient releasability cannot be obtained, and if it exceeds 1 μm, not only will the releasability saturate and not improve, but the cohesive force will decrease and the resin will be more likely to transfer to the adherend.
本発明の離型フィルムにおける樹脂層は、予めγ線を照射させた酸変性ポリオレフィン樹脂水性分散体と、架橋剤とを液状媒体中に含有してなる樹脂層形成用液状物を、未延伸または延伸された基材フィルムの少なくとも片面に塗布して乾燥することで形成される。 The resin layer in the release film of the present invention is formed by applying a liquid for forming a resin layer, which contains an aqueous dispersion of an acid-modified polyolefin resin that has been irradiated with gamma rays in advance and a crosslinking agent in a liquid medium, to at least one side of an unstretched or stretched substrate film and then drying it.
本発明において使用するγ線の照射線量は、離型性能向上の観点で、１０～４００ｋＧｙであることが好ましく、５０～３００ｋＧｙがより好ましく、１００～２００が特に好ましい。照射線量が１０ｋＧｙより少ないと、得られる樹脂層の離型性能向上効果が不十分となる場合があり、４００ｋＧｙを超えると水性分散体の架橋構造が破壊され、剥離強度が大きくなる場合がある。 The exposure dose of gamma rays used in the present invention is preferably 10 to 400 kGy, more preferably 50 to 300 kGy, and particularly preferably 100 to 200, from the viewpoint of improving release performance. If the exposure dose is less than 10 kGy, the effect of improving the release performance of the resulting resin layer may be insufficient, and if it exceeds 400 kGy, the crosslinked structure of the aqueous dispersion may be destroyed, resulting in an increase in peel strength.
本発明において、樹脂層形成用液状物を構成する液状媒体は、水性媒体であることが好ましい。水性媒体とは、水と両親媒性有機溶剤とを含み、水の含有量が２質量％以上である溶媒を意味し、水のみでもよい。
両親媒性有機溶剤とは、２０℃における有機溶剤に対する水の溶解性が５質量％以上である有機溶剤をいう（２０℃における有機溶剤に対する水の溶解性については、例えば「溶剤ハンドブック」（講談社サイエンティフィク、１９９０年第１０版）等の文献に記載されている）。
両親媒性有機溶剤の具体例としては、メタノール、エタノール、ｎ－プロパノール、イソプロパノール等のアルコール類、テトラヒドロフラン、１，４－ジオキサン等のエーテル類、アセトン、メチルエチルケトン等のケトン類、酢酸メチル、酢酸－ｎ－プロピル、酢酸イソプロピル、プロピオン酸メチル、プロピオン酸エチル、炭酸ジメチル等のエステル類、エチレングリコール－ｎ－ブチルエーテル等のエチレングリコール誘導体類、そのほか、アンモニアを含む、ジエチルアミン、トリエチルアミン、ジエタノールアミン、トリエタノールアミン、Ｎ，Ｎ－ジメチルエタノールアミン、Ｎ，Ｎ－ジエチルエタノールアミン等の有機アミン化合物、２－ピロリドン、Ｎ－メチル－２－ピロリドンなどのラクタム類等を挙げることができる。
In the present invention, the liquid medium constituting the resin layer-forming liquid material is preferably an aqueous medium. The aqueous medium means a solvent containing water and an amphipathic organic solvent and having a water content of 2% by mass or more, or may be water alone.
An amphipathic organic solvent refers to an organic solvent in which the solubility of water in the organic solvent at 20° C. is 5% by mass or more (the solubility of water in organic solvents at 20° C. is described in literature such as “Solvent Handbook” (Kodansha Scientific, 10th edition, 1990)).
Specific examples of amphipathic organic solvents include alcohols such as methanol, ethanol, n-propanol, and isopropanol; ethers such as tetrahydrofuran and 1,4-dioxane; ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate, n-propyl acetate, isopropyl acetate, methyl propionate, ethyl propionate, and dimethyl carbonate; ethylene glycol derivatives such as ethylene glycol n-butyl ether; organic amine compounds containing ammonia such as diethylamine, triethylamine, diethanolamine, triethanolamine, N,N-dimethylethanolamine, and N,N-diethylethanolamine; and lactams such as 2-pyrrolidone and N-methyl-2-pyrrolidone.
樹脂層形成用液状物は、この方法に限定されるものではないが、たとえば酸変性ポリオレフィン樹脂水性分散体に、架橋剤を添加することにより、調製することができる。
酸変性ポリオレフィン樹脂水性分散体の固形分濃度は、特に限定されるものではないが、水性分散体の粘性を適度に保つためには、１～６０質量％が好ましく、５～３０質量％がより好ましい。
The liquid material for forming the resin layer can be prepared, for example, by adding a crosslinking agent to an aqueous dispersion of an acid-modified polyolefin resin, although the method is not limited to this.
The solids concentration of the acid-modified polyolefin resin aqueous dispersion is not particularly limited, but in order to maintain the viscosity of the aqueous dispersion at an appropriate level, it is preferably 1 to 60% by mass, and more preferably 5 to 30% by mass.
樹脂層形成用液状物の固形分濃度は、積層条件、目的とする厚さや性能等により適宜選択でき、特に限定されるものではない。しかし、液状物の粘性を適度に保ち、かつ、均一な樹脂層を形成させるためには、２～３０質量％が好ましく、３～２０質量％がより好ましい。
樹脂層形成用液状物には、その性能が損なわれない範囲で、酸化防止剤、紫外線吸収剤、滑剤、着色剤などを添加することもできる。
The solid content concentration of the liquid material for forming the resin layer is not particularly limited and can be appropriately selected depending on lamination conditions, the desired thickness and performance, etc. However, in order to maintain the viscosity of the liquid material at an appropriate level and form a uniform resin layer, the solid content is preferably 2 to 30% by mass, and more preferably 3 to 20% by mass.
The liquid material for forming the resin layer may contain additives such as antioxidants, ultraviolet absorbers, lubricants, and colorants, provided that the properties of the liquid material are not impaired.
本発明において、前記樹脂層形成用液状物を基材フィルムに塗布する方法としては、公知の方法、例えば、グラビアロールコーティング、リバースロールコーティング、ワイヤーバーコーティング、リップコーティング、エアナイフコーティング、カーテンフローコーティング、スプレーコーティング、浸漬コーティング、はけ塗り法等を挙げることができ、上記樹脂層形成用液状物は、コートスジの発生を抑制できるため、特にグラビアロールコーティングする場合に有効である。 In the present invention, the method for applying the liquid material for forming the resin layer to the substrate film can be a known method, such as gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, brush coating, etc., and the liquid material for forming the resin layer is particularly effective when gravure roll coating is used, since it can suppress the occurrence of coating streaks.
基材フィルムを構成する樹脂としては、例えば、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリ（１，４－シクロヘキシレンジメチレンテレフタレート）、ポリ乳酸（ＰＬＡ）などのポリエステル、ポリプロピレンなどのポリオレフィン、ポリスチレン、ポリアミド６、ポリ－ｐ－キシリレンアジパミド（ＭＸＤ６ナイロン）、ポリアミド６６、ポリアミド４６、ポリアミド４Ｔ、ポリアミド６Ｔ、ポリアミド９Ｔなどのポリアミド、ポリカーボネート、ポリアクリルニトリル、ポリイミドなどが挙げられる。
基材フィルムとしては、これらの樹脂からなる単層体や、複層体（例えば、ポリアミド６／ＭＸＤ６ナイロン／ポリアミド６、ポリアミド６／エチレン－ビニルアルコール共重合体／ポリアミド６）や、混合体などが挙げられ、機械的強度や寸法安定性を有するポリエステルフィルムや、ポリアミドフィルムが好ましい。
Examples of resins constituting the base film include polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), poly(1,4-cyclohexylene dimethylene terephthalate), and polylactic acid (PLA); polyolefins such as polypropylene; polystyrene, polyamide 6, poly-p-xylylene adipamide (MXD6 nylon), polyamide 66, polyamide 46, polyamide 4T, polyamide 6T, and polyamide 9T; polycarbonate, polyacrylonitrile, and polyimide.
Examples of the substrate film include monolayers and multilayers (e.g., polyamide 6/MXD6 nylon/polyamide 6, polyamide 6/ethylene-vinyl alcohol copolymer/polyamide 6) and mixtures of these resins, and polyester films and polyamide films having mechanical strength and dimensional stability are preferred.
基材フィルムを構成する樹脂の固有粘度は、特に限定されず、例えばポリエステルの場合であれば、０．５５～０．８０であることが好ましく、０．６０～０．７５であることがより好ましい。樹脂の固有粘度が上記範囲未満であると、製膜時にフィルムの切断が起こり易く、安定的にフィルムを生産するのが困難であり、得られたフィルムは強度が低いことがある。一方、固有粘度が上記範囲を超える場合には、フィルムの生産工程において、樹脂の溶融押出時に剪断発熱が大きくなり、押出機にかかる負荷が大きくなることで、生産速度を犠牲にせざるを得なかったり、フィルムの厚み制御も難しくなる等、フィルムの生産性が低下することがある。また、得られたフィルムは、熱分解やゲル化物が増加して、表面欠点や異物、表面粗大突起が増加することがある。また、あまりに固有粘度の高いものは、重合時間や重合プロセスが長く、コストを押し上げる要因ともなる。 The intrinsic viscosity of the resin constituting the base film is not particularly limited, and in the case of polyester, for example, it is preferably 0.55 to 0.80, and more preferably 0.60 to 0.75. If the intrinsic viscosity of the resin is less than the above range, the film is likely to break during film formation, making it difficult to produce the film stably, and the strength of the resulting film may be low. On the other hand, if the intrinsic viscosity exceeds the above range, shear heat generation during melt extrusion of the resin in the film production process increases, and the load on the extruder increases, making it necessary to sacrifice the production speed and making it difficult to control the thickness of the film, which may result in a decrease in film productivity. In addition, the resulting film may have an increase in thermal decomposition and gelation, and may have an increase in surface defects, foreign matter, and surface coarse protrusions. In addition, if the intrinsic viscosity is too high, the polymerization time and polymerization process are long, which can also be a factor in increasing costs.
基材フィルムを構成する樹脂の重合方法は特に限定されず、例えばポリエステルの場合であれば、エステル交換法、直接重合法等が挙げられる。エステル交換触媒としては、Ｍｇ、Ｍｎ、Ｚｎ、Ｃａ、Ｌｉ、Ｔｉなどの酸化物、酢酸塩等の化合物が挙げられる。また、重縮合触媒としては、Ｓｂ、Ｔｉ、Ｇｅなどの酸化物、酢酸塩等の化合物が挙げられる。
重合後のポリエステルは、モノマーやオリゴマー、副生成物のアセトアルデヒド等を含有しているため、減圧もしくは不活性ガス流通下、２００℃以上の温度で固相重合してもよい。
The polymerization method of the resin constituting the base film is not particularly limited, and in the case of polyester, for example, transesterification, direct polymerization, etc. can be mentioned. Examples of transesterification catalysts include compounds such as oxides and acetates of Mg, Mn, Zn, Ca, Li, Ti, etc. Examples of polycondensation catalysts include compounds such as oxides and acetates of Sb, Ti, Ge, etc.
Since the polyester after polymerization contains monomers, oligomers, and by-products such as acetaldehyde, it may be subjected to solid-phase polymerization at a temperature of 200° C. or higher under reduced pressure or in an inert gas stream.
基材フィルムには必要に応じ、添加剤、例えば、酸化防止剤、熱安定剤、紫外線吸収剤、帯電防止剤、ピニング剤等を添加することができる。酸化防止剤としては、ヒンダードフェノール系化合物、ヒンダードアミン系化合物等が挙げられ、熱安定剤としては、リン系化合物等が挙げられ、紫外線吸収剤としては、ベンゾフェノン系化合物、ベンゾトリアゾール系化合物等が挙げられる。 Additives such as antioxidants, heat stabilizers, UV absorbers, antistatic agents, pinning agents, etc. can be added to the base film as necessary. Examples of antioxidants include hindered phenol compounds and hindered amine compounds, examples of heat stabilizers include phosphorus compounds, etc., and examples of UV absorbers include benzophenone compounds and benzotriazole compounds.
基材フィルムとしてのポリエステルフィルムの製造方法の一例を示す。
十分に乾燥されたポリエステル樹脂を、押出機に供給し、十分に可塑化され、流動性を示す温度以上で溶融し、必要に応じて選ばれたフィルターを通過させ、その後Ｔダイを通じてシート状に押出す。このシートを、ポリエステルのガラス転移温度（Ｔｇ）以下に温度調節した冷却ドラム上に密着させて、未延伸フィルムを得る。
得られた未延伸フィルムを一軸延伸法により一軸配向させるか、もしくは二軸延伸法により二軸配向させる。二軸延伸法としては、特に限定はされないが、同時二軸延伸法や逐次二軸延伸法を用いることができる。
An example of a method for producing a polyester film as the base film will be described.
A sufficiently dried polyester resin is fed to an extruder, melted at a temperature at which it is sufficiently plasticized and exhibits fluidity, passed through a filter selected as necessary, and then extruded into a sheet through a T-die. This sheet is brought into close contact with a cooling drum whose temperature is adjusted to a temperature below the glass transition temperature (Tg) of the polyester, to obtain an unstretched film.
The unstretched film thus obtained is uniaxially oriented by a uniaxial stretching method, or biaxially oriented by a biaxial stretching method. The biaxial stretching method is not particularly limited, but a simultaneous biaxial stretching method or a sequential biaxial stretching method can be used.
一軸延伸法では、未延伸フィルムを、樹脂のＴｇ～Ｔｇより５０℃高い温度の範囲で、長手もしくは巾方向に、２～６倍程度の延伸倍率となるよう延伸する。
同時二軸延伸法では、未延伸フィルムを、樹脂のＴｇ～Ｔｇより５０℃高い温度の範囲で、長手および巾方向にそれぞれ２～４倍程度の延伸倍率となるよう二軸延伸する。同時二軸延伸機に導く前に、未延伸フィルムに１．２倍程度までの予備縦延伸を施しておいてもよい。
また、逐次二軸延伸法では、未延伸フィルムを、加熱ロールや赤外線等で加熱し、長手方向に延伸して縦延伸フィルムを得る。縦延伸は２個以上のロールの周速差を利用し、樹脂のＴｇ～Ｔｇより４０℃高い温度の範囲で、延伸倍率２．５～４．０倍とするのが好ましい。縦延伸フィルムを、続いて連続的に、巾方向に横延伸、熱固定、熱弛緩の処理を順次施して、二軸配向フィルムとする。横延伸は樹脂のＴｇ～Ｔｇより４０℃高い温度で開始し、最高温度は樹脂の融点（Ｔｍ）より（１００～４０）℃低い温度であることが好ましい。横延伸の倍率は最終的なフィルムの要求物性に依存し調整されるが、３．５倍以上、さらには３．８倍以上とするのが好ましく、４．０倍以上とするのがより好ましい。長手方向と巾方向に延伸後、さらに、長手方向および／または巾方向に再延伸することにより、フィルムの弾性率を高めたり寸法安定性を高めたりすることもできる。
延伸に続き、樹脂のＴｍより（５０～１０）℃低い温度で数秒間の熱固定処理と、熱固定処理と同時にフィルム巾方向に１～１０％の弛緩することが好ましい。熱固定処理後、フィルムをＴｇ以下に冷却して二軸延伸フィルムを得る。
In the uniaxial stretching method, an unstretched film is stretched in the longitudinal or transverse direction at a stretch ratio of about 2 to 6 times in the temperature range of the Tg of the resin to a temperature 50° C. higher than the Tg.
In the simultaneous biaxial stretching method, an unstretched film is biaxially stretched to a stretch ratio of about 2 to 4 times in each of the longitudinal and transverse directions in a temperature range of from the Tg of the resin to a temperature 50° C. higher than the Tg. Before being introduced into the simultaneous biaxial stretching machine, the unstretched film may be subjected to preliminary longitudinal stretching up to about 1.2 times.
In the sequential biaxial stretching method, an unstretched film is heated with a heating roll or infrared rays, and stretched in the longitudinal direction to obtain a longitudinally stretched film. The longitudinal stretching is preferably performed by utilizing the peripheral speed difference between two or more rolls, and at a stretching ratio of 2.5 to 4.0 times in the range of the Tg of the resin to a temperature 40° C. higher than Tg. The longitudinally stretched film is then continuously subjected to transverse stretching in the width direction, heat setting, and heat relaxation in sequence to obtain a biaxially oriented film. The transverse stretching is started at a temperature of Tg to a temperature 40° C. higher than Tg of the resin, and the maximum temperature is preferably a temperature (100 to 40)° C. lower than the melting point (Tm) of the resin. The transverse stretching ratio is adjusted depending on the required physical properties of the final film, but is preferably 3.5 times or more, further 3.8 times or more, and more preferably 4.0 times or more. After stretching in the longitudinal direction and the width direction, the film can be further stretched again in the longitudinal direction and/or the width direction to increase the elastic modulus and dimensional stability of the film.
Following the stretching, it is preferable to heat set the film for several seconds at a temperature (50 to 10)°C lower than the Tm of the resin, and simultaneously relax the film by 1 to 10% in the width direction. After the heat setting, the film is cooled to below the Tg to obtain a biaxially stretched film.
上記製造方法によって単層のフィルムが得られるが、離型フィルムを構成する基材フィルムは、２種以上の層を積層してなる多層フィルムであってもよい。
多層フィルムは、上記製造方法において、それぞれの層を構成する樹脂を別々に溶融して、複層ダイスを用いて押出し、固化前に積層融着させた後、二軸延伸、熱固定する方法や、２種以上の樹脂を別々に溶融、押出してそれぞれフィルム化し、未延伸状態で、または延伸後に、それらを積層融着させる方法などによって製造することができる。プロセスの簡便性から、複層ダイスを用い、固化前に積層融着させることが好ましい。
Although a single-layer film can be obtained by the above-mentioned production method, the base film constituting the release film may be a multi-layer film having two or more kinds of layers laminated thereon.
The multilayer film can be produced by the above-mentioned production method, in which the resins constituting each layer are melted separately, extruded using a multilayer die, laminated and fused before solidification, and then biaxially stretched and heat-set, or by a method in which two or more resins are melted separately, extruded to form films, and laminated and fused in an unstretched state or after stretching, etc. From the viewpoint of process simplicity, it is preferable to use a multilayer die and laminate and fused before solidification.
本発明の離型フィルムの製造方法においては、樹脂層形成用液状物を基材フィルムの製造工程中に塗布する工程と、基材フィルムと共に乾燥する工程を含む。さらに、配向延伸や熱固定処理する工程を含むことが好ましい。
樹脂層形成用液状物を基材フィルムの製造工程中に塗布することにより、基材フィルム表面の配向結晶化の程度が小さい状態で樹脂層を形成することができるため、基材フィルムと樹脂層の密着力が向上する。また、基材フィルムが緊張した状態で、より高温で樹脂層を熱処理できるので、基材フィルムの品位を低下させることなく、離型性や残存接着力を向上させることができる。
逐次二軸延伸法を採用して、一軸方向に延伸された基材フィルムに前記液状物を塗布し、液状物の塗布された基材フィルムを乾燥、その後、基材フィルムを前記方向と直交する方向にさらに延伸し、熱処理することが、簡便さや操業上の理由から好ましい。
The method for producing a release film of the present invention includes a step of applying a liquid material for forming a resin layer during the production process of a base film, and a step of drying the liquid material together with the base film. It is preferable that the method further includes a step of performing an orientation stretching or a heat setting treatment.
By applying the resin layer-forming liquid during the manufacturing process of the base film, the resin layer can be formed in a state where the degree of oriented crystallization on the surface of the base film is small, so that the adhesive strength between the base film and the resin layer is improved. In addition, since the resin layer can be heat-treated at a higher temperature while the base film is in a tensed state, the releasability and residual adhesive strength can be improved without deteriorating the quality of the base film.
It is preferable to employ a sequential biaxial stretching method in which the liquid is applied to a substrate film stretched in a uniaxial direction, the substrate film to which the liquid has been applied is dried, and then the substrate film is further stretched in a direction perpendicular to the uniaxial direction and heat-treated, for reasons of simplicity and operational feasibility.
以下、実施例によって本発明を具体的に説明するが、本発明はこれらによって限定されるものではない。離型フィルムの特性は下記の方法で測定した。 The present invention will be described in detail below with reference to examples, but the present invention is not limited to these. The properties of the release film were measured by the following methods.
＜アクリル系粘着剤に対する剥離力＞
得られた離型フィルムの樹脂層側に、巾５０ｍｍ、長さ１５０ｍｍのアクリル系粘着テープ（日東電工社製Ｎｏ．３１Ｂ／アクリル系粘着剤）をゴムロールで圧着して試料とした。試料を、金属板／ゴム板／試料／ゴム板／金属板の形で挟み、２ｋＰａ荷重、７０℃の雰囲気で２０時間放置し、その後３０分以上冷却して常温に戻して剥離強度測定用試料を得た。
剥離強度測定用試料の、粘着テープと離型フィルムとの剥離強度を、２３℃の恒温室で引張試験機（島津製作所社製オートグラフＡＧＳ－１００Ｂ）にて、剥離角度１８０度、剥離速度３００ｍｍ／分の条件で測定した。
<Peeling strength against acrylic adhesive>
A 50 mm wide, 150 mm long acrylic adhesive tape (Nitto Denko No. 31B/acrylic adhesive) was pressed with a rubber roll onto the resin layer side of the obtained release film to prepare a sample. The sample was sandwiched in the form of metal plate/rubber plate/sample/rubber plate/metal plate, and left for 20 hours under a load of 2 kPa in an atmosphere of 70°C, and then cooled for 30 minutes or more to return to room temperature to obtain a sample for measuring peel strength.
The peel strength between the adhesive tape and the release film of the peel strength measurement sample was measured in a thermostatic chamber at 23° C. using a tensile tester (Shimadzu Corporation, Autograph AGS-100B) at a peel angle of 180° and a peel speed of 300 mm/min.
＜エポキシプリプレグに対する剥離力＞
６０ｍｍ×１００ｍｍの大きさのエポキシプリプレグ（住友ベークライト社製ＥＩ－６７６５）の両面を、得られた離型フィルムの樹脂層側で挟み、１．０７ｋＰａ（８Ｔｏｒｒ）の真空プレス機中で、３０℃から１５０℃まで１５℃／分で昇温し、１５０℃で２２分間保持した後、さらに５℃／分で１９０℃まで昇温し、５ｋｇ／ｃｍ２の圧力を１０分間のかけた後、１５ｋｇ／ｃｍ２の圧力をかけながら、１９０℃で７０分間保持した。その後、室温まで冷却を行うことで、剥離強度測定用試料を得た。
得られた試料の、硬化後のエポキシプリプレグと離型フィルムとの剥離力を、２３℃の恒温室で引張試験機（島津製作所社製オートグラフＡＧＳ－１００Ｂ）にて、剥離角度は１８０度、剥離速度３００ｍｍ／分の条件で測定した。
<Peel strength against epoxy prepreg>
Both sides of an epoxy prepreg (EI-6765 manufactured by Sumitomo Bakelite Co., Ltd.) measuring 60 mm x 100 mm were sandwiched between the resin layer side of the obtained release film, and the temperature was raised from 30 ° C. to 150 ° C. at 15 ° C./min in a 1.07 kPa (8 Torr) vacuum press, and after holding at 150 ° C. for 22 minutes, the temperature was further raised to 190 ° C. at 5 ° C./min, and a pressure of 5 kg/cm 2 was applied for 10 minutes, and then the pressure of 15 kg/cm 2 was applied while holding at 190 ° C. for 70 minutes. After that, the sample was cooled to room temperature to obtain a sample for measuring peel strength.
The peel strength between the cured epoxy prepreg and the release film of the obtained sample was measured in a thermostatic chamber at 23° C. using a tensile tester (Shimadzu Corporation, Autograph AGS-100B) at a peel angle of 180 degrees and a peel speed of 300 mm/min.
＜ゴム系粘着剤に対する剥離力＞
得られた離型フィルムを１０ｃｍ角に切り取り、外径が１０．５ｃｍの紙管に貼り付け、その上から、下記の方法によって調製したゴム系被着体のゴム層が離型フィルムの樹脂層と接するように貼り付けた。その上に、ポリエステルフィルム（ユニチカ社製、ＰＥＴ－１２）を、巻取り張力１１８Ｎ／ｍ、巻取り接圧１１８Ｎ／ｍ、巻取り速度１００ｍ／分の条件で２０００ｍ巻き付け、６０℃×３日間、熱風乾燥器中で静置した。圧着処理終了後、冷却し、表層の巻き付けたポリエステルフィルムを除去して、離型フィルムとゴム系被着体とが貼り付いた状態の試料を取り出した。
２３℃×５０％ＲＨで２時間以上調湿した試料を１５ｍｍ幅に切り出した後、離型フィルムの樹脂層とゴム系被着体との間の剥離抵抗を、島津製作所社製オートグラフを使って測定した。すなわち、離型フィルムを上部のチャックに固定し、ゴム系被着体を下部のチャックに固定し、離型フィルムが一直線になるように未剥離部分をゴム系被着体側に折り曲げ、３００ｍｍ／分で剥離した際の剥離抵抗を計測した。５回の測定結果の平均を剥離力とした。
<Release strength against rubber-based adhesive>
The obtained release film was cut into 10 cm squares and attached to a paper tube with an outer diameter of 10.5 cm, and attached from above so that the rubber layer of a rubber-based adherend prepared by the following method was in contact with the resin layer of the release film. A polyester film (PET-12, manufactured by Unitika Ltd.) was wound on top of the film at 2000 m under the conditions of a winding tension of 118 N/m, a winding contact pressure of 118 N/m, and a winding speed of 100 m/min, and left to stand in a hot air dryer at 60°C for 3 days. After the pressure bonding process was completed, the film was cooled, the polyester film wound on the surface was removed, and a sample in which the release film and the rubber-based adherend were attached was taken out.
After conditioning the sample for 2 hours or more at 23°C x 50% RH, the sample was cut into a width of 15 mm, and the peel resistance between the resin layer of the release film and the rubber-based adherend was measured using an autograph manufactured by Shimadzu Corporation. That is, the release film was fixed to the upper chuck, the rubber-based adherend was fixed to the lower chuck, the unpeeled portion of the release film was folded toward the rubber-based adherend so that it was in a straight line, and the peel resistance was measured when peeling at 300 mm/min. The average of the results of five measurements was taken as the peel force.
＜ゴム系被着体の調製＞
ゴム層として、スチレン－ブタジエン共重合体（電気化学工業社製「クリアレン」、スチレン／ブタジエン＝３０／７０（質量比））４５質量部と、ポリオレフィン樹脂（三井化学社製「タフマー」）４５質量部と、耐衝撃性ポリエチレン（東洋スチレン社製「ＨＩ－Ｅ６」）１０質量部とからなる樹脂混合物を用い、支持層として、ポリオレフィン樹脂（三井化学社製「タフマー」）６０質量部と、低密度ポリエチレン（宇部興産社製「ＵＢＥポリエチレン」）４０質量部とからなる樹脂混合物を用いて、Ｔ－ダイ法共押出法により、総厚み３０μｍの２層フィルム（ゴム層厚み１０μｍ／支持層厚み２０μｍ）を作製した。その際、Ｔ－ダイより押出されたフィルムを、シリコンゴム製のマットロール（支持層側）と、平均表面粗さを０．８μｍに調整した金属製の冷却ロール（ゴム層側）で挟持して引き取った。
厚さ１６μｍの二軸延伸ポリエチレンテレフタレートフィルム（ユニチカ社製「エンブレットＳ－１６」）を基材層として、この上に、前記２層フィルムの支持層側の面を積層面として、溶融押出した低密度ポリエチレンを介して、押出ラミネーションをおこない、ゴム系被着体（ゴム層／支持層／低密度ポリエチレン／基材層）を作製した。
<Preparation of Rubber-Based Adherend>
As the rubber layer, a resin mixture consisting of 45 parts by mass of styrene-butadiene copolymer ("Clearen" manufactured by Denki Kagaku Kogyo Co., Ltd., styrene / butadiene = 30 / 70 (mass ratio)), 45 parts by mass of polyolefin resin ("Tafmer" manufactured by Mitsui Chemicals, Inc.), and 10 parts by mass of impact resistant polyethylene ("HI-E6" manufactured by Toyo Styrene Co., Ltd.) was used, and as the support layer, a resin mixture consisting of 60 parts by mass of polyolefin resin ("Tafmer" manufactured by Mitsui Chemicals, Inc.) and 40 parts by mass of low density polyethylene ("UBE Polyethylene" manufactured by Ube Industries, Ltd.) was used to produce a two-layer film (rubber layer thickness 10 μm / support layer thickness 20 μm) with a total thickness of 30 μm by T-die method coextrusion method. At that time, the film extruded from the T-die was sandwiched and taken up between a silicone rubber mat roll (support layer side) and a metal cooling roll (rubber layer side) with an average surface roughness adjusted to 0.8 μm.
A 16 μm thick biaxially oriented polyethylene terephthalate film ("Emblet S-16" manufactured by Unitika Ltd.) was used as a substrate layer, and the surface of the two-layer film facing the support layer was used as the lamination surface, and extrusion lamination was performed via melt-extruded low-density polyethylene to produce a rubber-based adherend (rubber layer/support layer/low-density polyethylene/substrate layer).
＜酸変性ポリオレフィン樹脂水性分散体Ｏ－１の製造＞
プロピレン－ブテン－エチレン三元共重合体（プロピレン／ブテン／エチレン＝６８．０／１６．０／１６．０質量％）２８０ｇを、４つ口フラスコ中、窒素雰囲気下で加熱溶融させた後、系内温度を１７０℃に保って攪拌下、不飽和カルボン酸として無水マレイン酸３２．０ｇとラジカル発生剤としてジクミルパーオキサイド６．０ｇをそれぞれ１時間かけて加え、その後１時間反応させた。反応終了後、得られた反応物を多量のアセトン中に投入し、樹脂を析出させた。この樹脂をさらにアセトンで数回洗浄し、未反応の無水マレイン酸を除去した後、減圧乾燥機中で減圧乾燥して、酸変性ポリオレフィン樹脂を得た。
ヒーター付きの密閉できる耐圧１リットル容ガラス容器を備えた撹拌機を用いて、上記方法で製造した６０．０ｇの酸変性ポリオレフィン樹脂と、４５．０ｇのエチレングリコール－ｎ－ブチルエーテル（沸点１７１℃）と、６．９ｇのＮ，Ｎ－ジメチルエタノールアミン（沸点１３４℃、樹脂中の無水マレイン酸単位のカルボキシル基に対して１．０倍当量）と、１８８．１ｇの蒸留水とを、上記のガラス容器内に仕込み、撹拌翼の回転速度を３００ｒｐｍとして撹拌した。そうしたところ、容器底部には樹脂の沈澱は認められず、浮遊状態となっていることが確認された。そこでこの状態を保ちつつ、１０分後にヒーターの電源を入れ加熱した。そして系内温度を１４０℃に保ってさらに６０分間撹拌した。その後、空冷にて、回転速度３００ｒｐｍのまま撹拌しつつ室温（約２５℃）まで冷却した。さらに、３００メッシュのステンレス製フィルター（線径０．０３５ｍｍ、平織）で加圧濾過（空気圧０．２ＭＰａ）することで、乳白黄色の均一な酸変性ポリオレフィン樹脂水性分散体Ｏ－１（固形分濃度２５質量％）を得た。
<Preparation of Acid-Modified Polyolefin Resin Aqueous Dispersion O-1>
280 g of propylene-butene-ethylene terpolymer (propylene/butene/ethylene=68.0/16.0/16.0% by mass) was heated and melted in a four-neck flask under a nitrogen atmosphere, and then 32.0 g of maleic anhydride as an unsaturated carboxylic acid and 6.0 g of dicumyl peroxide as a radical generator were added over 1 hour while stirring while maintaining the temperature in the system at 170° C., and then reacted for 1 hour. After the reaction was completed, the reaction product obtained was poured into a large amount of acetone to precipitate a resin. This resin was further washed several times with acetone to remove unreacted maleic anhydride, and then dried under reduced pressure in a vacuum dryer to obtain an acid-modified polyolefin resin.
Using a stirrer equipped with a sealable pressure-resistant 1-liter glass container with a heater, 60.0 g of the acid-modified polyolefin resin produced by the above method, 45.0 g of ethylene glycol-n-butyl ether (boiling point 171 ° C), 6.9 g of N,N-dimethylethanolamine (boiling point 134 ° C, 1.0 times equivalent to the carboxyl group of the maleic anhydride unit in the resin), and 188.1 g of distilled water were charged into the above glass container, and the stirring blade rotation speed was set to 300 rpm and stirred. As a result, no precipitation of the resin was observed at the bottom of the container, and it was confirmed that the resin was in a floating state. Therefore, while maintaining this state, the heater was turned on after 10 minutes and heated. Then, the temperature in the system was kept at 140 ° C and stirred for another 60 minutes. After that, the mixture was cooled to room temperature (about 25 ° C) by air cooling while stirring at a rotation speed of 300 rpm. Further, pressure filtration (air pressure 0.2 MPa) was performed using a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) to obtain a milky yellow uniform acid-modified polyolefin resin aqueous dispersion O-1 (solid content concentration 25% by mass).
＜酸変性ポリオレフィン樹脂水性分散体Ｏ－２の製造＞
ヒーター付きの密閉できる耐圧１リットル容ガラス容器を備えた撹拌機を用いて、６０．０ｇの酸変性ポリオレフィン樹脂（アルケマ社製ボンダインＬＸ－４１１０、エチレン／アクリル酸エチル／無水マレイン酸＝９１／７／２（質量％）、ＭＦＲ：５ｇ／１０分、融点：１０７℃、ビカット軟化点：８３℃）、９０．０ｇのイソプロパノール（ＩＰＡ）、３．０ｇのＮ，Ｎ－ジメチルエタノールアミン（ＤＭＥＡ、樹脂中の無水マレイン酸単位のカルボキシル基に対して１．０倍当量）および１４７．０ｇの蒸留水をガラス容器内に仕込んだ。そして、撹拌翼の回転速度を３００ｒｐｍとし、系内温度を１４０～１４５℃に保って、６０分間撹拌した。その後、水浴につけて、回転速度３００ｒｐｍのまま撹拌しつつ室温（約２５℃）まで冷却した。その後、水性媒体から有機溶剤を除去するために、ロータリーエバポレーターを用い、水を添加しながら、浴温８０℃で水性媒体の一部を留去した。その後、空冷にて室温（２５℃）まで冷却したあと、３００メッシュのステンレス製フィルター（線径０．０３５ｍｍ、平織）で加圧濾過（空気圧０．２ＭＰａ）した。これによって、乳白色の均一な酸変性ポリオレフィン樹脂水性分散体Ｏ－２（固形分濃度２０質量％）を得た。
<Preparation of Acid-Modified Polyolefin Resin Aqueous Dispersion O-2>
Using a stirrer equipped with a sealable pressure-resistant 1-liter glass container with a heater, 60.0 g of acid-modified polyolefin resin (Arkema Corp. Bondine LX-4110, ethylene/ethyl acrylate/maleic anhydride = 91/7/2 (mass%), MFR: 5 g/10 min, melting point: 107 ° C., Vicat softening point: 83 ° C.), 90.0 g of isopropanol (IPA), 3.0 g of N,N-dimethylethanolamine (DMEA, 1.0 times equivalent to the carboxyl group of the maleic anhydride unit in the resin), and 147.0 g of distilled water were charged into the glass container. Then, the rotation speed of the stirring blade was set to 300 rpm, and the temperature in the system was kept at 140 to 145 ° C., and the mixture was stirred for 60 minutes. Thereafter, the mixture was placed in a water bath and cooled to room temperature (about 25 ° C.) while stirring at a rotation speed of 300 rpm. Thereafter, in order to remove the organic solvent from the aqueous medium, a rotary evaporator was used to distill off a part of the aqueous medium at a bath temperature of 80° C. while adding water. Thereafter, the mixture was cooled to room temperature (25° C.) by air cooling, and then pressure filtered (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (line diameter 0.035 mm, plain weave). As a result, a milky white uniform acid-modified polyolefin resin aqueous dispersion O-2 (solid content concentration 20% by mass) was obtained.
＜酸変性ポリオレフィン樹脂水性分散体Ｏ－３の製造＞
ヒーター付きの密閉できる耐圧１リットル容ガラス容器を備えた撹拌機を用いて、酸変性プロピレン樹脂（三洋化成社製ユーメックス１００１、プロピレン／無水マレイン酸＝９７．７／２．３（質量％）、酸価：２６ｍｇＫＯＨ／ｇ、ＭＦＲ：６５ｇ／１０分（１６０℃下での測定結果）、融点：１５３℃）を６０ｇ、ＤＭＥＡを６．３ｇ、ＩＰＡを６０ｇ、蒸留水を１７４ｇ仕込み、密閉した後、３００ｒｐｍで撹拌翼しながら１６０℃（内温）まで加熱した。撹拌下、１６０℃で１時間保持した後、ヒーターの電源を切り室温まで撹拌下で自然冷却し、冷却後、水性媒体から有機溶剤を除去するために、ロータリーエバポレーターを用い、水を添加しながら、浴温８０℃で水性媒体の一部を留去した。その後、空冷にて室温（２５℃）まで冷却したあと、３００メッシュのステンレス製フィルター（線径０．０３５ｍｍ、平織）で加圧濾過（空気圧０．２ＭＰａ）し、乳白色の均一な酸変性ポリオレフィン水性分散体Ｏ－３（固形分濃度：２０質量％、ＩＰＡ：０質量％、ＤＭＥＡ：２．０質量％）を得た。数平均粒子径は９０ｎｍであった。
<Preparation of Acid-Modified Polyolefin Resin Aqueous Dispersion O-3>
Using a stirrer equipped with a sealable pressure-resistant 1-liter glass container equipped with a heater, 60 g of acid-modified propylene resin (UMEX 1001 manufactured by Sanyo Chemical Industries, Ltd., propylene/maleic anhydride = 97.7/2.3 (mass%), acid value: 26 mgKOH/g, MFR: 65 g/10 min (measured at 160°C), melting point: 153°C), 6.3 g of DMEA, 60 g of IPA, and 174 g of distilled water were charged and sealed, and then heated to 160°C (internal temperature) with a stirring blade at 300 rpm. After maintaining at 160°C for 1 hour under stirring, the heater was turned off and the container was naturally cooled to room temperature under stirring. After cooling, in order to remove the organic solvent from the aqueous medium, a rotary evaporator was used to distill off a part of the aqueous medium at a bath temperature of 80°C while adding water. Thereafter, the mixture was cooled to room temperature (25° C.) by air cooling, and then pressure filtered (air pressure 0.2 MPa) with a 300 mesh stainless steel filter (wire diameter 0.035 mm, plain weave) to obtain a milky white uniform acid-modified polyolefin aqueous dispersion O-3 (solid content concentration: 20 mass%, IPA: 0 mass%, DMEA: 2.0 mass%). The number average particle diameter was 90 nm.
樹脂層形成用液状物を調製するためにポリビニルアルコールを使用する場合、下記の水溶液を使用した。
ＶＣ－１０：日本酢ビ・ポバール社製ＶＣ－１０、ケン化率９９．３％以上、重合度１，０００、固形分濃度８質量％
When polyvinyl alcohol was used to prepare the liquid material for forming the resin layer, the following aqueous solution was used.
VC-10: VC-10 manufactured by Japan Vinyl Acetate & Poval Corporation, saponification rate 99.3% or more, polymerization degree 1,000, solid content concentration 8% by mass
架橋剤としては以下の化合物を使用した。
ＷＳ－７００：日本触媒社製エポクロスＷＳ－７００、オキサゾリン化合物、固形分濃度２５質量％
ＳＶ－０２：日清紡社製カルボジライトＳＶ－０２、カルボジイミド化合物、固形分濃度２５質量％
The following compounds were used as crosslinking agents.
WS-700: Epocross WS-700 manufactured by Nippon Shokubai Co., Ltd., an oxazoline compound, solid content concentration of 25% by mass
SV-02: Carbodilite SV-02 manufactured by Nisshinbo Corporation, a carbodiimide compound, solid content concentration 25% by mass
実施例１
＜樹脂層形成用液状物の調製＞
酸変性ポリオレフィン樹脂水性分散体Ｏ－１にγ線を１５０ｋＧｙ照射し、得られたγ線照射後の酸変性ポリオレフィン樹脂水性分散体と、ポリビニルアルコール水溶液「ＶＣ－１０」と、架橋剤としてＷＳ７００とを、それぞれ固形分が、１００質量部と、３００質量部と、７質量部とになるように混合し、最終固形分濃度が６．０質量％になるように水で調整して、液状物Ｕ－１０を得た。
＜離型フィルムの製造＞
平均粒径２．３μｍの無定形シリカ粒子を０．０８質量％含有するポリエチレンテレフタレート（重合触媒：三酸化アンチモン、固有粘度：０．６２、ガラス転移温度：７８℃、融点：２５５℃）を２８０℃で溶融押出し、Ｔダイ法－静電ピニング方式でキャスティングドラムに密着急冷し、厚さ６００μｍの未延伸フィルムを成形した。続いてこの未延伸フィルムを９０℃に加熱した縦延伸ロールで３．５倍に延伸した。
この縦延伸したフィルムの片面に、リバースグラビアコーターを用いて、液状物Ｕ－１０を６ｇ／ｍ２（ＷＥＴ換算）の塗布量になるように塗布し、横延伸テンターにおいて１２０℃で４．５倍延伸後、２３０℃で１０秒間熱処理したのち、冷却し巻き取った。得られた離型フィルムの厚さは３８μｍであり、樹脂層の厚さはおよそ０．１２μｍであった。
Example 1
<Preparation of Liquid for Forming Resin Layer>
The acid-modified polyolefin resin aqueous dispersion O-1 was irradiated with 150 kGy of gamma rays, and the obtained acid-modified polyolefin resin aqueous dispersion after gamma rays irradiation was mixed with the polyvinyl alcohol aqueous solution "VC-10" and WS700 as a crosslinking agent so that the solid contents were 100 parts by mass, 300 parts by mass and 7 parts by mass, respectively, and the mixture was adjusted with water so that the final solid concentration was 6.0% by mass, thereby obtaining a liquid material U-10.
<Production of Release Film>
Polyethylene terephthalate (polymerization catalyst: antimony trioxide, intrinsic viscosity: 0.62, glass transition temperature: 78°C, melting point: 255°C) containing 0.08% by mass of amorphous silica particles having an average particle size of 2.3 μm was melt-extruded at 280°C, and then quenched in close contact with a casting drum using a T-die method-electrostatic pinning method to form an unstretched film having a thickness of 600 μm. This unstretched film was then stretched 3.5 times with longitudinal stretching rolls heated to 90°C.
On one side of this longitudinally stretched film, liquid material U-10 was applied using a reverse gravure coater so as to give a coating amount of 6 g/ m2 (wet equivalent), and the film was stretched 4.5 times at 120°C in a transverse stretching tenter, then heat-treated at 230°C for 10 seconds, cooled, and wound up. The thickness of the obtained release film was 38 μm, and the thickness of the resin layer was approximately 0.12 μm.
実施例２～１０、比較例２～４、６～７
実施例１の樹脂層形成用液状物の調製と同様に、液状物Ｕ－１１～Ｕ－１９、Ｕ－２１～Ｕ－２３、Ｕ－２５～Ｕ－２６を得た。なお、樹脂層形成用液状物の組成、γ線照射量は表１に記載した。
また、液状物Ｕ－１０に代えて液状物液状物Ｕ－１１～Ｕ－１９、Ｕ－２１～Ｕ－２３、Ｕ－２５～Ｕ－２６を用いた以外は、実施例１と同様に離型フィルムを製造した。
Examples 2 to 10, Comparative Examples 2 to 4, 6 to 7
Liquid materials U-11 to U-19, U-21 to U-23, and U-25 to U-26 were obtained in the same manner as in the preparation of the liquid material for forming a resin layer in Example 1. The compositions of the liquid materials for forming a resin layer and the doses of gamma rays irradiated are shown in Table 1.
In addition, release films were produced in the same manner as in Example 1, except that liquid materials U-11 to U-19, U-21 to U-23, and U-25 to U-26 were used instead of liquid material U-10.
比較例１
＜樹脂層形成用液状物の調製＞
酸変性ポリオレフィン樹脂水性分散体Ｏ－１と、ポリビニルアルコール水溶液「ＶＣ－１０」と、架橋剤としてＷＳ７００とを、それぞれ固形分が、１００質量部と、３００質量部と、７質量部とになるように混合し、最終固形分濃度が６．０質量％になるように水で調整して、液状物Ｕ－２０を得た。
＜離型フィルムの製造＞
平均粒径２．３μｍの無定形シリカ粒子を０．０８質量％含有するポリエチレンテレフタレート（重合触媒：三酸化アンチモン、固有粘度：０．６２、ガラス転移温度：７８℃、融点：２５５℃）を２８０℃で溶融押出し、Ｔダイ法－静電ピニング方式でキャスティングドラムに密着急冷し、厚さ６００μｍの未延伸フィルムを成形した。続いてこの未延伸フィルムを９０℃に加熱した縦延伸ロールで３．５倍に延伸した。
この縦延伸したフィルムの片面に、リバースグラビアコーターを用いて、液状物Ｕ－１０を６ｇ／ｍ２（ＷＥＴ換算）の塗布量になるように塗布し、横延伸テンターにおいて１２０℃で４．５倍延伸後、２３０℃で１０秒間熱処理したのち、冷却し巻き取った。次いで、離型フィルムの樹脂層面にγ線を１５０ｋＧｙ照射した。得られた離型フィルムの厚さは３８μｍであり、樹脂層の厚さはおよそ０．１２μｍであった。
Comparative Example 1
<Preparation of Liquid for Forming Resin Layer>
The acid-modified polyolefin resin aqueous dispersion O-1, the polyvinyl alcohol aqueous solution "VC-10", and WS700 as a crosslinking agent were mixed so that the solid contents were 100 parts by mass, 300 parts by mass, and 7 parts by mass, respectively, and the mixture was adjusted with water so that the final solid concentration was 6.0% by mass, thereby obtaining a liquid material U-20.
<Production of Release Film>
Polyethylene terephthalate (polymerization catalyst: antimony trioxide, intrinsic viscosity: 0.62, glass transition temperature: 78°C, melting point: 255°C) containing 0.08% by mass of amorphous silica particles having an average particle size of 2.3 μm was melt-extruded at 280°C, and was then quenched in close contact with a casting drum using a T-die method-electrostatic pinning method to form an unstretched film having a thickness of 600 μm. This unstretched film was then stretched 3.5 times with longitudinal stretching rolls heated to 90°C.
On one side of this longitudinally stretched film, liquid material U-10 was applied using a reverse gravure coater so as to give a coating amount of 6 g/m 2 (wet equivalent), and the film was stretched 4.5 times at 120°C in a transverse stretching tenter, and then heat-treated at 230°C for 10 seconds, cooled, and wound up. Next, the resin layer surface of the release film was irradiated with γ-rays at 150 kGy. The thickness of the obtained release film was 38 μm, and the thickness of the resin layer was approximately 0.12 μm.
比較例５
酸変性ポリオレフィン樹脂水性分散体をＯ－１に代えてＯ－２を用いた以外は、比較例１と同様に行い、厚さ３８μｍ、樹脂層厚み０．１２μｍの離型フィルムを得た。
Comparative Example 5
The same procedure as in Comparative Example 1 was carried out except that the acid-modified polyolefin resin aqueous dispersion O-2 was used instead of O-1, to obtain a release film having a thickness of 38 μm and a resin layer thickness of 0.12 μm.
比較例８～１０
樹脂層形成用液状物の組成を表１の組成に変更し、γ線の照射を行わなかった以外は比較例１と同様に行い、厚さ３８μｍ、樹脂層厚み０．１２μｍの離型フィルムを得た。
Comparative Examples 8 to 10
The same procedure as in Comparative Example 1 was carried out except that the composition of the resin layer-forming liquid was changed to the composition in Table 1 and gamma-ray irradiation was not performed, to obtain a release film having a thickness of 38 μm and a resin layer thickness of 0.12 μm.
実施例、比較例で得られた離型フィルムについて各種評価を行った結果を表１に示す。 The results of various evaluations of the release films obtained in the examples and comparative examples are shown in Table 1.
実施例１～１０の離型フィルムは、酸変性ポリオレフィン樹脂水性分散体にγ線を１０～４００ｋＧｙの範囲で照射した樹脂層形成用液状物を塗布して形成した樹脂層であるため、アクリル系粘着剤やエポキシプリプレグに対する剥離強度が本発明で規定する範囲内という良好な離型性を示した。 The release films of Examples 1 to 10 were resin layers formed by applying a liquid for forming a resin layer to an aqueous dispersion of acid-modified polyolefin resin, which was irradiated with gamma rays in the range of 10 to 400 kGy. Therefore, they showed good releasability, with peel strength against acrylic adhesives and epoxy prepregs falling within the range specified by the present invention.
比較例１、５の離型フィルムは、酸変性ポリオレフィン樹脂水性分散体にγ線を照射せず、離型フィルム形成後の樹脂層にγ線照射を施したため、離型性能は向上しなかった。
比較例２、６の離型フィルムは、酸変性ポリオレフィン樹脂水性分散体へのγ線照射量が少なすぎたため、γ線照射による効果が小さく、本発明で規定する離型性能を示す離型フィルムが得られなかった。
比較例３、７の離型フィルムは、酸変性ポリオレフィン樹脂水性分散体へのγ線照射量が多すぎたため、水性分散体の架橋構造が破壊され、離型性に劣っていた。
比較例４の離型フィルムは、樹脂層に架橋剤を含有していなかったため、離型性が劣っていた。
比較例８～１０の離型フィルムは、γ線照射を行わなかったため、各種被着体に対して優れた離型性能を得ることができなかった。
In the release films of Comparative Examples 1 and 5, the acid-modified polyolefin resin aqueous dispersion was not irradiated with gamma rays, but the resin layer after the release film formation was irradiated with gamma rays, and therefore the release performance was not improved.
In the release films of Comparative Examples 2 and 6, the amount of gamma ray irradiation of the acid-modified polyolefin resin aqueous dispersion was too small, so the effect of gamma ray irradiation was small and no release films exhibiting the release performance specified in the present invention were obtained.
In the release films of Comparative Examples 3 and 7, the amount of gamma radiation applied to the acid-modified polyolefin resin aqueous dispersion was too high, so that the crosslinked structure of the aqueous dispersion was destroyed and the release properties were poor.
The release film of Comparative Example 4 had poor releasability because the resin layer did not contain a crosslinking agent.
The release films of Comparative Examples 8 to 10 were not irradiated with gamma rays, and therefore could not obtain excellent release performance for various adherends.
Claims (6)
（イ）アクリル系被着体を樹脂層に貼り付けて７０℃で熱処理後測定したときの剥離力が１．５Ｎ／ｃｍ以下であること
（ロ）エポキシ系被着体を樹脂層に貼り付けて１９０℃で熱処理後測定したときの剥離力が０．２Ｎ／ｃｍ以下であること A release film comprising a polyester film as a base film and a resin layer provided on at least one side thereof, the resin layer containing an acid-modified polyolefin resin and a crosslinking agent, and satisfying the following requirements (i) and (ii).
(a) The peel strength when an acrylic adherend is attached to a resin layer and heat-treated at 70°C is 1.5 N/cm or less. (b) The peel strength when an epoxy adherend is attached to a resin layer and heat-treated at 190°C is 0.2 N/cm or less.
（イ）アクリル系被着体を樹脂層に貼り付けて７０℃で熱処理後測定したときの剥離力が１．５Ｎ／ｃｍ以下であること
（ロ）エポキシ系被着体を樹脂層に貼り付けて１９０℃で熱処理後測定したときの剥離力が０．２Ｎ／ｃｍ以下であること A method for producing a release film in which a resin layer containing an acid-modified polyolefin resin and a crosslinking agent is provided on at least one surface of a base film and satisfies the following requirements (a) and (b), in which the resin layer is formed by applying an aqueous dispersion of acid-modified polyolefin resin that has been irradiated with gamma rays to the base film.
(a) The peel strength when an acrylic adherend is attached to a resin layer and heat-treated at 70°C is 1.5 N/cm or less. (b) The peel strength when an epoxy adherend is attached to a resin layer and heat-treated at 190°C is 0.2 N/cm or less.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009025063A1 (en) | 2007-08-22 | 2009-02-26 | Unitika Ltd. | Release sheet |
| WO2014103781A1 (en) | 2012-12-26 | 2014-07-03 | 三井化学東セロ株式会社 | Mold release film and method for producing same |
| WO2018062266A1 (en) | 2016-09-30 | 2018-04-05 | ユニチカ株式会社 | Mold release sheet |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009025063A1 (en) | 2007-08-22 | 2009-02-26 | Unitika Ltd. | Release sheet |
| WO2014103781A1 (en) | 2012-12-26 | 2014-07-03 | 三井化学東セロ株式会社 | Mold release film and method for producing same |
| WO2018062266A1 (en) | 2016-09-30 | 2018-04-05 | ユニチカ株式会社 | Mold release sheet |
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