JP4590346B2 - Release sheet - Google Patents
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- JP4590346B2 JP4590346B2 JP2005354552A JP2005354552A JP4590346B2 JP 4590346 B2 JP4590346 B2 JP 4590346B2 JP 2005354552 A JP2005354552 A JP 2005354552A JP 2005354552 A JP2005354552 A JP 2005354552A JP 4590346 B2 JP4590346 B2 JP 4590346B2
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本発明は、合成皮革などの用途における樹脂膜製造の際に工程シートとして使用される離型シートに関する。さらに詳しくは、樹脂膜製造工程において、樹脂膜が離型シートから剥離することなく、また、製膜後の剥離工程において樹脂膜が破れることなく離型シートから容易に剥離する、すなわち、塗布時の基材に対する樹脂の濡れ性と剥離剤層からの樹脂膜の剥離性との両方をバランスよく具備した離型シートに関するものである。 The present invention relates to a release sheet used as a process sheet in the production of a resin film in applications such as synthetic leather. More specifically, in the resin film manufacturing process, the resin film does not peel from the release sheet, and in the peeling process after film formation, the resin film is easily peeled off from the release sheet, that is, at the time of application. The present invention relates to a release sheet having a good balance between the wettability of the resin with respect to the base material and the peelability of the resin film from the release agent layer.
従来、合成皮革などの製造はウレタン樹脂、塩化ビニル樹脂、ポリアミド樹脂などを離型シート上に塗布・乾燥し、必要に応じて基布と貼合する方法で行われている（乾式法）。また、耐水性の離型シート上に、たとえば、ウレタン樹脂を塗布してウレタン樹脂層を形成し、この離型シート上のウレタン樹脂層に基布を貼り合わせた後、凝固槽中に導きウレタン樹脂を凝固させて成膜し、水洗・乾燥する方法でも製造が行われている（湿式法）。
合成皮革などを上記のような方法で製造する際に使用されている離型シートとしては、紙を基材とし、その表面にポリプロピレンやポリメチルペンテンからなる剥離性樹脂層を設けたもの（特許文献１）、シリコーン系剥離剤組成物または非シリコーン系剥離剤組成物としてアルキド樹脂とアミノ樹脂との混合物を剥離層として用いたもの（特許文献２、特許文献３）などが知られている。しかしながら、樹脂膜の種類によっては離型シートとの剥離性が大きく異なり、剥離が重すぎて、剥離工程で樹脂膜が破れたり、逆に剥離が軽すぎて、製造工程における離型シートを除去するまでの過程で浮きが生じたりするという問題があり、剥離特性の改善が望まれていた。
Conventionally, synthetic leather and the like have been manufactured by applying urethane resin, vinyl chloride resin, polyamide resin, etc. on a release sheet, drying, and bonding to a base fabric as necessary (dry method). Also, for example, a urethane resin is applied on a water-resistant release sheet to form a urethane resin layer, a base fabric is bonded to the urethane resin layer on the release sheet, and then guided into a coagulation tank. Manufacture is also performed by solidifying the resin to form a film, washing with water and drying (wet method).
The release sheet used when manufacturing synthetic leather and the like by the above method is a paper base material with a release resin layer made of polypropylene or polymethylpentene on its surface (patent Document 1), a silicone release agent composition or a non-silicone release agent composition using a mixture of an alkyd resin and an amino resin as a release layer (Patent Document 2, Patent Document 3) and the like are known. However, depending on the type of resin film, the releasability from the release sheet varies greatly, the release is too heavy, the resin film is torn in the release process, or the release is too light to remove the release sheet in the manufacturing process. There has been a problem that floating may occur in the process up to, and improvement of the peeling characteristics has been desired.
このような状況の下、本発明の課題は、樹脂膜が製造工程中に離型シートから浮いたり、剥離を生じることがなく、また、剥離特性のコントロールが容易で特性にバラツキがなく、さらに、剥離特性が経時変化することなく、剥離工程において、比較的容易に剥離し得る適度な剥離性を有する、特に合成皮革製造用の工程シートとして好適な離型シートを提供することである。 Under such circumstances, the problem of the present invention is that the resin film does not float from the release sheet or peel off during the manufacturing process, and the peeling characteristics can be easily controlled and the characteristics do not vary. An object of the present invention is to provide a release sheet suitable for a process sheet for producing synthetic leather, having an appropriate releasability that can be peeled relatively easily in a peeling step without causing the peeling properties to change with time.
本発明者らは、上記課題を達成すべく種々の研究を重ねた結果、基材の少なくとも一方の面に、結晶性ポリオレフィン樹脂および非結晶性ポリオレフィン樹脂を所定比率で含む熱可塑性樹脂組成物を用いて形成された剥離層を有することにより、上記課題を達成できることを見出し、本発明に到達した。
すなわち、本発明は、下記（１）〜（５）
（１）基材の少なくとも一方の面に、（Ａ）結晶性ポリオレフィン樹脂２５〜９３質量％および（Ｂ）非結晶性ポリオレフィン樹脂７５〜７質量％からなる樹脂混合物を含む熱可塑性樹脂組成物を用いて形成された剥離層を有することを特徴とする合成皮革製造用離型シート、
（２）前記結晶性ポリオレフィン樹脂が、ＪＩＳ Ｋ７１２２に準拠して示差走査熱量計で測定して得られる結晶の融解に基づく主ピークの位置（融点）が８０〜１７６℃である結晶性ポリプロピレン系樹脂である前記１に記載の離型シート、
（３）前記結晶性ポリプロピレン系樹脂がプロピレン単独重合体である前記２に記載の離型シート、
（４）前記非結晶性ポリオレフィン樹脂がプロピレン-1-ブテン共重合体である前記１から３のいずれかに記載の離型シート、
（５）前記プロピレン-1-ブテン共重合体のプロピレン単位含有率が５０〜９９質量％である前記４に記載の離型シート
を提供する。
As a result of various studies to achieve the above-mentioned problems, the present inventors have developed a thermoplastic resin composition containing a crystalline polyolefin resin and an amorphous polyolefin resin in a predetermined ratio on at least one surface of a substrate. It has been found that the above-mentioned problems can be achieved by having a release layer formed using the present invention, and the present invention has been achieved.
That is, the present invention provides the following (1) to (5).
(1) A thermoplastic resin composition comprising a resin mixture comprising (A) 25 to 93% by mass of a crystalline polyolefin resin and (B) 75 to 7% by mass of an amorphous polyolefin resin on at least one surface of a substrate. A release sheet for producing synthetic leather , characterized by having a release layer formed using
(2) A crystalline polypropylene resin in which the crystalline polyolefin resin has a main peak position (melting point) based on melting of crystals obtained by measuring with a differential scanning calorimeter in accordance with JIS K7122 at 80 to 176 ° C. The release sheet as described in 1 above,
(3) The release sheet as described in 2 above, wherein the crystalline polypropylene resin is a propylene homopolymer,
(4) The release sheet according to any one of 1 to 3, wherein the amorphous polyolefin resin is a propylene-1-butene copolymer,
(5) The release sheet according to 4 above, wherein the propylene unit content of the propylene-1-butene copolymer is 50 to 99% by mass.
本発明により、合成皮革などの樹脂膜の製造において、工程シートとして用いられ、樹脂塗布時のぬれ性と製膜後の剥離剤層からの樹脂膜の剥離性との両方をバランスよく有する離型シートが得られる。 According to the present invention, in the production of resin films such as synthetic leather, it is used as a process sheet, and has a good balance between wettability during resin application and releasability of the resin film from the release agent layer after film formation. A sheet is obtained.
本発明の離型シートにおいて、基材としてはクラフト紙、上質紙、模造紙、アート紙、コート紙のような紙類、これらの紙基材にポリエチレンなどをラミネートしたラミネート紙、合成紙、不織布、あるいはポリオレフィン、ポリエーテルエーテルケトン、ポリエーテルケトン、ポリイミド、ポリエーテルスルホン及びポリエステル系樹脂等のプラスチックフィルムが使用される。
基材として紙類が使用される場合、その坪量は特に制限はないが、好ましくは、３０〜３００ｇ/ｍ2、より好ましくは、４０〜２００ｇ/ｍ2である。
基材としてプラスチックフィルムが使用される場合、その厚みは特に制限はないが、好ましくは、１０〜５００μｍ、さらに好ましくは、５０〜２５０μｍである。
紙類の坪量の範囲およびプラスチックフィルムの厚みの範囲を上記のように設定することにより、熱可塑性樹脂組成物を用いて形成された剥離層をラミネートする際および合成皮革等樹脂膜を製造する際、機械適性を良好に保つことができ、かつ、離型シートを運搬・保管するためのロール巻き取りが容易であり、離型シートのロール替えの頻度も上がらず、生産性を高く保つことができる。
In the release sheet of the present invention, the base material is kraft paper, fine paper, imitation paper, art paper, coated paper such as coated paper, laminated paper obtained by laminating polyethylene etc. on these paper base materials, synthetic paper, non-woven fabric Alternatively, plastic films such as polyolefin, polyether ether ketone, polyether ketone, polyimide, polyether sulfone, and polyester resin are used.
When paper is used as the substrate, its basis weight is not particularly limited, but is preferably 30 to 300 g / m 2 , more preferably 40 to 200 g / m 2 .
When a plastic film is used as the substrate, the thickness is not particularly limited, but is preferably 10 to 500 μm, and more preferably 50 to 250 μm.
By setting the range of the basis weight of papers and the range of the thickness of the plastic film as described above, when laminating the release layer formed using the thermoplastic resin composition and producing a resin film such as synthetic leather At the time, the machine suitability can be kept good, the roll for transporting and storing the release sheet can be easily taken up, the roll of the release sheet is not changed frequently, and the productivity is kept high. Can do.
基材としてプラスチックフィルムが使用される場合、プラスチックフィルムと後に述べる剥離層との密着性を向上させるため、プラスチックフィルムの剥離層が設けられる側の面に必要に応じて酸化法や凹凸化法などの物理的または化学的表面処理を施すことができる。酸化法としては、たとえば、コロナ放電処理、クロム酸処理、火炎処理、熱風処理、オゾン・紫外線照射処理などが挙げられる。また、凹凸化法としては、たとえば、サンドブラスト法、溶剤処理法などが挙げられる。これらの表面処理法はプラスチックフィルムの種類に応じて適宜選択される。また、プライマー処理を施すこともできる。なお、本発明の離型シートを湿式法による合成皮革の製造に用いる場合には合成紙もしくはプラスチックシートのような耐水性を有する基材を用いることが好ましい。 When a plastic film is used as the base material, the surface of the plastic film on which the release layer is provided is subjected to an oxidation method, an unevenness method, or the like as necessary in order to improve the adhesion between the plastic film and the release layer described later. Physical or chemical surface treatment can be applied. Examples of the oxidation method include corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. Examples of the uneven method include a sand blast method and a solvent treatment method. These surface treatment methods are appropriately selected according to the type of plastic film. Moreover, primer treatment can also be performed. In addition, when using the release sheet of this invention for manufacture of the synthetic leather by a wet method, it is preferable to use the base material which has water resistance like a synthetic paper or a plastic sheet.
本発明の離型シートは上記のような基材の少なくとも一方の面に（Ａ）結晶性ポリオレフィン樹脂および（Ｂ）非結晶性ポリオレフィン樹脂からなる樹脂混合物を含む熱可塑性樹脂組成物を用いて形成された剥離層を有することを特徴としている。
（Ａ）成分の結晶性ポリオレフィン樹脂としては、結晶性ポリプロピレン系樹脂が好ましい。ポリプロピレン系樹脂の中でアイソタクチックまたはシンジオタクチックシーケンス構造を主として有しているもので、ホモポリマーでも良いし、エチレンまたは1-ブテンや１−ペンテンのようなα−オレフィンの1種以上のコモノマー成分を含むランダムタイプやブロックタイプのコポリマー、またはプロピレンのホモポリマーにポリエチレンがブレンドされたものでもよい。好ましくは、ＪＩＳ Ｋ７１２２に準拠した示差走査熱量計（ＤＳＣ）による測定で１Ｊ/ｇ以上、好ましくは、３０〜１２０Ｊ/ｇ、さらに好ましくは、６０〜１２０Ｊ/ｇの結晶融解熱量を有するものであり、結晶融解に基づく主ピークの位置（融点）が８０〜１７６℃であるもの、さらに好ましくは、１２０〜１７６℃のものである。結晶融解熱量および融点が上記範囲のものであれば、高密度〜低密度ポリエチレン、直鎖状低密度ポリエチレン等のポリエチレン系樹脂、ポリブテン系樹脂でも良い。結晶性ポリオレフィン樹脂の数平均分子量については特に制限はないが、好ましくは、１０,０００〜１,０００,０００程度である。
（Ａ）成分の結晶性ポリオレフィン樹脂の具体例としては、サンアロマー（株）製のポリプロピレン「ＰＨ９０３Ａ」、日本ポリケム社製のポリプロピレン「ＦＬ２５Ｔ」や「ＦＬ２５ＨＡ」、（株）プライムポリマー社製のポリプロピレン「Ｆ１０９Ｖ」等が挙げられる。
The release sheet of the present invention is formed using a thermoplastic resin composition containing a resin mixture composed of (A) a crystalline polyolefin resin and (B) an amorphous polyolefin resin on at least one surface of the base material as described above. It is characterized by having a release layer formed.
As the (A) component crystalline polyolefin resin, a crystalline polypropylene resin is preferred. The polypropylene resin mainly has an isotactic or syndiotactic sequence structure, and may be a homopolymer, or one or more α-olefins such as ethylene or 1-butene and 1-pentene. A random type or block type copolymer containing a comonomer component, or a propylene homopolymer may be blended with polyethylene. Preferably, it has a crystal melting calorie of 1 J / g or more, preferably 30 to 120 J / g, more preferably 60 to 120 J / g as measured by a differential scanning calorimeter (DSC) according to JIS K7122. The main peak position (melting point) based on crystal melting is from 80 to 176 ° C, more preferably from 120 to 176 ° C. As long as the amount of heat of crystal fusion and the melting point are within the above ranges, polyethylene resins such as high density to low density polyethylene and linear low density polyethylene, and polybutene resins may be used. The number average molecular weight of the crystalline polyolefin resin is not particularly limited but is preferably about 10,000 to 1,000,000.
Specific examples of the crystalline polyolefin resin of component (A) include polypropylene “PH903A” manufactured by Sun Allomer Co., Ltd., polypropylene “FL25T” and “FL25HA” manufactured by Nippon Polychem, and polypropylene “manufactured by Prime Polymer Co., Ltd.” F109V "etc. are mentioned.
（Ｂ）成分の非結晶性ポリオレフィン樹脂としては、ＪＩＳ Ｋ７１２２に準拠したＤＳＣによる測定で結晶の融解に基づく１Ｊ/ｇ以上のピークおよび結晶化に基づく１Ｊ/ｇ以上のピークのいずれをも有していないものである。
非結晶性ポリオレフィン樹脂としては、エチレンおよび炭素数３〜２０のα−オレフィンを必須とし、任意にポリエン化合物、環状オレフィン及びビニル芳香族化合物から選ばれる１種以上のモノマー成分を共重合して得られる非晶性オレフィン系共重合体、エチレン、プロピレンおよび炭素数４〜２０のα−オレフィンを必須とし、任意にポリエン化合物、環状オレフィン及びビニル芳香族化合物から選ばれる１種以上のモノマー成分を共重合して得られる非晶性オレフィン系共重合体、プロピレンおよび炭素数４〜２０のα−オレフィンを必須とし、任意にポリエン化合物、環状オレフィン及びビニル芳香族化合物から選ばれる１種以上のモノマー成分を共重合して得られる非晶性オレフィン系共重合体、エチレン、炭素数４〜２０のα−オレフィンおよびポリエン化合物からなる非晶性オレフィン系共重合体等がある。特に、プロピレン単位含有率が５０〜９９質量％のプロピレン-1-ブテン共重合体が好ましく、プロピレン単位含有率が９５質量％程度のものが特に好ましい。
（Ｂ）成分の非結晶性ポリオレフィン樹脂の具体例としては、住友化学（株）製のポリプロピレン「タフセレンＸ−１１０２」や「タフセレンＸ−１１０４」等が挙げられる。
The non-crystalline polyolefin resin of component (B) has both a peak of 1 J / g or more based on melting of crystals and a peak of 1 J / g or more based on crystallization as measured by DSC in accordance with JIS K7122. It is not.
As an amorphous polyolefin resin, ethylene and an α-olefin having 3 to 20 carbon atoms are essential, and optionally obtained by copolymerizing one or more monomer components selected from a polyene compound, a cyclic olefin, and a vinyl aromatic compound. An amorphous olefin copolymer, ethylene, propylene, and an α-olefin having 4 to 20 carbon atoms, and optionally containing at least one monomer component selected from a polyene compound, a cyclic olefin, and a vinyl aromatic compound. Amorphous olefin copolymer obtained by polymerization, propylene, and α-olefin having 4 to 20 carbon atoms are essential, and optionally one or more monomer components selected from polyene compounds, cyclic olefins and vinyl aromatic compounds Amorphous olefin copolymer obtained by copolymerization of ethylene, ethylene, α-carbon having 4 to 20 carbon atoms There are olefins and consisting polyene compound amorphous olefin copolymer. In particular, a propylene-1-butene copolymer having a propylene unit content of 50 to 99% by mass is preferable, and a propylene unit content of about 95% by mass is particularly preferable.
Specific examples of the non-crystalline polyolefin resin as component (B) include polypropylene “Tough Selenium X-1102” and “Tough Selenium X-1104” manufactured by Sumitomo Chemical Co., Ltd.
上記（Ａ）成分と（Ｂ）成分の混合比は（Ａ）/（Ｂ）が（２５〜９３質量％）/（７５〜７質量％）、好ましくは、（Ａ）/（Ｂ）が（３０〜９０質量％）/（７０〜１０質量％）である。（Ａ）成分と（Ｂ）成分の混合比を上記範囲に設定することにより、樹脂塗布時のぬれ性と製膜後の剥離層からの樹脂膜の剥離性との両方をバランスよく有する離型シートを得ることができる。 The mixing ratio of the component (A) and the component (B) is (A) / (B) is (25 to 93% by mass) / (75 to 7% by mass), preferably (A) / (B) is ( 30 to 90% by mass) / (70 to 10% by mass). By setting the mixing ratio of the component (A) and the component (B) in the above range, the mold release has a good balance between the wettability at the time of resin coating and the release property of the resin film from the release layer after film formation. A sheet can be obtained.
上記のような（Ａ）成分である結晶性ポリオレフィン樹脂および（Ｂ）成分である非結晶性ポリオレフィン樹脂からなる樹脂混合物を含む熱可塑性樹脂組成物を用いて形成された剥離層の厚みは、好ましくは、１０〜５００μｍ、さらに好ましくは、２０〜１００μｍである。剥離層の厚みを上記範囲に設定することにより、合成皮革等のウレタン樹脂膜を製造する際、機械適性を確保することができ、かつ、離型シートを運搬・保管するためのロール巻き取りが容易であるので好ましい。
剥離層の光沢はマット系からミラー系までさまざまな光沢度を有していてもよく、また、公知の方法によりエンボス加工（砂目、石目、木目、皮紋等）がなされていてもよい。剥離層を基材に設けるには、押し出しラミネート法によるのが一般的である。
The thickness of the release layer formed using a thermoplastic resin composition comprising a resin mixture comprising the crystalline polyolefin resin as component (A) and the amorphous polyolefin resin as component (B) is preferably Is 10 to 500 μm, more preferably 20 to 100 μm. By setting the thickness of the release layer within the above range, when manufacturing a urethane resin film such as synthetic leather, it is possible to ensure mechanical suitability and roll-up for transporting and storing the release sheet. It is preferable because it is easy.
The gloss of the release layer may have various glossiness from a mat system to a mirror system, and may be embossed (sand grain, stone grain, wood grain, skin pattern, etc.) by a known method. . In order to provide the release layer on the base material, the extrusion laminating method is generally used.
本発明の離型シートでは、通常はロールで保管された場合でもブロッキングが生じないため、使用する際に基材の紙が破れたり、繰り出しが困難になるなどの不具合は生じない。しかしながら、基材に使用する材料によっては、ブロッキングが発生する可能性もあり、その場合には、基材の剥離層と反対側の面にブロッキング防止剤層を設けることもできる。ブロッキング防止剤としては、フッ素系樹脂、シリコーン系樹脂、長鎖アルキル系樹脂等の公知のものを使用することができる。ブロッキング防止剤の具体例としては、旭硝子（株）製「アサヒガードＡＧ-５３０」、一方社油脂工業（株）製「ピーロイル１０１０」、「ピーロイル１０５０」、中京油脂（株）製「レゼムＫ−２５６」、信越化学工業（株）製「ＫＭ−７６８」、「Ｘ−５２−１９５」などが挙げられる。 In the release sheet of the present invention, since blocking does not usually occur even when stored in a roll, problems such as tearing of the paper of the base material and difficulty of feeding out do not occur. However, depending on the material used for the substrate, blocking may occur. In that case, an anti-blocking agent layer may be provided on the surface of the substrate opposite to the release layer. As the anti-blocking agent, known ones such as fluorine resins, silicone resins, and long chain alkyl resins can be used. Specific examples of the anti-blocking agent include “Asahi Guard AG-530” manufactured by Asahi Glass Co., Ltd., while “Pyrole 1010” and “Piloyl 1050” manufactured by Yushi Kogyo Co., Ltd. “Rezem K-” manufactured by Chukyo Yushi Co., Ltd. 256 ”,“ KM-768 ”,“ X-52-195 ”manufactured by Shin-Etsu Chemical Co., Ltd., and the like.
また、離型シートの帯電性を防止するため、剥離層の樹脂中に帯電防止剤を含有させたり、または基材と剥離層との間あるいは基材の剥離層とは反対側の面に帯電防止層を設けることもできる。 In addition, in order to prevent the chargeability of the release sheet, an antistatic agent is contained in the resin of the release layer, or the surface on the side opposite to the release layer of the substrate is charged between the substrate and the release layer. A prevention layer can also be provided.
次に、本発明を実施例によりさらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
（離型シート作製用材料）
（１）基材：上質紙（坪量１２７．９ｇ/ｍ2）
（２）（Ａ）結晶性ポリオレフィン樹脂：サンアロマー（株）製ポリプロピレン「ＰＨ９０３Ａ」[ポリプロピレンホモポリマー/低密度ポリエチレン＝８６/１４（質量比）ブレンド物（数平均分子量：３２，０００）]
この結晶性ポリオレフィン樹脂のＪＩＳ Ｋ７１２２に準拠したＤＳＣによる測定で主ピークの結晶融解熱量は８２Ｊ/ｇ、結晶の融解に基づく主ピークの位置（融点）は１６２℃であった。
（３）（Ｂ）非結晶性ポリオレフィン樹脂：住友化学（株）製ポリプロピレン、「タフセレンＸ−１１０２」[プロピレン-１-ブテン共重合体（プロピレン単量体含有量：９５質量％）]
この非結晶性ポリオレフィン樹脂のＪＩＳ Ｋ７１２２に準拠したＤＳＣによる測定で結晶融解熱量１Ｊ/ｇ以上の結晶融解ピークおよび結晶化に基づくピークはいずれも観察されなかった。
(Material for mold release sheet)
(1) Substrate: fine paper (basis weight 127.9 g / m 2 )
(2) (A) Crystalline polyolefin resin: Polypropylene “PH903A” manufactured by Sun Allomer Co., Ltd. [polypropylene homopolymer / low density polyethylene = 86/14 (mass ratio) blend (number average molecular weight: 32,000)]
The crystalline polyolefin resin was measured by DSC in accordance with JIS K7122, and the crystal melting heat amount of the main peak was 82 J / g, and the position (melting point) of the main peak based on the melting of the crystal was 162 ° C.
(3) (B) Amorphous polyolefin resin: polypropylene manufactured by Sumitomo Chemical Co., Ltd., “Tufselen X-1102” [propylene-1-butene copolymer (propylene monomer content: 95 mass%)]
As a result of DSC measurement based on JIS K7122 for this amorphous polyolefin resin, neither a crystal melting peak with a crystal melting heat of 1 J / g or more nor a peak based on crystallization was observed.
（評価方法）
１．剥離強度
＜ＰＵ法（No.1）＞
表皮層用熱可塑性ポリウレタン樹脂（大日本インキ化学工業製、クリスボン７３６７ＳＬ）を硬化後の厚みが３０μｍになるように前記の離型シートの剥離層面にアプリケーターを用いて塗布して１３０℃、２分間加熱硬化した後、ポリエステルテープＮｏ．３１Ｂ[日東電工（株）製]を貼り付けて補強し、温度２３℃、相対湿度５０％下３０分放置後、３ｃｍ幅にカットして引っ張り速度１ｍ/分でポリウレタン樹脂側１８０度ピールして剥離強度（単位：ｍＮ/３０ｍｍ）を測定した。
＜ＰＵ法（No.2）＞
上記クリスボン７３６７ＳＬ層を塗布後、さらに熱硬化性接着層用２液型ポリウレタン樹脂[大日本インキ化学工業（株）製、クリスボン４０１０の１００質量部にイソシアネート系硬化剤であるクリスボンＮＸの１０質量部を混ぜたもの]を厚み５０μｍになるように塗布し、この接着層の上に基布をウェットラミ後、１３０℃、２分間加熱して接着層を硬化させた後、さらに４０℃、２日間放置し、硬化を促進させた。温度２３℃、相対湿度５０％下３０分放置し、３ｃｍ幅にカットして引っ張り速度１ｍ/分で基布側１８０度ピールして剥離強度（単位：ｍＮ/３０ｍｍ）を測定した。
２．ブロッキング性
上記のように作製した幅１０ｃｍ、長さ約５００ｍの離型シート[上質紙に剥離層をラミネートしたもの]を外径１ｃｍの紙製コアに剥離層が内面になるようにロール状に巻き取り（ロール外径約３８ｃｍ）、これを横に寝かせた状態で４０℃雰囲気下、１ヶ月放置した。その後、温度２３℃、相対湿度５０％で１日放冷して繰り出し展開したときの巻き取りで接触していた上質紙と剥離層とのブロッキング状態を観察して、以下の基準で評価した。
○：ブロッキングは観察されなかった。
△：展開時、剥がれる音がした。
×：ブロッキングしており、展開時、上質紙に破れが発生した。
３．ウレタン樹脂層の浮き（はがれ度合い）
剥離強度測定用試験片を押し切りカッターで幅３ｃｍに切断して作製した際、離型面とウレタン樹脂層との間に部分的に浮き（剥がれ）現象が観測された場合を×、剥がれがなく、離型面にウレタン樹脂層が密着している場合を〇とした。
(Evaluation methods)
1. Peel strength <PU method (No. 1)>
A thermoplastic polyurethane resin for skin layer (Dai Nippon Ink Chemical Co., Ltd., Crisbon 7367SL) is applied to the release layer surface of the release sheet with an applicator so that the thickness after curing is 30 μm, and 130 ° C. for 2 minutes. After heat-curing, polyester tape no. 31B [manufactured by Nitto Denko Co., Ltd.] is pasted and reinforced, left to stand at a temperature of 23 ° C. and a relative humidity of 50% for 30 minutes, cut to a width of 3 cm, and peeled 180 ° from the polyurethane resin side at a pulling speed of 1 m / min. The peel strength (unit: mN / 30 mm) was measured.
<PU method (No. 2)>
After applying the above-described Crisbon 7367SL layer, two-part polyurethane resin for thermosetting adhesive layer [Dainippon Ink & Chemicals, Ltd., 100 parts by weight of Crisbon 4010 and 10 parts by weight of Crisbon NX which is an isocyanate curing agent Is applied to the adhesive layer to a thickness of 50 μm, and the base fabric is wet-laminated on the adhesive layer, heated at 130 ° C. for 2 minutes to cure the adhesive layer, and then further left at 40 ° C. for 2 days. And promoted curing. It was left to stand at a temperature of 23 ° C. and a relative humidity of 50% for 30 minutes, cut to a width of 3 cm, peeled 180 ° at the base fabric side at a pulling speed of 1 m / min, and the peel strength (unit: mN / 30 mm) was measured.
2. Blocking property The release sheet 10 cm wide and about 500 m long produced as described above (a laminate of fine paper with a release layer) is rolled into a paper core having an outer diameter of 1 cm so that the release layer is the inner surface. Winding up (roll outer diameter: about 38 cm), and letting it lie down, left in a 40 ° C. atmosphere for one month. Thereafter, the state of blocking between the fine paper and the release layer that had been in contact by winding when the film was allowed to cool for one day at a temperature of 23 ° C. and a relative humidity of 50% and unfolded was evaluated and evaluated according to the following criteria.
○: No blocking was observed.
Δ: A sound was peeled off during deployment.
X: Blocking occurred, and tearing occurred in the high-quality paper during development.
3. Urethane resin layer floating (peeling degree)
When a peeling strength measurement test piece was cut into a 3 cm width with a push-off cutter, a partial floating (peeling) phenomenon was observed between the release surface and the urethane resin layer. The case where the urethane resin layer is in close contact with the mold release surface is marked as ◯.
実施例１
幅３０ｍｍ、長さ約５００ｍの上記上質紙をスクリューサイズ３０ｍｍφを有するＴダイ加工機のダイ出口に供給しながら溶融樹脂温度２８０℃で樹脂層が５０μｍになるように押し出しラミネート加工を行ない、上質紙の一方の面に樹脂がラミネートされた離型シートを作製した。使用した樹脂は、（Ａ）結晶性ポリオレフィン樹脂/（Ｂ）非結晶性ポリオレフィン樹脂＝３０/７０（質量比）ブレンド物である。各特性の測定結果を表１に示す。
Example 1
While supplying the above high quality paper with a width of 30 mm and a length of about 500 m to the die exit of a T-die processing machine having a screw size of 30 mmφ, the high quality paper is extruded and laminated so that the resin layer becomes 50 μm at a molten resin temperature of 280 ° C. A release sheet having a resin laminated on one surface was prepared. The resin used was a blend of (A) crystalline polyolefin resin / (B) non-crystalline polyolefin resin = 30/70 (mass ratio). Table 1 shows the measurement results of each characteristic.
実施例２〜４および比較例１〜３
上記（Ａ）結晶性ポリオレフィン樹脂と（Ｂ）非結晶性ポリオレフィン樹脂を表１に示す比率でブレンドした以外は実施例１と同様に行い、剥離強度等を測定した。各特性の測定結果を表１に示す。
Examples 2 to 4 and Comparative Examples 1 to 3
Peel strength and the like were measured in the same manner as in Example 1 except that (A) the crystalline polyolefin resin and (B) the amorphous polyolefin resin were blended at the ratio shown in Table 1. Table 1 shows the measurement results of each characteristic.
Claims (5)
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