JP5127158B2 - Methylpentene polymer resin composition for release layer of release paper, film or sheet thereof, and laminate containing the resin composition layer - Google Patents
Methylpentene polymer resin composition for release layer of release paper, film or sheet thereof, and laminate containing the resin composition layer Download PDFInfo
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本発明は、剥離紙の離型層用のメチルペンテン系重合体樹脂組成物、該樹脂組成物からなるフィルム又はシート、該樹脂組成物層を含む積層体、に関する。 The present invention relates to a methylpentene polymer resin composition for a release layer of a release paper, a film or sheet comprising the resin composition, and a laminate including the resin composition layer.
４−メチル−１−ペンテン重合体、３−メチル−１−ペンテン重合体又はそれらを主体とする樹脂組成物からなるメチルペンテン系重合体樹脂、所謂、ＴＰＸは、透明、柔軟で、耐熱性、耐スチ−ム性、耐薬品性、酸素等のガス透過性に優れ、然も軽量であるため、例えば、高圧ゴムホース製造用シース・マンドレルやＬＥＤモール等の産業資材分野、耐熱ラップフィルム、青果物用鮮度保持袋などの食品包装分野、理化学実験器具や電子レンジ食器等の各分野に多用されている。
例えば、特許文献１には、４−メチル−１−ペンテン重合体を主成分とした樹脂組成物からなる鮮度保持包装フィルムが提案されている。
4-methyl-1-pentene polymer, 3-methyl-1-pentene polymer or a methylpentene polymer resin composed of a resin composition mainly composed thereof, so-called TPX, is transparent, flexible, heat resistant, Excellent in steam resistance, chemical resistance, oxygen permeability, etc., and lightweight, for example, industrial material fields such as sheaths and mandrels for manufacturing high-pressure rubber hoses and LED moldings, heat-resistant wrap films, and fruits and vegetables Widely used in food packaging fields such as freshness-keeping bags, physics and chemistry laboratory instruments, microwave oven dishes, and other fields.
For example, Patent Document 1 proposes a freshness-keeping packaging film made of a resin composition containing a 4-methyl-1-pentene polymer as a main component.
更に、ＴＰＸは、表面張力が２４dyne/cmとフッ素樹脂に次いで小さく、剥離性、離型性に優れている。
このため、例えば、粘着ラベル、シート等の剥離紙、ウレタン・エポキシ等他素材からの工程剥離紙、プリント基板用離型フィルム等、離型フィルムや剥離紙に広く使用されている。
例えば、特許文献２にはポリメチルペンテン又はポリメチルペンテンとα−オレフィンとの共重合体を離型層としたフレキシブルプリント配線板の製造工程で用いられる離型フィルムの発明が開示されている。
For this reason, it is widely used for release films and release papers such as adhesive labels, release papers such as sheets, process release papers from other materials such as urethane and epoxy, and release films for printed boards.
For example, Patent Document 2 discloses an invention of a release film used in a production process of a flexible printed wiring board using a release layer of polymethylpentene or a copolymer of polymethylpentene and α-olefin.
しかしながら、メチルペンテン重合体樹脂は、一般に、高結晶性で、融点も２２０〜２４０℃とポリエチレン等と比較して高く、溶融粘度は１０２〜１０３poise と他のポリオレフィンに比較して低いレベルにあり、成形加工性然も、溶融粘度の温度依存性が大きい傾向にある等、成形加工性、特に押出しコーティングにおける加工性が不十分である。例えば、Ｔダイ押出やインフレーション、押出ラミネーション等によるフィルム・シート成形に際する混練条件や押出条件等の適正な設定が可成り困難であり、押出機のスクリュー回転を高速にするとサージングによる押出量に変化が起きたり、フィルムドローダウンやネックイン等の不都合が起きやすく、その結果として、フィルム成形時等の高速引取性は、ポリエチレン、ポリプロピレン等汎用のポリオレフィン樹脂に比べて可成り劣ると云う問題がある。また、メチルペンテン重合体樹脂は通常紙等の基材との接着性が劣る。 However, the methylpentene polymer resin is generally highly crystalline, has a melting point of 220 to 240 ° C., which is higher than that of polyethylene and the like, and has a melt viscosity of 10 2 to 10 3 poise, which is a low level compared to other polyolefins. However, the moldability, particularly the processability in extrusion coating, is insufficient because the temperature dependence of the melt viscosity tends to be large. For example, proper settings such as kneading conditions and extrusion conditions for film and sheet forming by T-die extrusion, inflation, extrusion lamination, etc. are quite difficult. Changes are likely to occur, and inconveniences such as film drawdown and neck-in are likely to occur, and as a result, the high-speed take-up property at the time of film molding etc. is considerably inferior to general-purpose polyolefin resins such as polyethylene and polypropylene. is there. Further, the methylpentene polymer resin usually has poor adhesion to a substrate such as paper.
このことは、他のオレフィン樹脂に比べフィルムの生産性が損なわれることを意味する。
特に、上記問題は、インフレーションによるフィルム成形や、押出ラミネーションによる積層体成形の際にコスト高と云う形で顕著に表れる。
This means that the productivity of the film is impaired as compared with other olefin resins.
In particular, the above-mentioned problem appears remarkably in the form of high cost in film formation by inflation or laminate formation by extrusion lamination.
従って、本発明の目的は、ＴＰＸが本来保持する属性、例えば粘着性樹脂や接着剤等に対する好適な剥離性、離型性等の優れた属性を損なうことなく成形加工性、特に押出しコーティングにおける加工性が顕著に改善されたメチルペンテン系重合体樹脂組成物を提供するにある。 Accordingly, an object of the present invention is to provide molding processability, particularly processing in extrusion coating, without impairing attributes that TPX originally retains, for example, excellent attributes such as suitable releasability and release properties for adhesive resins and adhesives. The object of the present invention is to provide a methylpentene polymer resin composition with significantly improved properties.
又、本発明の他の目的は、本発明のメチルペンテン系重合体樹脂組成物からなるフィルム又はシートを提供することにある。
更に、本発明の別の目的は、該樹脂組成物層を含む積層体、及び、該樹脂組成物の層を離型性層として紙基材に積層してなる剥離紙を提供するにある。
Another object of the present invention is to provide a film or sheet comprising the methylpentene polymer resin composition of the present invention.
Furthermore, another object of the present invention is to provide a laminate comprising the resin composition layer, and a release paper obtained by laminating the resin composition layer on a paper substrate as a releasable layer.
本発明によれば、メチルペンテン重合体樹脂（Ａ）５０〜７９質量部とエチレン・（メタ）アクリル酸共重合体樹脂（ａ）及びそのアイオノマー（ｂ）から選ばれる少なくとも１種のエチレン系共重合体樹脂（Ｂ）２１〜５０質量部（但し、（Ａ）と（Ｂ）の合計は１００質量部）からなる剥離紙の離型層用のメチルペンテン系重合体樹脂組成物が提供される。 According to the present invention, 50 to 79 parts by mass of methylpentene polymer resin (A), at least one ethylene-based copolymer selected from ethylene / (meth) acrylic acid copolymer resin (a) and ionomer (b) thereof. There is provided a methylpentene polymer resin composition for a release layer of release paper comprising 21 to 50 parts by mass of polymer resin (B) (however, the sum of (A) and (B) is 100 parts by mass). .
本発明の樹脂組成物は、メチルペンテン重合体樹脂を主成分とし、これにエチレン・（メタ）アクリル酸共重合体樹脂及び／又はそのアイオノマーのエチレン系共重合体樹脂の少なくとも一種を特定量比で配合した点を構成上の特徴とする。 The resin composition of the present invention is mainly composed of methylpentene polymer resin, which in ethylene (meth) specific amount of at least one acrylic acid copolymer resin and / or ethylene copolymer resins of the ionomer over The point which mix | blended with ratio is the characteristic on a structure.
上記組成物はメチルペンテン重合体樹脂単体に比較してＴダイ押出、インフレーション、押出ラミネーション等に於ける成形加工性が極めて良好で、単品フィルム、シートはもとより、特に、基材上に押出ラミネートした場合のラミネーションフィルム、シートの成形時に於ける引取速度を顕著に向上させることが出来る。
然も、紙、他のプラスチック等の基材上に剥離剤層として形成した本発明の樹脂組成物層は、粘着面との間の層間剥離強度が適度で、粘着性面又は接着性面に対する離型性、剥離性に優れる。
又、成形、積層に溶剤等を使用しないため、安全、労働衛生面、環境等の問題を起こすことも無い。
The above composition has extremely good molding processability in T-die extrusion, inflation, extrusion lamination, etc. compared to the methylpentene polymer resin alone, and it was extruded and laminated not only on single-piece films and sheets, but also on substrates. In this case, the take-up speed in forming the lamination film and sheet can be remarkably improved.
However, the resin composition layer of the present invention formed as a release agent layer on a substrate such as paper or other plastic has a moderate delamination strength between the adhesive surface and the adhesive surface or adhesive surface. Excellent releasability and releasability.
In addition, since no solvent or the like is used for molding and lamination, problems such as safety, occupational health and the environment are not caused.
本発明の樹脂組成物に於いては、前記メチルペンテン重合体樹脂（Ａ）が４−メチル−１−ペンテン重合体からなる樹脂であることが好ましい。
又、前記エチレン系共重合体樹脂（Ｂ）はエチレン・（メタ）アクリル酸共重合体樹脂（ａ）が好ましく、特に、エチレン・（メタ）アクリル酸二元共重合体樹脂又はエチレン・（メタ）アクリル酸・（メタ）アクリル酸エステル三元共重合体樹脂であることが好ましい。
In the resin composition of the present invention, the methylpentene polymer resin (A) is preferably a resin composed of a 4-methyl-1-pentene polymer.
The ethylene-based copolymer resin (B) is preferably an ethylene / (meth) acrylic acid copolymer resin (a), and in particular, an ethylene / (meth) acrylic acid binary copolymer resin or ethylene / (meta ) Acrylic acid / (meth) acrylic acid ester terpolymer resin is preferred.
本発明によれば、又、前記本発明の樹脂組成物よりなるフィルム又はシート、該樹脂組成物層を含む積層体、及び、該樹脂組成物の層を離型性層として紙基材に積層してなる剥離紙がそれぞれ提供される。 According to the present invention, a film or sheet made of the resin composition of the present invention, a laminate including the resin composition layer, and a layer of the resin composition are laminated on a paper substrate as a release layer. Each release paper is provided.
本発明のメチルペンテン系重合体樹脂組成物は、メチルペンテン重合体にエチレン・（メタ）アクリル酸共重合体、そのアイオノマーの特定極性基含有共重合体を特定量配合したことより、メチルペンテン単独重合体や従来のポリメチルペンテン系樹脂組成物に比べ成形加工性、特に押出しコーティングにおける加工性が顕著に優れたものとなる。 Methylpentene polymer resin composition of the present invention, ethylene (meth) acrylic acid copolymer methylpentene polymer, than that specified amount of a specific polar group-containing copolymer of the ionomer over, methylpentene Compared to homopolymers and conventional polymethylpentene resin compositions, the molding processability, particularly the processability in extrusion coating, is significantly improved.
例えば、フィルムやシートのＴダイ押出成形時やインフレーション成形時に於ける高速引取速度、或いは、紙、プラスチック等の基材上に押出ラミネートする際の高速引取性等の加工性を従来品に比べ顕著に向上出来る。
このため、本発明に係る上記樹脂組成物を素材として用いることにより、フィルム、シート、積層体、工程剥離紙等の成形品の生産性を著しく高めることが出来、製作コストを低減出来る。
また本発明の樹脂組成物は、例えば押し出しコーティングにより紙に積層した場合、紙と良好な接着性を示す。
For example, workability such as high-speed take-up speed at the time of T-die extrusion molding and inflation molding of films and sheets, or high-speed take-up performance when laminated on paper, plastic, etc., is remarkable compared to conventional products. Can be improved.
For this reason, by using the said resin composition concerning this invention as a raw material, productivity of molded articles, such as a film, a sheet | seat, a laminated body, a process release paper, can be raised remarkably, and manufacturing cost can be reduced.
The resin composition of the present invention exhibits good adhesion to paper when it is laminated on paper by, for example, extrusion coating.
以下に、本発明に係る好適実施形態について、詳細且つ具体的に説明する。
本発明のメチルペンテン系重合体樹脂組成物は、メチルペンテン重合体樹脂に特定のエチレン系共重合体樹脂を特定量比で配合してなる樹脂組成物である点を特徴とする。
Hereinafter, preferred embodiments according to the present invention will be described in detail and specifically.
The methylpentene polymer resin composition of the present invention is characterized in that it is a resin composition obtained by blending a specific ethylene copolymer resin in a specific amount ratio with a methylpentene polymer resin.
本発明の樹脂組成物に於いて、主樹脂成分であるメチルペンテン重合体樹脂（Ａ）としては、３−メチル−１−ペンテン系重合体樹脂、４−メチル−１−ペンテン重合体樹脂等が例示出来る。 In the resin composition of the present invention, the methylpentene polymer resin (A) as the main resin component includes 3-methyl-1-pentene polymer resin, 4-methyl-1-pentene polymer resin, and the like. It can be illustrated.
本発明で用いられる上記メチルペンテン重合体樹脂は、３−メチル−１−ペンテン、４−メチル−１−ペンテン等のメチルペンテンもしくはメチルペンテンを主成分とするモノマーを重合して得られた重合体であり、例えば、メチルペンテンの単独重合体、もしくはメチルペンテンと、該メチルペンテンと共重合可能な他の化合物との共重合体が挙げられる。これらのメチルペンテン重合体樹脂としては所謂、ＴＰＸと称される重合体樹脂が例示される。
本発明ではメチルペンテン重合体樹脂の中で、特に４−メチル−１−ペンテンの単独重合体樹脂もしくは４−メチル−１−ペンテン共重合体樹脂が好ましい。
The methylpentene polymer resin used in the present invention is a polymer obtained by polymerizing methylpentene such as 3-methyl-1-pentene or 4-methyl-1-pentene or a monomer containing methylpentene as a main component. Examples thereof include a homopolymer of methylpentene or a copolymer of methylpentene and another compound copolymerizable with the methylpentene. Examples of these methylpentene polymer resins include so-called polymer resins called TPX.
In the present invention, among methylpentene polymer resins, 4-methyl-1-pentene homopolymer resin or 4-methyl-1-pentene copolymer resin is particularly preferable.
メチルペンテンと共重合可能な他の化合物としては、例えば、エチレン、プロピレン、１−ブテン、１−ヘキセン、１−オクテン、１−デセン、１−テトラデセン、１−オクタデセン等の炭素原子数２〜２０のα−オレフィンなどが挙げられる。
これらは１種又は２種以上が、メチルペンテン系重合体中に含まれていてもよい。
メチルペンテン系重合体中のメチルペンテンの含有量は、通常、８５モル％以上、好ましくは９０モル％以上である。
Examples of other compounds copolymerizable with methylpentene include 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-tetradecene and 1-octadecene. Α-olefins and the like.
One or more of these may be contained in the methylpentene polymer.
The content of methylpentene in the methylpentene polymer is usually 85 mol% or more, preferably 90 mol% or more.
このメチルペンテン系重合体のメルトフローレート（ＭＦＲ）は、通常、０．０５〜５００ｇ／１０分（ＡＳＴＭ Ｄ１２３８、荷重：５Ｋｇ、温度：２６０℃で測定）、好ましくは０．１〜３００ｇ／１０分である。 The melt flow rate (MFR) of this methylpentene polymer is usually 0.05 to 500 g / 10 min (ASTM D1238, load: 5 Kg, temperature: measured at 260 ° C.), preferably 0.1 to 300 g / 10. Minutes.
本発明の樹脂組成物に於いて、もう一方の樹脂成分であるエチレン系共重合体樹脂（Ｂ）は、エチレン・（メタ）アクリル酸共重合体樹脂（ａ）及びそのアイオノマー（ｂ）から選ばれる少なくとも１種からなる。 In the resin composition of the present invention, which is another resin component ethylene copolymer resin (B), ethylene (meth) acrylic acid copolymer resin (a) and its ionomers (b) or al It consists of at least one selected.
これらの内、エチレン・（メタ）アクリル酸共重合体樹脂（ａ）は、エチレンとアクリル酸及び／又はメタクリル酸との共重合体、或いは、該エチレンと（メタ）アクリル酸に、他の不飽和単量体成分が共重合されたものである。
前記他の不飽和単量体成分としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリル酸ｉ−プロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸ｓ−ブチル、（メタ）アクリル酸ｉ−ブチル、（メタ）アクリル酸ｎ−ヘキシル、（メタ）アクリル酸ｉ−ヘキシル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸イソオクチル等の（メタ）アクリル酸アルキルエステル成分、酢酸ビニル、プロピオン酸ビニル等のビニルエステル成分、エチレン以外のオレフィン類、一酸化炭素、二酸化硫黄等の単量体を挙げることができる。
Among these, the ethylene / (meth) acrylic acid copolymer resin (a) is a copolymer of ethylene and acrylic acid and / or methacrylic acid, or the ethylene and (meth) acrylic acid. A saturated monomer component is copolymerized.
Examples of the other unsaturated monomer component include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and (meth) acrylic acid n. -Butyl, s-butyl (meth) acrylate, i-butyl (meth) acrylate, n-hexyl (meth) acrylate, i-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth ) (Meth) acrylic acid alkyl ester components such as isooctyl acrylate, vinyl ester components such as vinyl acetate and vinyl propionate, monomers such as olefins other than ethylene, carbon monoxide, and sulfur dioxide.
これらの内ではエチレン・（メタ）アクリル酸二元共重合体樹脂又はエチレン・（メタ）アクリル酸・（メタ）アクリル酸エステル三元共重合体樹脂が好ましく、その内でも、エチレン・（メタ）アクリル酸・（メタ）アクリル酸エステル三元共重合体樹脂は、得られる樹脂組成物の押出コーティング加工性、耐熱性、剥離性等の諸物性が全く損なわれないため特に好ましい。 Among these, ethylene / (meth) acrylic acid binary copolymer resin or ethylene / (meth) acrylic acid / (meth) acrylic acid ester terpolymer resin is preferable, and among them, ethylene / (meth) Acrylic acid / (meth) acrylic acid ester terpolymer resins are particularly preferred because the physical properties of the resulting resin composition such as extrusion coating processability, heat resistance and peelability are not impaired at all.
本発明では得られる樹脂組成物はフィルム、シート又は積層体に成形される関係から、エチレン系共重合体樹脂（Ｂ）のメルトフローレート（ＭＦＲ）は、１〜５００ｇ／１０分（ＪＩＳ Ｋ７２１０（１９９９）、荷重：２．１６Ｋｇ、温度：１９０℃で測定）が好ましく、より好ましくは１〜１００ｇ／１０分である。
又、前記樹脂（ａ）に於いて、（メタ）アクリル酸成分の含有率は１〜２０質量％、特に、５〜１５質量％のものが好ましい。
In the present invention, since the resin composition obtained is formed into a film, sheet or laminate, the melt flow rate (MFR) of the ethylene-based copolymer resin (B) is 1 to 500 g / 10 min (JIS K7210 ( 1999), load: 2.16 Kg, temperature: measured at 190 ° C.), more preferably 1 to 100 g / 10 min.
Moreover, in the said resin (a), the content rate of a (meth) acrylic acid component is 1-20 mass%, Especially the thing of 5-15 mass% is preferable.
次に、そのアイオノマー（ｂ）としては、前記エチレン・（メタ）アクリル酸共重合体樹脂（ａ）の金属イオン塩からなるアイオノマーであれば特に限定されることなく使用でき、このようなアイオノマーとして、Ｌｉ、Ｎａ、Ｋ等のアルカリ金属イオンアイオノマー、Ｂｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ等のアルカリ土類金属イオンアイオノマー、その他Ｚｎイオンアイオノマー等を例示できる。
これらの内では、Ｎａ、Ｚｎアイオノマーが好ましい。
上記アイオノマーの中和度は、1モル％以上、特に１０〜７０モル％のものが好ましい。
Next, as the ionomer (b), any ionomer composed of a metal ion salt of the ethylene / (meth) acrylic acid copolymer resin (a) can be used without any particular limitation. Examples include alkali metal ion ionomers such as Li, Na and K, alkaline earth metal ion ionomers such as Be, Mg, Ca, Sr and Ba, and other Zn ion ionomers.
Of these, Na and Zn ionomers are preferred.
The neutralization degree of the ionomer is preferably 1 mol% or more, particularly preferably 10 to 70 mol%.
本発明の樹脂組成物に於いて、前記メチルペンテン重合体樹脂（Ａ）とエチレン系共重合体樹脂（Ｂ）の配合量は樹脂（Ａ）が５０〜７９質量部、樹脂（Ｂ）が２１〜５０質量部、（但し、（Ａ）、（Ｂ）の合計量は１００質量部）。
樹脂（Ｂ）の配合量が２１質量％より少ない場合は、本発明の目的とするＴダイ押出成形、インフレーション成形、押出積層成形等の際の引取性能を充分に向上させることが出来ない。
In the resin composition of the present invention, the methylpentene amount of polymer resin (A) and the ethylene-based copolymer resin (B) resin (A) is 50 to 79 parts by weight, dendritic fat (B) is 21 to 50 parts by mass ( however, the total amount of (A) and (B) is 100 parts by mass).
When the blending amount of the resin (B) is less than 21 % by mass, it is not possible to sufficiently improve the take-up performance at the time of T-die extrusion molding, inflation molding, extrusion lamination molding and the like as the object of the present invention.
一方、樹脂（Ｂ）の配合量が５０質量％を超える場合は、メチルペンテン樹脂が本来有する優れた特性、例えば、耐熱特性、耐スチーム性、剥離性等の諸特性が低下する。 On the other hand, when the compounding quantity of resin (B) exceeds 50 mass%, the outstanding characteristics which methylpentene resin originally has, for example, various characteristics, such as a heat resistance characteristic, steam resistance, and peelability, will fall.
本発明の樹脂組成物を調製するには、樹脂（Ａ）と樹脂（Ｂ）をそれぞれ処方に従い計量し、押出機、混練機等を用いて混合、溶融混練することによって調製出来る。
上記溶融混練等により得られた樹脂組成物は直ちに積層成形に用いてもよく、又、一旦ペレット化した後に積層成形に用いても良い。
In order to prepare the resin composition of the present invention, the resin (A) and the resin (B) can be respectively measured according to the formulation, mixed and melt-kneaded using an extruder, a kneader or the like.
The resin composition obtained by the above melt-kneading or the like may be used immediately for laminate molding, or may be once pelletized and then used for laminate molding.
本発明の樹脂組成物調製法に於いて、特に好適な調製法として、例えば（Ｂ）樹脂の所定量を予め少量の（Ａ）樹脂に混合したマスターバッチを調製し、このマスターバッチと残余の（Ａ）成分を常法により溶融混練する方法を挙げることが出来る。 In the resin composition preparation method of the present invention, as a particularly suitable preparation method, for example, a masterbatch in which a predetermined amount of (B) resin is previously mixed with a small amount of (A) resin is prepared, (A) The method of melt-kneading a component by a conventional method can be mentioned.
上記方法で調製された樹脂組成物は、組成が均質であることは勿論、その理由は未だ完全に解明されていないが、押出コーティンク゛加工性等の他の諸属性も向上する。 The resin composition prepared by the above method has a homogeneous composition, and the reason is not completely understood yet, but other attributes such as extrusion coating processability are also improved.
本発明の上記樹脂組成物は、これを溶融下に、Ｔダイ押出、インフレーション等の成形方法によりフィルム、シート等の成形体とすることができる。
更に、紙、他樹脂フィルム、シート等の基材上にラミネーション、又はメチルペン展重合体樹脂単独、又は他の樹脂との共押し出しする等により積層体とすることも出来る。
本発明の樹脂組成物及び樹脂組成物よりなるフィルム又はシートは、粘着ラベル、シート等の剥離紙、ウレタン・エポキシ等他素材からの工程紙や剥離紙、プリント基板用離型フィルム等、離型フィルムに（於ける剥離層として）好適に用いられる。また本発明の樹脂組成物からなる層を紙基材に積層した積層体は、粘着ラベル、シート等の剥離紙、ウレタン・エポキシ等他素材からの工程紙として好ましく用いられる。
The above-mentioned resin composition of the present invention can be formed into a molded body such as a film or sheet by a molding method such as T-die extrusion or inflation while being melted.
Furthermore, it can also be made into a laminate by lamination on a substrate such as paper, other resin film, sheet, or the like, or by coextrusion with a methylpen-extended polymer resin alone or with another resin.
The resin composition of the present invention and the film or sheet comprising the resin composition are release labels such as adhesive labels, release paper such as sheets, process paper and release paper from other materials such as urethane and epoxy, release films for printed boards, etc. It is preferably used in a film (as a release layer). Moreover, the laminated body which laminated | stacked the layer which consists of the resin composition of this invention on a paper base material is preferably used as process paper from release paper, such as an adhesive label and a sheet | seat, urethane, an epoxy, etc. other materials.
前記、基材としては、例えば、クラフト紙、グラシン紙、スーパーカレンダード紙、パーチメント紙、ポリスチレン、ポリエチレン等よりなる合成紙等の紙類、クレーコート紙、ポリエチレンラミネート紙等の表面加工紙、ポリエステル（ＰＥＴ）、ポリプロピレン（ＯＰＰ）、ポリエチレン（ＰＥ）等のプラスチックフィルム等を挙げることが出来る。 Examples of the base material include craft paper, glassine paper, supercalendered paper, parchment paper, paper such as synthetic paper made of polystyrene and polyethylene, surface-treated paper such as clay coated paper and polyethylene laminated paper, polyester, and the like. Examples thereof include plastic films such as (PET), polypropylene (OPP), and polyethylene (PE).
前記樹脂組成物は、基材の片面又は両面に積層されることが出来る。
積層する樹脂組成物層の厚さは、その用途や形状、基材厚さ等により異なりそれぞれ適宜設定されるが、例えば、クラフト紙等の紙基材に、本発明の樹脂組成物を押出積層して積層体を製造する場合、通常５〜５０μｍ、好ましくは１０〜３０μｍ程度である。
The resin composition can be laminated on one side or both sides of a substrate.
The thickness of the resin composition layer to be laminated varies depending on its use, shape, substrate thickness, etc., and is set appropriately. For example, the resin composition of the present invention is extrusion laminated to a paper substrate such as kraft paper. And when manufacturing a laminated body, it is 5-50 micrometers normally, Preferably it is about 10-30 micrometers.
本発明の積層体は、溶剤を使用した塗布等の方法により製造することも出来るが、押出ラミネーションにより積層成形することが特に好ましい。
例えば、ダイ付き押出機と冷却、ニップ両ロールを備え、紙、ＰＥＴ等の基材に樹脂を積層するのに一般的に用いられる押出ラミネーターを用いて、紙又はＰＥＴ等の基材をニップロールと冷却ロールとの間隙に繰り出し、冷却ロールに沿わせながら引取る。
The laminate of the present invention can be produced by a method such as coating using a solvent, but it is particularly preferred to laminate by extrusion lamination.
For example, it is equipped with an extruder with a die and both cooling and nip rolls, and an extrusion laminator generally used for laminating a resin on a base material such as paper or PET, and a base material such as paper or PET is a nip roll. It is fed into the gap with the cooling roll and taken along the cooling roll.
そして、溶融混練された本発明の組成物をＴダイ内から押圧流下させ、マニホールドでダイの全幅に広げた後、溶融ウエブとしてＴダイ外に押出す。
Ｔダイ外に押出された溶融ウエブ層は基材面に圧着された後、冷却されて積層が完了する、そしてこれを引取ることにより積層シートを得る。
このようにして得られた積層シートは、剥離紙としての所定形状に裁断される。
Then, the melt-kneaded composition of the present invention is pressed down from the inside of the T die, spreads to the full width of the die with a manifold, and then extruded out of the T die as a molten web.
After the molten web layer extruded out of the T-die is pressure-bonded to the surface of the base material, it is cooled to complete the lamination, and the laminated sheet is obtained by taking it out.
The laminated sheet thus obtained is cut into a predetermined shape as release paper.
本発明を次の実施例により具体的に説明するが、本発明はこれら実施例により何ら限定されるものではない。
尚、下記の実施例・比較例・参考例で用いたメチルペンテン重合体樹脂（Ａ）及びエチレン系共重合体樹脂（Ｂ）の組成はそれぞれ下記の通りである。
The present invention will be specifically described by the following examples, but the present invention is not limited to these examples.
The compositions of the methylpentene polymer resin (A) and the ethylene copolymer resin (B) used in the following examples, comparative examples, and reference examples are as follows.
１．メチルペンテン重合体樹脂（Ａ）： 試料（イ） 三井化学（株）社製ＴＰＸ（ＤＸ８２０）、ＭＦＲ１８０ｇ／分（（ＡＳＴＭ Ｄ１２３８、荷重：５Ｋｇ、温度：２６０℃）、密度８３３ｋｇ／ｍ３、融点２３８℃
２．エチレン系共重合体樹脂（Ｂ）： 試料（ロ） エチレン（Ｅ）・メタクリル酸（ＭＡＡ）・アクリル酸イソブチル（ＩＢＡ）三元共重合体樹脂、ＭＦＲ１０ｇ／分（ＪＩＳ Ｋ７２１０（１９９９）、荷重：２．１６Ｋｇ、温度：１９０℃）、ＭＡＡ含量１１質量％、ＩＢＡ含量８質量％
試料（ハ） エチレン・メタクリル酸二元共重合体樹脂、ＭＦＲ８ｇ／分（ＪＩＳ Ｋ７２１０（１９９９）、荷重：２．１６Ｋｇ、温度：１９０℃）、ＭＡＡ含量９質量％
試料（ニ） エチレン・メタクリル酸二元共重合体（ＭＡＡ含量９質量％）の亜鉛アイオノマー ＭＦＲ５．５ｇ／分（ＪＩＳ Ｋ７２１０（１９９９）、荷重：２．１６Ｋｇ、温度：１９０℃）、金属イオン種：Ｚｎ 中和度：１７モル％
試料マスターバッチ（ＭＢ）ＴＰＸ（Ａ）４０質量％＋エチレン共重合体（Ｂ）６０質量％（試料（ロ）（ハ）（ニ）の何れかと試料（イ）を６０：４０の質量比で配合、溶融混練してマスターバッチとしたもの）
1. Methylpentene polymer resin (A): Sample (I) TPX (DX820) manufactured by Mitsui Chemicals, Inc., MFR 180 g / min ((ASTM D1238, load: 5 Kg, temperature: 260 ° C.), density 833 kg / m 3 , melting point 238 ° C
2. Ethylene-based copolymer resin (B): Sample (b) Ethylene (E) / methacrylic acid (MAA) / isobutyl acrylate (IBA) terpolymer resin, MFR 10 g / min (JIS K7210 (1999), load: 2.16 kg, temperature: 190 ° C.), MAA content 11 mass%, IBA content 8 mass%
Sample (C) Ethylene / methacrylic acid binary copolymer resin, MFR 8 g / min (JIS K7210 (1999), load: 2.16 Kg, temperature: 190 ° C.), MAA content 9% by mass
Sample (d) Zinc ionomer of ethylene / methacrylic acid binary copolymer (MAA content 9 mass%) MFR 5.5 g / min (JIS K7210 (1999), load: 2.16 Kg, temperature: 190 ° C.), metal ion species : Zn Neutralization degree: 17 mol%
Sample masterbatch (MB) TPX (A) 40% by mass + ethylene copolymer (B) 60% by mass (sample (b) (c) (d) and sample (a) at a mass ratio of 60:40 (Mixed, melt kneaded into a master batch)
「参考例」
ＴＰＸ（Ａ）として試料（イ）８０質量部とエチレン系共重合体樹脂として試料（ロ）２０質量部とを配合し、３０ｍｍΦ２軸押出機を用いてスクリュー回転数２００ｍｉｎ−１（設定温度（℃）：Ｃ１／Ｃ２−Ｃ９／Ａ・Ｄ＝２００／２６０／２５０）で溶融混練りして樹脂組成物試料（１）を得た。
Reference example
80 parts by mass of sample (ii ) as TPX (A) and 20 parts by mass of sample (ii) as ethylene copolymer resin are blended, and a screw rotation speed of 200 min −1 (set temperature (° C.) using a 30 mmΦ twin screw extruder. ): C1 / C2-C9 / A · D = 200/260/250) to obtain a resin composition sample (1).
次いで、押出ラミネーター（口径４０ｍｍφ、ダイ：４５０ｍｍ幅、 冷却ロール３５ｍｍφ、ニップロール２００ｍｍφ）を用いてクラフト紙（５０ｇ／ｍ２）基材面に上記樹脂組成物（１）を、４５ｍ／ｍｉｎで２０μｍの押出量で押出し、加工不安定＊となる直前の引取速度（ｍ／ｍｉｎ）を加工性の評価値とした。
次に、約２０μｍ厚さに前記クラフト紙面上に積層した樹脂組成物試料（１）層の表面をコロナ処理し、次いでセロテープ（ニチバン社製）を貼り付け、荷重１ｋｇ×５分間放置後の剥離強度（Ｎ／１８ｍｍ）を測定し、剥離紙層としての性能を評価した。
結果を表１に示した。
上記剥離強度測定条件：引張試験機による剥離強度測定試験；試験幅；１８ｍｍ（セロテープ幅）、剥離強度測定距離;３０ｍｍ、剥離角度；１８０度剥離
引張速度；３００ｍｍ／分
Next, the above resin composition (1) was applied to a kraft paper (50 g / m 2 ) substrate surface using an extrusion laminator (caliber 40 mmφ, die: 450 mm width, cooling roll 35 mmφ, nip roll 200 mmφ) at 20 m at 45 m / min. The take-off speed (m / min) just before the extrusion amount and the processing instability * occurred was taken as the evaluation value of workability.
Next, the surface of the resin composition sample (1) layer laminated on the surface of the kraft paper to a thickness of about 20 μm is subjected to corona treatment, and then a cello tape (manufactured by Nichiban Co., Ltd.) is applied, and the load is peeled off after standing for 1 kg × 5 minutes. The strength (N / 18 mm) was measured and the performance as a release paper layer was evaluated.
The results are shown in Table 1.
Peel strength measurement conditions: Peel strength measurement test using a tensile tester; Test width: 18 mm (cello tape width), peel strength measurement distance: 30 mm, peel angle: 180 ° peel tensile speed: 300 mm / min
「実施例１」
試料（ロ）６０質量％＋試料（イ）４０質量％のＭＢ３５質量部に試料（イ）６５質量部を配合した以外は参考例と同様にして樹脂組成物試料（２）を調製し（調製後成分組成（イ）７９質量％、（ロ）２１質量％）、それを用いて参考例と同様に、クラフト紙基材への押出ラミネート時の加工性、及び、積層体の樹脂組成物試料（２）層のセロテープ剥離強度を測定した。
結果を表１に示した。
"Example 1 "
A resin composition sample (2) was prepared in the same manner as in the Reference Example except that 65 parts by mass of sample (b) was blended with 35 parts by mass of sample (b) 60% by mass + sample (b) 40% by mass (preparation) Post-component composition (A) 79% by mass, (B) 21% by mass), using the same as in the reference example , processability during extrusion lamination to a kraft paper substrate, and resin composition sample of laminate (2) The cellotape peel strength of the layer was measured.
The results are shown in Table 1.
「実施例２」
試料（ハ）６０質量％＋試料（イ）４０質量％のＭＢ３５質量部に試料（イ）６５質量部を配合した以外は参考例と同様にして樹脂組成物試料（３）を調製し（調製後成分組成（イ）７９質量％、（ハ）２１質量％）、それを用いて参考例と同様に、クラフト紙基材への押出ラミネート時の加工性、及び、積層体の樹脂組成物試料（３）層のセロテープ剥離強度を測定した。
結果を表１に示した。
"Example 2 "
A resin composition sample (3) was prepared in the same manner as in Reference Example except that 65 parts by mass of sample (I) was blended with 35 parts by mass of MB of 60% by mass of sample (C) + 40% by mass of sample (I) (preparation) Post-component composition (A) 79% by mass, (C) 21% by mass), using the same as in the reference example , processability during extrusion lamination to a kraft paper base material, and resin composition sample of laminate (3) The cellotape peel strength of the layer was measured.
The results are shown in Table 1.
「実施例３」
試料（ニ）６０質量％＋試料（イ）４０質量％のＭＢ３５質量部に試料（イ）６５質量部を配合した以外は参考例と同様にして樹脂組成物試料（４）を調製し（調製後成分組成（イ）７９質量％、（ニ）２１質量％）、それを用いて参考例と同様に、クラフト紙基材への押出ラミネート時の加工性、及び、積層体の樹脂組成物試料（４）層のセロテープ剥離強度を測定した。
結果を表１に示した。
なお参考例と実施例１〜３のクラフト紙と樹脂組成物試料の積層体のクラフト紙／樹脂組成物試料間を剥離した結果、いずれも紙基材が破壊し、紙と樹脂組成物は良好な接着性を示した。
"Example 3 "
A resin composition sample (4) was prepared in the same manner as in the Reference Example except that 65 parts by mass of sample (b) was blended with 35 parts by mass of sample (d) 60% by mass + sample (b) 40% by mass (preparation) rear component composition (i) 79 wt%, (d) 21 wt%), similar to the reference example by using the workability in extrusion lamination to kraft paper substrate, and a resin composition sample of laminate (4) The cellotape peel strength of the layer was measured.
The results are shown in Table 1.
In addition, as a result of peeling between the kraft paper / resin composition sample of the laminate of the kraft paper and the resin composition sample of Reference Example and Examples 1 to 3 , the paper base material was destroyed in both cases, and the paper and the resin composition were good. Showed good adhesion.
「比較例１」
試料（イ）のＴＰＸをそのまま用いて参考例と同様に、クラフト紙基材への押出ラミネート時の加工性、及び、積層体の樹脂組成物試料（４）層のセロテープ剥離強度を測定した。
結果を表１に示した。
“Comparative Example 1”
Similar to Reference Example using as the TPX sample (a), processability in extrusion lamination to kraft paper substrate and was measured cellophane tape peel strength of the resin composition sample (4) layers of the laminate.
The results are shown in Table 1.
表１の結果から、本発明の樹脂組成物は、従来品ＴＰＸに比べ成形時の加工性に顕著に優れ、然も、「セロテープ」等の粘着面に対し適度な剥離強度（離型性）を有し、剥離紙の離型層として極めて好適であることがわかる。 From the results of Table 1, the resin composition of the present invention is remarkably superior in workability at the time of molding as compared with the conventional product TPX, but it has an appropriate peel strength (releasability) with respect to an adhesive surface such as “cello tape”. It can be seen that it is extremely suitable as a release layer for release paper.
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Family Cites Families (3)
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| JP3290812B2 (en) * | 1994-07-12 | 2002-06-10 | 三井化学株式会社 | Release paper for synthetic leather production |
| JP2001023597A (en) * | 1999-07-02 | 2001-01-26 | Toyo Kohan Co Ltd | Safety valve material for battery, its manufacture, and battery using same |
| US20060063888A1 (en) * | 2004-09-21 | 2006-03-23 | Dean David M | Trivalent cation-neutralized ionomers and foams thereof |
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| US8459856B2 (en) | 2007-12-19 | 2013-06-11 | Oree, Inc. | Planar white illumination apparatus |
| US8550684B2 (en) | 2007-12-19 | 2013-10-08 | Oree, Inc. | Waveguide-based packaging structures and methods for discrete lighting elements |
| US8624527B1 (en) | 2009-03-27 | 2014-01-07 | Oree, Inc. | Independently controllable illumination device |
| US8727597B2 (en) | 2009-06-24 | 2014-05-20 | Oree, Inc. | Illumination apparatus with high conversion efficiency and methods of forming the same |
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