JP5047994B2 - Biaxially oriented laminated film - Google Patents

Biaxially oriented laminated film Download PDF

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JP5047994B2
JP5047994B2 JP2008555063A JP2008555063A JP5047994B2 JP 5047994 B2 JP5047994 B2 JP 5047994B2 JP 2008555063 A JP2008555063 A JP 2008555063A JP 2008555063 A JP2008555063 A JP 2008555063A JP 5047994 B2 JP5047994 B2 JP 5047994B2
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film
ethylene
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material layer
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JPWO2008090871A1 (en
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正文 小野
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Mitsui Chemicals Tohcello Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/023—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
    • B29C33/68—Release sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene

Description

本発明は基材層がエチレン系共重合体からなる二軸に配向されたフィルムからなり、それに離型層または粘着層が積層された積層フィルムに関する。   The present invention relates to a laminated film in which a base material layer is made of a biaxially oriented film made of an ethylene copolymer, and a release layer or an adhesive layer is laminated thereon.

線状低密度ポリエチレン（ＬＬＤＰＥ）などのエチレンとα−オレフィンとのランダム共重合体を用いて、インフレーション成形やＴダイによる無延伸の成形で得られたフィルムを離型フィルムや粘着フィルムの基材フィルムに用いることは既に提案されている。   Using a random copolymer of ethylene and α-olefin such as linear low-density polyethylene (LLDPE), a film obtained by inflation molding or non-stretching molding by a T-die is used as a release film or adhesive film substrate. It has already been proposed for use in films.

しかし、離型フィルムや保護フィルムにおいて、インフレーション成形やＴダイによる無延伸の成形で得られたフィルムでは、強度が十分ではない。   However, in a release film or a protective film, a film obtained by inflation molding or non-stretching molding by a T die does not have sufficient strength.

また、エチレンとα−オレフィンのランダム共重合体フィルムの透明性や機械的強度を改良する方法としてエチレン・α−オレフィンランダム共重合体を二軸延伸することは既に提案されている。しかし、これらを離型フィルムや粘着フィルムの基材層に用いることは知られていない。   Further, it has already been proposed to biaxially stretch an ethylene / α-olefin random copolymer as a method for improving the transparency and mechanical strength of a random copolymer film of ethylene and α-olefin. However, it is not known that these are used for a base layer of a release film or an adhesive film.

本発明は、エチレン系共重合体からなり、二軸に配向したフィルムが離型フィルム及び粘着フィルム等の保護フィルムの基材として好適であることを見いだしたことに基づく。   The present invention is based on the finding that a biaxially oriented film made of an ethylene copolymer is suitable as a base material for a protective film such as a release film and an adhesive film.

すなわち、本発明は密度が９１０〜９４０Ｋｇ／ｍ3の範囲にあるエチレン系共重合体（Ａ）からなる基材層が二軸方向に配向され、かつ基材層に離型層または粘着層が積層されてなることを特徴とする積層フィルムに関する。That is, in the present invention, a base material layer made of an ethylene copolymer (A) having a density in the range of 910 to 940 Kg / m 3 is biaxially oriented, and a release layer or an adhesive layer is provided on the base material layer. It is related with the laminated | multilayer film characterized by being laminated | stacked.

本発明によれば、基材層として密度が９１０〜９４０Ｋｇ／ｍ3の範囲にあるエチレン系共重合体（Ａ）からなる二軸方向に配向されたフィルムを用いることにより、その実使用の際の寸法安定性に優れ、温度１００℃における収縮が、その縦方向（ＭＤ）で５％未満、横方向（ＴＤ）で５％未満の積層フィルムが得られ、各種の離型フィルム、粘着フィルム、保護フィルムとして利用することができる。According to the present invention, by using a biaxially oriented film made of an ethylene copolymer (A) having a density in the range of 910 to 940 Kg / m 3 as the base material layer, A laminated film with excellent dimensional stability and shrinkage at a temperature of 100 ° C. of less than 5% in the machine direction (MD) and less than 5% in the transverse direction (TD) can be obtained. Various release films, adhesive films, and protective films It can be used as a film.

以下、本発明の積層フィルムについて説明する。   Hereinafter, the laminated film of the present invention will be described.

［エチレン系重合体（Ａ）］
本発明に用いられるエチレン系共重合体（Ａ）は、密度が９１０〜９４０Ｋｇ／ｍ3、好ましくは９１５〜９３５Ｋｇ／ｍ3 のエチレン系共重合体である。[Ethylene polymer (A)]
The ethylene copolymer (A) used in the present invention is an ethylene copolymer having a density of 910 to 940 Kg / m 3 , preferably 915 to 935 Kg / m 3 .

密度が上記範囲外である場合は、二軸延伸フィルムの成形が困難な場合がある。   When the density is outside the above range, it may be difficult to form a biaxially stretched film.

エチレン系共重合体（Ａ）は、フィルムに成形できる限り、メルトフローレート（ＭＦ
Ｒ：ＡＳＴＭ Ｄ１２３８ 荷重２１６０ｇ、温度１９０℃）は特に限定はされないが、通常、０．５〜１０ｇ／１０分、好ましくは０．８〜５ｇ／１０分の範囲である。As long as the ethylene copolymer (A) can be formed into a film, the melt flow rate (MF)
R: ASTM D1238 (load 2160 g, temperature 190 ° C.) is not particularly limited, but is usually in the range of 0.5 to 10 g / 10 minutes, preferably 0.8 to 5 g / 10 minutes.

本発明に用いられるエチレン系重合体（Ａ）の密度は密度勾配管により測定される。   The density of the ethylene polymer (A) used in the present invention is measured by a density gradient tube.

本発明におけるエチレン系共重合体（Ａ）は、エチレンと炭素数４〜１０のα−オレフィン、例えば、１−ブテン、１−ヘプテン、１−ヘキセン、１−オクテン、４−メチル−１−ペンテン等のα−オレフィンから選ばれる少なくとも１種類以上のα−オレフィンとのランダム共重合体である。   The ethylene-based copolymer (A) in the present invention includes ethylene and an α-olefin having 4 to 10 carbon atoms, such as 1-butene, 1-heptene, 1-hexene, 1-octene, 4-methyl-1-pentene. And a random copolymer with at least one α-olefin selected from α-olefins such as.

なお、エチレン系共重合体（Ａ）は、上記の密度の範囲内であれば、１種あるいは２種以上の混合物であってもよい。特に、密度が８９５〜９２５Ｋｇ／ｍ3、好ましくは９００〜９２０Ｋｇ／ｍ3の範囲にあるエチレン・α−オレフィン共重合体（Ａ１）成分と密度が９２５〜９５０Ｋｇ／ｍ3、好ましくは９３０〜９４０Ｋｇ／ｍ3の範囲にあるエチレン・α−オレフィンランダム共重合体（Ａ２）成分とからなるエチレン共重合体（Ａ）が好適であり、その比率は（Ａ１）２０〜８０重量％と（Ａ２）８０〜２０重量％、好ましくは（Ａ１）３０〜７０重量％と（Ａ２）７０〜３０重量％（なお、（Ａ１）＋（Ａ２）の合計で１００重量％とする。）が通常である。The ethylene copolymer (A) may be one type or a mixture of two or more types as long as it is within the above-mentioned density range. In particular, density 895~925Kg / m 3, preferably an ethylene · alpha-olefin copolymer (A1) component and density 925~950Kg / m 3 in the range of 900~920Kg / m 3, preferably 930~940Kg An ethylene copolymer (A) comprising an ethylene / α-olefin random copolymer (A2) component in the range of / m 3 is preferable, and the ratio thereof is (A1) 20 to 80% by weight and (A2). 80 to 20% by weight, preferably (A1) 30 to 70% by weight and (A2) 70 to 30% by weight (note that the total of (A1) + (A2) is 100% by weight).

このようなエチレン系共重合体（Ａ）は、分子量分布（重量平均分子量：Ｍｗ、と数平均分子量：Ｍｎ、との比：Ｍｗ／Ｍｎで表示）が通常１．５〜４．０、好ましくは１．８〜３．５の範囲にあることが望ましい。このＭｗ／Ｍｎはゲル透過クロマトグラフィー（ＧＰＣ）によって測定できる。なお、エチレン系共重合体（Ａ）が、上記のように２成分からなる場合は、それぞれの成分について、上記の分子量分布を有することが望ましい。   Such an ethylene-based copolymer (A) has a molecular weight distribution (weight average molecular weight: Mw, number average molecular weight: Mn, ratio: expressed as Mw / Mn) is usually 1.5 to 4.0, preferably Is preferably in the range of 1.8 to 3.5. This Mw / Mn can be measured by gel permeation chromatography (GPC). In addition, when an ethylene-type copolymer (A) consists of two components as mentioned above, it is desirable to have said molecular weight distribution about each component.

これらエチレン・α−オレフィン共重合体（Ａ１）は、チーグラー触媒、シングルサイト触媒等を用いた従来公知の製造法により製造することができる。中でも、シングルサイト触媒（メタロセン触媒）により得られた共重合体がとくに好ましい。このメタロセン化合物を含む触媒は、（ａ）遷移金属のメタロセン化合物と、（ｂ）有機アルミニウムオキシ化合物と、（ｃ）担体とから形成されることが好ましく、さらに必要に応じて、これらの成分と（ｄ）有機アルミニウム化合物および／または有機ホウ素化合物とから形成さていてもよい。   These ethylene / α-olefin copolymers (A1) can be produced by a conventionally known production method using a Ziegler catalyst, a single site catalyst or the like. Among these, a copolymer obtained by a single site catalyst (metallocene catalyst) is particularly preferable. The catalyst containing the metallocene compound is preferably formed from (a) a transition metal metallocene compound, (b) an organoaluminum oxy compound, and (c) a carrier, and if necessary, these components and (D) It may be formed from an organoaluminum compound and / or an organoboron compound.

このようなメタロセン化合物を含むオレフィン重合用触媒、および触媒を用いたエチレン・α−オレフィン共重合体（Ａ１）の調製方法は、たとえば特開平８−２６９２７０号公報に記載されている。   An olefin polymerization catalyst containing such a metallocene compound and a method for preparing an ethylene / α-olefin copolymer (A1) using the catalyst are described in, for example, JP-A-8-269270.

エチレン系共重合体（Ａ）には、必要に応じて高圧法低密度ポリエチレン、中密度ポリエチレン樹脂等を配合することも行われる。これらを配合する場合は、エチレン系共重合体（Ａ）１００重量部に対して、１０〜１００重量部、中でも３０〜９０重量部が好適である。   The ethylene copolymer (A) may be blended with a high-pressure method low-density polyethylene, a medium-density polyethylene resin, or the like, if necessary. When mix | blending these, 10-100 weight part with respect to 100 weight part of ethylene-type copolymers (A), 30-90 weight part is suitable especially.

本発明のエチレン系共重合体（Ａ）に特に配合すること望ましい他の成分として高圧法低密度ポリエチレンがある。   Another component that is particularly desirable to be blended in the ethylene copolymer (A) of the present invention is high-pressure low-density polyethylene.

高圧法低密度ポリエチレンは、通常密度が９１０〜９３５Ｋｇ／ｍ3、好ましくは９１５〜９３０Ｋｇ／ｍ3の範囲にある。これら高圧法低密度ポリエチレンは、高圧下で重合されるエチレンの単独重合体が一般的であるが、５重量％未満の他のα−オレフィンあるいは酢酸ビニル等のビニル化合物との共重合体も例示することができる。The high-pressure low-density polyethylene usually has a density in the range of 910 to 935 Kg / m 3 , preferably 915 to 930 Kg / m 3 . These high-pressure low-density polyethylenes are generally ethylene homopolymers polymerized under high pressure, but examples include copolymers with other α-olefins less than 5% by weight or vinyl compounds such as vinyl acetate. can do.

高圧法低密度ポリエチレンのメルトフローレート（ＭＦＲ：ＡＳＴＭ Ｄ１２３８ 荷重２１６０ｇ、温度１９０℃）は、前述のエチレン系共重合体（Ａ）との組成物をフィルムに成形する形成能がある限りとくに限定はされないが、通常、０．１〜３０ｇ／１０分、好ましくは０．１〜１０ｇ／１０分である。   The melt flow rate (MFR: ASTM D1238 load 2160 g, temperature 190 ° C.) of the high-pressure low-density polyethylene is not particularly limited as long as it has the ability to form a composition with the above-mentioned ethylene copolymer (A) into a film. However, it is usually 0.1 to 30 g / 10 min, preferably 0.1 to 10 g / 10 min.

エチレン系重合体（Ａ）、あるいは更に高圧法低密度ポリエチレンとの組成物には本発明の目的を損なわない範囲で、通常用いられる酸化防止剤、耐候安定剤、帯電防止剤、防曇剤、ブロッキング防止剤、滑剤、核剤、顔料等の添加剤或いは他の重合体を必要に応じて配合することができる。   As long as the object of the present invention is not impaired in the composition with the ethylene polymer (A) or the high-pressure method low-density polyethylene, the antioxidant, weathering stabilizer, antistatic agent, antifogging agent, Additives such as antiblocking agents, lubricants, nucleating agents, pigments, or other polymers can be blended as necessary.

［二軸配向した基材層］
本発明における基材層は、上記のエチレン系共重合体（Ａ）またはそれを主成分とする基材層からなり、二軸に配向している。[Biaxially oriented substrate layer]
The base material layer in this invention consists of said ethylene-type copolymer (A) or a base material layer which has it as a main component, and is biaxially oriented.

基材層の厚さは、通常５〜１５０μｍ、好ましくは１５〜８０μｍである。   The thickness of a base material layer is 5-150 micrometers normally, Preferably it is 15-80 micrometers.

基材層は、単層の場合の他、表面層／中間層／表面層からなる複合フィルムとすることも行われる。両側の表面層と中間層の樹脂組成は同一でもよく、異なる組成とすることも行われる。例えば、表面層の組成として、上記のエチレン共重合体（Ａ）の組成１００重量部に対して更に高密度ポリエチレンを１０〜３０重量部配合してその層の離型性を高めることも行われる。   In addition to a single layer, the base material layer may be a composite film comprising a surface layer / intermediate layer / surface layer. The resin composition of the surface layer and the intermediate layer on both sides may be the same or different. For example, as a composition of the surface layer, 10 to 30 parts by weight of high density polyethylene is further blended with respect to 100 parts by weight of the composition of the above-mentioned ethylene copolymer (A) to improve the releasability of the layer. .

さらに、基材層の表面には、離型層や粘着層との密着性を改良するために、基材層のうちの離型層や粘着層と貼り合せる面の表面を、例えば、コロナ処理、火炎処理、プラズマ処理、アンダーコート処理等の表面活性化処理を行っておいてもよい。   Furthermore, in order to improve the adhesion with the release layer or the adhesive layer, the surface of the surface of the base material layer to be bonded to the release layer or the adhesive layer is treated with, for example, a corona treatment. Surface activation treatment such as flame treatment, plasma treatment, and undercoat treatment may be performed.

［基材層の製造方法］
二軸に配向した基材層は、未延伸のフィルムを逐次二軸延伸または同時二軸延伸により成形することができる。[Manufacturing method of base material layer]
The biaxially oriented base material layer can be formed by successively biaxially or simultaneously biaxially stretching an unstretched film.

使用される未延伸のフィルムは通常の押出成形法により成形される。多層フィルムの場合は共押出により成形される。   The unstretched film used is formed by a normal extrusion method. In the case of a multilayer film, it is formed by coextrusion.

逐次二軸延伸にはフラット方式（テンター方式）が例示される。
これら二軸延伸において、一方向の延伸倍率は３〜１４倍、好ましくは５〜１０倍及び他方向の延伸倍率は３〜１４倍、好ましくは５〜１０倍の範囲で縦（ＭＤ）方向及び横（ＴＤ）方向に二軸延伸される。A flat system (tenter system) is exemplified for the sequential biaxial stretching.
In these biaxial stretching, the stretching ratio in one direction is 3 to 14 times, preferably 5 to 10 times, and the stretching ratio in the other direction is 3 to 14 times, preferably 5 to 10 times in the longitudinal (MD) direction and Biaxially stretched in the transverse (TD) direction.

フラット方式による二軸延伸の場合は、通常、押出し成形して得たシートを９０〜１２５℃の温度範囲で縦方向に延伸した後、９０〜１３０℃の温度範囲で横方向に延伸することにより得られる。二軸延伸した後は、用途により、８０〜１５０℃の温度範囲でヒートセットを行うことが望ましい。ヒートセットは、オンライン若しくはオフラインのいずれでもよい。ヒートセットの温度は目的とする熱収縮率に応じて適宜変更される。   In the case of biaxial stretching by the flat method, usually, a sheet obtained by extrusion molding is stretched in the longitudinal direction at a temperature range of 90 to 125 ° C, and then stretched in the transverse direction at a temperature range of 90 to 130 ° C. can get. After biaxial stretching, it is desirable to perform heat setting in the temperature range of 80 to 150 ° C. depending on the application. The heat set may be either online or offline. The temperature of the heat setting is appropriately changed according to the target heat shrinkage rate.

特に寸法安定性が求められる用途においては、熱処理を行うことにより、１００℃における基材層の収縮率が、その縦方向（ＭＤ）で通常５％未満、好ましくは４％未満、さらに好ましくは３％未満、かつ横方向（ＴＤ）で通常５％未満、好ましくは４％未満、さらに好ましくは３％未満の基材層とすることができる。さらに、６０℃における基材層の収縮率は、その縦方向（ＭＤ）および横方向（ＴＤ）のいずれも０％の基材層とすることができる。   Especially in applications where dimensional stability is required, the shrinkage rate of the base material layer at 100 ° C. is usually less than 5%, preferably less than 4%, more preferably 3 by performing heat treatment in the machine direction (MD). % And in the transverse direction (TD) usually less than 5%, preferably less than 4%, more preferably less than 3%. Furthermore, the shrinkage ratio of the base material layer at 60 ° C. can be 0% of the base material layer in both the vertical direction (MD) and the horizontal direction (TD).

ここで、フィルムの収縮率（％）は、試料のフィルムから長さ方向がフィルムの流れ方向（ＭＤ）、幅方向（ＴＤ）となるように１５ｍｍ幅、２００ｍｍ長さの短冊状の試験片を切り出し、１５０ｍｍ間隔に穴を開け、これを所定温度のオーブン内に１５分間放置後、取り出して室温まで放冷した後に穴の距離を測定し、その収縮率を求めた値である。   Here, the shrinkage rate (%) of the film is determined by measuring a strip-shaped test piece having a width of 15 mm and a length of 200 mm so that the length direction from the sample film is the film flow direction (MD) and the width direction (TD). This is a value obtained by cutting out and opening holes at intervals of 150 mm, leaving them in an oven at a predetermined temperature for 15 minutes, taking them out and allowing them to cool to room temperature, then measuring the distance between the holes and determining the shrinkage.

また、基材層の引張弾性率（ＭＰａ）は縦方向（ＭＤ）が３５０〜６００ＭＰａ、中でも４４０〜５５０ＭＰａ、横方向が４００〜１２００ＭＰａ、好ましくは６００〜１１００ＭＰａ、さらに好ましくは８００〜１０００ＭＰａの範囲である。基材層の引っ張り弾性率（ＭＰａ）がこのような範囲にあると優れた収縮率（％）を示す基材層とすることができる点で望ましい。さらに、基材層の破断点強度は縦方向（ＭＤ）が７０〜２００ＭＰａ、中でも１００〜１５０ＭＰａ、横方向（ＴＤ）が１００〜２００ＭＰａ、中でも１４０〜１８０ＭＰａの範囲が好適である。基材層の破断点強度（ＭＰａ）がこのような範囲にあると優れた収縮率（％）を示す基材層とすることができる点で望ましい。さらに、基材層の破断点伸度（％）は縦方向（ＭＤ）が２５０％以下、好ましくは２３０％以下、横方向（ＴＤ）が１００％以下、中でも８０％以下が好適である。基材層の破断点伸度（％）がこのような範囲にあると優れた収縮率（％）を示す基材層とすることができる点で望ましい。
基材層に離型層または粘着層を形成する方法としては、ドライラミネート法、無溶剤ラミネート法、押出しラミネート法、共押出し成形法などが例示される。
［離型層］
基材層に積層される離型層には、従来公知の種々のものが例示される。離型層を形成する材料は、離型性を有するものであれば特に限定されるものではなく、硬化型シリコーン樹脂や更にウレタン樹脂、エポキシ樹脂等とのグラフト重合等によって変性されたシリコーン樹脂等が例示される。これらの中でも、硬化型シリコーン樹脂を主成分とするものが好ましい。Further, the tensile modulus (MPa) of the base material layer is 350 to 600 MPa in the machine direction (MD), particularly 440 to 550 MPa, 400 to 1200 MPa in the transverse direction, preferably 600 to 1100 MPa, more preferably 800 to 1000 MPa. is there. If the tensile modulus (MPa) of the base material layer is in such a range, it is desirable in that it can be a base material layer exhibiting an excellent shrinkage rate (%). Further, the strength at break of the base material layer is preferably in the range of 70 to 200 MPa in the machine direction (MD), particularly 100 to 150 MPa, and 100 to 200 MPa in the transverse direction (TD), particularly 140 to 180 MPa. When the strength at break (MPa) of the base material layer is in such a range, it is desirable in that it can be a base material layer exhibiting an excellent shrinkage rate (%). Further, the elongation at break (%) of the base material layer is preferably 250% or less in the machine direction (MD), preferably 230% or less, and 100% or less in the transverse direction (TD), particularly 80% or less. When the elongation at break (%) of the base material layer is in such a range, it is desirable in that the base material layer can exhibit an excellent shrinkage rate (%).
Examples of the method for forming the release layer or the adhesive layer on the base material layer include a dry laminating method, a solventless laminating method, an extrusion laminating method, and a coextrusion molding method.
[Release layer]
Various conventionally well-known things are illustrated by the release layer laminated | stacked on a base material layer. The material for forming the release layer is not particularly limited as long as it has releasability, such as a curable silicone resin, a silicone resin modified by graft polymerization with a urethane resin, an epoxy resin, or the like. Is exemplified. Among these, what has a curable silicone resin as a main component is preferable.

硬化型シリコーン樹脂には、溶剤付加型、溶剤縮合型、溶剤紫外線硬化型、無溶剤付加型、無溶剤縮合型、無溶剤紫外線硬化型、無溶剤電子線硬化型等いずれの硬化反応タイプでも使用することができる。例えば、信越化学工業（株）製のＫＳ−７７４、ＫＳ−７７５、ＫＳ−７７８、ＫＳ−７７９Ｈ、ＫＳ−８５６、Ｘ−６２−２４２２、Ｘ−６２−２４６１、ＫＮＳ−３０５、ＫＮＳ−３０００、Ｘ−６２−１２５６等、東レ・ダウコーニング・シリコーン（株）製のＬＴＣ７５０Ａ、ＬＴＣ３００Ｂ、ＳＤ７２２３、ＳＤ７２２６、ＳＤ７２２９、ＳＲＸ−２１０等が例示される。   For curable silicone resin, any curing reaction type such as solvent addition type, solvent condensation type, solvent ultraviolet curing type, solventless addition type, solventless condensation type, solventless ultraviolet curing type, solventless electron beam curing type, etc. can do. For example, KS-774, KS-775, KS-778, KS-779H, KS-856, X-62-2422, X-62-2461, KNS-305, KNS-3000, manufactured by Shin-Etsu Chemical Co., Ltd. Examples include X-62-1256, LTC750A, LTC300B, SD7223, SD7226, SD7229, SRX-210 and the like manufactured by Toray Dow Corning Silicone.

離型層の塗工量は、通常０．０１〜１０ｇ／ｍ2、中でも０．０５〜５ｇ／ｍ2の範囲が好適である。The coating amount of the release layer is usually 0.01 to 10 g / m 2, is preferably in a range among them of 0.05-5 g / m 2.

これら離型層は、基材層の片面のみ、あるいは両面に形成することができる。
［粘着層］
基材層に積層される粘着層には、従来公知の種々のものが例示される。These release layers can be formed on only one side or both sides of the base material layer.
[Adhesive layer]
Various conventionally well-known things are illustrated by the adhesion layer laminated | stacked on a base material layer.

粘着剤としては、一般に知られているアクリル系、ゴム系、シリコーン系など限定なく用いることができる。さらに、微粘着層とする場合は、エチレン−α−オレフィン共重合体に石油樹脂等を配合した組成物も例示される。例えば、アクリル系についてはエマルジョン型、ソルベント型、ゴム系についてはエマルジョン型、ソルベント型、ホットメルト型、さらにシリコーン系についてはソルベント型が例示される。これらの粘着剤は、種々の方法で塗布することができる。   As the pressure-sensitive adhesive, generally known acrylic, rubber-based, silicone-based and the like can be used without limitation. Furthermore, when it is set as a slightly adhesion layer, the composition which mix | blended petroleum resin etc. with the ethylene-alpha-olefin copolymer is illustrated. For example, an acrylic type is exemplified by an emulsion type, a solvent type, a rubber type is exemplified by an emulsion type, a solvent type, a hot melt type, and a silicone type is exemplified by a solvent type. These pressure-sensitive adhesives can be applied by various methods.

これらの粘着剤は、例えばソルベント型の粘着剤を塗布する場合、ナイフコーターやリバースコーターを用いて基材層に塗布される。必要に応じて、粘着層には離型紙が仮積層される。   For example, when applying a solvent-type pressure-sensitive adhesive, these pressure-sensitive adhesives are applied to the base material layer using a knife coater or a reverse coater. If necessary, release paper is temporarily laminated on the adhesive layer.

また、石油樹脂等を配合したエチレン−α−オレフィン共重合体等の樹脂を粘着層とする場合は、基材層にドライラミネーション、押出被覆等により成形される。   Moreover, when using resin, such as an ethylene-alpha-olefin copolymer which mix | blended petroleum resin etc., as an adhesion layer, it shape | molds by dry lamination, extrusion coating, etc. to a base material layer.

これら粘着層は基材層の片面、あるいは両面に形成することができる。   These adhesive layers can be formed on one side or both sides of the base material layer.

次に本発明を、実施例により説明する。
（１）メルトフローレート（ｇ／１０分）
ＡＳＴＭ Ｄ １２３８に準拠し、荷重２１６０ｇ、温度１９０℃の条件で測定した。
（２）密度（Ｋｇ／ｍ3）
ＭＦＲを測定して得た重合体ストランドを１２０℃で２時間処理し、１時間かけて室温（２３℃）まで徐冷した後、ＪＩＳ Ｋ ７１１２に準拠し、Ｄ法（密度勾配管）により測定した。
（３）熱収縮率（％）
フィルムの長さ方向がフィルムの流れ方向（ＭＤ）、幅方向（ＴＤ）となるように１５ｍｍ幅、２００ｍｍ長さの短冊状の試験片を切り出し、１５０ｍｍ間隔に穴を開け、これを所定温度のオーブン内に１５分間放置後、取り出して室温まで放冷した後に穴の距離を測定し収縮率を測定した。
（４）引張弾性率（ＭＰａ）
ＪＩＳ Ｋ ７１２７に準拠し、株式会社オリエンテック社製 型式RTC-1225を用いて、縦方向（ＭＤ）横方向（ＴＤ）の引張弾性率の測定を行った。
（５）破断点強度（ＭＰａ）
ＪＩＳ Ｋ ７１２７に準拠し、株式会社オリエンテック社製 型式RTC-1225を用いて、縦方向（ＭＤ）横方向（ＴＤ）の破断点強度の測定を行った。
（６）破断点伸度（ＭＰａ）
ＪＩＳ Ｋ ７１２７に準拠し、株式会社オリエンテック社製 型式RTC-1225を用いて、縦方向（ＭＤ）横方向（ＴＤ）の破断点伸度の測定を行った。
実施例１
下記の（１）、（２）及び（３）のポリマーからなる組成物（（１）：（２）：（３）の重量比３５：５０：１５）を、池貝鉄工社製二軸押出機（４６ｍｍφ）を用いて組成物を得た。
（１）エチレン−１−ヘキセンランダム共重合体
メタロセン触媒を用いた重合体、密度９０５Ｋｇ／ｍ3、ＭＦＲ；０．５ｇ／１０分。
（２）エチレン−１−ヘキセンランダム共重合体
メタロセン触媒を用いた重合体、密度；９１５Ｋｇ／ｍ3、ＭＦＲ；０．５ｇ／１０分。
（３）高圧法低密度ポリエチレン
密度；９２１Ｋｇ／ｍ3、ＭＦＲ；０．６ｇ／１０分。Next, the present invention will be described by way of examples.
(1) Melt flow rate (g / 10 min)
In accordance with ASTM D 1238, the measurement was performed under the conditions of a load of 2160 g and a temperature of 190 ° C.
(2) Density (Kg / m 3 )
The polymer strand obtained by measuring MFR was treated at 120 ° C. for 2 hours, slowly cooled to room temperature (23 ° C.) over 1 hour, and then measured by the D method (density gradient tube) according to JIS K 7112. did.
(3) Thermal contraction rate (%)
Cut out strip-shaped test pieces having a width of 15 mm and a length of 200 mm so that the length direction of the film is the film flow direction (MD) and the width direction (TD), and holes are formed at intervals of 150 mm. After leaving it in the oven for 15 minutes, it was taken out and allowed to cool to room temperature, and then the distance between the holes was measured to measure the shrinkage.
(4) Tensile modulus (MPa)
Based on JIS K7127, the tensile modulus in the machine direction (MD) and the transverse direction (TD) was measured using model RTC-1225 manufactured by Orientec Co., Ltd.
(5) Strength at break (MPa)
Based on JIS K7127, the strength at break in the machine direction (MD) and the transverse direction (TD) was measured using model RTC-1225 manufactured by Orientec Corporation.
(6) Elongation at break (MPa)
In accordance with JIS K 7127, the elongation at break in the machine direction (MD) and the transverse direction (TD) was measured using model RTC-1225 manufactured by Orientec Corporation.
Example 1
A composition comprising the following polymers (1), (2), and (3) (weight ratio 35:50:15 of (1) :( 2) :( 3)) was made into a twin-screw extruder manufactured by Ikegai Iron Works A composition was obtained using (46 mmφ).
(1) Polymer using ethylene-1-hexene random copolymer metallocene catalyst, density 905 Kg / m 3 , MFR; 0.5 g / 10 min.
(2) Ethylene-1-hexene random copolymer Polymer using metallocene catalyst, density: 915 Kg / m 3 , MFR: 0.5 g / 10 min.
(3) High pressure low density polyethylene density: 921 Kg / m 3 , MFR: 0.6 g / 10 min.

この組成物を二軸延伸フィルム成形機を用いて溶融押出しし、Ｔ−ダイで賦形した後、冷却ロール上にて急冷し厚さ約１．３ｍｍのシートを得た。このシートを１１２℃で加熱しフィルムの流れ方向（縦方向）に５倍延伸した。この５倍延伸したシートを１１６℃で加熱し流れ方向に対して直交する方向（横方向）に１０倍延伸して厚さ４０μｍの二軸延伸エチレン系共重合体のフィルムを得た。
この二軸延伸エチレン共重合体のフィルムを基材層として、その片面に、シリコーン系離型剤を塗布して離型フィルムとした。また、アクリル系のエマルジョン型の粘着材を塗布して粘着フィルムとした。これらは、離型フィルム、粘着フィルムとして利用することができる。
この基材層の収縮率は、以下の通りであった。

加熱温度（℃） 収縮率（％）
縦方向（ＭＤ） 横方向（ＴＤ）
５０ ０ ０
６０ ０ ０
７０ ０．５ ０．１
８０ ０．８ ０．１
９０ １．５ ０．４
１００ ２．６ １．６
１１０ ３．８ ３．８
１２０ ４．８ ６．２
また、この基材層の物性値は以下の通りであった。

引張弾性率 破断点強度 破断点伸度
（ＭＰａ） （ＭＰａ） （％）
ＭＤ ＴＤ ＭＤ ＴＤ ＭＤ ＴＤ
４４０ ８００ １００ １４０ ２３０ ８０
This composition was melt-extruded using a biaxially stretched film molding machine, shaped with a T-die, and then rapidly cooled on a cooling roll to obtain a sheet having a thickness of about 1.3 mm. This sheet was heated at 112 ° C. and stretched 5 times in the film flow direction (longitudinal direction). The 5-fold stretched sheet was heated at 116 ° C. and stretched 10 times in the direction perpendicular to the flow direction (lateral direction) to obtain a biaxially stretched ethylene copolymer film having a thickness of 40 μm.
The biaxially stretched ethylene copolymer film was used as a base material layer, and a silicone release agent was applied to one side of the film to form a release film. Also, an acrylic emulsion-type adhesive material was applied to form an adhesive film. These can be used as a release film or an adhesive film.
The shrinkage ratio of this base material layer was as follows.

Heating temperature (° C) Shrinkage rate (%)
Vertical direction (MD) Horizontal direction (TD)
50 0 0
60 0 0
70 0.5 0.1
80 0.8 0.1
90 1.5 0.4
100 2.6 1.6
110 3.8 3.8
120 4.8 6.2
Moreover, the physical property value of this base material layer was as follows.

Tensile modulus Tensile strength at break Elongation at break
(MPa) (MPa) (%)
MD TD MD TD MD TD
440 800 100 140 230 80

本発明の積層フィルムは、離型フィルム、粘着フィルムの用途に、各種保護フィルムとして広く用いることができる。特に、寸法安定性が求められる用途に、包装材として、産業材として用いることができる。   The laminated film of the present invention can be widely used as various protective films in applications of release films and adhesive films. In particular, it can be used as an industrial material as a packaging material for applications requiring dimensional stability.

Claims (4)

密度が９１０〜９４０Ｋｇ／ｍ3の範囲にあるエチレン系共重合体（Ａ）１００重量部、および密度が９１０〜９３５Ｋｇ／ｍ3の範囲にある高圧法低密度ポリエチレン１０〜１００重量部を含む組成物からなる基材層が二軸方向に配向され、かつ基材層に離型層または粘着層が積層されてなり、
上記エチレン系共重合体（Ａ）が、エチレンと炭素数４〜１０のα−オレフィンとの共重合体であることを特徴とする積層フィルム。Ethylene copolymer having a density in the range of 910~940Kg / m 3 (A) 100 parts by weight, and density composition including a high-pressure low density polyethylene 10 to 100 parts by weight in the range of 910~935Kg / m 3 base layer made of the object is oriented biaxially, and Ri release layer or an adhesive layer to the substrate layer name are stacked,
The said ethylene-type copolymer (A) is a copolymer of ethylene and a C4-C10 alpha olefin, The laminated film characterized by the above-mentioned . 基材層が逐次二軸延伸または同時二軸延伸により二軸方向に延伸されたフィルムであることを特徴とする請求項１に記載の積層フィルム。The laminated film according to claim 1, wherein the base material layer is a film stretched biaxially by sequential biaxial stretching or simultaneous biaxial stretching. 温度１００℃における収縮率が、その縦方向（ＭＤ）で５％未満、かつ横方向（ＴＤ）で５％未満であることを特徴とする請求項１または２に記載の積層フィルム。 3. The laminated film according to claim 1, wherein the shrinkage rate at a temperature of 100 ° C. is less than 5% in the machine direction (MD) and less than 5% in the transverse direction (TD). 請求項１〜３のいずれかに記載の離型フィルム又は粘着フィルム。The release film or adhesive film in any one of Claims 1-3 .
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