JP2018176661A - Heat-shrinkable laminate film and bag - Google Patents

Heat-shrinkable laminate film and bag Download PDF

Info

Publication number
JP2018176661A
JP2018176661A JP2017083707A JP2017083707A JP2018176661A JP 2018176661 A JP2018176661 A JP 2018176661A JP 2017083707 A JP2017083707 A JP 2017083707A JP 2017083707 A JP2017083707 A JP 2017083707A JP 2018176661 A JP2018176661 A JP 2018176661A
Authority
JP
Japan
Prior art keywords
heat
surface layer
film
particles
laminated film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP2017083707A
Other languages
Japanese (ja)
Other versions
JP6990984B2 (en
Inventor
友紀 黒須
Yuki Kurosu
友紀 黒須
高木　直樹
Naoki Takagi
直樹 高木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asahi Kasei Corp
Original Assignee
Asahi Kasei Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Kasei Corp filed Critical Asahi Kasei Corp
Priority to JP2017083707A priority Critical patent/JP6990984B2/en
Priority to KR1020180038203A priority patent/KR102189385B1/en
Priority to CN201810347393.1A priority patent/CN108724866B/en
Publication of JP2018176661A publication Critical patent/JP2018176661A/en
Application granted granted Critical
Publication of JP6990984B2 publication Critical patent/JP6990984B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/418—Refractive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B32B2307/736—Shrinkable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/08—Dimensions, e.g. volume
    • B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
    • B32B2309/105—Thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging

Landscapes

  • Laminated Bodies (AREA)
  • Wrappers (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide a heat-shrinkable laminate film that has both of slipperiness and transparency, which have been inconsistent with each other, and a bag containing the same.SOLUTION: A heat-shrinkable laminate film has an external surface layer (A) on at least one outermost surface. The external surface layer (A) contains particles having an average particle size 1.2-10.0 times as large as the thickness of the external surface layer (A).SELECTED DRAWING: Figure 1

Description

本発明は、複数の層を積層した積層フィルムであって、加熱により収縮する熱収縮性フィルムに関し、とりわけ、食品（例えば、肉類、加工肉類、水産物類、水産加工品）や機械部品等の効率的な包装処理が可能な、滑り性に優れ、透明性を兼ね揃えた熱収縮性積層フィルム及びそれを用いた袋に関する。   The present invention relates to a heat-shrinkable film which is a laminated film in which a plurality of layers are laminated and shrinks by heating, and in particular, the efficiency of food (eg, meats, processed meats, fish products, fishery products), machine parts, etc. TECHNICAL FIELD The present invention relates to a heat-shrinkable laminated film having excellent slipperiness and transparency, and a bag using it.

一般的に食品、医療機器、機械部品等の包装には、熱収縮性積層フィルムが用いられる。熱収縮性積層フィルムは様々な性質を有する各層により、用途に応じた機能が付与される。
熱収縮性フィルムが包装用に用いられる場合には、熱収縮性の他に、バリア性、透明性、ヒートシール性が重視される。
さらに、このような熱収縮性フィルムの多くは、製袋作業のようなフィルム二次加工の工程を要する。ここで必要とされる特性として、フィルム原反の繰り出し易さ、ヒートシールバーへのフィルムの付着し難さ、フィルム−設備間の滑り易さが挙げられる。さらに、製袋された袋において、積み重ねられた袋の取り出し易さ、つまりはフィルム−フィルム間の滑り易さが要求される。このような特性を総称してハンドリング性という。 Generally, heat-shrinkable laminated films are used for packaging of food, medical devices, machine parts and the like. The heat-shrinkable laminated film is provided with a function according to the application by each layer having various properties.
When a heat-shrinkable film is used for packaging, in addition to heat-shrinkability, the barrier property, the transparency, and the heat sealability are important.
Furthermore, many of such heat-shrinkable films require steps of film secondary processing, such as bagging operations. The properties required here include the ease of delivery of the film stock, the difficulty of adhering the film to the heat seal bar, and the ease of film-equipment slippage. Furthermore, in bag making bags, ease of removal of stacked bags, that is, film-film slippage is required. Such characteristics are generically called handleability.

特許文献１及び特許文献２に記載されるように、熱収縮性フィルムに上述のハンドリング性を付与する方法としては、その表面に澱粉粉末を付着（パウダリング）することが一般的である。
しかしながら、澱粉粉末は白い為、フィルムの透明性や光沢性が損なわれる。表面に付着した澱粉粉末は、水等によって除去しない限り透明性は改善されないため、透明性が強く求められる機械部品等の包装には適さない。
さらに、パウダリングした粉末はフィルムから落ち易く、フィルム生産時及び二次加工時、袋使用時において周辺に飛散し、周辺環境の汚染や人への吸入が懸念される。また、ヒートシールにてフィルムを袋状に製袋する際に、シールバーに澱粉粉末が堆積して熱伝導が悪くなり、シール不良を引き起こす。 As described in Patent Document 1 and Patent Document 2, as a method of imparting the above-described handling property to a heat-shrinkable film, it is common to attach starch powder on the surface (powdering).
However, since the starch powder is white, the transparency and the gloss of the film are impaired. The starch powder adhered to the surface is not improved in transparency unless it is removed by water or the like, and therefore, it is not suitable for packaging of machine parts and the like for which transparency is strongly required.
Furthermore, powdering powder is likely to fall off the film, and scatters around the film production and secondary processing, and when the bag is used, which may cause contamination of the surrounding environment and inhalation to humans. In addition, when the film is formed into a bag shape by heat sealing, starch powder is deposited on the seal bar, the heat conduction is deteriorated, and sealing failure occurs.

また、特許文献３には、熱収縮性フィルムではないが、平均粒子径が０．５μｍ以上、外層の厚みの２倍以下又は４μｍ以下のうち小さい方である球状シリカを両外層に含有する、滑り性、透明性等に優れた易引き裂き性積層フィルムが記載されている。
本文献においては、外層の厚みよりも著しく大きな粒子を用いた場合には、粒子の脱落や透明性が悪化するとして、粒子の平均粒子径の上限を、外層の厚みの２倍以下、あるいは４μｍの小さい方としている。 Further, in Patent Document 3, both outer layers contain spherical silica which is not a heat-shrinkable film but which is smaller among an average particle diameter of 0.5 μm or more and twice or less of the thickness of the outer layer or 4 μm or less. An easily tearable laminated film excellent in slipperiness, transparency and the like is described.
In the present document, when particles significantly larger than the thickness of the outer layer are used, the upper limit of the average particle diameter of the particles is not more than twice the thickness of the outer layer, or 4 μm. The smaller one.

このように、滑り性等のハンドリング性と、透明性、光沢性とを両立した熱収縮性フィルムは得られていない。   As described above, a heat-shrinkable film having compatibility in handling properties such as slipperiness, transparency and glossiness has not been obtained.

特許第４８４８０２０号広報Patent No. 4848020 PR 特開２０１６−１４７３７３号広報Japanese Patent Application Laid-Open No. 2016-147373 特許第５０６１５２２号広報Patent No. 5061522 public information

本発明は、上記問題点に鑑み、両立の困難であった滑り性と透明性等を兼ね揃えた熱収縮性積層フィルム及びそれから成る袋を提供することを目的とする。   An object of the present invention is to provide a heat-shrinkable laminated film having both slipperiness, transparency, etc. which were difficult to be compatible in view of the above problems, and a bag made of the same.

本発明者は、前記課題を解決するため鋭意研究を重ねた結果、外表面層（Ａ）に、大きい粒子を含有させることで、透明性等を損なわずに滑り性（ハンドリング性）の高い熱収縮性フィルムを得られることを見出した。   As a result of intensive studies to solve the above-mentioned problems, the present inventor contains large particles in the outer surface layer (A), thereby causing thermal property to be high in slipperiness (handling property) without impairing transparency and the like. It has been found that a shrinkable film can be obtained.

一般に、滑り性の改善のために表面に凹凸を設けることは知られているが、フィルムの外表面層に凹凸を与えるような大きな粒子を含有させると、透明性や光沢性が損なわれたり、使用中に粒子が脱落し、ヒートシール性の低下や汚染等の種々の問題を引き起こす。そのため、外表面層に大きな粒子を含有させることは、少なくとも外観（透明性、光沢性）が重視され、その取り扱われ方からみて粒子の脱落が予想されるような物品においてはこれまでは行われていなかった。
しかしながら、本発明者は、熱収縮性積層フィルムを熱収縮させる際には、フィルムを構成する各層の厚みの増加が伴い、外表面層に粒子が含まれている場合には表面にとどまることなく外表面層中に沈降して埋まるため、外表面層に大きい粒子を含有させた場合でも、熱収縮後のフィルムの透明性や光沢性を低下させたり、外表面層から脱落することがないこと、また、熱収縮性積層フィルムにおいては、透明性や光沢性が求められるのも粒子の脱落の危険が高まるのも、実際に利用される熱収縮後であるが、滑り性が求められる場面は、製袋工程等の熱収縮加工前であるということを発見、認識した。そして、このような知見に基づき、外表面層（Ａ）に特定の平均粒子径を有する粒子を含有させれば、熱収縮前にあってはフィルムに滑り性を与え、熱収縮後にあっては透明性や光沢性を低下させたり、脱落したりしない熱収縮性積層フィルムとすることができることを見出し、本発明を完成させた。 Generally, it is known to provide surface irregularities to improve slipperiness, but the inclusion of large particles that impart asperities to the outer surface layer of the film impairs transparency and gloss, The particles fall off during use, causing various problems such as a decrease in heat sealability and contamination. Therefore, the inclusion of large particles in the outer surface layer has hitherto been performed in an article in which at least the appearance (transparency, glossiness) is important and in which the dropping of particles is expected from the handling method. It was not.
However, when thermally shrinking the heat-shrinkable laminated film, the present inventors are accompanied by an increase in the thickness of each layer constituting the film, and when the outer surface layer contains particles, it does not stay on the surface. Because it sinks and is embedded in the outer surface layer, it does not lower the transparency and gloss of the film after heat shrinkage or fall off from the outer surface layer even when large particles are contained in the outer surface layer In heat-shrinkable laminated films, the need for transparency and gloss, and the increased risk of particles falling off, is also after heat shrinking that is actually used, but where the sliding properties are required Discovered and recognized that it is before heat shrink processing such as bag making process. And, if particles having a specific average particle diameter are contained in the outer surface layer (A) based on such findings, the film will have slipperiness before heat shrinkage, and after heat shrinkage The inventors have found that a heat-shrinkable laminated film which does not lower the transparency and glossiness or does not fall off can be found to complete the present invention.

すなわち、本発明は下記の通りである。
〔１〕外表面層（Ａ）を少なくとも一方の最表面に有する熱収縮性積層フィルムであって、
前記外表面層（Ａ）が、当該外表面層（Ａ）の厚みに対して１．２〜１０．０倍の平均粒子径を有する粒子を含む、
熱収縮性積層フィルム。
〔２〕前記外表面層（Ａ）の厚みが０．１〜３．０μｍである、
〔１〕に記載の熱収縮性積層フィルム。
〔３〕前記外表面層（Ａ）が、樹脂又は樹脂組成物と、前記粒子とから構成され、
前記樹脂又は樹脂組成物と前記粒子の屈折率の差が０．０５以下である、
〔１〕又は〔２〕に記載の熱収縮性積層フィルム。
〔４〕流れ方向と横方法の７５℃における熱収縮率が、共に、１０％以上６５％以下である、〔１〕〜〔３〕いずれかに記載の熱収縮性積層フィルム。
〔５〕接着層（Ｂ）、バリア層（Ｃ）及び内表面層（Ｄ）をさらに含み、
外表面層（Ａ）、接着層（Ｂ）、バリア層（Ｃ）及び内表面層（Ｄ）がこの順に積層されている、〔１〕〜〔４〕いずれかに記載の熱収縮性積層フィルム。
〔６〕曇り度が２０％以下である、〔１〕〜〔５〕いずれかに記載の熱収縮性積層フィルム。
〔７〕熱収縮後の曇り度が５０％以下である、〔１〕〜〔６〕いずれかに記載の熱収縮性積層フィルム。
〔８〕〔１〕〜〔７〕いずれかに記載の熱収縮性積層フィルムを含む袋。 That is, the present invention is as follows.
[1] A heat-shrinkable laminated film having an outer surface layer (A) on at least one outermost surface,
The outer surface layer (A) contains particles having an average particle diameter of 1.2 to 10.0 times the thickness of the outer surface layer (A).
Heat shrinkable laminated film.
[2] The thickness of the outer surface layer (A) is 0.1 to 3.0 μm,
The heat-shrinkable laminated film according to [1].
[3] The outer surface layer (A) is composed of a resin or a resin composition and the particles,
The difference between the refractive index of the resin or the resin composition and the particles is 0.05 or less.
The heat-shrinkable laminated film according to [1] or [2].
[4] The heat-shrinkable laminate film according to any one of [1] to [3], wherein the heat shrinkage rates at 75 ° C. in the flow direction and in the transverse direction are both 10% or more and 65% or less.
[5] An adhesive layer (B), a barrier layer (C) and an inner surface layer (D) are further included,
The heat-shrinkable laminated film according to any one of [1] to [4], wherein the outer surface layer (A), the adhesive layer (B), the barrier layer (C) and the inner surface layer (D) are laminated in this order .
[6] The heat-shrinkable laminated film according to any one of [1] to [5], which has a haze of 20% or less.
[7] The heat-shrinkable laminated film according to any one of [1] to [6], which has a haze of 50% or less after heat-shrinkage.
The bag containing the heat-shrinkable laminated film in any one of [8] [1]-[7].

本発明によれば、これまで両立が困難であった滑り性と透明性、光沢性の両方を有し、シール性にも優れた熱収縮性積層フィルムを提供することができる。
また、本発明のフィルムを用いた袋によれば、効率的で確実な包装作業が行える。また熱収縮包装に際しては皺が少なく、光沢及び透明性にも優れるので、美麗に包装することができる。 According to the present invention, it is possible to provide a heat-shrinkable laminated film having both slipperiness, transparency, and gloss, which have hitherto been difficult to achieve simultaneously, and also having excellent sealability.
Moreover, according to the bag using the film of this invention, efficient and reliable packaging operation can be performed. In addition, the heat shrinkable packaging can be beautifully packaged since it has few wrinkles and is excellent in gloss and transparency.

本実施形態の熱収縮性積層フィルムの好ましい層構成を示す模式図である。It is a schematic diagram which shows the preferable laminated constitution of the heat-shrinkable laminated film of this embodiment.

本発明を実施するための形態（以下、「本実施形態」という。）について、以下に具体的に説明するが、本発明はこれに限定されるものではなく、その要旨を逸脱しない範囲で様々な変形が可能である。   The mode for carrying out the present invention (hereinafter referred to as "the present embodiment") will be specifically described below, but the present invention is not limited to this, and various modifications can be made within the scope of the present invention. Variations are possible.

本実施形態の熱収縮性積層フィルムは、少なくとも一方の最表面に位置する外表面層（Ａ）とその他の内層を有する。特に、外表面層（Ａ）、接着層（Ｂ）、バリア層（Ｃ）、内表面層（Ｄ）の少なくとも４層が、この順に積層されたものであることが好ましい。
そして、本実施形態の熱収縮性積層フィルムは、加熱により収縮する特性（熱収縮性）を有しており、これにより、内容物に密着した包装を可能とする。
その熱収縮率に限定はないが、流れ方向と横方法の７５℃における熱収縮率が、共に１０％以上５０％以下であることが好ましい。
ここで、フィルムの流れ方向及び横方向とは、各々、積層フィルムを押出成形した際の長尺方向及び幅方向（流れ方向と直交する方向）をいう。 The heat-shrinkable laminate film of the present embodiment has an outer surface layer (A) positioned on at least one outermost surface and the other inner layer. In particular, it is preferable that at least four layers of the outer surface layer (A), the adhesive layer (B), the barrier layer (C), and the inner surface layer (D) are laminated in this order.
And the heat-shrinkable laminated film of this embodiment has the characteristic (heat-shrinkability) which shrink | contracts by heating, and thereby enables the package closely_contact | adhered to the contents.
Although the heat shrinkage rate is not limited, it is preferable that the heat shrinkage rates at 75 ° C. in the flow direction and in the lateral direction are both 10% or more and 50% or less.
Here, the flow direction and the transverse direction of the film mean the longitudinal direction and the width direction (direction orthogonal to the flow direction) when the laminated film is extrusion-formed, respectively.

本実施形態の熱収縮性積層フィルムにおいて、外表面層（Ａ）は、積層フィルムの強度を保持するための層の１つであり、外表面層（Ａ）が一方の最表面にのみ存在する場合、袋に加工する際には外側に位置させることが好ましい。
本実施形態において外表面層（Ａ）は、樹脂又は樹脂組成物と、外表面層（Ａ）の厚みに対して１．２〜１０．０倍の平均粒子径を有する粒子を含む。本実施形態においては、このように比較的大きな粒子を外表面層（Ａ）に含ませることにより、これまで困難であった透明性、光沢性（熱収縮後）と、滑り性の両立を実現した。 In the heat-shrinkable laminate film of the present embodiment, the outer surface layer (A) is one of the layers for maintaining the strength of the laminate film, and the outer surface layer (A) is present only on one outermost surface. In the case of processing into a bag, it is preferable to be located outside.
In the present embodiment, the outer surface layer (A) contains a resin or resin composition and particles having an average particle diameter of 1.2 to 10.0 times the thickness of the outer surface layer (A). In the present embodiment, by including relatively large particles in the outer surface layer (A) in this way, it is possible to achieve both transparency, gloss (after heat shrinkage) and slipperiness, which had been difficult until now. did.

外表面層（Ａ）に使用する樹脂に限定はないが、溶解温度が比較的高い樹脂、例えば、プロピレン共重合体、エステル共重合体、アミド樹脂等が好ましく使用できる。
エステル共重合体の具体例としては、ポリエチレンテレフタレート、ポリブチレンテレフタレート等が挙げられる。アミド樹脂の具体例としては、ナイロン−６、ナイロン−１２等の脂肪族アミド樹脂；ナイロン−６，６６、ナイロン−６，１２等の脂肪族アミド共重合体；ナイロン−６，６６，１２等の脂肪族三元共重合体が挙げられ、その中でもナイロン−６，６６は高い熱収縮性が得られる点で好ましい。
本実施形態においては、上述の樹脂のみを外表面層（Ａ）の構成材料としてもよいし、上述の樹脂と、後述する各種添加剤を混合した樹脂組成物を外表面層（Ａ）の構成材料として用いてもよい。 The resin used for the outer surface layer (A) is not limited, but a resin having a relatively high melting temperature, for example, a propylene copolymer, an ester copolymer, an amide resin, etc. can be preferably used.
Specific examples of the ester copolymer include polyethylene terephthalate and polybutylene terephthalate. Specific examples of the amide resin include aliphatic amide resins such as nylon-6 and nylon-12; aliphatic amide copolymers such as nylon-6, 66 and nylon-6, 12; nylon-6, 66, 12 and the like Aliphatic terpolymers are preferred, and among them, nylon-6, 66 is preferred in that high heat shrinkability can be obtained.
In the present embodiment, only the above-mentioned resin may be used as the constituent material of the outer surface layer (A), or a resin composition obtained by mixing the above-mentioned resin and various additives described later will be a configuration of the outer surface layer (A). You may use as a material.

本実施形態の熱収縮性積層フィルムは、フィルムの流れ方向、横方向の７５℃における熱収縮率が、共に、１５％以上５０％以下であることがより好ましい。
熱収縮率を高めることにより、熱収縮後の外表面層（Ａ）の厚みがより増加し、粒子の脱落防止効果がより一層高まる。
粒子の脱落を防ぎ、包装体がタイトかつ美麗に包装される点で熱収縮率が２０％以上であることが好ましい。一方、収縮により厚くなりすぎると透明性が悪化するため、熱収縮率は５０％以下が好ましい。
流れ方向及び横方向の熱収縮率が同じである必要はないが、方向による収縮差が２０％以下であると袋トリム部が綺麗になり好ましい。
包装袋に加工した際の外観の点からは、流れ方向及び横方向の７５℃における熱収縮率は、共に２５％以上４５％以下の熱収縮率があることがより好ましく、３０％以上４５％以下があることがなお好ましい。例えば、内容物が肉類の場合に、保存期間が延長できるため好ましい。
フィルムの熱収縮率は、フィルムの延伸温度や延伸倍率を適宜調整することにより容易に調整することができる。
また、包装体がタイトかつ美麗に包装される点で流れ方向と横方向の熱収縮率の合計は６５％以上であることが好ましい。 In the heat-shrinkable laminated film of the present embodiment, it is more preferable that the heat shrinkage ratio at 75 ° C. in the film flow direction and in the lateral direction is both 15% or more and 50% or less.
By increasing the thermal contraction rate, the thickness of the outer surface layer (A) after thermal contraction is further increased, and the falling-off preventing effect of the particles is further enhanced.
The heat shrinkage is preferably 20% or more in terms of preventing the particles from falling off and the package being tightly and beautifully packaged. On the other hand, when the thickness is too thick due to shrinkage, the transparency is deteriorated, so the heat shrinkage rate is preferably 50% or less.
The heat shrinkage rates in the flow direction and the lateral direction do not have to be the same, but if the difference in shrinkage between the directions is 20% or less, the bag trim portion is preferably clean.
From the viewpoint of appearance when processed into a packaging bag, it is more preferable that the thermal shrinkage at 75 ° C. in the flow direction and in the lateral direction both have a thermal shrinkage of 25% or more and 45% or less, and 30% or more and 45% It is more preferable that there be the following. For example, when the content is meat, it is preferable because the storage period can be extended.
The heat shrinkage of the film can be easily adjusted by appropriately adjusting the stretching temperature and the stretching ratio of the film.
In addition, the total thermal contraction rate in the flow direction and the lateral direction is preferably 65% or more in that the package is tightly and beautifully packaged.

外表面層（Ａ）の厚みに限定はないが、透明性や高い熱収縮性を実現するという観点から、０．１〜３．０μｍであることが好ましく、０．１〜２．０μｍであることがより好ましく、０．１〜１．０μｍがあることがさらに好ましい。   Although the thickness of the outer surface layer (A) is not limited, it is preferably 0.1 to 3.0 μm and 0.1 to 2.0 μm from the viewpoint of achieving transparency and high heat shrinkage. It is more preferable that there is 0.1 to 1.0 μm.

本実施形態において外表面層（Ａ）は、その厚みに対して１．２〜１０．０倍の平均粒子径を有する粒子を含有する。
本発明者の研究によれば、粒子の種類は限定されず、種々の粒子を用いて同様の効果が得られることが確認できた。すなわち、有機粒子であってもよいし、無機粒子であってもよいし、有機無機複合粒子であってもよい。溶融押出時の熱でも形状（粒径）が変化しにくいという点では、無機粒子が好ましい。
有機粒子としては、例えば、ポリメタクリル酸メチルやスチレン−アクリル酸メチル共重合体等のアクリル系樹脂粒子；スチレン樹脂粒子；ポリエステル粒子；ナイロン粒子；フッ素樹脂粒子等が挙げられる。また、無機粒子としては、例えば、シリカ、ゼオライト、アルミナ、酸化チタン、酸化ジルコニウム等の金属酸化物粒子や炭酸カルシウム粒子、硫酸バリウム粒子、シリコーン粒子等が挙げられるが、透明性の観点からゼオライト粒子が好ましい。
粒子の形状についても特に限定はなく、針状粒子や平板状粒子であってもよいが、球状粒子の場合には、引っかかりが少なく取扱い性に優れ、脱落が少ないことやフィルムの滑り性の点でも好ましい。 In the present embodiment, the outer surface layer (A) contains particles having an average particle diameter of 1.2 to 10.0 times the thickness.
According to the research of the present inventor, it has been confirmed that the kind of particles is not limited, and similar effects can be obtained using various particles. That is, it may be organic particles, inorganic particles, or organic-inorganic composite particles. Inorganic particles are preferred in that the shape (particle diameter) is unlikely to change even by heat during melt extrusion.
Examples of the organic particles include acrylic resin particles such as polymethyl methacrylate and styrene-methyl acrylate copolymer; styrene resin particles; polyester particles; nylon particles; and fluorine resin particles. Further, examples of the inorganic particles include metal oxide particles such as silica, zeolite, alumina, titanium oxide and zirconium oxide, calcium carbonate particles, barium sulfate particles, silicone particles and the like, but zeolite particles from the viewpoint of transparency Is preferred.
The shape of the particles is also not particularly limited, and may be needle-like particles or tabular particles, but in the case of spherical particles, there is little catching, excellent handleability, little falling off, and slipperiness of the film. But it is preferable.

粒子の平均粒子径が、外表面層（Ａ）の厚みに対して１．２〜１０．０倍であると、熱収縮前においてフィルム表面に凹凸を得ることができ、滑り性に優れたフィルムとすることができる。
ここで、平均粒子径とは、コールター法によって決定される平均粒子径をいい、ＩＳＯ １３３１９に従って測定できる。
粒子の平均粒子径が外表面層（Ａ）の厚みに対して１０．０倍を超えるとフィルム表面が粗面化し、熱収縮後の透明性が劣るだけでなく、熱収縮後においても粒子の脱落が生じる。 When the average particle diameter of the particles is 1.2 to 10.0 times the thickness of the outer surface layer (A), it is possible to obtain irregularities on the film surface before heat shrinkage, and a film excellent in slipperiness It can be done.
Here, the average particle size refers to the average particle size determined by the Coulter method, which can be measured according to ISO 13319.
When the average particle size of the particles exceeds 10.0 times the thickness of the outer surface layer (A), the film surface is roughened, and the transparency after heat shrinkage is not only inferior, but also after heat shrinkage. Dropout occurs.

滑り性と熱収縮後の粒子脱落防止の点から、外表面層（Ａ）の厚みに対する粒子の平均粒子径は、２．０〜９．０倍であることが好ましく、３．０〜７．０倍であることがより好ましい。
粒子の平均粒子径が、外表面層（Ａ）の厚みに対して１．２倍以下であると、製袋する際にシールバーに付着し易くなり、シール性能が悪くなる。 The average particle diameter of the particles with respect to the thickness of the outer surface layer (A) is preferably 2.0 to 9.0 times, from the viewpoint of slipperiness and prevention of particles falling off after thermal contraction, and 3.0 to 7. More preferably, it is 0 times.
When the average particle diameter of the particles is 1.2 times or less of the thickness of the outer surface layer (A), the particles easily adhere to the seal bar during bag-making, and the sealing performance is deteriorated.

外表面層（Ａ）の基材材料と含有粒子の屈折率の差が小さいほど透明性が良好なフィルムを得ることができる。したがって、外表面層（Ａ）を構成する樹脂（外表面層（Ａ）が、樹脂及び上記粒子以外の添加剤を含む場合には、樹脂及び当該添加剤からなる樹脂組成物）と粒子の屈折率の差が０．０５以下であることが好ましく、０．０３以下であることがより好ましい。
なお、各成分の屈折率は、ＪＩＳ Ｋ７１４２「プラスチックの屈折率測定方法」のうち、Ｂ法（顕微鏡を用いる液浸法（ベッケ線法））によって測定される値をいう。 The smaller the difference in refractive index between the base material of the outer surface layer (A) and the contained particles, the better the film can be obtained. Therefore, when the resin constituting the outer surface layer (A) (when the outer surface layer (A) contains the resin and the additive other than the particles, the resin and the resin composition comprising the additive) and the refraction of the particles The difference in rate is preferably 0.05 or less, more preferably 0.03 or less.
In addition, the refractive index of each component says the value measured by B method (the liquid immersion method (Becke-wire method) using a microscope) among JISK7142 "refractive index of plastics".

外表面層（Ａ）の粒子の含有量に限定はないが、滑り性及び透明性の点で０．０２〜１．００質量％であることが好ましく、０．１０〜０．８０質量％であることがより好ましい。   The content of particles in the outer surface layer (A) is not limited, but is preferably 0.02 to 1.00% by mass in terms of slipperiness and transparency, and 0.10 to 0.80% by mass It is more preferable that

外表面層（Ａ）には、必要に応じて、グリセリン脂肪酸エステル系界面活性剤等の界面活性剤；酸化防止剤；帯電防止剤；石油樹脂、ミネラルオイル、脂肪酸アミド系の滑剤等の熱収縮性フィルムや袋用フィルムの分野において公知の各種添加剤を透明性を損なわない程度に添加することができる。中でも、滑剤として脂肪酸アミドを添加すると、フィルム表面のベタツキが抑えられ、フィルムの滑り性が良好となる。   In the outer surface layer (A), if necessary, a surfactant such as glycerin fatty acid ester surfactant; antioxidant; antistatic agent; heat shrinkage such as petroleum resin, mineral oil, fatty acid amide lubricant and the like Various additives known in the field of organic films and films for bags can be added to the extent that they do not impair transparency. Above all, when fatty acid amide is added as a lubricant, the stickiness of the film surface is suppressed and the slipperiness of the film becomes good.

本実施形態の熱収縮性積層フィルムは、一方の最表面に位置する外表面層（Ａ）とその他の内層を有し、特に、外表面層（Ａ）、接着層（Ｂ）、バリア層（Ｃ）、内表面層（Ｄ）の少なくとも４層が、この順に積層されたものであることが好ましい。
さらに、本実施形態の熱収縮性積層フィルムは、図１に示すように、上述の外表面層（Ａ）１、接着層（Ｂ）２、バリア層（Ｃ）３、及び内表面層（Ｄ）５の他にも、例えば、バリア層（Ｃ）と内表面層（Ｄ）とを接着するための接着層（Ｅ）４等、必要に応じて各種の層を有することができる。
以下に、外表面層（Ａ）以外の層について説明する。 The heat-shrinkable laminate film of the present embodiment has an outer surface layer (A) and other inner layers located on one outermost surface, and in particular, the outer surface layer (A), the adhesive layer (B), the barrier layer ( C) At least four layers of the inner surface layer (D) are preferably laminated in this order.
Furthermore, as shown in FIG. 1, the heat-shrinkable laminated film of the present embodiment has the above-mentioned outer surface layer (A) 1, adhesive layer (B) 2, barrier layer (C) 3 and inner surface layer (D). In addition to 5), various layers may be provided as needed, such as an adhesive layer (E) 4 for bonding the barrier layer (C) and the inner surface layer (D), for example.
The layers other than the outer surface layer (A) will be described below.

内表面層（Ｄ）は、袋に加工した場合に最も内側となり、袋を密封するためのヒートシール層となる層である。この層に使用する樹脂は、重ねシール性の点において、外表面層（Ａ）に使用する樹脂より融解温度が６５〜１５０℃低い樹脂であることが好ましい。例えば、ポリエチレン；エチレン−α−オレフィン共重合体、エチレン−酢酸ビニル共重合体等のエチレン共重合体等、或いはそれらの混合物等から選んで使用できる。その中でもエチレン−α−オレフィン共重合体が、延伸性、ヒートシール性に優れているので好ましい。
内表面層（Ｄ）にはさらに、グリセリン脂肪酸エステル等の界面活性剤；酸化防止剤；帯電防止剤；石油樹脂、ミネラルオイル、脂肪酸アミド等の滑剤；酸化珪素、炭酸カルシウム、タルク等のアンチブロッキング剤；、抗菌剤等の各種添加剤が、シール性、透明性を損なわない程度に添加されていても構わない。
フィルム全層から外表面層（Ａ）のみ除いたフィルム構成層の厚みの合計（図１中に示す６の範囲）に対する内表面層（Ｄ）の厚みの比率（以下、対外表面層除く厚み比率、ということもある）は、ヒートシール性や高い熱収縮性の観点から、５〜６０％であることが好ましく、１０〜２５％がより好ましい。 The inner surface layer (D) is a layer which becomes the innermost when processed into a bag and becomes a heat seal layer for sealing the bag. The resin used for this layer is preferably a resin having a melting temperature lower than that of the resin used for the outer surface layer (A) by 65 to 150 ° C. in terms of lap sealability. For example, polyethylene, ethylene-α-olefin copolymer, ethylene copolymer such as ethylene-vinyl acetate copolymer, etc., or a mixture thereof can be used. Among them, ethylene-α-olefin copolymers are preferable because they are excellent in stretchability and heat sealability.
Further, in the inner surface layer (D), surfactants such as glycerin fatty acid ester; antioxidants; antistatic agents; lubricants such as petroleum resin, mineral oil, fatty acid amide, etc .; antiblocking such as silicon oxide, calcium carbonate, talc etc. Agents, and various additives such as antibacterial agents may be added to the extent that the sealing properties and transparency are not impaired.
Ratio of the thickness of the inner surface layer (D) to the total thickness (range 6 shown in FIG. 1) of the thickness of the film constituting layer excluding only the outer surface layer (A) from the entire film layer (hereinafter referred to as thickness ratio excluding outer surface layer) Or the like) is preferably 5 to 60%, more preferably 10 to 25%, from the viewpoint of heat sealability and high heat shrinkability.

バリア層（Ｃ）は、ガスバリア性、特に酸素バリア性を有することで、袋としたときに内容物の酸化劣化を防止する機能を果たす層である。バリア層の材料に特に限定はないが、酸素バリア性能の観点から塩化ビニリデン共重合体を好ましく用いることができる。塩化ビニリデン共重合体とは、塩化ビニリデンとその他モノマーとの重合体である。その他モノマーの種類は特に限定しないが、塩化ビニルモノマー又はメチルアクリレートモノマーが好ましい。塩化ビニリデン共重合体における塩化ビニリデンの含有比率は、６０〜９５重量％が好ましく、７０〜９３重量％がより好ましい。
塩化ビニリデン共重合体以外のバリア性樹脂としては、特に限定されないが、例えば、塩化ビニリデン単独重合体、エチレン−ビニルアルコール共重合体、ポリアミド系樹脂、ポリクロロトリフルオロエチレン系樹脂、ポリアクリロニトリル系樹脂が挙げられる。
なお、これらのバリア性樹脂は、１種単独で用いても、２種以上を併用してもよい。 内容物の品質維持のため、バリア層（Ｃ）の酸素透過率は４００ｃｃ／ｍ2・ｄａｙ・ＭＰａ（２３℃×６５％ＲＨ）以下であることが好ましい。
なお、バリア層には、溶融加工を容易にし、安定的に製造するために、熱安定剤や可塑剤を本発明の効果に影響しない範囲で添加しても良い。さらに脂肪酸アミド系滑剤等の滑剤や、酸化珪素、炭酸カルシウム、タルク等の紛体を添加しても良い。これらの添加剤は、１〜１０質量％の範囲で添加することが好ましい。
フィルム全層から外表面層（Ａ）のみ除いたフィルム構成層の厚みの合計に対するバリア層（Ｃ）の厚み比率は、良好な酸素透過率の観点から、５〜３０％が好ましく、６〜２０％であることがより好ましい。 The barrier layer (C) is a layer that has a gas barrier property, in particular, an oxygen barrier property, and when it is formed into a bag, functions to prevent the oxidative deterioration of the contents. The material of the barrier layer is not particularly limited, but in view of oxygen barrier performance, a vinylidene chloride copolymer can be preferably used. The vinylidene chloride copolymer is a polymer of vinylidene chloride and another monomer. The type of other monomers is not particularly limited, but vinyl chloride monomers or methyl acrylate monomers are preferred. 60-95 weight% is preferable and, as for the content rate of the vinylidene chloride in a vinylidene chloride copolymer, 70-93 weight% is more preferable.
The barrier resin other than the vinylidene chloride copolymer is not particularly limited. For example, vinylidene chloride homopolymer, ethylene-vinyl alcohol copolymer, polyamide resin, polychlorotrifluoroethylene resin, polyacrylonitrile resin Can be mentioned.
These barrier resins may be used alone or in combination of two or more. In order to maintain the quality of the contents, the oxygen permeability of the barrier layer (C) is preferably 400 cc / m 2 · day · MPa (23 ° C. × 65% RH) or less.
In order to facilitate melt processing and stably manufacture the barrier layer, a heat stabilizer or a plasticizer may be added within a range not affecting the effect of the present invention. Furthermore, lubricants such as fatty acid amide lubricants and powders such as silicon oxide, calcium carbonate and talc may be added. These additives are preferably added in the range of 1 to 10% by mass.
The thickness ratio of the barrier layer (C) to the total thickness of the film constituting layers obtained by removing only the outer surface layer (A) from the entire film layer is preferably 5 to 30%, from the viewpoint of good oxygen permeability, More preferably, it is%.

次に、接着層（Ｂ）は、外表面層（Ａ）とバリア層（Ｃ）とを接着する層であり、このような層を設けることで接着力が向上する。接着層（Ｂ）の材料には、ポリオレフィン系樹脂を用いることが好ましい。
ポリオレフィン系樹脂は、ポリエチレン；ポリエチレンアイオノマー；ポリプロピレン；エチレン−α−オレフィン共重合体、エチレン−酢酸ビニル共重合体等、エチレン−アクリル酸共重合体、エチレン−アクリル酸エチル共重合体、エチレン−無水マレイン酸共重合体等のエチレン共重合体や変性ポリオレフィン等が使用できる。
接着層（Ｂ）の上下に、層を接着させることを目的として、さらに接着層（Ｂ’）が存在していても良い。
フィルム全層から外表面層（Ａ）のみ除いたフィルム構成層の厚みの合計に対する接着層（Ｂ）の厚み比率は、安定な延伸性が得られる観点から、１０〜７０％であることが好ましく、２５〜６５％がより好ましい。 Next, the adhesive layer (B) is a layer for adhering the outer surface layer (A) and the barrier layer (C), and the adhesion is improved by providing such a layer. It is preferable to use polyolefin resin as a material of the adhesive layer (B).
The polyolefin resin is polyethylene; polyethylene ionomer; polypropylene; ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer, etc., ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-anhydride Ethylene copolymers such as maleic acid copolymers and modified polyolefins can be used.
An adhesive layer (B ′) may further be present on the upper and lower sides of the adhesive layer (B) for the purpose of adhering the layers.
The thickness ratio of the adhesive layer (B) to the total thickness of the film constituting layers obtained by removing only the outer surface layer (A) from the entire film layer is preferably 10 to 70% from the viewpoint of obtaining stable stretchability. And 25 to 65% are more preferable.

熱収縮性熱収縮性積層フィルムは、延伸工程の前に電離性放射線を照射しても良い。これにより、特に接着層（Ｂ）が架橋され、フィルムの延伸性が付与される。電離性放射線の効果深度は加速電圧で調節することが一般的である。電離性放射線照射としては、α線、β線、γ線、中性子線、電子線等の電離性放射線を照射する。   The heat-shrinkable heat-shrinkable laminated film may be irradiated with ionizing radiation prior to the stretching step. Thereby, in particular, the adhesive layer (B) is crosslinked, and the stretchability of the film is imparted. The depth of effect of ionizing radiation is generally adjusted by an accelerating voltage. As the ionizing radiation, ionizing radiation such as α-ray, β-ray, γ-ray, neutron beam and electron beam is applied.

本実施形態の熱収縮性積層フィルムの製造方法に限定はなく、例えば、外表面層（Ａ）の構成材料として予め粒子を混合した樹脂組成物を用意し、これを用いて従来公知の方法で多層フィルムを製造すればよい。
積層フィルムは、具体的には、シングルバブルインフレーション法、ダブルバブルインフレーション法、トリプルバブルインフレーション法、テンター法等の方法によって製造することができる。
得られるフィルムの諸物性のバランスからダブルバブルインフレーション法、トリプルバブルインフレーション法が好ましい。
ここではダブルバブルインフレーション法についてその概略を説明する。 There is no limitation on the method of producing the heat-shrinkable laminated film of the present embodiment. For example, a resin composition in which particles are mixed in advance is prepared as a constituent material of the outer surface layer (A). A multilayer film may be produced.
Specifically, the laminated film can be produced by a method such as a single bubble inflation method, a double bubble inflation method, a triple bubble inflation method, or a tenter method.
The double bubble inflation method and the triple bubble inflation method are preferable from the balance of various physical properties of the obtained film.
Here, the outline of the double bubble inflation method will be described.

各層の構成材料である樹脂（樹脂組成物）のペレットを、樹脂の融解温度以上で溶融し、層数に対応した台数の押出機を用いて各層を同時に押出す。ポリマーパイプ、ダイスを介してチューブ状に連続押出成形して積層フィルムとする。これを水冷等により冷却固化する。
次に、外表面層（Ａ）の方から電離性放射線を照射し、所望のゲル分率に架橋する。照射の度合いとしては、延伸性の点で、加速電圧は１５０〜３００ｋＶで、照射量は２０〜１５０ｋＧｙが好ましい。
次にチューブ状のフィルムを延伸工程へと導く。フィルムの延伸倍率は、熱収縮性、熱収縮後の良好な透明性、生産安定性の面から、流れ方向（ＭＤ）及び幅方向（ＴＤ）共に２．０〜６．０倍の延伸を行うのが好ましく、２．５〜４．０倍がより好ましい。延伸に先立ち６０〜９８℃で予熱し延伸するとより好ましい。延伸方法としては、透明性の点からは、バブルインフレーション法による延伸が好ましい。
熱収縮性積層フィルムの延伸温度は、製袋加工をした後の寸法安定性、熱収縮性、収縮後の良好な透明性を得るには５０〜９０℃とするのが好ましい。さらに６０〜８０℃で行うのがより好ましい。なお、延伸温度は、バブルインフレーション法の場合であれば、インフレーションバブルの延伸し始めのネック部と呼ばれる部分のフィルム表面を温度計で実測することにより測定することができる。
本実施形態においては、延伸後、連続製袋機での使用時、スリット時、袋詰め時に操作性を損なうフィルムのカールを抑制するため、ヒートセットと呼ばれている熱処理を４０〜８０℃の温度で数秒間行うことが好ましい。
さらに、本実施形態の熱収縮性積層フィルムには、必要に応じ、コロナ処理やプラズマ処理等の表面処理、印刷処理が行われてもよい。 Pellets of a resin (resin composition), which is a constituent material of each layer, are melted at a temperature equal to or higher than the melting temperature of the resin, and the layers are simultaneously extruded using the number of extruders corresponding to the number of layers. The polymer pipe is continuously extruded into a tube shape through a die to form a laminated film. This is cooled and solidified by water cooling or the like.
Next, ionizing radiation is irradiated from the outer surface layer (A) to crosslink it to a desired gel fraction. The degree of irradiation is preferably 150 to 300 kV at an accelerating voltage of 20 to 150 kGy in terms of stretchability.
The tubular film is then led to the drawing step. The draw ratio of the film is 2.0 to 6.0 times in both the machine direction (MD) and the cross direction (TD) from the viewpoint of heat shrinkage, good transparency after heat shrinkage, and production stability. Is preferable, and 2.5 to 4.0 times is more preferable. It is more preferable to preheat and stretch at 60 to 98 ° C. prior to stretching. From the viewpoint of transparency, as the stretching method, stretching by the bubble inflation method is preferable.
The stretching temperature of the heat-shrinkable laminated film is preferably 50 to 90 ° C. in order to obtain dimensional stability after bag-making, heat-shrinkability, and good transparency after shrinkage. It is more preferable to carry out at 60 to 80 ° C. In the case of the bubble inflation method, the stretching temperature can be measured by measuring the film surface of a portion called the neck portion at which the inflation bubble starts stretching with a thermometer.
In the present embodiment, heat treatment called heat setting is performed at 40 to 80 ° C. in order to suppress curling of the film which impairs operability at the time of slitting and bagging at the time of slitting and when used in a continuous bag making machine after stretching. It is preferable to carry out for a few seconds at the temperature.
Furthermore, the heat-shrinkable laminated film of the present embodiment may be subjected to surface treatment such as corona treatment or plasma treatment, or printing treatment, if necessary.

本実施形態において熱収縮性積層フィルムの厚みの限定はないが、バリア性、袋の強度、生産性の点で２０〜１５０μｍが好ましく、２５〜８０μｍがより好ましい。
上記のようなインフレーション法によりフィルムを製造する場合には、同時二軸延伸における面積延伸倍率を調整することによって、フィルム厚みを調整することが可能である。 In the present embodiment, the thickness of the heat-shrinkable laminated film is not limited, but is preferably 20 to 150 μm, more preferably 25 to 80 μm, in terms of barrier property, strength of the bag, and productivity.
When producing a film by the above-mentioned inflation method, it is possible to adjust film thickness by adjusting the area draw ratio in simultaneous biaxial stretching.

本実施形態の熱収縮性積層フィルムは、袋に加工して使用できる。
例えば、一般に底シールバッグと呼ばれるような、２辺シール式の袋として使用できる。このような袋は、主に筒状、チューブ状のフィルムに対して、巾方向にシールとカットを行うことにより製造することができる。袋への加工と、包装を同時に行うこともできる。例えば、筒状、チューブ状のフィルムに対して、巾方向にシールとカットを行い、内容物を入れて、口をシールして製造する。
また、一般にサイドシールバッグと呼ばれる袋としても使用できる。このような袋はフィルムに対して溶断シール等を行うことによって製造することができる。 The heat-shrinkable laminated film of the present embodiment can be used by processing it into a bag.
For example, it can be used as a two-sided sealed bag generally called a bottom sealed bag. Such a bag can be manufactured mainly by sealing and cutting a tubular or tubular film in the width direction. It can be processed at the same time as packaging and packaging. For example, a tubular or tubular film is sealed and cut in the width direction, the contents are put, and the mouth is sealed and manufactured.
Moreover, it can also be used as a bag generally called a side seal bag. Such a bag can be manufactured by melt-sealing a film or the like.

本実施形態の熱収縮性積層フィルムの透明性に関しては、内容物充填時の視認性の点から、その曇り度（ＨＡＺＥ）（熱収縮前）が２０％以下であることが好ましく、１５％以下であることがより好ましく、１０％以下であることがさらに好ましい。
ここで、曇り度は、ＡＳＴＭ Ｄ−１００３に従って測定することができる。 With regard to the transparency of the heat-shrinkable laminated film of the present embodiment, the haze (HAZE) (before thermal contraction) is preferably 20% or less, preferably 15% or less, from the viewpoint of visibility when the contents are filled. Is more preferably 10% or less.
Here, the haze can be measured according to ASTM D-1003.

本実施形態の熱収縮性積層フィルムで真空包装された包装体は、概ね７０〜１３０℃程度に加熱すると（例えば、７０〜１００℃の熱水槽に数秒間浸漬したり、７０〜１３０℃の雰囲気下に数秒間静置する等の方法で加熱すると）、熱収縮性積層フィルムが熱収縮してタイトで美麗な包装体に仕上がる。
例えば、生肉包装では、タイトに緊張包装することによって、包装肉の見栄えが良くなり商品価値が上がる。また、肉汁や血の溜まりを抑制し、結果として内容物の腐敗を抑制する効果も得られる。
包装を美麗に仕上げると共に内容物の視認性を保って商品価値を上げるためには、熱収縮後のフィルムも良好な透明性と色調を示すことが好ましい。そのような観点から、本実施形態の熱収縮性積層フィルムは、熱収縮後の曇り度が５０％以下であることが好ましく、４０％以下であることがより好ましく、３０％以下であることがさらに好ましい。ここで、熱収縮後とは、フィルムを７５℃の温水槽に４秒間浸漬した後のことをいう。 The package vacuum-wrapped with the heat-shrinkable laminated film of the present embodiment is heated to about 70 to 130 ° C. (for example, dipped in a 70 to 100 ° C. heat water bath for several seconds, or 70 to 130 ° C. atmosphere) When it is heated by a method such as standing still for several seconds under), the heat-shrinkable laminated film is thermally shrunk and finished into a tight and beautiful package.
For example, in raw meat packaging, by tightly and tightly packing, the appearance of the packaged meat is improved and the commercial value is increased. In addition, the effect of suppressing the accumulation of meat and blood and, as a result, suppressing the decay of the contents can also be obtained.
In order to finish the package beautifully and maintain the visibility of the contents to increase the commercial value, it is preferable that the heat-shrinkable film also exhibit good transparency and color tone. From such a point of view, the heat-shrinkable laminated film of this embodiment preferably has a haze of 50% or less after heat-shrinkage, more preferably 40% or less, and 30% or less More preferable. Here, the term “after thermal contraction” means that the film is immersed in a 75 ° C. water bath for 4 seconds.

ハンドリング性の点で、前記外表面層（Ａ）同士の静止摩擦係数が、０．１より大きく、１．０を超えないことが好ましい。静止摩擦係数が１．０以下であると、フィルム原反を良好に繰り出すことができ、０．１以上であると滑りすぎて製袋機内のローラーに巻き付く等といった恐れもなく、良好な製袋性が得られる。   From the viewpoint of handleability, the static friction coefficient between the outer surface layers (A) is preferably greater than 0.1 and not more than 1.0. When the coefficient of static friction is 1.0 or less, the original film can be drawn out well, and if it is 0.1 or more, there is no risk that the film slips too much and is wound around a roller in the bag making machine, etc. The bag property is obtained.

以下に実施例と比較例を用いて、本発明をより詳細に説明する。
なお、各種物性の評価方法は下記の通りである。ここで、熱収縮性積層フィルムの押出機からの流れ方向（長尺方向）をＭＤ方向、それと直行する横方向（幅方向）をＴＤ方向と呼ぶ。
《平均粒子径》
測定装置：平均粒子径は、日科機株式会社製のコールターマルチサイザー粒子測定装置ＴＡ−ＩＩ型を用いた。
測定方法：ＩＳＯ１３３１９「粒径分布の求め方−電気検出ゾーン法」に従って測定を行い、ＪＩＳ Ｚ ８８１９−２に従って平均粒子径を算出した。 Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples.
In addition, the evaluation method of various physical properties is as follows. Here, the flow direction (long direction) of the heat-shrinkable laminated film from the extruder is referred to as the MD direction, and the transverse direction (width direction) orthogonal thereto is referred to as the TD direction.
<< Average particle size >>
Measurement device: The average particle diameter used Coulter multisizer particle measurement device TA-II type manufactured by Nikkaki Co., Ltd.
Measurement method: Measurement was performed according to ISO13319 "How to determine particle size distribution-electrical detection zone method", and the average particle size was calculated according to JIS Z 8819-2.

《７５℃における熱収縮率の評価》
測定方法：ＡＳＴＭ Ｄ−２７３２に従って測定を行った。具体的には、以下の手順で測定を行った。
（ｉ）測定試料（実施例のフィルム）の流れ方向（ＭＤ）及び横方向（ＴＤ）に１００ｍｍの間隔をあけて印をつけ、７５℃の温水槽に４秒間浸漬して自由熱収縮させた。
（ｉｉ）収縮後、印の間隔を測定し、次式よりフィルムの熱収縮率を求めた。
７５℃における熱収縮率（％）
＝（（１００（ｍｍ）−収縮後の間隔（ｍｍ））／１００（ｍｍ））×１００ << Evaluation of thermal contraction rate at 75 ° C >>
Measurement method: Measurement was performed according to ASTM D-2732. Specifically, measurement was performed according to the following procedure.
(I) The flow direction (MD) and the transverse direction (TD) of the measurement sample (the film of the example) were marked at intervals of 100 mm and immersed in a 75 ° C. water bath for 4 seconds for free heat contraction .
(Ii) After shrinkage, the distance between the marks was measured, and the heat shrinkage of the film was determined by the following equation.
Thermal contraction rate at 75 ° C (%)
= ((100 (mm)-interval after contraction (mm)) / 100 (mm)) x 100

《熱収縮前の曇り度》
測定装置：日本電色工業社製ＮＤＨ２０００曇り度測定器（ＨＡＺＥメーター、商品名）を用いた。
測定方法：ＡＳＴＭ Ｄ−１００３に従って測定を行った。具体的には、測定試料（実施例のフィルム）を２枚に重ね合わせ、その曇り度（％）を測定した。曇り度の値が小さいほど透明性が高いことを意味する。 «Haze before heat shrinkage»
Measurement device: NDH 2000 haze measurement device (HAZE meter, trade name) manufactured by Nippon Denshoku Industries Co., Ltd. was used.
Measurement method: Measurement was performed according to ASTM D-1003. Specifically, measurement samples (the films of the examples) were superimposed on two sheets, and their haze (%) was measured. The smaller the haze value, the higher the transparency.

《熱収縮後の曇り度》
測定装置：日本電色工業社製ＮＤＨ２０００曇り度測定器（ＨＡＺＥメーター）を用いた。
測定方法：ＡＳＴＭ Ｄ−１００３に従って測定した。具体的には、測定試料（実施例のフィルム）を７５℃の温水槽に４秒間浸漬して自由熱収縮させ、その曇り度を測定した。曇り度の値が小さいほど透明性が高いことを意味する。 << Haze after heat shrinkage >>
Measuring device: NDH2000 haze measurement device (HAZE meter) made by Nippon Denshoku Industries Co., Ltd. was used.
Measurement method: Measured according to ASTM D-1003. Specifically, the measurement sample (film of the example) was immersed in a 75 ° C. water bath for 4 seconds for free heat contraction, and the haze was measured. The smaller the haze value, the higher the transparency.

《酸素バリア性の評価（酸素透過率）》
測定装置：ＭＯＣＯＮ社製の酸素透過分析装置（ＯＸ−ＴＲＡＮ（登録商標）２００Ｈ）を使用した。
測定方法：測定試料（実施例、比較例のフィルム）を６５％ＲＨ、温度２３℃の下に置き、３時間経過後の酸素透過率（ｃｃ／ｍ2・ｄａｙ・ＭＰａ）の値を測定した。酸素透過率が小さいほど酸素バリア性が大きいことを意味する。 << Evaluation of oxygen barrier properties (oxygen permeability) >>
Measurement device: An oxygen permeation analyzer (OX-TRAN (registered trademark) 200H) manufactured by MOCON was used.
Measurement method: Measurement samples (films of the examples and comparative examples) were placed at a temperature of 23 ° C. under 65% RH, and the value of oxygen permeability (cc / m 2 · day · MPa) after 3 hours was measured . The smaller the oxygen permeability, the higher the oxygen barrier property.

《滑り性の評価（静止摩擦係数）》
測定装置：東洋精機製ＴＲ−２摩擦測定機を使用した。
測定方法：ＪＩＳ−Ｋ−７１２５「摩擦係数試験方法」に従って測定を行った。具体的には、実施例、比較例の多層フィルムを物理的に剥離させ、外表面層（Ａ）のみとし、外表面層（Ａ）の最表面側の静止摩擦係数を測定した。静止摩擦係数の値が大きいほど滑り性に劣ることを意味する。 Evaluation of slipperiness (coefficient of static friction)
Measuring device: A Toyo Seiki TR-2 friction measuring device was used.
Measurement method: It measured according to JIS-K-7125 "friction coefficient test method". Specifically, the multilayer films of Examples and Comparative Examples were physically peeled off to make only the outer surface layer (A), and the coefficient of static friction on the outermost surface side of the outer surface layer (A) was measured. As the value of the coefficient of static friction is larger, it means that the slipperiness is inferior.

［実施例１−３、８、９及び１２］
ダブルバブルインフレーション法にて、５層の積層フィルムを作成した。
表１に示す樹脂又は樹脂組成物を用いて、対外表面層除く厚み比率が接着層（Ｂ）＝３５％、バリア層（Ｃ）＝１０％、接着層（Ｅ）＝３０％、内表面層（Ｄ）＝２５％となるような樹脂押出量として、ダブルバブルインフレーション法にて５層フィルムを成形した。
その後、ＭＤ方向及びＴＤ方向に表１に示した延伸倍率で２軸延伸を行い、全層及び外表面層（Ａ）の厚みが表１に示した通りである延伸積層フィルムを得た。なお、ＭＤ方向の延伸倍率はバブル間のピンチロールの速度比で調節し、ＴＤ方向の延伸倍率はバブルに封入するエアーの体積によって調節した。
外表面層（Ａ）は、ナイロン−６，６６（屈折率 １．５３）に、ゼオライト粒子（水澤化学工業株式会社製 ＪＣ−２０、屈折率 １．５０、平均粒子径２μｍ）を表に示す添加量となるように添加した樹脂組成物を用いて形成した。 [Examples 1-3, 8, 9 and 12]
A 5-layer laminated film was prepared by the double bubble inflation method.
Using the resin or resin composition shown in Table 1, the thickness ratio excluding the outer surface layer is adhesion layer (B) = 35%, barrier layer (C) = 10%, adhesion layer (E) = 30%, inner surface layer A five-layer film was formed by a double bubble inflation method as a resin extrusion amount such that (D) = 25%.
Thereafter, biaxial stretching was performed in the MD direction and the TD direction at the draw ratio shown in Table 1 to obtain a stretched laminated film in which the thicknesses of all layers and the outer surface layer (A) were as shown in Table 1. The draw ratio in the MD direction was adjusted by the speed ratio of the pinch roll between the bubbles, and the draw ratio in the TD direction was adjusted by the volume of air sealed in the bubble.
The outer surface layer (A) shows zeolite particles (JC-20 manufactured by Mizusawa Chemical Industry Co., Ltd., refractive index 1.50, average particle diameter 2 μm) in nylon-6, 66 (refractive index 1.53). It formed using the resin composition added so that it might become an addition amount.

［実施例４］
外表面層（Ａ）に添加する粒子としてポリメタクリル酸メチル粒子（株式会社日本触媒製 エポスターＭＡ１００２、屈折率 １．５１、平均粒子径２μｍ）を用いた以外は実施例１と同様にして、延伸積層フィルムを得た。 Example 4
Stretching was carried out in the same manner as in Example 1 except that polymethyl methacrylate particles (Nippon Shokuhin Co., Ltd. Eper MA1002, refractive index 1.51, average particle diameter 2 μm) were used as particles to be added to the outer surface layer (A). A laminated film was obtained.

［実施例５、６］
外表面層（Ａ）に添加する粒子として、ゼオライト粒子（水澤化学工業株式会社製 ＪＣ−５０、屈折率 １．５０、平均粒子径５μｍ）を用いた以外は実施例１と同様にして、延伸積層フィルムを得た。 [Examples 5, 6]
As the particles to be added to the outer surface layer (A), stretching was performed in the same manner as in Example 1, except that zeolite particles (JC-50 manufactured by Mizusawa Chemical Industry Co., Ltd., refractive index 1.50, average particle diameter 5 μm) were used. A laminated film was obtained.

［実施例７］
外表面層（Ａ）に添加する粒子として、ポリメタクリル酸メチル粒子（株式会社日本触媒製 エポスターＭＡ１０１０、屈折率 １．５１、平均粒子径１０μｍ）を用いた以外は実施例１と同様にして、延伸積層フィルムを得た。 [Example 7]
As particles added to the outer surface layer (A), in the same manner as in Example 1, except that polymethyl methacrylate particles (manufactured by Nippon Shokuhin Co., Ltd. Eper MA1010, refractive index 1.51, average particle diameter 10 μm) were used, A stretched laminated film was obtained.

［実施例１０］
外表面層（Ａ）に添加する粒子として、シリカ粒子（株式会社アドマテックス製 ＳＯ−Ｅ６、屈折率 １．４５、平均粒子径２μｍ）を用いた以外は実施例１と同様にして、延伸積層フィルムを得た。 [Example 10]
As the particles to be added to the outer surface layer (A), stretched and laminated in the same manner as in Example 1 except that silica particles (SO-E6 manufactured by Admatex Co., Ltd., refractive index 1.45, average particle diameter 2 μm) were used. I got a film.

［実施例１１］
外表面層（Ａ）に添加する粒子として、炭酸カルシウム粒子（白石工業株式会社製 Ｓｉｌｖｅｒ−Ｗ、屈折率 １．６０、平均粒子径１．５μｍ）を用いた以外は実施例１と同様にして、延伸積層フィルムを得た。 [Example 11]
As particles added to the outer surface layer (A), the same procedure as in Example 1 was used except that calcium carbonate particles (Silver-W, manufactured by Shiroishi Kogyo Co., Ltd., refractive index 1.60, average particle diameter 1.5 μm) were used. , Stretched laminated film was obtained.

結果を以下の表１に示す。
The results are shown in Table 1 below.

本発明の熱収縮性積層フィルムは、熱収縮することが求められる各種用途に利用することができる。
とりわけ、本発明の熱収縮性積層フィルムは、透明性及び滑り性に優れるので、包装用袋の材料に好適に使用することができる。 The heat-shrinkable laminate film of the present invention can be used for various applications where heat-shrinkage is required.
In particular, the heat-shrinkable laminate film of the present invention is excellent in transparency and slipperiness, and thus can be suitably used as a packaging bag material.

１・・・外表面層（Ａ）
２・・・接着層（Ｂ）
３・・・バリア層（Ｃ）
４・・・接着層（Ｅ）
５・・・内表面層（Ｄ）
６・・・フィルム全層から外表面層（Ａ）のみ除いたフィルム構成層の厚みの合計 1 · · · Outer surface layer (A)
2 ・ ・ ・ Adhesive layer (B)
3 ・ ・ ・ barrier layer (C)
4 ・ ・ ・ Adhesive layer (E)
5 ・ ・ ・ inner surface layer (D)
6 ··· Total thickness of film constituting layers excluding only the outer surface layer (A) from all layers of film

Claims (8)

外表面層（Ａ）を少なくとも一方の最表面に有する熱収縮性積層フィルムであって、
前記外表面層（Ａ）が、当該外表面層（Ａ）の厚みに対して１．２〜１０．０倍の平均粒子径を有する粒子を含む、
熱収縮性積層フィルム。 A heat-shrinkable laminated film having an outer surface layer (A) on at least one outermost surface, comprising:
The outer surface layer (A) contains particles having an average particle diameter of 1.2 to 10.0 times the thickness of the outer surface layer (A).
Heat shrinkable laminated film. 前記外表面層（Ａ）の厚みが０．１〜３．０μｍである、
請求項１に記載の熱収縮性積層フィルム。 The thickness of the outer surface layer (A) is 0.1 to 3.0 μm,
The heat-shrinkable laminated film according to claim 1. 前記外表面層（Ａ）が、樹脂又は樹脂組成物と、前記粒子とから構成され、
前記樹脂又は樹脂組成物と前記粒子の屈折率の差が０．０５以下である、
請求項１又は２に記載の熱収縮性積層フィルム。 The outer surface layer (A) is composed of a resin or a resin composition and the particles,
The difference between the refractive index of the resin or the resin composition and the particles is 0.05 or less.
The heat-shrinkable laminated film according to claim 1. 流れ方向と横方法の７５℃における熱収縮率が、共に、１０％以上６５％以下である、
請求項１〜３いずれかに記載の熱収縮性積層フィルム。 The thermal contraction rates at 75 ° C. in the flow direction and in the transverse direction are both 10% or more and 65% or less,
The heat-shrinkable laminated film according to any one of claims 1 to 3. 接着層（Ｂ）、バリア層（Ｃ）及び内表面層（Ｄ）をさらに含み、
外表面層（Ａ）、接着層（Ｂ）、バリア層（Ｃ）及び内表面層（Ｄ）がこの順に積層されている、
請求項１〜４いずれかに記載の熱収縮性積層フィルム。 It further includes an adhesive layer (B), a barrier layer (C) and an inner surface layer (D),
The outer surface layer (A), the adhesive layer (B), the barrier layer (C) and the inner surface layer (D) are laminated in this order,
The heat-shrinkable laminated film according to any one of claims 1 to 4. 曇り度が２０％以下である、請求項１〜５いずれかに記載の熱収縮性積層フィルム。   The heat-shrinkable laminated film according to any one of claims 1 to 5, which has a haze of 20% or less. 熱収縮後の曇り度が５０％以下である、請求項１〜６いずれかに記載の熱収縮性積層フィルム。   The heat-shrinkable laminated film according to any one of claims 1 to 6, which has a haze of 50% or less after heat-shrinkage. 請求項１〜７いずれかに記載の熱収縮性積層フィルムを含む袋。   The bag containing the heat-shrinkable laminated film in any one of Claims 1-7.
JP2017083707A 2017-04-20 2017-04-20 Heat shrinkable laminated film and bag Active JP6990984B2 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2017083707A JP6990984B2 (en) 2017-04-20 2017-04-20 Heat shrinkable laminated film and bag
KR1020180038203A KR102189385B1 (en) 2017-04-20 2018-04-02 Heat-shrinkable laminate film and bag
CN201810347393.1A CN108724866B (en) 2017-04-20 2018-04-18 Heat-shrinkable laminated film and bag

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2017083707A JP6990984B2 (en) 2017-04-20 2017-04-20 Heat shrinkable laminated film and bag

Publications (2)

Publication Number Publication Date
JP2018176661A true JP2018176661A (en) 2018-11-15
JP6990984B2 JP6990984B2 (en) 2022-01-12

Family

ID=63939073

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2017083707A Active JP6990984B2 (en) 2017-04-20 2017-04-20 Heat shrinkable laminated film and bag

Country Status (3)

Country Link
JP (1) JP6990984B2 (en)
KR (1) KR102189385B1 (en)
CN (1) CN108724866B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113400612A (en) * 2021-06-21 2021-09-17 天津新兴东方临近空间航天科技有限公司 Fluororesin-based good-stability multilayer co-extrusion film production process

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5622780A (en) * 1994-05-11 1997-04-22 W. R. Grace & Co.-Conn. Microwaveable multilayer films with metal-like appearance
JP2000066603A (en) * 1998-08-20 2000-03-03 Fuji Seal Inc Polystyrene-based frost-tone thermal contraction label
JP2001001468A (en) * 1999-06-17 2001-01-09 Asahi Chem Ind Co Ltd Heat-shrinkable multilayered film
JP2003145667A (en) * 2001-11-09 2003-05-20 Toray Ind Inc Vapor-deposited film
US20060269710A1 (en) * 2005-05-30 2006-11-30 Inglis Thomas L Film and sheet for folding packaging containers
JP2006337933A (en) * 2005-06-06 2006-12-14 Fuji Seal International Inc Plastic label and labeled container
WO2008099799A1 (en) * 2007-02-14 2008-08-21 Asahi Kasei Chemicals Corporation Stretched laminated film and bag
JP2010284941A (en) * 2009-06-15 2010-12-24 Gunze Ltd Heat shrinkable multilayered film and heat shrinkable label
US20110236668A1 (en) * 2008-09-26 2011-09-29 Bader Michael J Films Having Low Density and Low Haze
JP2014206728A (en) * 2013-03-18 2014-10-30 王子ホールディングス株式会社 Body having fine protrusion and recession on surface and method for manufacturing body having fine protrusion and recession on surface
WO2014178378A1 (en) * 2013-05-02 2014-11-06 株式会社クレハ Heat-shrinkable multilayer film

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4228446B2 (en) * 1999-01-20 2009-02-25 Ｊｓｒ株式会社 Multilayer film
CA2313399C (en) * 1999-07-08 2005-02-15 Kuraray Co., Ltd. Thermoplastic resin composition and multilayered container using the same
JP4766220B2 (en) * 2002-11-13 2011-09-07 東洋紡績株式会社 Polyamide-based laminated film used as a packaging bag
JP5061522B2 (en) 2006-07-28 2012-10-31 東洋紡績株式会社 Polyester resin laminated film
WO2008029666A1 (en) * 2006-09-06 2008-03-13 Toyo Boseki Kabushiki Kaisha Polyester film for molding
JP2016147373A (en) 2013-05-02 2016-08-18 株式会社クレハ Heat-shrinkable multi-layered film

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5622780A (en) * 1994-05-11 1997-04-22 W. R. Grace & Co.-Conn. Microwaveable multilayer films with metal-like appearance
JP2000066603A (en) * 1998-08-20 2000-03-03 Fuji Seal Inc Polystyrene-based frost-tone thermal contraction label
JP2001001468A (en) * 1999-06-17 2001-01-09 Asahi Chem Ind Co Ltd Heat-shrinkable multilayered film
JP2003145667A (en) * 2001-11-09 2003-05-20 Toray Ind Inc Vapor-deposited film
US20060269710A1 (en) * 2005-05-30 2006-11-30 Inglis Thomas L Film and sheet for folding packaging containers
JP2006337933A (en) * 2005-06-06 2006-12-14 Fuji Seal International Inc Plastic label and labeled container
WO2008099799A1 (en) * 2007-02-14 2008-08-21 Asahi Kasei Chemicals Corporation Stretched laminated film and bag
US20110236668A1 (en) * 2008-09-26 2011-09-29 Bader Michael J Films Having Low Density and Low Haze
JP2010284941A (en) * 2009-06-15 2010-12-24 Gunze Ltd Heat shrinkable multilayered film and heat shrinkable label
JP2014206728A (en) * 2013-03-18 2014-10-30 王子ホールディングス株式会社 Body having fine protrusion and recession on surface and method for manufacturing body having fine protrusion and recession on surface
WO2014178378A1 (en) * 2013-05-02 2014-11-06 株式会社クレハ Heat-shrinkable multilayer film

Also Published As

Publication number Publication date
CN108724866A (en) 2018-11-02
KR20180118042A (en) 2018-10-30
JP6990984B2 (en) 2022-01-12
KR102189385B1 (en) 2020-12-11
CN108724866B (en) 2020-07-10

Similar Documents

Publication Publication Date Title
JP4848020B2 (en) Stretched laminated film and bag
JP2958363B2 (en) Stretch / shrink film with improved oxygen permeability
TWI783928B (en) Polypropylene-based resin multilayer film and package using the polypropylene-based resin multilayer film
JP2005246969A (en) Multilayer heat-shrinkable film containing styrene polymer or styrene polymer blend
JP6467825B2 (en) Sealant film
JP2001526599A (en) Improved compositions for uniaxially heat-shrinkable biaxially oriented polypropylene films
US10611132B2 (en) Polyethylene sealant film having high strength and package using the same
JP5041958B2 (en) Anti-fogging multilayer film
WO2000047406A1 (en) Packaging laminate
WO2017169208A1 (en) Heat-shrinkable film and method for producing heat-shrinkable film
JP2011104816A (en) Heat-shrinkable polyolefinic film
JP6990984B2 (en) Heat shrinkable laminated film and bag
JP7253036B2 (en) Superhydrophobic thermoplastic film for packaging
JP7379109B2 (en) laminated film
JP2007045047A (en) Heat-sealable polyolefinic foamed film
RU2760225C1 (en) Multilayer shrink film
JP2019166830A (en) Biaxially oriented polypropylene-based resin film and package using the same
JP3914656B2 (en) Heat shrinkable laminated film
JP7040007B2 (en) Sealant film for packaging materials, packaging materials, and packaging materials
JP5068130B2 (en) Polyolefin-based multilayer shrink film and packaging method
WO2018016281A1 (en) Heat-shrinkable multilayer film
WO2020158281A1 (en) Biaxially-oriented polyamide film and polyamide film mill roll
JP2004223795A (en) Sealant film, laminated film and packaging bag
CN116512717A (en) BOPP (biaxially-oriented polypropylene) antibacterial touch shrinkage tobacco film and preparation method and application thereof
JP2000351183A (en) Heat-shrinkable film

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20200124

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20210126

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20210309

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20210806

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20210928

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20211130

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20211207

R150 Certificate of patent or registration of utility model

Ref document number: 6990984

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150