JP4722263B2 - Pouch - Google Patents

Description

【０１００】
［密度０．９４ｇ／ｃｍ³ 以下のポリエチレン系樹脂］
高圧法低密度ポリエチレン：ＨＰ−ＬＤＰＥ
ＭＦＲ＝２．０ｇ／１０ｍｉｎ、密度＝０．９２３ｇ／ｃｍ³
［曲げ弾性率２５００ｋｇｆ／ｃｍ²以上のポリオレフィン系樹脂］
（１）高密度ポリエチレン
エチレン・１−ブテン共重合体（ＨＤＰＥ：ＭＦＲ＝１．５ｇ／１０分、密度＝０．９５１ｇ／ｃｍ³ 、曲げ弾性率＝１１，０００）
（２）エチレン・１−ブテン共重合体（ＭＤＰＥ：ＭＦＲ＝１．０ｇ／１０分、密度＝０．９４２ｇ／ｃｍ³ 、曲げ弾性率＝１０，０００）
（３）エチレン・プロピレン共重合体（ＰＰ：エチレン含有量＝３重量％、曲げ弾性率＝１２，５００）
【０１０１】
［実施例１〜６、比較例１〜３］
酸化防止剤（イルガノックス１０７６＝０．１重量％、イルガフォス１６８＝０．１重量％）とステアリン酸カルシウム（中和剤＝０．１重量％）を配合した表２〜表４に示すＨＤＰＥ、ＨＰ−ＬＤＰＥ、ＬＬＤＰＥ（ただし、ＬＬＤＰＥ−３には酸化防止剤を加えない）を、トミー機械工業（株）製２層インフレーション成形機（４０ｍｍφ押出機２台）を用い、成形リップギャップ３ｍｍ、成形温度２００℃の条件下で成形し、巾が３００ｍｍであり、表２〜表４に示す層厚み構成を有する積層体を製造した。
ついで、Ｏ−ナイロン（厚み１５μｍ、ユニチカ（株）製）を接着剤（アンカーコート剤：東洋モートンＴＭ―３２９）を使用しドライラミネート法により貼り合わせた。
【０１０２】
さらに、積層体の第III層同士を３ｋｇ荷重ヒートシール温度＋５℃の温度で、圧力１ｋｇ／ｃｍ²、１秒間でヒートシールして内容量５００ｍｌのスタンディングパウチを製造し、積層体およびパウチの評価を行った。結果を表２〜表４に示す。
【０１０３】
【表２】

【０１０４】
【表３】

【０１０５】
【表４】

【０１０６】
表２および表３の結果から明らかなように、実施例の積層体は、ヒートシール性、耐ピンホール性、水蒸気バリア性、透明性および機械的強度に優れていることがわかる。また、実施例のパウチは、十分な耐熱性および落下強度を有していた。特に、ハロゲンがほとんど含まれていないＬＬＤＰＥ−１を内層（第II層）に用いたパウチは、臭気が少なく、衛生性に優れていた。
【０１０７】
一方、表４の結果から明らかなように、比較例１の積層体およびパウチは、第II層に特定の（Ａ）線状低密度ポリエチレンを用いず、ＭＤＰＥを用いたため、ヒートシール強度、耐ピンホール性、引張衝撃強さ、落下強度に劣っていた。
比較例２の積層体およびパウチは、第II層に（Ａ）線状低密度ポリエチレンを用いず、ＨＰ−ＬＤＰＥを用いたため、ヒートシール強度、耐ピンホール性、引張衝撃強さ、落下強度に劣り、しかも、臭気が激しく、衛生性が悪かった。
比較例３の積層体およびパウチも、第II層に（Ａ）線状低密度ポリエチレンを用いず、Ｚ−ＬＬＤＰＥを用いたため、ヒートシール強度、耐ピンホール性、引張衝撃強さ、落下強度に劣り、しかも、臭気を有し、衛生性が悪かった。
比較例４の積層体およびパウチは第Ｉ層にＬＤＰＥを用いているため、耐熱性、落下強度、自立性が劣るものであった。
【０１０８】
【発明の効果】
以上説明したように、本発明のパウチは、曲げ弾性率が２５００ｋｇｆ／ｃｍ² 以上であるポリオレフィン系樹脂材料（ｉ）からなる第Ｉ層と、上述の（ａ）〜（ｄ）の要件を満足する（Ａ）線状低密度ポリエチレンを主成分とする樹脂材料（ii）からなる第II層とが積層された積層体を、第II層が内側となるように袋状に成形してなるものであるので、剛性、低温ヒートシール性、水蒸気バリア性、保香性、衛生性、耐熱性に優れ、高いヒートシール強度、突刺強度を有する。
【０１０９】
また、第II層同士をヒートシールしたときのヒートシール強度が３ｋｇ／１５ｍｍとなるようなヒートシール温度が、８５〜１２５℃の範囲であれば、耐熱性、高速充填性がさらに向上する。
また、積層体の厚さが１０μｍ〜０．５ｍｍであり、かつ第Ｉ層および第II層の厚さがそれぞれ３μｍ〜０．４ｍｍの範囲であれば、使いやすく、各層の特性が十分に発揮されたパウチとなる。
また、積層体がさらにバリア層（III）を有していれば、パウチの水蒸気バリア性、保香性がさらに向上する。
また、第Ｉ層および第II層のいずれかの層が、積層体をリサイクルすることで得られる樹脂材料（ｉ）および樹脂材料（ii）のブレンド樹脂で形成されている、もしくは、該ブレンド樹脂からなるリサイクル樹脂層（IV）が、さらに設けられていれば、リサイクルされたブレンド樹脂を用いることが可能となり、リサイクル性が良好となる。
【０１１０】
また、前記（Ａ）線状低密度ポリエチレンが、さらに上述の（ｅ）および（ｆ）の要件を満足する（Ａ１）線状低密度ポリエチレンであれば、パウチの耐熱性、衛生性、剛性がさらに向上する。
また、前記（Ａ）線状低密度ポリエチレンが、さらに上述の（ｇ）および（ｈ）の要件を満足する（Ａ２）線状低密度ポリエチレンであれば、パウチの耐熱性、ヒートシール強度がさらに向上する。
また、前記（Ａ２）線状低密度ポリエチレンが、さらに上述の（ｉ）の要件を満足すれば、成形加工性がさらに向上する。
【０１１１】
また、前記（Ａ）線状低密度ポリエチレンが、少なくとも共役二重結合を持つ有機環状化合物と周期律表第IV族の遷移金属化合物を含む触媒の存在下にエチレンとα−オレフィンを共重合させて得られる直鎖状のエチレン共重合体であれば、パウチの機械的特性、ヒートシール性、耐熱ブロッキング性、耐熱性がさらに向上する。
また、前記樹脂材料（ii）に配合された添加剤が実質的に被接触物に移行しない添加剤である、もしくは前記樹脂材料（ii）に添加剤が配合されていなければ、臭いが少なく、衛生性を有するパウチを得ることができる。
また、樹脂材料（ii）のハロゲン濃度が、１０ｐｐｍ以下であれば、化学的安定性、衛生性が優れ、特に食品用包装材料等の分野において好適に活用されるパウチを提供することができる。
【図面の簡単な説明】
【図１】 本発明における（Ａ）または（Ａ２）線状低密度ポリエチレンの溶出温度−溶出量曲線を示すグラフである。
【図２】 本発明における（Ａ１）線状低密度ポリエチレンの溶出温度−溶出量曲線を示すグラフである。
【図３】 メタロセン系触媒によるエチレン共重合体の溶出温度−溶出量曲線を示すグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to pouches used in detergents, cosmetics, foodstuffs, etc., and has excellent rigidity, low-temperature heat sealability, water vapor barrier properties, fragrance retention, hygiene, high heat seal strength, puncture strength, especially standing The present invention relates to a pouch suitable for pouches, retort pouches and the like.
[0002]
[Prior art]
Conventionally, liquid detergents, shampoos, rinses, edible oils, seasonings and the like have been used in containers with spouts. Recently, in order to save resources, refill products containing supplementary contents such as standing pouches (for example, self-supporting bags of bottom gussets) have been sold separately for the purpose of reusing containers.
As another form of the pouch, a retort pouch for retort food, a pouch with a spout for drinking used in a sucking jelly, and the like are also known.
[0003]
For such a pouch, a single-layer film made of high-density polyethylene, linear low-density polyethylene, low-density polyethylene, or the like, or a laminated film of high-density polyethylene and low-density polyethylene, or linear low-density polyethylene is used. ing. These pouches are required to be easy to heat seal, to obtain high heat seal strength, and to easily obtain a bag shape. In recent years, pouches obtained from such single-layer films and laminated films are desired to have higher performance and cost reduction, and to maintain the quality of the contents, they have improved water vapor barrier properties and aroma retention properties. Excellent; excellent hygiene so that taste and quality do not change due to the transfer of low molecular weight components from the pouch, and odor does not transfer to the contents from the pouch; no pinholes are generated by vibration during product transportation Therefore, it is required to have sufficient puncture strength. Further, the standing pouch is further required to have sufficient rigidity (waist) necessary for independence. Furthermore, recently, from the viewpoint of resource saving, environmental protection, etc., containers and packaging materials are required to be easily recyclable and recoverable, and may satisfy the above performance, recyclability and recoverability. It has been demanded.
[0004]
[Problems to be solved by the invention]
However, pouches made of these high-density polyethylene and linear low-density polyethylene or laminated film of low-density polyethylene are inferior in low-temperature heat-sealability and need to be heat-sealed at a high temperature in order to obtain sufficient seal strength. . Therefore, it is inferior in high-speed filling property and high-speed moldability, and odor and the like are easily generated in the pouch, causing the quality of the contents to deteriorate, and does not satisfy the above required performance at the same time.
[0005]
Therefore, an object of the present invention is to provide a pouch having excellent heat seal strength, excellent rigidity, low temperature heat sealability, water vapor barrier properties, aroma retention, hygiene, heat resistance, pinhole resistance, Furthermore, since it is comprised with the same kind of resin material, it is providing the pouch excellent in recyclability.
[0006]
[Means for Solving the Problems]
  The pouch of the present invention isDensity 0.93g / cm ^Three Based on the above medium and high density polyethylene and / or polypropylene resin,Flexural modulus is 2500kgf / cm² A first layer comprising the polyolefin-based resin material (i) as described above;Produced in the presence of a catalyst containing an organocyclic compound with at least a conjugated double bond and a transition metal compound of Group IV of the Periodic Table(A) satisfying the following requirements (a) to (d): (A) a second layer composed of a resin material (ii) mainly composed of linear low density polyethylene;A barrier layer (III) comprising a barrier material (iii) bonded to the first layer;Is formed into a bag shape so that the second layer is on the inside.
(A) Density is 0.86-0.94 g / cm^Three ,
(B) A melt flow rate of 0.01 to 50 g / 10 minutes,
(C) molecular weight distribution (Mw / Mn) is 1.5 to 4.5,
(D) Temperature T at which 25% of the total elution temperature obtained from the integrated elution curve of elution temperature-elution volume curve by continuous temperature rising elution fractionation method (TREF) is eluted_{twenty five}And the temperature T at which 75% of the total elution occurs₇₅Difference with T₇₅-T_{twenty five}And the density d satisfies the following relationship (Formula 1)
  (Formula 1) T₇₅-T_{twenty five}≦ −670 × d + 644
[0007]
  In the pouch of the present invention, the second layers are bonded to each other with a heat seal pressure of 1 kg / cm² The heat seal temperature is preferably in the range of 85 to 125 ° C. so that the heat seal strength is 3 kg / 15 mm when heat seal is performed under the condition of a heat seal time of 1 second.
[0008]
The thickness of the laminate is preferably 10 μm to 0.5 mm, and the thicknesses of the I layer and the II layer are preferably in the range of 3 μm to 0.4 mm, respectively.
In addition, a recycled resin layer (I or II) is formed of a blend resin of the resin material (i) and the resin material (ii) obtained by recycling the pouch, or made of the blend resin ( It is desirable that IV) is further provided in the laminate.
[0009]
The (A) linear low density polyethylene is preferably (A1) linear low density polyethylene that further satisfies the following requirements (e) and (f).
(E) Orthodichlorobenzene (ODCB) soluble amount X (wt%), density d and melt flow rate (MFR) at 25 ° C. satisfy the relationship of the following (formula 2) and (formula 3).
(Formula 2) When d−0.008log MFR ≧ 0.93
X <2.0
(Formula 3) When d−0.008log MFR <0.93
X <9.8 × 10^Three× (0.9300-d + 0.008logMFR)²+2.0
(F) Multiple peaks of elution temperature-elution amount curve by continuous temperature rising elution fractionation method (TREF) exist.
[0010]
The (A) linear low density polyethylene is preferably (A2) linear low density polyethylene that further satisfies the following requirements (g) and (h).
(G) There is one peak of the elution temperature-elution amount curve by continuous temperature rising elution fractionation method (TREF), and T₇₅-T_{twenty five}And the density d satisfies the following relationship (Formula 4)
(Formula 4) T₇₅-T_{twenty five}≧ −300 × d + 285
(H) 1 to 2 melting points, and the highest melting point T_mlAnd the density d satisfy the following relationship (Formula 5)
(Formula 5) T_ml≧ 150 × d−17
The (A2) linear low density polyethylene preferably further satisfies the following requirement (i).
(I) Melt tension (MT) and melt flow rate (MFR) satisfy the following (formula 6).
(Formula 6) logMT ≦ −0.572 × logMFR + 0.3
[0011]
  Moreover, it is desirable that the additive blended in the resin material (ii) is an additive that does not substantially transfer to the contacted object, or the additive is not blended in the resin material (ii).
  The halogen concentration of the resin material (ii) is desirably 10 ppm or less.
  Moreover, it is preferable that the shape of the pouch is one selected from a gusset bag, a four-side seal bag, a three-sided seal bag with a palm joint, and a bag that seals the top and bottom of a tubular film by an inflation method.
  The pouch is preferably any one of food packaging materials, daily necessities packaging materials, and medical packaging materials.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The resin material (i) forming the first layer has a flexural modulus of 2500 kgf / cm.² It is necessary to be the above polyolefin resin material. The flexural modulus is preferably 3500 kgf / cm.² Or more, more preferably 4500 kgf / cm² The above is desirable. The flexural modulus is 2500 kgf / cm² If it is less than this, the rigidity (waist) of the pouch is lowered, the independence is lost, and the automatic filling performance is lowered. Here, the flexural modulus of the resin material (i) is measured according to JIS K 7203.
[0013]
Flexural modulus of 2500 kgf / cm for forming the first layer² The above-mentioned polyolefin resin material (i) has a density of 0.93 g / cm.^Three The above-mentioned medium / high-density polyethylene and / or polypropylene resin is the main component, and other polyethylene resins are blended as necessary.
For medium density polyethylene and high density polyethylene, the density is 0.93 g / cm.^Three If it is the above, various things can be utilized. Specifically, from a homopolymer composed only of ethylene, a copolymer composed of ethylene and another monomer (for example, an α-olefin such as propylene, 1-butene, 1-hexene), or ethylene and two or more monomers And the like.
[0014]
The density of medium and high density polyethylene is 0.93g / cm^Three If it is less than 1, the waist strength (rigidity), water vapor barrier property, fragrance retention property, moisture resistance, heat resistance, etc. of the obtained pouch are impaired.
The MFR (190 ° C.) of the medium / high-density polyethylene is preferably in the range of 0.01 to 50 g / 10 minutes, more preferably 0.05 to 30 g / min, and further preferably 0.1 to 10 g / min. . When the MFR (190 ° C.) is less than 0.01 g / 10 minutes, there is a problem in workability, and when it exceeds 50 g / 10 minutes, the strength of the pouch tends to decrease.
[0015]
Examples of the polypropylene resin include homopolypropylene, propylene / ethylene block copolymer, propylene / ethylene random copolymer, propylene / α-olefin block copolymer, propylene / α-olefin random copolymer, and the like.
The MFR (based on JIS K 6758) of the polypropylene resin is preferably in the range of 0.1 to 50 g / 10 minutes, more preferably in the range of 0.1 to 20 g / min. If the MFR is less than 0.1 g / 10 minutes, there is a problem in workability, and if it exceeds 50 g / 10 minutes, the strength of the laminate tends to decrease.
[0016]
The blending ratio of the medium / high-density polyethylene and / or polypropylene resin in the resin material (i) forming the first layer is 50 to 100% by weight, preferably 70 to 100% by weight. When these proportions are less than 50% by weight, the rigidity (waist), water vapor barrier property, and aroma retention of the laminate are lowered.
[0017]
Examples of other polyethylene-based resins that can be blended in the resin material (i) include linear low-density polyethylene obtained by a Ziegler-type catalyst, a metallocene-based catalyst, a high-pressure radical method ethylene-based polymer, and a specific (A) described later. Examples include linear low density polyethylene.
[0018]
The melt flow rate (hereinafter referred to as MFR) of the linear low density polyethylene obtained by the Ziegler type catalyst is generally 0.01 to 50 g / 10 minutes, preferably 0.5 to 30 g / 10 minutes, more preferably 0. 5 to 10 g / min. When the MFR is less than 0.01 g / 10 min, a decrease in fluidity (moldability of a laminate by inflation) is observed, and when it exceeds 50 g / 10 min, a decrease in strength and the like is observed.
[0019]
High pressure radical polymerization method Ethylene polymers include low density polyethylene (LDPE), ethylene / vinyl ester copolymer, copolymer of ethylene and α, β-unsaturated carboxylic acid or its derivatives, etc. Is mentioned.
[0020]
The MFR of the low density polyethylene (LDPE) is in the range of 0.01 to 50 g / 10 minutes, preferably 0.05 to 30 g / minute, more preferably 0.1 to 10 g / 10 minutes. If it is this range, melt tension will become an appropriate range and a moldability will improve. On the other hand, when the MFR exceeds 20 g / 10 min, the strength of the laminate is insufficient.
The density of LDPE is 0.91 to 0.94 g / cm.^Three More preferably, 0.912-0.935 g / cm^Three Range. If it is this range, melt tension will become an appropriate range and a moldability will improve. The melt tension of LDPE is 1.5 to 25 g, preferably 3 to 20 g, more preferably 3 to 15 g. Moreover, the molecular weight distribution Mw / Mn of LDPE is 3.0-12, Preferably it is 4.0-8.0.
[0021]
The ethylene-vinyl ester copolymer is vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, trifluoroacetic acid, which are mainly produced by high-pressure radical polymerization. It is a copolymer with vinyl ester monomers such as vinyl. Among these, vinyl acetate is particularly preferable. A copolymer comprising 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of vinyl ester, and 0 to 49.5% by weight of other copolymerizable unsaturated monomers is preferred. In particular, the vinyl ester content ranges from 3 to 30% by weight, preferably from 5 to 25% by weight. The MFR of the ethylene / vinyl ester copolymer is in the range of 0.01 to 50 g / 10 min, preferably 0.05 to 30 g / min, and more preferably 0.1 to 10 g / 10 min.
[0022]
Examples of the copolymer of ethylene and an α, β-unsaturated carboxylic acid or a derivative thereof include ethylene / (meth) acrylic acid or an alkyl ester copolymer thereof, and these comonomers include acrylic acid, methacrylic acid, Acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, cyclohexyl acrylate, Examples include cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl acrylate, and glycidyl methacrylate. Among these, alkyl esters such as methyl and ethyl of (meth) acrylic acid are particularly preferable. In particular, the content of (meth) acrylic acid ester is in the range of 3 to 30% by weight, preferably 5 to 25% by weight. The MFR of the copolymer of ethylene and an α, β-unsaturated carboxylic acid or derivative thereof is 0.01 to 50 g / 10 minutes, preferably 0.05 to 30 g / 10 minutes, more preferably 0.1 to 10 g / 10 minutes.
[0023]
The resin material (ii) mainly composed of (A) linear low density polyethylene forming the second layer is a specific (A) linear low density polyethylene that satisfies the following requirements (a) to (d) As a main component and, if necessary, other polyethylene-based resins are blended.
[0024]
(A) A linear low density polyethylene is an ethylene copolymer obtained by copolymerizing ethylene and an α-olefin, and ethylene and an α- having 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms. It is a copolymer with olefin.
Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-hexene, and 1-octene. (A) The structural unit derived from an α-olefin having 3 to 20 carbon atoms in the linear low density polyethylene is 1 to 7 mol%, preferably 1 to 5 mol%, more preferably 2 to 3 mol%. . When the structural unit derived from an α-olefin having 3 to 20 carbon atoms exceeds 7 mol%, the impact resistance, creep resistance, and heat seal strength are decreased, and when it is less than 1 mol%, the transparency is decreased. It can be seen.
[0025]
The (a) density of the linear low density polyethylene (A) in the present invention is 0.86 to 0.94 g / cm.^Three , Preferably 0.89-0.94 g / cm^Three More preferably, 0.90 to 0.93 g / cm^Three Range. Density is 0.86 g / cm^Three If it is less than the range, rigidity (waist strength) and heat resistance may be lowered. The density is 0.94 g / cm^Three If it exceeds 1, pinhole resistance, tear strength, impact resistance and the like may be insufficient.
[0026]
(B) MFR of (A) linear low density polyethylene in this invention is 0.01-50 g / 10min, Preferably it is 0.05-30 g / 10min, More preferably, it is 0.1-10 g / 10 Minutes. When the MFR is less than 0.01 g / 10 minutes, a decrease in fluidity (moldability of the laminate) is observed, and when it exceeds 50 g / 10 minutes, a decrease in strength is observed.
[0027]
(C) Molecular weight distribution (Mw / Mn) of (A) linear low density polyethylene in the present invention is 1.5 to 4.5, preferably 2.0 to 4.0, more preferably 2.5 to 3. .0 range. If Mw / Mn is less than 1.5, the moldability is inferior, and if Mw / Mn exceeds 4.5, the pinhole resistance, tear strength, impact resistance and the like are inferior.
Here, the molecular weight distribution (Mw / Mn) of the linear low density polyethylene is obtained by calculating the weight average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography (GPC), and the ratio (Mw / Mn). Mn) can be obtained by calculating.
[0028]
The (A) linear low density polyethylene in the present invention is, for example, as shown in FIG. 1, as shown in FIG. 1, (d) the whole elution temperature-elution amount curve obtained by the continuous temperature rising elution fractionation method (TREF) Temperature T at which 25% elutes_{twenty five}And temperature T at which 75% of the total elution occurs₇₅Difference with T₇₅-T_{twenty five}And the density d satisfies the following relationship (Formula 1).
(Formula 1) T₇₅-T_{twenty five}≦ −670 × d + 644
T₇₅-T_{twenty five}When the density d does not satisfy the relationship of the above (formula 1), the low temperature heat sealability is inferior.
[0029]
The measuring method of TREF is as follows. First, a sample is added to ODCB to which an antioxidant (for example, butylhydroxytoluene) is added so that the sample concentration is 0.05% by weight, and is heated and dissolved at 135 ° C. 5 ml of this sample solution is injected into a column filled with glass beads, cooled to 25 ° C. at a cooling rate of 0.1 ° C./min, and the sample is deposited on the surface of the glass beads. Next, the sample is sequentially eluted while increasing the column temperature at a constant rate of 50 ° C./hr while flowing ODCB through the column at a constant flow rate. At this time, the concentration of the sample eluted in the solvent was set to the wave number 2925 cm of the asymmetric stretching vibration of methylene.^-1Is continuously detected by measuring the absorption with respect to an infrared detector. From this value, the concentration of the ethylene copolymer in the solution is quantitatively analyzed to determine the relationship between the elution temperature and the elution rate.
According to the TREF analysis, since a change in elution rate with respect to a temperature change can be continuously analyzed with a very small amount of sample, a relatively fine peak that cannot be detected by a fractionation method can be detected.
[0030]
The (A) linear low density polyethylene in the present invention further satisfies the following requirements (e) and (f): (A1) linear low density polyethylene, or further described in (g) and (h) It is preferably any of (A2) linear low density polyethylene that satisfies the requirements.
[0031]
In the present invention, (A) the amount X (wt%) of the ODCB soluble content at 25 ° C. of the linear low density polyethylene (D) and the density d and MFR satisfy the relationship of the following (formula 2) and (formula 3). And
(Formula 2) When d−0.008log MFR ≧ 0.93,
X <2.0
(Formula 3) When d−0.008 log MFR <0.93,
X <9.8 × 10^Three× (0.9300-d + 0.008logMFR)²+2.0
And preferably satisfies
When d-0.008log MFR ≧ 0.93,
X <1.0
If d−0.008log MFR <0.93,
X <7.4 × 10^Three× (0.9300-d + 0.008logMFR)²+2.0
And more preferably,
When d-0.008log MFR ≧ 0.93,
X <0.5
If d−0.008log MFR <0.93,
X <5.6 × 10^Three× (0.9300-d + 0.008logMFR)²+2.0
Satisfied with the relationship.
[0032]
Here, the amount X of soluble ODCB at 25 ° C. is measured by the following method. A sample of 0.5 g is heated with 20 ml of ODCB at 135 ° C. for 2 hours to completely dissolve the sample, and then cooled to 25 ° C. The solution is allowed to stand at 25 ° C. overnight and then filtered through a Teflon filter to collect the filtrate. This filtrate, which is a sample solution, was subjected to a wave number of 2925 cm of asymmetric stretching vibration of methylene using an infrared spectrometer.^-1The absorption peak intensity in the vicinity is measured, and the sample concentration is calculated using a calibration curve prepared in advance. From this value, the amount of soluble ODCB at 25 ° C. is obtained.
[0033]
The ODCB soluble content at 25 ° C. is a high branching component and a low molecular weight component contained in linear low density polyethylene, which causes a decrease in heat resistance and stickiness of the surface of the molded body, and causes sanitary problems and the inner surface of the molded body. This content is preferably small because it causes blocking. The amount of ODCB solubles is affected by the α-olefin content and molecular weight of the entire copolymer, ie, density and MFR. Accordingly, the fact that the density and the amount of soluble components of MFR and ODCB satisfying the above relationship indicate that the α-olefin contained in the entire copolymer is less unevenly distributed.
[0034]
The (A1) linear low density polyethylene in the present invention has a plurality of peaks in the elution temperature-elution amount curve obtained by (f) continuous temperature rising elution fractionation (TREF). It is particularly preferable that the plurality of peak temperatures exist between 85 ° C and 100 ° C. The presence of this peak increases the melting point, increases the crystallinity, and improves the heat resistance and rigidity of the molded body.
[0035]
Here, as shown in FIG. 2, (A1) linear low density polyethylene has a special peak having substantially a plurality of peaks in an elution temperature-elution amount curve obtained by a continuous temperature rising elution fractionation method (TREF). It is a linear low density polyethylene (ethylene / α-olefin copolymer). On the other hand, the ethylene copolymer in FIG. 3 is a linear low density polyethylene having substantially one peak in the elution temperature-elution amount curve obtained by the continuous temperature rising elution fractionation method (TREF). This corresponds to an ethylene / α-olefin copolymer using a novel metallocene catalyst.
[0036]
As shown in FIG. 1, the (A2) linear low density polyethylene in the present invention has one peak of the elution temperature-elution amount curve by (g) continuous temperature rising elution fractionation method (TREF), and T₇₅-T_{twenty five}And the density d satisfies the following relationship (Formula 4).
(Formula 4) T₇₅-T_{twenty five}≧ −300 × d + 285
T₇₅-T_{twenty five}When the density d does not satisfy the relationship of (Equation 4), the heat seal strength and heat resistance are inferior.
The (A2) linear low density polyethylene in the present invention has (h) one or two melting points, and the highest melting point T among them._mlAnd the density d satisfy the following relationship (Formula 5).
(Formula 5) T_ml≧ 150 × d−17
If the melting point Tm1 and the density d do not satisfy the relationship of the above (formula 5), the heat resistance will be poor.
[0037]
Among (A2) linear low-density polyethylene, linear low-density polyethylene that satisfies the following requirement (i) is preferable.
(I) The melt tension (MT) and the melt flow rate (MFR) satisfy the relationship of the following (formula 6).
(Formula 6) logMT ≦ −0.572 × logMFR + 0.3
When MT and MFR satisfy the relationship of the above (formula 6), the moldability of the laminated body or the like becomes good.
[0038]
Here, although (A2) linear low density polyethylene has one TREF peak as shown in FIG. 1, an ethylene copolymer by a conventional typical metallocene catalyst is based on the above (formula 4). This is not satisfactory, and is distinguished from the conventional ethylene copolymer by a typical metallocene catalyst.
[0039]
The (A) linear low density polyethylene in the present invention is not particularly limited to a catalyst, a production method or the like as long as the above parameters are satisfied, but preferably an organic cyclic compound having at least a conjugated double bond and a periodic rule. A linear ethylene (co) polymer obtained by (co) polymerizing ethylene and an α-olefin in the presence of a catalyst containing a transition metal compound of Table IV group is desirable. Such a linear ethylene (co) polymer has a narrow molecular weight distribution and composition distribution, so it has excellent mechanical properties, heat sealability, heat blocking resistance, etc., and also has good heat resistance. .
[0040]
In the production of the linear low density polyethylene (A) in the present invention, it is particularly desirable to polymerize with a catalyst obtained by mixing the following compounds a1 to a4.
a1: General formula Me¹R¹ _pR² _q(OR^Three)_rX¹ _4-pqr A compound represented by the formula:¹ Represents zirconium, titanium, hafnium, R¹ And R^Three Are each a hydrocarbon group having 1 to 24 carbon atoms, R² Is a 2,4-pentanedionate ligand or a derivative thereof, a benzoylmethanato ligand, a benzoylacetonate ligand or a derivative thereof, X¹ Represents a halogen atom, and p, q and r are integers satisfying the ranges of 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 4 and 0 ≦ p + q + r ≦ 4, respectively)
a2: General formula Me²R^Four _m(OR^Five)_nX² _zmn A compound represented by the formula:² Is a group I-III element of the periodic table, R^Four And R^Five Are each a hydrocarbon group having 1 to 24 carbon atoms, X² Is a halogen atom or a hydrogen atom (however, X² Me is a hydrogen atom² Is only for Group III elements of the Periodic Table), z is Me² And m and n are integers satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively, and 0 ≦ m + n ≦ z)
a3: an organic cyclic compound having a conjugated double bond
a4: Modified organoaluminum oxy compound and / or boron compound containing Al—O—Al bond
[0041]
Further details will be described below.
General formula Me of the catalyst component a1¹R¹ _pR² _q(OR^Three)_rX¹ _4-pqr In the formula of the compound represented by¹ Represents zirconium, titanium, and hafnium, and the types of these transition metals are not limited, and a plurality of them can be used, but it is particularly preferable that zirconium having excellent weather resistance of the copolymer is included. R¹ And R^Three Are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group; alkenyl groups such as vinyl group and allyl group; phenyl group, tolyl group, xylyl group, mesityl group, indenyl group and naphthyl group And aryl groups such as benzyl group, trityl group, phenethyl group, styryl group, benzhydryl group, phenylbutyl group, and neofoyl group. These may be branched. R² Represents a 2,4-pentanedionato ligand or a derivative thereof, a benzoylmethanato ligand, a benzoylacetonate ligand or a derivative thereof. X¹ Represents a halogen atom such as fluorine, iodine, chlorine and bromine. p and q are integers satisfying the ranges of 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 4, and 0 ≦ p + q + r ≦ 4, respectively.
[0042]
Examples of the compound represented by the general formula of the catalyst component a1 include tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium, tetrapropoxyzirconium, tripropoxymonochlorozirconium, tetraethoxyzirconium, tetrabutoxyzirconium, tetrabutoxytitanium, tetrabutoxy Hafnium and the like, especially Zr (OR) such as tetrapropoxyzirconium and tetrabutoxyzirconium_Four Compounds are preferred, and two or more of these may be used in combination. Specific examples of the 2,4-pentanedionato ligand or derivative thereof, benzoylmethanato ligand, benzoylacetonate ligand or derivative thereof include tetra (2,4-pentandionato) zirconium. , Tri (2,4-pentanedionato) chloride zirconium, di (2,4-pentandedionato) dichloride zirconium, (2,4-pentandedionato) trichloride zirconium, di (2,4-pentandedionato) Diethoxide zirconium, di (2,4-pentanedionato) di-n-propoxide zirconium, di (2,4-pentanedionato) di-n-butoxide zirconium, di (2,4-pentane) Diato) dibenzylzirconium, di (2,4-pentanedionate) dineoyl zirconium, tetra ( Benzoylmethanato) zirconium, di (dibenzoylmethanato) diethoxide zirconium, di (dibenzoylmethanato) di-n-propoxide zirconium, di (dibenzoylmethanato) di-n-butoxidezirconium, di (benzoyl) Acetonato) diethoxide zirconium, di (benzoylacetonato) di-n-propoxide zirconium, di (benzoylacetonato) di-n-butoxide zirconium and the like.
[0043]
General formula Me of the catalyst component a2²R^Four _m(OR^Five)_nX² _zmn In the formula of the compound represented by² Represents Group I to III elements of the Periodic Table, such as lithium, sodium, potassium, magnesium, calcium, zinc, boron, aluminum and the like. R^Four And R^Five Are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, specifically alkyl such as methyl group, ethyl group, propyl group, isopropyl group and butyl group. Group: alkenyl group such as vinyl group and allyl group; aryl group such as phenyl group, tolyl group, xylyl group, mesityl group, indenyl group, naphthyl group; benzyl group, trityl group, phenethyl group, styryl group, benzhydryl group, phenyl Examples thereof include aralkyl groups such as a butyl group and a neofoyl group. These may be branched. X² Represents a halogen atom or hydrogen atom such as fluorine, iodine, chlorine and bromine. However, X² Me is a hydrogen atom² Is limited to Group III elements of the periodic table exemplified by boron, aluminum and the like. Z is Me² M and n are integers satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively, and 0 ≦ m + n ≦ z.
[0044]
Examples of the compound represented by the general formula of the catalyst component a2 include organic lithium compounds such as methyl lithium and ethyl lithium; organic magnesium compounds such as dimethyl magnesium, diethyl magnesium, methyl magnesium chloride, and ethyl magnesium chloride; dimethyl zinc and diethyl Organic zinc compounds such as zinc; organic boron compounds such as trimethylboron and triethylboron; trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, tridecylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum Sesquichloride, diethylaluminum ethoxide, diethylaluminum hydride Any derivative of an organic aluminum compounds, and the like.
[0045]
The organic cyclic compound having a conjugated double bond of the catalyst component a3 is cyclic, having one or more rings having 2 or more, preferably 2 to 4, more preferably 2 to 3 conjugated double bonds. A cyclic hydrocarbon compound having 4 to 24 carbon atoms, preferably 4 to 12 carbon atoms; the cyclic hydrocarbon compound is partially a hydrocarbon residue having 1 to 6 carbon atoms (typically having 1 to A cyclic hydrocarbon compound substituted with 12 alkyl groups or an aralkyl group; having 1 or 2 rings having 2 or more, preferably 2 to 4, more preferably 2 to 3 conjugated double bonds An organosilicon compound having a cyclic hydrocarbon group having a total carbon number of 4 to 24, preferably 4 to 12; the cyclic hydrocarbon group is partially a hydrocarbon residue or alkali metal salt (sodium 1-6) Or lithium salt) The organosilicon compound is contained. Particularly preferred is one having a cyclopentadiene structure in any of the molecules.
[0046]
Suitable examples of the compound include cyclopentadiene, indene, azulene, or alkyl, aryl, aralkyl, alkoxy or aryloxy derivatives thereof. Moreover, the compound which these compounds couple | bonded (bridge | crosslinked) via the alkylene group (The carbon number is 2-8 normally, Preferably 2-3) is also used suitably.
[0047]
The organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula.
A_LSiR_4-L
Here, A represents the cyclic hydrogen group exemplified by cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, and substituted indenyl group, and R represents methyl group, ethyl group, propyl group, isopropyl group, butyl group An alkyl group such as a group; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group; an aryl group such as a phenyl group; an aryloxy group such as a phenoxy group; an aralkyl group such as a benzyl group; To 24, preferably 1 to 12 hydrocarbon residues or hydrogen, L is 1 ≦ L ≦ 4, preferably 1 ≦ L ≦ 3.
[0048]
Specific examples of the organic cyclic hydrocarbon compound of component a3 include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, 1,3-dimethylcyclopentadiene, indene, 4-methyl-1-indene, and 4,7-dimethylindene. Butylcycloheptadiene, 1-methyl-3-propylcyclopentadiene and indene, 1-methyl-3-butylcyclopentadiene and indene, propylcyclopentadiene, 1-methyl-3-ethylcyclopentadiene, 1,2,4- Cyclopolyene having 5 to 24 carbon atoms such as trimethylcyclopentadiene cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, azulene, fluorene, methylfluorene or substituted cyclopolyene, monocyclopentadienyl Orchids, biscyclopentadienyl silane, tris cyclopentadienyl silane, mono indenyl silane, bis indenyl silane, tris indenyl silane, and the like methylcyclopentadienyl entry methylsilane.
[0049]
In the present invention, a modified organoaluminum compound and / or boron compound containing an a4: Al—O—Al bond is used.
Specific examples of the modified organoaluminum oxy compound containing an Al—O—Al bond include a modified organoaluminum oxy compound usually referred to as aluminoxane obtained by reacting an alkylaluminum compound with water. Examples of the modified organoaluminum oxy compound include those containing 1 to 100, preferably 1 to 50, Al—O—Al bonds in the molecule. The modified organoaluminum oxy compound may be linear or cyclic.
[0050]
The reaction between organoaluminum and water is usually carried out in an inert hydrocarbon. As the inert hydrocarbon, aliphatic, alicyclic and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, benzene, toluene and xylene are preferable.
The reaction ratio (water / Al molar ratio) between water and the organoaluminum compound is usually 0.25 / 1 to 1.2 / 1, preferably 0.5 / 1 to 1/1.
[0051]
Examples of boron compounds include triethylaluminum tetra (pentafluorophenyl) borate, tri (ethylpentafluorophenyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate, and butyl. Ammonium tetra (pentafluorophenyl) borate, N, N-dimethylanilinium tetra (pentafluorophenyl) borate, N, N-dimethylanilinium tetra (3,5-difluorophenyl) borate and the like can be mentioned.
[0052]
The catalyst may be used by mixing and contacting a1 to a4, but it is preferable to use the catalyst supported on an inorganic carrier and / or a particulate polymer carrier (a5).
Examples of the inorganic carrier and / or particulate polymer carrier (a5) include carbonaceous materials, metals, metal oxides, metal chlorides, metal carbonates or mixtures thereof, thermoplastic resins, thermosetting resins, and the like. Suitable metals that can be used for the inorganic carrier include iron, aluminum, nickel and the like.
Specifically, SiO₂, Al₂O_Three, MgO, ZrO₂TiO₂, B₂O_Three, CaO, ZnO, BaO, ThO₂Etc. or a mixture thereof, SiO 2₂-Al₂O_Three, SiO₂-V₂O_Five, SiO₂-TiO₂, SiO₂-V₂O_Five, SiO₂-MgO, SiO₂-Cr₂O_ThreeEtc. Among these, SiO₂And Al₂O_ThreeThe main component is at least one component selected from the group consisting of:
As the organic compound, any of a thermoplastic resin and a thermosetting resin can be used. Specifically, particulate polyolefin, polyester, polyamide, polyvinyl chloride, poly (meth) acrylate, polystyrene, Examples include norbornene, various natural polymers, and mixtures thereof.
[0053]
The inorganic carrier and / or the particulate polymer carrier can be used as they are, but preferably, as a pretreatment, these carriers are contacted with an organoaluminum compound or a modified organoaluminum compound containing an Al—O—Al bond. After that, it can also be used as component a5.
[0054]
In the present invention, (A) a method for producing linear low density polyethylene is produced by a gas phase polymerization method, a slurry polymerization method, a solution polymerization method, etc. substantially free of a solvent in the presence of the catalyst, and substantially oxygen. Examples are aliphatic hydrocarbons such as butane, pentane, hexane, and heptane, aromatic hydrocarbons such as benzene, toluene, and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. Produced in the presence or absence of an inert hydrocarbon solvent. The polymerization conditions are not particularly limited, but the polymerization temperature is usually 15 to 350 ° C., preferably 20 to 200 ° C., more preferably 50 to 110 ° C., and the polymerization pressure is usually normal pressure to 70 kg / cm in the case of the low-medium pressure method.² G, preferably normal pressure to 20 kg / cm² G, usually 1500 kg / cm for high pressure method² G or less is desirable. The polymerization time is usually from 3 minutes to 10 hours, preferably from about 5 minutes to 5 hours in the case of the low and medium pressure method. In the case of the high pressure method, it is usually 1 minute to 30 minutes, preferably about 2 minutes to 20 minutes. In addition, the polymerization is not particularly limited to a one-stage polymerization method, but also a two-stage or more multi-stage polymerization method in which polymerization conditions such as hydrogen concentration, monomer concentration, polymerization pressure, polymerization temperature, and catalyst are different from each other. A particularly preferable production method includes the method described in JP-A-5-132518.
[0055]
The (A) linear low density polyethylene in the present invention is produced by using a catalyst containing no halogen such as chlorine in the above catalyst component, so that the halogen concentration is at most 10 ppm or less, preferably 5 ppm or less. More preferably, it may be substantially free (ND: 2 ppm or less).
By using such a halogen-free linear low-density polyethylene such as chlorine, it becomes unnecessary to use a conventional acid neutralizing agent, and it is excellent in chemical stability and hygiene, especially for food packaging materials, etc. It is possible to provide a pouch that is suitably used in the field.
[0056]
The blending ratio of the linear low density polyethylene (A) in the resin material (ii) forming the second layer is 50 to 100% by weight, preferably 70 to 100% by weight. When the proportion of the linear low density polyethylene is less than 50% by weight, the heat resistance, puncture strength, low temperature heat sealability, heat seal strength, and mechanical strength of the laminate are lowered.
[0057]
Other polyethylene polymers that can be blended in the resin material (ii) include high / medium / low pressure methods using Ziegler type catalysts and the like, ethylene homopolymers by known methods, ethylene and α having 3 to 12 carbon atoms. -The copolymer with an olefin, the ethylene-type (co) polymer by a high pressure radical polymerization method, etc. are mentioned.
[0058]
The ethylene homopolymer or copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms by a high, medium or low pressure method using the Ziegler type catalyst or the like and other known methods has a density of 0.94 to 0. .97 g / cm^Three High density polyethylene, density 0.91-0.94 g / cm^Three Linear low density polyethylene (LLDPE), density 0.86-0.91 g / cm^Three Very low density polyethylene (VLDPE), density 0.86-0.91 g / cm^Three And ethylene / α-olefin copolymer rubber such as ethylene / propylene copolymer rubber and ethylene / propylene / diene copolymer rubber.
[0059]
The LLDPE with the Ziegler type catalyst has a density of 0.91 to 0.94 g / cm.^Three , Preferably 0.91 to 0.93 g / cm^Three The α-olefin is a copolymer having 3 to 20 carbon atoms, preferably 4 to 12 carbon atoms. Specifically, propylene, 1-butene, 4 -Methyl-1-pentene, 1-hexene, 1-octene and the like.
[0060]
Moreover, the very low density polyethylene (VLDPE) by the said Ziegler type catalyst has a density of 0.86-0.91 g / cm.^Three , Preferably 0.88-0.905 g / cm^Three It is an ethylene / α-olefin copolymer in the range of 5 and is a polyethylene having intermediate properties between LLDPE and ethylene / α-olefin copolymer rubber (EPR, EPDM).
[0061]
The ethylene / α-olefin copolymer rubber has a density of 0.86 to 0.91 g / cm.^Three Ethylene / propylene copolymer rubber, ethylene / propylene / diene copolymer rubber, and the like. Examples of the ethylene / propylene rubber include a random copolymer (EPM) mainly composed of ethylene and propylene, and Examples of the third component include a random copolymer (EPDM) containing as a main component a diene monomer (dicyclopentadiene, ethylidene norbornene, or the like).
[0062]
The resin material (i) in the present invention may be blended with known additives and fillers.
In addition, for the resin material (ii), by using (A) linear low-density polyethylene produced using a halogen-free catalyst, and without adding additives such as an antioxidant and a neutralizing agent, A clean molded body can be provided.
[0063]
In the present invention, the resin material (ii) includes an antioxidant, an antiblocking agent, a lubricant, an antistatic agent, an antifogging agent, an ultraviolet absorber, an organic or inorganic pigment, a nucleating agent, a crosslinking agent, and the like. Additive that does not migrate to the contacted object such as the contents even if the additive is added to the resin material (ii) It is desirable that
In the present invention, an additive that elutes to the outside, for example, when the content is a liquid, an additive that elutes into the liquid, an additive that migrates odors, or with time Since the additive which is unevenly distributed on the film surface is not contained in the resin material (ii), it is possible to provide a hygienic and clean laminate and container with less odor.
[0064]
In the present invention, the additive that does not substantially transfer to the contacted material is a filler such as an organic or inorganic filler, does not change the property of the contacted material, and essentially has the characteristics of the resin sheet of the present invention. It is an additive that can be added as long as it does not interfere with the above.
Inorganic fillers include calcium carbonate, talc, silica, clay, carion, alumina, aluminum hydroxide, magnesia, magnesium hydroxide, calcium sulfate, calcium sulfite, barium sulfate, aluminum silicate, calcium silicate, sodium silicate, potassium silicate, carbonic acid Examples include magnesium, barium carbonate, calcium oxide, titanium oxide, zinc oxide, mica, glass flake, zeolite, diatomaceous earth, perlite, permiculite, shirasu balloon, glass microsphere, fly ash, and glass beads.
Examples of the organic filler include polymethyl methacrylate cross-linked product, polyethylene terephthalate cross-linked product, phenol resin and other synthetic resin powders and fine beads, wood powder, and pulp powder.
These fillers can be blended for the purpose of improving the rigidity of the laminate.
[0065]
The laminate in the present invention has a first layer made of the polyolefin resin material (i) and a second layer made of the resin material (ii) mainly composed of the linear low density polyethylene (A). It is.
[0066]
In addition, when the laminated body in the present invention is formed into a pouch, a layer corresponding to the innermost layer of the pouch is formed as a second layer, and characteristics of each layer (layer I: rigidity, water vapor barrier property, aroma retaining property) , Layer II: low temperature heat sealability, heat seal strength, puncture strength, hygiene) is essential.
Another layer may be interposed between the I layer and the II layer. Examples of the other layer include an adhesive resin layer for bonding the I layer and the II layer more firmly.
[0067]
In the laminate of the present invention, the second layers are bonded to each other at a heat seal temperature of 120 ° C. and a heat seal pressure of 1 kg / cm.² The heat seal strength (hereinafter referred to as 120 ° C. heat seal strength) when heat-sealed under the condition of a heat seal time of 1 second is preferably in the range of 2.5 to 6 kg / 15 mm.
[0068]
Here, the 120 ° C. heat seal strength is specifically measured as follows.
Using a heat seal tester (seal bar width 1 mm), the pouch's II layers were sealed at a seal temperature of 120 ° C. and a seal pressure of 1 kg / cm.² After heat conditioning at room temperature 23 ° C. and humidity 50% for 24 hours, the heat seal part was cut into a strip shape with a width of 15 mm, and the heat seal part was peeled off at 300 mm / min with a tensile tester. Measure maximum load.
[0069]
In the laminate of the present invention, the second layers are bonded to each other with a heat seal pressure of 1 kg / cm² The heat seal temperature (hereinafter referred to as a 3 kg load heat seal temperature) that gives a heat seal strength of 3 kg / 15 mm when heat sealed under the condition of a heat seal time of 1 second is in the range of 85 to 125 ° C. Is desirable. When the 3 kg load heat seal temperature is less than 85 ° C., the heat resistance is poor, and when it exceeds 125 ° C., the high-speed filling property is poor.
[0070]
Here, the 3 kg load heat seal temperature is specifically measured as follows.
Using a heat seal tester (seal bar width 1 mm), pouch II layers were heated at a heat seal temperature of 80 ° C. and a heat seal pressure of 1 kg / cm.² After heat conditioning at room temperature 23 ° C. and humidity 50% for 24 hours, the heat seal part was cut into a strip shape with a width of 15 mm, and the heat seal part was peeled off at 300 mm / min with a tensile tester. Measure the maximum load (heat seal strength).
The above measurement is repeated while increasing the heat seal temperature by 5 ° C., and the heat seal strength at 85, 90, 95, 100, 105, 110, 115, 120, 125 and 130 ° C. is measured. The heat seal strength is plotted against the heat seal temperature to create a heat seal temperature-heat seal strength curve, and the heat seal temperature at a heat seal strength of 3 kg / 15 mm is read from this curve.
[0071]
The thickness of the laminate in the present invention varies depending on the purpose, application, etc., but is generally in the range of 10 μm to 0.5 mm, preferably 30 μm to 0.3 mm, more preferably 50 μm to 0.2 mm. Is preferably selected.
Further, the thickness of each of the first layer and the second layer of the laminate of the present invention is 3 μm to 0.4 mm, preferably selected in the range of 10 μm to 0.2 mm / 10 μm to 02 mm, respectively. It is preferable. Moreover, it is preferable that the thickness ratio (I layer: II layer) of each layer is 1: 10-10: 1.
[0072]
The laminate in the present invention may have a barrier layer (III) that adheres to the first layer. By providing the barrier layer (III), the water vapor barrier property and the aroma retaining property are further improved. The barrier layer (III) can also serve as a pouch reinforcement, a protective layer, a printing layer, and a light shielding layer, and further serves as a heat-resistant layer for maintaining the shape of the pouch during heat sealing. I'm in charge.
[0073]
Examples of the barrier layer (III) include polypropylene resins, polyamide resins, polyester resins, saponified ethylene-vinyl acetate copolymers, polyvinylidene chloride, polycarbonate and other plastic films or sheets (stretched products and printed materials thereof). And metal foils such as aluminum, iron, copper, and alloys containing these as main components. Further, a metal plate, cellophane, paper, woven fabric, non-woven fabric or the like may be used in some cases without departing from the spirit of the present invention.
[0074]
Moreover, you may form with the blend resin of the resin material (i) obtained by recycle | recycling any one of the said 1st layer and the 2nd layer which comprises a laminated body. Moreover, the laminated body which comprises the pouch of this invention may further have the recycled resin layer (IV) which consists of the said blend resin. Here, the blend resin obtained by recycling the laminate is a defective product of the laminate, a collected product of the pouch made of the laminate, a mixed resin obtained by pulverizing burrs and the like generated in the finishing stage after processing on the pouch and the like. That is.
As described above, the pouch of the present invention can use a recycled blend resin, and has good recyclability because the same kind of resin material is used.
[0075]
Examples of the laminate include I / II /, I / III / II, III / I / II, I / adhesive / IV / adhesive / II, and the like. More specifically, HD / SLL, HD + LL / SLL, HD / SLL + LD, HD + LL / SLL + LD, RC / SLL, RC / HD / SLL, RC + HD / SLL, HD / LL, barrier layer (EVOH, PA, PEs, OPP Etc.) / Adhesive / HD / SLL, etc. (where HD: high density polyethylene, LD: high pressure radical polymerization low density polyethylene, LL: linear low density polyethylene, SLL: specific (A) linear Low density polyethylene, RC: Recycled blend resin, EVOH: Saponified ethylene-vinyl acetate copolymer, PA: Polyamide resin, PEs: Polyester resin, OPP: Oriented polypropylene resin, Adhesive: Acid-modified polyethylene resin ).
[0076]
Since the laminate in the present invention is excellent in rigidity (waist), it can be suitably used for a standing pouch that requires independence.
In addition, since the laminate in the present invention can exhibit sufficient heat seal strength even at a relatively low heat seal temperature, a pouch or the like can be manufactured with a low temperature heat seal, and the manufactured pouch or the like , Odor is not generated and the quality of the contents is not deteriorated.
[0077]
The laminate in the present invention can be produced by various methods, but is preferably produced by molding the I layer and the II layer by a coextrusion method. As a molding method, it can be manufactured with high productivity by, for example, a multilayer inflation molding method, a multilayer cast molding method, or the like. Among these, the multilayer inflation molding method is preferably used in terms of economy, moldability, and the like.
[0078]
The production of the sheet by the multilayer inflation molding method can be performed by a conventional air-cooled blown film production apparatus. For example, each resin material is extruded through a circular die from an extruder at a temperature of 150 to 250 ° C., and then from an air-cooled air ring. It is brought into contact with the air blown out, rapidly cooled, solidified, taken up with a pinch roll, and then wound around a frame.
[0079]
In addition to air-cooling method inflation molding, it can also be produced by water-cooling method inflation molding, T-die method, etc., and a sheet having good transparency and low-temperature impact properties can be obtained.
[0080]
It is also possible to sandwich a hollow tube obtained by multi-layer inflation molding at least the resin material (i) and the resin material (ii) to form a laminate of three or more layers. As a method of obtaining such a laminate, a method of crushing a hollow tube formed by extruding each resin material through a circular die with a pinch roll at a temperature higher than the melting point of the inner layer resin material, Examples include a method in which a hollow tube formed by extruding each resin material through a circular die is brought into contact with air blown from an air-cooled air ring, cooled and solidified, and then sandwiched with a heated pinch roll. According to such a manufacturing method, an inexpensive and economical laminate can be obtained.
[0081]
Thus, by producing a laminate by the multilayer inflation molding method, (1) there is no unevenness as in the laminate obtained by the T-die method, and (2) the resin is uniformly crystallized due to slow cooling by air cooling. (3) Blow-up ratio (BUR): (3) Blow-up ratio (BUR) can be obtained. Can be adjusted and quality can be controlled. (5) Compared with T-die method, there is no ear loss, high productivity and excellent economy. (6) Multiply by crushing with pinch rolls The thick sheet can be formed at a time and the thickness can be homogenized.
[0082]
In the pouch of the present invention, the above laminate is heat-sealed so that the second layer is on the inside to form a bag.
Types of pouches include self-supporting standing pouches, retort pouches for retort foods having a barrier layer made of aluminum foil, pouches with a spout for drinking, and more specifically, flexible spout pouches, dual chamber pouches, Examples include dispenser pouches.
Examples of the shape of the pouch include a gusset bag, a four-side seal bag, a three-sided seal bag with a palm joint, and a bag in which the top and bottom of a tubular film are sealed by an inflation method.
[0083]
As a heat sealing method, a known method can be used, and examples thereof include an external heating method such as a heating bar, a heating knife, a heating wire, and an impulse seal, and an internal heating method such as an ultrasonic seal and a dielectric heat seal.
[0084]
The pouch according to the present invention, particularly the standing pouch, is excellent in rigidity (waist), and thus has excellent self-sustainability, and can be reduced in thickness and weight.
In addition, the pouch of the present invention can exhibit sufficient heat seal strength even at a relatively low heat seal temperature, so that the laminate can be manufactured with a low temperature heat seal, and the occurrence of odor is low, The quality of the contents is not deteriorated.
[0085]
Such pouches can be widely used as food packaging materials such as edible oils, seasonings, dried foods, processed foods; daily packaging materials such as liquid detergents, shampoos and rinses; medical packaging materials such as infusion bags. it can.
[0086]
【Example】
EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in more detail, this invention is not limited by these Examples.
[0087]
The test method in this example is as follows.
[density]
Conforms to JIS K6760.
[MFR]
Conforms to JIS K6760.
[Mw / Mn]
GPC (Waters 150C type) was used, and ODCB at 135 ° C. was used as a solvent. The column used was Shodex HT806M.
[0088]
[T by DSC_mlMeasurement]
A sheet having a thickness of 0.2 mm was formed by hot pressing, and a sample of about 5 mg was punched from the sheet. The sample was held at 230 ° C. for 10 minutes and then cooled to 0 ° C. at 2 ° C./min. Thereafter, the temperature was raised again to 170 ° C. at 10 ° C./min, and the temperature at the top of the maximum temperature peak that appeared was defined as the maximum peak temperature Tml.
[TREF]
With the column kept at 140 ° C., a sample was injected into the column, the temperature was lowered to 25 ° C. at 0.1 ° C./min, the polymer was deposited on glass beads, and then the column was heated under the following conditions. The polymer concentration eluted at each temperature was detected with an infrared detector. (Solvent: ODCB, flow rate: 1 ml / min, heating rate: 50 ° C./hr, detector: infrared spectrometer (wavelength 2925 cm^-1), Column: 0.8 cmφ × 12 cmL (filled with glass beads), sample concentration: 0.05 wt%)
[0089]
[Melt tension (MT)]
The stress when the molten polymer was stretched at a constant speed was determined by measuring with a strain gauge. The measurement sample was granulated into pellets and measured using an MT measuring device manufactured by Toyo Seiki Seisakusho. The orifice used has a hole diameter of 2.09 mmφ and a length of 8 mm. The measurement conditions are a resin temperature of 190 ° C., a cylinder lowering speed of 20 mm / min, and a winding speed of 15 m / min.
[Chlorine concentration]
When measured by a fluorescent X-ray method and 10 ppm or more of chlorine was detected, this was used as an analytical value. When it was less than 10 ppm, it was measured with a TOX-100 type chlorine / sulfur analyzer manufactured by Dia Instruments Co., Ltd., and 2 ppm or less was regarded as ND, which was not substantially included.
[0090]
<Evaluation of laminate>
[Heat seal strength]
Tester Sangyo Co., Ltd. heat seal tester (seal bar width 1mm, seal pressure 1kg / cm² ), The layers II of the laminate were sealed for 1 second at a heat seal temperature of 120 ° C., conditioned for 24 hours at a room temperature of 23 ° C. and a humidity of 50%, and then the seal portion was cut into a strip shape with a width of 15 mm and pulled. The seal part was peeled off at 300 mm / min with a testing machine, and the maximum load was measured.
[3kg load heat seal temperature]
Tester Sangyo Co., Ltd. heat seal tester (seal bar width 1mm, seal pressure 1kg / cm² ), The two layers of the laminate are heated at a heat seal temperature of 80 ° C. and a heat seal pressure of 1 kg / cm.² After heat conditioning at room temperature 23 ° C. and humidity 50% for 24 hours, the heat seal part was cut into a strip shape with a width of 15 mm, and the heat seal part was peeled off at 300 mm / min with a tensile tester. Maximum load (heat seal strength) was measured
The above measurement was repeated while increasing the heat seal temperature by 5 ° C., and the heat seal strength at 85, 90, 95, 100, 105, 110, 115, 120, 125 and 130 ° C. was measured. The heat seal strength was plotted against the heat seal temperature to create a heat seal temperature-heat seal strength curve, and the heat seal temperature at a heat seal strength of 3 kg / 15 mm was read from this curve.
[0091]
[Pinhole resistance]
A test piece having a width of 200 mm and a length of 300 mm was cut from the laminate in the flow direction during molding. This test piece was attached to a gelbo flex tester manufactured by Rigaku Kogyo Co., Ltd., and after 3000 stroke load at room temperature, the number of pinholes of the test piece was measured. The same test was repeated three times, and the average number of pinholes was determined.
[Water vapor transmission rate]
Conforms to JIS K7129.
[Haze]
Conforms to ASTM D1003.
[Tensile modulus]
Based on ASTM D882, it measured about MD (extrusion direction).
[Tensile impact strength]
Based on ASTM D1822, it measured about MD (extrusion direction).
[0092]
<Evaluation of pouch>
[Odor and hygiene]
Distilled water (500 ml) was filled, stored in an oven at 40 ° C. for 72 hours, cooled to room temperature, 20 ml of the content liquid was transferred to a porcelain vessel, and a sensory test was conducted for the presence of suspended matter, odor, and taste.
◎: Good
○: Relatively good
Δ: Somewhat bad
×: Defect
[0093]
[Heat-resistant]
The container filled with 500 ml of distilled water was autoclaved at 121 ° C. for 20 minutes, and the deformation was visually observed.
○: No deformation
Δ: Slightly deformed
×: Significant deformation
[Drop test]
After the containers filled with 500 ml of distilled water were conditioned for 24 hours in an atmosphere at 5 ° C., 10 containers were dropped from a height of 1.2 m, and the number of broken containers was examined.
○: No bag breakage
Δ: 1-2 broken bags
×: Three or more bags broken
[Autonomy]
A cylinder having a diameter of 200 mmφ and a height of 300 mm was produced and judged from the deflection of the upper opening when it was self-supporting.
○: No tampering
Δ: Slightly deflected
×: Deflection is remarkable
[0094]
Various components used in Examples and Comparative Examples are as follows.
[(A) Linear low density polyethylene]
1) (A1) A specific linear low density polyethylene was polymerized by the following method.
(Preparation of solid catalyst)
To a catalyst preparation apparatus equipped with an electromagnetic induction stirrer, 1000 ml of toluene purified under nitrogen, tetraethoxyzirconium (Zr (OEt))_Four 22 g and 74 g of indene were added, and 100 g of tripropylaluminum was added dropwise over 100 minutes while maintaining the temperature at 90 ° C., and then reacted at the same temperature for 2 hours. After cooling to 40 ° C., 3200 ml of a toluene solution of methylalumoxane (concentration 2.5 mmol / ml) was added and stirred for 2 hours. Next, silica pre-fired at 450 ° C. for 5 hours (Grace, # 952, surface area 300 m² / G) After adding 2000 g and stirring at room temperature for 1 hour, nitrogen blowing and vacuum drying were performed at 40 ° C. to obtain a solid catalyst having good fluidity.
[0095]
(Gas phase polymerization)
Using a continuous fluidized bed gas phase polymerization apparatus, polymerization temperature 80 ° C., total pressure 20 kgf / cm² With G, ethylene and 1-hexene were copolymerized. The solid catalyst was continuously supplied, and ethylene, 1-hexene and hydrogen were supplied so as to maintain a predetermined molar ratio, and polymerization was performed to obtain an ethylene copolymer (LLDPE-1). Moreover, what is the same ethylene copolymer as LLDPE-1 and does not contain an additive was designated as LLDPE-3. These physical properties are shown in Table 1.
[0096]
2) (A2) The specific linear low density polyethylene was polymerized by the following method.
Using the above-described continuous fluidized bed gas phase polymerization apparatus, polymerization temperature 75 ° C., total pressure 20 kgf / cm² With G, ethylene and 1-hexene were copolymerized. The solid catalyst was continuously supplied, and ethylene, 1-hexene and hydrogen were supplied so as to maintain a predetermined molar ratio, and polymerization was performed to obtain an ethylene copolymer (LLDPE-2). The physical properties are shown in the table.
[0097]
[Other linear low density polyethylene]
1) Ethylene hexene-1 copolymer (M-LLDPE) with a general metallocene catalyst
Purified toluene is put into a pressure reactor equipped with a stirrer substituted with nitrogen, 1-hexene is added, and a mixed solution of bis (n-butylcyclopentadienyl) zirconium dichloride and methylalumoxane (MAO) is added. After adding (Al / Zr molar ratio = 500), the temperature was raised to 80 ° C. to prepare a metallocene catalyst. Next, ethylene is put in, and the total pressure is 6 kg / cm while continuously polymerizing ethylene.^Three Polymerization was carried out while maintaining an ethylene / hexene-1 copolymer (M-LLDPE).
The physical properties are shown in Table 1.
[0098]
2) Linear low density polyethylene (Z-LLDPE) using a commercially available Ziegler type catalyst
The physical properties are shown in Table 1.
[0099]
[Table 1]

[0100]
[Density 0.94g / cm^Three The following polyethylene resins]
High pressure low density polyethylene: HP-LDPE
MFR = 2.0 g / 10 min, density = 0.923 g / cm^Three
[Bend elastic modulus 2500kgf / cm²Above polyolefin resin]
(1) High density polyethylene
Ethylene / 1-butene copolymer (HDPE: MFR = 1.5 g / 10 min, density = 0.951 g / cm^Three , Flexural modulus = 11,000)
(2) Ethylene / 1-butene copolymer (MDPE: MFR = 1.0 g / 10 min, density = 0.842 g / cm^Three , Flexural modulus = 10,000)
(3) Ethylene / propylene copolymer (PP: ethylene content = 3 wt%, flexural modulus = 12,500)
[0101]
[Examples 1-6, Comparative Examples 1-3]
HDPE and HP shown in Tables 2 to 4 in which an antioxidant (Irganox 1076 = 0.1% by weight, Irgaphos 168 = 0.1% by weight) and calcium stearate (neutralizing agent = 0.1% by weight) were blended. -LDPE, LLDPE (however, no antioxidant is added to LLDPE-3) using a two-layer inflation molding machine (two 40 mmφ extruders) manufactured by Tommy Machine Industry Co., Ltd., molding lip gap 3 mm, molding temperature Molded under the conditions of 200 ° C., a laminate having a width of 300 mm and having a layer thickness configuration shown in Tables 2 to 4 was produced.
Then, O-nylon (thickness 15 μm, manufactured by Unitika Co., Ltd.) was bonded by a dry laminating method using an adhesive (anchor coating agent: Toyo Morton TM-329).
[0102]
Further, the third layers of the laminated body are placed at a temperature of 3 kg load heat seal temperature + 5 ° C. and a pressure of 1 kg / cm.²A standing pouch with an internal volume of 500 ml was manufactured by heat sealing for 1 second, and the laminate and the pouch were evaluated. The results are shown in Tables 2-4.
[0103]
[Table 2]

[0104]
[Table 3]

[0105]
[Table 4]

[0106]
As is clear from the results in Tables 2 and 3, it can be seen that the laminates of the examples are excellent in heat sealability, pinhole resistance, water vapor barrier properties, transparency, and mechanical strength. Moreover, the pouches of the examples had sufficient heat resistance and drop strength. In particular, the pouch using LLDPE-1 containing almost no halogen in the inner layer (the second layer) has little odor and excellent hygiene.
[0107]
On the other hand, as is clear from the results of Table 4, the laminate and pouch of Comparative Example 1 did not use the specific (A) linear low density polyethylene in the second layer, but used MDPE, so the heat seal strength, It was inferior in pinhole property, tensile impact strength, and drop strength.
Since the laminate and pouch of Comparative Example 2 used HP-LDPE instead of (A) linear low-density polyethylene for the II layer, the heat seal strength, pinhole resistance, tensile impact strength, and drop strength were improved. It was inferior and the odor was intense and the hygiene was poor.
Since the laminate and the pouch of Comparative Example 3 also used Z-LLDPE instead of (A) linear low-density polyethylene in the II layer, heat seal strength, pinhole resistance, tensile impact strength, and drop strength were achieved. It was inferior and had an odor and poor hygiene.
The laminate and pouch of Comparative Example 4 were inferior in heat resistance, drop strength, and independence because LDPE was used for the first layer.
[0108]
【The invention's effect】
As described above, the pouch of the present invention has a flexural modulus of 2500 kgf / cm.² From the first layer made of the polyolefin-based resin material (i) and the resin material (ii) mainly composed of linear low-density polyethylene that satisfies the requirements (a) to (d) described above Since the layered product with the second layer is formed into a bag shape so that the second layer is on the inside, rigidity, low temperature heat sealability, water vapor barrier property, aroma retention, hygiene Excellent heat resistance and high heat seal strength and puncture strength.
[0109]
Moreover, if the heat seal temperature is such that the heat seal strength when heat-sealing the second layers is 3 kg / 15 mm is in the range of 85 to 125 ° C., the heat resistance and the high-speed filling property are further improved.
In addition, if the thickness of the laminate is 10 μm to 0.5 mm and the thickness of each of the first and second layers is in the range of 3 μm to 0.4 mm, it is easy to use and the characteristics of each layer are sufficiently exhibited. Become a pouch.
Moreover, if the laminated body further has a barrier layer (III), the water vapor barrier property and the aroma retaining property of the pouch are further improved.
Further, any one of the first layer and the second layer is formed of a blend resin of the resin material (i) and the resin material (ii) obtained by recycling the laminate, or the blend resin If the recycled resin layer (IV) made of is further provided, a recycled blend resin can be used, and the recyclability is improved.
[0110]
Further, if the (A) linear low density polyethylene further satisfies the above requirements (e) and (f) (A1) linear low density polyethylene, the pouch has heat resistance, hygiene and rigidity. Further improve.
Further, if the (A) linear low density polyethylene further satisfies the above-mentioned requirements (g) and (h) (A2), the heat resistance and heat seal strength of the pouch are further increased. improves.
Further, if the (A2) linear low density polyethylene further satisfies the requirement (i) described above, the moldability is further improved.
[0111]
The (A) linear low density polyethylene is obtained by copolymerizing ethylene and an α-olefin in the presence of a catalyst containing at least an organic cyclic compound having a conjugated double bond and a transition metal compound of Group IV of the periodic table. If it is a linear ethylene copolymer obtained in this way, the mechanical characteristics, heat sealing properties, heat blocking properties, and heat resistance of the pouch are further improved.
In addition, the additive blended in the resin material (ii) is an additive that does not substantially transfer to a contacted object, or if the additive is not blended in the resin material (ii), there is little odor, A sanitary pouch can be obtained.
Moreover, if the halogen concentration of the resin material (ii) is 10 ppm or less, it is possible to provide a pouch that is excellent in chemical stability and hygiene and that is suitably used particularly in the field of food packaging materials and the like.
[Brief description of the drawings]
FIG. 1 is a graph showing an elution temperature-elution amount curve of (A) or (A2) linear low density polyethylene in the present invention.
FIG. 2 is a graph showing an elution temperature-elution amount curve of (A1) linear low density polyethylene in the present invention.
FIG. 3 is a graph showing an elution temperature-elution amount curve of an ethylene copolymer with a metallocene catalyst.

Claims (11)

A first layer made of a polyolefin resin material (i) having a density of 0.93 g / cm ³ or more as a main component and medium and high density polyethylene and / or polypropylene resin and a flexural modulus of 2500 kgf / cm ² or more; Satisfying the following requirements (a) to (d) produced in the presence of a catalyst comprising at least an organic cyclic compound having a conjugated double bond and a transition metal compound of Group IV of the Periodic Table (A) linear low A layered body in which a layer II composed of a resin material (ii) mainly composed of high density polyethylene and a barrier layer (III) composed of a barrier material (iii) bonded to the layer I is layered II A pouch formed into a bag shape so that the layer is on the inside.
(A) a density of 0.86 to 0.94 g / cm ³ ,
(B) A melt flow rate of 0.01 to 50 g / 10 minutes,
(C) molecular weight distribution (Mw / Mn) is 1.5 to 4.5,
(D) Difference between temperature T _{25 at} which 25% of the elution is obtained from the integral elution curve of the elution temperature-elution amount curve by continuous temperature rising elution fractionation method (TREF) and temperature T _{75 at} which 75% of the elution is eluted T ₇₅ −T ₂₅ and density d satisfy the relationship of the following (formula 1) (formula 1) T ₇₅ −T ₂₅ ≦ −670 × d + 644 The heat seal temperature is such that the heat seal strength is 3 kg / 15 mm when the second layers are heat sealed under conditions of a heat seal pressure of 1 kg / cm ² and a heat seal time of 1 second. The pouch according to claim 1 , wherein the pouch is provided. The pouch according to claim 1 or 2 , wherein the laminate has a thickness of 10 µm to 0.5 mm, and each of the first layer and the second layer has a thickness of 3 µm to 0.4 mm. . The I layer or the II layer is formed of a blend resin of the resin material (i), the resin material (ii) and the barrier material (iii) obtained by recycling the pouch, or from the blend resin The pouch according to any one of claims 1 to 3, wherein a recycled resin layer (IV) is further provided in the laminate. (A) the linear low density polyethylene further below (e) and claims 1, characterized in that it is satisfying the requirements of (f) (A1) linear low density polyethylene to 4 any one The pouch described.
(E) The amount of orthodichlorobenzene (ODCB) soluble component X (wt%), density d and melt flow rate (MFR) at 25 ° C. satisfy the relationship of the following (formula 2) and (formula 3) (formula 2) When d−0.008log MFR ≧ 0.93, X <2.0
(Formula 3) When d−0.008 log MFR <0.93 X <9.8 × 10 ³ × (0.9300−d + 0.008 log MFR) ² +2.0
(F) Multiple peaks of elution temperature-elution amount curve by continuous temperature rising elution fractionation method (TREF) exist. (A) the linear low density polyethylene further (g) below and claims 1, characterized in that it is satisfying the requirements of (h) (A2) linear low density polyethylene to 4 any one The pouch described.
(G) There is one peak of the elution temperature-elution amount curve by continuous temperature rising elution fractionation method (TREF), and T ₇₅ -T ₂₅ and density d satisfy the relationship of the following (formula 4). Formula 4) T ₇₅ −T ₂₅ ≧ −300 × d + 285
(H) It has 1 to 2 melting point peaks, and the highest melting point T _ml and density d satisfy the relationship of the following (formula 5) (formula 5) T _ml ≧ 150 × d−17 The pouch according to claim 6, wherein the (A2) linear low density polyethylene further satisfies the following requirement (i).
(I) Melt tension (MT) and melt flow rate (MFR) satisfy the following (formula 6) (formula 6) logMT ≦ −0.572 × logMFR + 0.3 The additive blended in the resin material (ii) is an additive that does not substantially transfer to a contacted object, or the additive is not blended in the resin material (ii). The pouch according to any one of 7 to 7 . The pouch according to any one of claims 1 to 8, wherein the halogen concentration of the resin material (ii) is 10 ppm or less. The shape of the pouch is one selected from a gusset bag, a four-sided seal bag, a three-sided seal bag with a palm joint, and a bag that seals the top and bottom of a tubular film by an inflation method. The pouch described. The pouch according to any one of claims 1 to 10, wherein the pouch is any one of food packaging materials, daily necessities packaging materials, and medical packaging materials.

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