JP2012139848A - Packaging material and liquid packaging bag using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a packaging material which includes a base material layer, an intermediate layer and a sealant layer and is excellent in pressure-resistant strength, heat-sealing strength and a foreign matter heat-sealing property and enables high-speed filling over a wide sealing temperature range from low temperature to high temperature, and to provide a liquid packaging bag using the packaging material.SOLUTION: The packaging material includes the base material layer, the intermediate layer and the sealant layer, wherein an ethylene-α-olefin copolymer satisfying following conditions (a) to (c) is used as the intermediate layer; (a) density is 0.860 to 0.970 g/cmwhen measured based on JISK6992-2:1997 appendix (23°C), (b) a melt flow rate is 0.5 to 100g/10 minutes when measured based on JISK6992-2:1997 appendix (190°C and 21.18 N-load), (c) a ratio of viscosity η(Pa S) at a shear rate 60(sec) to viscosity η(Pa S) at a shear rate 1,200(sec) (η/η) is within a range between 3.5 and 7.0 when measured by a capillograph at 190°C.

Description

The present invention relates to a packaging material and a liquid packaging bag using the same, and more particularly to a packaging material having at least a base material layer, an intermediate layer and a sealant layer, and a liquid packaging bag using the packaging material.
In particular, the present invention is suitable for extrusion processing (reduction of mechanical load, film processability, laminate processability, etc.), automatic filling suitability when the packaging material is used as a packaging bag for liquids and sticky bodies in an automatic filling machine. In order to satisfy various performances (such as heat seal strength, heat seal temperature range, heat seal speed, hot tack property) and product characteristics (appearance, pressure resistance, bag breaking strength, puncture strength, etc.) A specific ethylene-α-olefin copolymer with high viscosity at shear rate and low viscosity at high shear rate, i.e. the ratio of high shear rate to low shear rate measured at a temperature close to the actual filling By using an ethylene / α-olefin copolymer in the range, the pressure resistance, heat seal strength and foreign matter heat sealability are high, and high speed filling is possible over a wide range of seal temperatures from low to high temperatures. In addition to satisfying the above-mentioned automatic filling suitability, it is improved so as to satisfy the extrusion processing suitability such as reduction of mechanical load at the same time.

Conventionally, polyamide resins, polyethylene terephthalate resins, polypropylene resins, etc. that are excellent in transparency and mechanical strength have been used as packaging substrates. However, these base materials have problems such as a high heat seal temperature, inability to increase the packaging speed, shrinkage of the film during heat sealing, deterioration of the packaging appearance, and low heat seal strength. Is rarely used alone, and usually a composite film provided with a heat seal layer is used.
For example, liquid and mucous bodies, and liquids including solids such as fibers and powders as insoluble substances, and packaging substrates such as mucous bodies include surface groups made of polyamide resin, polyethylene terephthalate resin, paper, aluminum foil, etc. There are known composite films in which a sealant layer is provided on a material layer, or packaging films obtained by laminating various intermediate layers on a substrate and further laminating a sealant layer thereon.

  As a film for the sealant layer of such a composite film, low density polyethylene (LDPE), ethylene-vinyl acetate copolymer (EVA), etc. were originally used, but LDPE film is a high-speed moldability (processability). However, although EVA is excellent in low temperature heat sealability, it has difficulties in heat resistance and hot tack property.

In order to improve these, on the base material layer, a random copolymer of ethylene having specific physical properties and a density of 0.910 to 0.940 g / cm ³ and an α-olefin having 4 to 10 carbon atoms, and high pressure A composite film in which a sealant layer made of a blend composition of a method low density polyethylene (hereinafter sometimes abbreviated as HPLD) is laminated has been proposed (see Japanese Patent Publication No. 02-004425).
Further, as a laminate composition that maintains the heat seal strength and hot tack property of the composite film, and further improves the low temperature heat seal property, a specific temperature rise elution fractionation (hereinafter abbreviated as TREF) produced with a metallocene catalyst. A blend composition of ethylene and a C3-C18 α-olefin exhibiting characteristics and a specific low-density polyethylene (Patent Document 2: Japanese Patent Laid-Open No. 07-026079) Alternatively, as a similar polyethylene composition for composite film, a density of 0.880 to 0.930 g / cm ³ produced with a metallocene catalyst and ethylene having a molecular weight distribution of 1.5 to 4.0 and a carbon number of 4 to 10 A composition comprising a random copolymer with an α-olefin and a high-pressure low-density polyethylene has been proposed (Patent Document 3: Special). See JP-A-flat 8 over 269,270).

  However, the sealant layer composed of the blend composition of the specific ethylene-α-olefin random copolymer and the high-pressure method low-density polyethylene as described above has a heat seal strength and a higher hot strength than the conventional low-density polyethylene sealant layer. Excellent tackiness. However, in the case of liquid packaging of soups, sauces, sauces, noodle soup, etc., the vertical and horizontal sealing of the composite film (packaging material) is performed using an automatic filling machine such as a die roll type. A filling bag is formed by being sandwiched between the rolls and sealed. However, when a sealant made of the above blend composition is used in such a heat seal method, the heat seal part is thinned, causing bag breakage or peeling between the base material and the sealant layer. was there.

In order to solve such a problem, a multilayer film in which an intermediate layer is provided between a base material and a sealant layer has been proposed. In such a multilayer film comprising the outer layer (A) / intermediate layer (B) / inner layer (C), the outer layer (A) and the inner layer (C) have an ethylene-α-olefin copolymer (1) and an intermediate layer (B ) An ethylene-α-olefin copolymer (2) having a density at least 0.003 g / cm ³ higher than the ethylene-α-olefin copolymer (1), and an ethylene-α-olefin copolymer (1) Proposed to be a co-extruded multilayer film for bonding using a resin composition comprising an ethylene-α-olefin copolymer (3) having the same density or lower density and low-density polyethylene by a high-pressure radical polymerization method (Patent Document 4: JP-A-10-323948),

In addition, as an intermediate layer of a multilayer film in which at least a base material layer, an intermediate layer and a sealant layer are laminated in this order, a mixing ratio of linear low density polyethylene (A) and high pressure method low density polyethylene (B) [(A) / (B)] is a resin composition having a ratio of 70/30 to 40/60, and the linear low-density polyethylene (A) is a copolymer of ethylene and an α-olefin having 4 or more carbon atoms. A polymer having a melt flow rate of 1 to 50 g / 10 min, a density of 0.890 to 0.930 g / cm ³ , and a molecular weight distribution of Mw / Mn of 1.5 to 4.0 It is also proposed to use a high-pressure low-density polyethylene (B) having a melt tension of 2 g or more (Patent Document 5: JP-A-11-010809).

  Furthermore, as an intermediate layer of a multilayer film in which at least a base material layer, an intermediate layer and a sealant layer are laminated in this order, 50 to 95% by weight of a linear low density polyethylene (A) produced from a metallocene catalyst and a high pressure method It has been proposed to use a resin composition of 50 to 5% by weight of low density polyethylene (B) (Patent Document 6: JP 2001-0099997 A).

  However, even in a multilayer film provided with an intermediate layer composed of these compositions, when the content is sealed as a contaminant in the seal portion when the content is filled, the seal portion is caused by pressure and heat received from the heat sealer portion. As a result, a resin pool (a state in which the sealant layer and the intermediate layer portion are raised in a bump shape) based on the peeling of the base material and the intermediate layer is generated, and a heat seal failure occurs. On the other hand, if the pressure and temperature of the heat sealer are lowered, heat seal failure such as reduced heat seal strength and pressure resistance strength will be caused, and liquid leakage due to foreign matter is likely to occur. As a result, it is necessary to lengthen the heat seal time As a result, the filling speed could not be increased.

On the other hand, in order to increase the filling speed, a multilayer film in which a crystal nucleating agent is blended with the composition of the intermediate layer has been proposed in an attempt to widen the heat seal temperature range and prevent bag breakage.
For example, in a packaging material having at least one sealant layer on a base film, the sealant layer is composed of an intermediate layer composed of an ethylene-α-olefin copolymer and a crystal nucleating agent, and an ethylene-α-olefin copolymer. A packaging material composed of an innermost layer is proposed (Patent Document 7: Japanese Patent Laid-Open No. 10-315409).

In addition, as an attempt to improve the heat seal temperature range, prevention of bag breakage, etc., both the crystallization start temperature and the melting end temperature were considered in which the intermediate layer has one or more melting peak temperatures and crystallization peak temperatures by DSC. A composition or the like has been proposed (Patent Document 8: Japanese Patent Laid-Open No. 11-254614).
Further, a polyethylene resin composition comprising an ethylene-α-olefin copolymer having a density of 0.90 to 0.93 g / cm ³ having three peaks by temperature rising elution fractionation (TREF), and a high-pressure radical method low-density polyethylene. Has been proposed (Patent Document 9: Japanese Patent Application Laid-Open No. 2007-204628).

Although the multilayer film improved by these has obtained a certain evaluation and has been put into practical use, in order to cope with various contents, differences in base materials, etc., a filling device such as a heat seal temperature is used. It is necessary to adjust the setting conditions. However, the conventional one has a narrow tolerance range for each packaging material, and it is necessary to search for an appropriate filling condition each time, and the problem of complications cannot be solved.
Moreover, in order to achieve further higher speed, low temperature heat sealability associated with high speed filling, improvement of a wide seal temperature range (width) from low temperature to high temperature, improvement of bag breaking strength performance, and the like are required.

Japanese Patent Publication No. 02-004425 Japanese Patent Application Laid-Open No. 07-026079 Japanese Patent Laid-Open No. 08-269270 JP-A-10-323948 Japanese Patent Laid-Open No. 11-010809 JP 2001-009997 A Japanese Patent Laid-Open No. 10-315409 JP-A-11-254614 JP 2007-204628 A

  An object of the present invention is to provide a packaging material having at least a base material layer, an intermediate layer and a sealant layer when used as a packaging bag for liquids and mucilages in an automatic filling machine. Materials with high viscosity and low viscosity at high shear rates, especially ethylene / α-olefin copolymers in which the ratio of high shear rate to low shear rate measured at temperatures close to the actual filling is in a specific range With high pressure resistance, heat seal strength and contaminant heat sealability, it enables high-speed filling in a wide sealing temperature range from low to high temperature, satisfies the above automatic filling suitability, and reduces mechanical load. It is an object of the present invention to provide a packaging material and a liquid packaging bag using the same that can satisfy the extrusion processability at the same time.

  In order to solve the above problems, the present inventors have conducted extensive studies to improve the problem of the high-pressure method low-density polyethylene, in which the appearance at the time of filling and the range of the filling temperature are good, but the pressure strength is weak, The viscosity at the low shear rate affects when sealing while pushing away impurities.If the viscosity at this time is low, the flow of the resin is fast, and the filler entrains air and the seal strength decreases. On the other hand, it is important that the viscosity at the speed is high. On the other hand, based on the knowledge that a high viscosity at a relatively high shear rate at the time of extrusion molding is not preferable because a large load is applied at the time of actual molding, Among materials with high viscosity and low viscosity at high shear rate, an ethylene / α-olefin copolymer whose ratio of high shear rate and low shear rate measured at a temperature close to the actual filling is within a specific range is intermediate By using the It and pressure strength sealing temperature range of the filling is expanded also confirmed that the strong material is obtained, it has found that the above problems can be solved, and have completed the present invention.

According to the first invention of the present application, in the packaging material having at least (I) a base material layer, (II) intermediate layer, and (III) sealant layer, the (II) intermediate layer includes the following (a) to (c): A packaging material characterized by using an ethylene / α-olefin copolymer (A) satisfying the above is provided.
(A) Density (according to JIS K6992-2: 1997 appendix (23 ° C.)) is 0.860 to 0.970 g / cm ³
(B) Melt flow rate (according to JIS K6992-2: 1997 appendix (190 ° C., 21.18 N load)) is 0.5-100 g / 10 min. (C) Measured by a capillograph at a measurement temperature of 190 ° C. The ratio (η ₆₀ / η ₁₂₀₀ ) of the viscosity η (Pa · S) between the shear rate 60 (sec ⁻¹ ) and the shear rate 1200 (sec ⁻¹ ) is in the range of 3.5 to 7.0. thing

  According to a second invention of the present application, in the first invention, the ethylene / α-olefin copolymer (A) is an ethylene / α-olefin copolymer produced by a single site catalyst. A packaging material is provided.

  According to a third invention of the present application, in the first or second invention, the ethylene / α-olefin copolymer (A) is an ethylene / α-olefin copolymer having a long chain branch. A characteristic packaging material is provided.

  According to a fourth invention of the present application, in any one of the first to third inventions, the base material layer (I) comprises a polyamide resin, a polyester resin, a polyolefin resin, a polyvinylidene chloride resin, an ethylene-vinyl acetate copolymer. There is provided a packaging material characterized in that it is at least one selected from a polymer saponified product, a polycarbonate resin, a polystyrene resin or a stretched product thereof, a metal foil, an inorganic oxide vapor deposited film, paper, or a nonwoven fabric.

According to a fifth invention of the present application, in any one of the first to fourth inventions, the (III) sealant layer is an ethylene / α-olefin copolymer having a density of 0.860 to 0.945 g / cm ^3. A packaging material is provided which is (B) and / or high pressure radical process polyethylene (C), and wherein the (III) sealant layer is lower than the melting point of the (II) intermediate layer.

According to the sixth aspect of the present invention, there is provided a liquid packaging bag using any one of the first to fifth packaging materials.
According to a seventh invention of the present application, in the sixth invention, (I) the base material layer, (II) the intermediate layer, and (III) the sealant layer are composed of the following materials. Is provided.
(I) Base material layer: selected from polyamide resin, polyester resin, polyvinylidene chloride resin, saponified ethylene-vinyl acetate copolymer, polycarbonate resin, polystyrene resin or stretched product thereof, metal foil, and inorganic oxide vapor deposited film At least one substrate.
(II) Intermediate layer: ethylene / α-olefin copolymer (A) satisfying the following (a) to (c)
(A) Density (according to JIS K6992-2: 1997 appendix (23 ° C.)) is 0.860 to 0.970 g / cm ³
(B) Melt flow rate (according to JIS K6992-2: 1997 appendix (190 ° C., 21.18 N load)) is 0.5-100 g / 10 min. (C) Measured by a capillograph at a measurement temperature of 190 ° C. The ratio (η ₆₀ / η ₁₂₀₀ ) of the viscosity η (Pa · S) between the shear rate 60 (sec ⁻¹ ) and the shear rate 1200 (sec ⁻¹ ) is in the range of 3.5 to 7.0. (III) Sealant layer: ethylene / α-olefin copolymer (B) having a density of 0.860 to 0.945 g / cm ³ and / or high-pressure radical polyethylene resin (C).

According to the present invention, in a packaging material such as a liquid or viscous packaging bag in an automatic filling machine, a resin composition containing a specific ethylene-α-olefin copolymer is used as an intermediate layer. High strength, heat seal strength and contaminant heat sealability, enabling high-speed filling in a wide range of sealing temperatures from low to high, satisfying the above automatic filling suitability, and extruding suitability such as reduction of mechanical load. Will also be satisfied.
Moreover, according to the liquid or sticky packaging bag using this packaging material, the bag breakage or separation of the base material and the sealant layer does not occur, and high-speed filling for the liquid or sticky body with an automatic filling machine is possible.

It is a schematic diagram which shows a time-dependent change of the ethylene-alpha-olefin copolymer which has elongation viscosity (long chain branching). It is a schematic diagram which shows a time-dependent change of the ethylene-alpha-olefin copolymer which does not have elongation viscosity (long-chain branching).

  Hereinafter, the packaging material having at least the base material layer, the intermediate layer and the sealant layer of the present invention, the raw materials constituting the packaging material, and the liquid packaging bag using the packaging material will be described.

1. Packaging Material The packaging material of the present invention is a material in which at least a base material layer, an intermediate layer, and a sealant layer are laminated.
<(I) Substrate>
In this invention, the base material which comprises a base material layer is a material which has comparatively big rigidity and intensity | strength used as one outer surface of a packaging material. Specifically, polyamide resin such as nylon 11 and nylon 12, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resin such as polyethylene resin and polypropylene resin, polystyrene resin, polyvinylidene chloride resin, polycarbonate resin, ethylene- Vinyl acetate copolymer saponified product, thermoplastic resin such as acrylic resin or stretched product thereof, inorganic oxide vapor-deposited film, metal vapor-deposited film ceramic vapor-deposited film or metal foil, paper, non-woven fabric, and at least selected from these laminates One type is mentioned.

The metal foil is not particularly limited depending on the material and thickness, and is 5 to 50 μm thick aluminum foil, tin foil, lead foil, galvanized thin steel plate, thin film of ionized metal by electrolysis, iron foil Etc. are used.
Moreover, it does not specifically limit by a material, thickness, etc. also about a metal vapor deposition film, Aluminum, zinc, etc. are mentioned as a vapor deposition metal, and the thing whose thickness is 0.01-0.2 micrometer normally is used preferably. The deposition method is not particularly limited, and a known method such as a vacuum deposition method, an ion plating method, or a sputtering method is used. Further, in the ceramic vapor-deposited film, examples of the ceramic to be vapor-deposited include, for example, silicon oxide represented by the general formula SiOx (0.5 ≦ x ≦ 2), and metals such as glass, alumina, magnesium oxide, and tin oxide. Examples thereof include metal fluorides such as oxide, fluorite, and selenium fluoride. The metal oxide may contain a trace amount of metal, other metal oxide, or metal hydroxide. Vapor deposition can also be performed by applying the various vapor deposition methods described above to at least one side of the film.
The thickness of a vapor deposition film is about 10-50 micrometers normally. Moreover, there is no restriction | limiting in particular as a vapor deposition film, Transparent films, such as a stretched polyester film, a polypropylene film, a polyamide film, are mentioned.

<(II) Intermediate layer>
In the present invention, the intermediate layer must use (A) an ethylene / α-olefin copolymer that satisfies the following (a) to (c).
(A) Density (according to JIS K6992-2: 1997 appendix (23 ° C.)) is 0.860 to 0.970 g / cm ³
(B) Melt flow rate (according to JIS K6992-2: 1997 appendix (190 ° C., 21.18 N load)) is 0.5-100 g / 10 min. (C) Measured by a capillograph at a measurement temperature of 190 ° C. The ratio (η ₆₀ / η ₁₂₀₀ ) of the viscosity η (Pa · S) between the shear rate 60 (sec ⁻¹ ) and the shear rate 1200 (sec ⁻¹ ) is in the range of 3.5 to 7.0. thing

<(A) Ethylene-α-olefin copolymer>
In the present invention, the ethylene-α-olefin copolymer (A) has a density measured according to (a) JIS K6992-2: 1997 appendix (23 ° C.) of 0.860 to 0.970 g / cm. ³ , preferably 0.870 to 0.960 g / cm ³ , more preferably 0.880 to 0.945 g / cm ³ . When the density is less than 0.860 g / cm ³ , the heat seal strength is not sufficient, and when it exceeds 0.970 g / cm ³ , the flexibility is lost and the heat seal temperature width is not sufficiently widened.

  The ethylene-α-olefin copolymer (A) has (b) MFR (190 ° C., 21.18 N load) of 0.1 to 100 g / 10 min, preferably 0.5 to 70 g / 10 min. More preferably, it is the range of 1.0-50 g / 10min. When the MFR is less than 0.1 g / 10 min, the workability deteriorates and high-speed filling is not performed. Moreover, when it exceeds 100 g / 10 minutes, there exists a possibility that heat seal intensity | strength may fall.

Further, (A) the ethylene / α-olefin copolymer of the present invention has (c) a shear rate of 60 (sec ⁻¹ ) measured by a capillograph at a measurement temperature of 190 ° C., and a shear rate of 1200 (sec ⁻¹ ). The ratio of the viscosity η (Pa · S) (η ₆₀ / η ₁₂₀₀ ) (hereinafter referred to as VPR) is in the range of 3.5 to 7.0, preferably VPR is 3.7 to 6.8, More preferably, it is in the range of 4.0 to 6.7. If the VPR is less than 3.5, the automatic filling suitability is not satisfied, and if the VPR exceeds 7.0, there is a concern that an industrially stable product is difficult to obtain.

The measurement method of VPR specified by this invention is shown below.
Using a capillograph (CAPIROGRAPH 1B manufactured by Toyo Seiki Seisakusho Co., Ltd.), measurement is performed under the following conditions.
[Measurement condition]
Measurement temperature: 190 ° C
[Capillary]
1-21BR manufactured by Toyo Seiki Seisakusho Co., Ltd.
Dimensions: D = 1.0mm, L = 40.00mm
Shape: A capillary is set on a flat capillograph, and after confirming that it is stable at the measurement temperature, 12 g of resin pellets are put into a barrel. After 6 minutes, the melt viscosity at each shear rate is measured from low to high.

  In the present invention, the ethylene / α-olefin copolymer (A) is preferably composed mainly of structural units derived from ethylene, and the ethylene content is 50 to 99% by weight, more preferably 60 to 97% by weight. More preferably, it is selected from the range of 70 to 95% by weight. Therefore, the α-olefin content is preferably selected from the range of 1 to 50% by weight, more preferably 3 to 40% by weight, and still more preferably 5 to 30% by weight. The ethylene content is determined by the 13C-NMR spectrum analysis shown below.

Solvent: Orthodichlorobenzene Sample concentration: 300 mg / 2 mL
Standard substance: Hexamethyldisiloxane Measurement temperature: 120 ° C
Frequency: 100MHz
Spectral width: 20000Hz
Pulse repetition time: 10 seconds Flip angle: 40 degrees

The α-olefin used as a comonomer is an α-olefin having 3 to 20 carbon atoms, preferably 4 to 12 carbon atoms, and more preferably 4 to 8 carbon atoms.
Specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4-methyl-pentene-1, 4-methyl-hexene-1, 4,4-dimethylpentene- 1 etc. can be mentioned. Among these ethylene / α-olefin copolymers, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 1-octene copolymer and the like are particularly preferable.

  The α-olefin is not limited to one type, but may be a multi-component copolymer using two or more types such as a terpolymer. Specific examples include an ethylene / propylene / 1-butene terpolymer and an ethylene / propylene / 1-hexene terpolymer.

The manufacturing method of an ethylene-alpha-olefin copolymer (A) is not specifically limited, It manufactures using a Ziegler type catalyst, a single site type catalyst, etc. In order to exhibit heat sealing performance such as low-temperature heat sealing properties and heat sealing strength, an ethylene-α-olefin copolymer produced with a single-site catalyst is preferred.
When a single-site catalyst is used, a polymer having a narrow crystallinity distribution is obtained as a polymer obtained by a single reaction. Therefore, by blending various ethylene / α-olefin copolymers having different crystallinity, There is an advantage that a composition satisfying the various physical property values can be easily obtained. Several types of ethylene / α-olefin copolymers corresponding to the respective components may be blended or produced by multistage polymerization.

  The single site catalyst used in the present invention includes (i) a transition metal compound belonging to Group 4 of the periodic table (including so-called metallocene compounds) containing at least one ligand having a conjugated five-membered ring structure, and (ii) It is a catalyst composed of a cocatalyst that can be activated to a stable ionic state by reacting with a metallocene compound, and (iii) an organoaluminum compound, if necessary, and any known catalyst can be used.

The metallocene compound (i) is, for example, disclosed in JP-A-58-19309, JP-A-59-95292, JP-A-59-23011, JP-A-60-35006, JP-A-60-35007, JP-A-60-35008, JP-A-60-35209, JP-A-61-130314, JP-A-3-163888, etc., EP publication 420,436, US Pat. No. 5,055,438, international publication WO91 / 04257, International Publication WO92 / 07123, and the like.
A preferred embodiment of such a metallocene compound can be exemplified as a compound represented by the following general formula [1], [2], [3] or [4] as described in JP-A No. 11-310612.

［ここで、Ａ^１〜Ａ^４は共役五員環構造を有する配位子（同一化合物内において、Ａ^１〜Ａ^４は同一でも異なっていてもよい）を、Ｑ^１は２つの共役五員環配位子を任意の位置で架橋する結合性基を、Ｚ^１、Ｚ^２はＭと結合している窒素原子、酸素原子、ケイ素原子、リン原子またはイオウ原子を含む配位子、水素原子、ハロゲン原子または炭化水素基を、Ｑ^２は共役五員環配位子の任意の位置とＺ^２を架橋する結合性基を、Ｍは周期律表４族から選ばれる金属原子を、そしてＸおよびＹはＭと結合した水素原子、ハロゲン原子、炭化水素基、アルコキシ基、アミノ基、リン含有炭化水素基またはケイ素含有炭化水素基を、それぞれ示す。］
Ａ^１〜Ａ^４は共役五員環配位子であり、これらは同一化合物内において同一でも異なっていてもよいことは前記した通りである。この共役五員環配位子（Ａ^１〜Ａ^４）の典型例としては、共役炭素五員環配位子、すなわちシクロペンタジエニル基を挙げることができる。このシクロペンタジエニル基は水素原子を５個有するもの［Ｃ_５Ｈ_５］であってもよく、また、その誘導体、すなわちその水素原子のいくつかが置換基で置換されているもの、であってもよい。この置換基の一つの具体例は、炭素数１〜２０、好ましくは１〜１２の炭化水素基であるが、この炭化水素基は一価の基としてシクロペンタジエニル基と結合していても、またこれが複数存在するときにそのうちの２個がそれぞれ他端（ω−端）で結合してシクロペンタジエニル基の一部とともに環を形成していてもよい。後者の代表例としてインデニル基、フルオレニル基、アズレニル基等が挙げられる。更にこの炭化水素基の代わりに、フリル基やアルキルシリル基等の含酸素炭化水素基、含硫黄炭化水素基、含窒素炭化水素基、含ケイ素炭化水素基を適宜使用することも可能である。

[Wherein A ^{1 to} A ⁴ represent a ligand having a conjugated five-membered ring structure (in the same compound, A ^{1 to} A ⁴ may be the same or different), and Q ¹ represents two conjugated five-membered members. A bonding group that bridges the ring ligand at an arbitrary position, Z ¹ and Z ² are a ligand containing a nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom, or a sulfur atom bonded to M, a hydrogen atom , A halogen atom or a hydrocarbon group, Q ² is a bonding group that bridges Z ² with any position of the conjugated five-membered ring ligand, M is a metal atom selected from Group 4 of the periodic table, and X And Y each represent a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group bonded to M. ]
A ^{1 to} A ⁴ are conjugated five-membered ring ligands, and these may be the same or different in the same compound as described above. Typical examples of the conjugated five-membered ring ligand (A ^{1 to} A ⁴ ) include a conjugated carbon five-membered ring ligand, that is, a cyclopentadienyl group. The cyclopentadienyl group may be one having five hydrogen atoms [C ₅ H ₅ ], and its derivative, that is, one in which some of the hydrogen atoms are substituted with substituents. May be. One specific example of this substituent is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, and this hydrocarbon group may be bonded to a cyclopentadienyl group as a monovalent group. When a plurality of these are present, two of them may be bonded at the other end (ω-end) to form a ring together with a part of the cyclopentadienyl group. Typical examples of the latter include indenyl group, fluorenyl group, azulenyl group and the like. Further, instead of this hydrocarbon group, an oxygen-containing hydrocarbon group such as a furyl group or an alkylsilyl group, a sulfur-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, or a silicon-containing hydrocarbon group can be used as appropriate.

Examples of Q ¹ and Q ² include a methylene group, an ethylene group, a silylene group, a dimethylsilylene group and the like. Q ¹ and Q ² are usually bridged at the position of the five-membered ring carbon in the conjugated five-membered ring ligand, but may form a crosslinked structure at a position in the substituent on the conjugated five-membered ring ligand. it can.

  M is a metal atom selected from Group 4 of the periodic table, specifically titanium, zirconium and hafnium, preferably zirconium and hafnium, particularly preferably zirconium.

Examples of Z ¹ and Z ² include amide compounds such as t-butylamide, phenylamide and cyclohexylamide.

  X and Y are each a hydrogen atom, a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an amino group, and carbon. A phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms (specifically, for example, a diphenylphosphine group), or a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. (Specific examples include trimethylsilyl group and bis (trimethylsilyl) methyl group). X and Y may be the same or different. Of these, halogen groups, hydrocarbon groups (particularly those having 1 to 8 carbon atoms) and amino groups are preferred. As in JP-A No. 2004-161760, it is also preferable that X or Y in the general formula [1] is also a conjugated carbon five-membered ring ligand.

  Therefore, among the compounds represented by the general formulas [1], [2], [3] or [4] which are preferable as the metallocene compound in the present invention, particularly preferable ones have respective substituents having the following contents. . Among the compounds represented by the general formula [1], [2], [3] or [4], the general formula [2] and the general formula [4] are more preferable, and the general formula [2] is more preferable.

A ^{1 to} A ⁴ = cyclopentadienyl, methyl-cyclopentadienyl, ethyl-cyclopentadienyl, propyl-cyclopentadienyl, butyl-cyclopentadienyl, furyl-cyclopentadienyl, tributylsilylfuryl- Cyclopentadienyl, dimethyl-cyclopentadienyl, diethyl-cyclopentadienyl, ethyl-n-butyl-cyclopentadienyl, ethyl-methyl-cyclopentadienyl, n-butyl-methyl-cyclopentadienyl, Indenyl, 2-methyl-indenyl, 3-methyl-indenyl, 2-methyl-4-phenylindenyl, 2-furyl-indenyl, 2-furyl-4-phenylindenyl, tetrahydroindenyl, 2-methyl-tetrahydroindenyl Nyl, benzoindenyl, 2-methyl- Benzoindenyl, dibenzoindenyl,
Q ¹ , Q ² = ethylene, dimethylsilylene, isopropylidene, diphenylmethylene,
Z ¹ , Z ² = t-butylamide, phenylamide, cyclohexylamide,
M = Ti, Zr, Hf,
X, Y = chlorine, methyl, diethylamino.

  In the present invention, the metallocene compound can be used as a mixture of two or more compounds within the same group of compounds represented by the above general formula and / or between compounds represented by different general formulas.

A specific example of this transition metal compound when M is zirconium is as follows.
(I) When the compound represented by the general formula [1] is given when the auxiliary ligands X and Y are chlorine, for example, (1) bis (cyclopentadienyl) zirconium dichloride,
(2) bis (methylcyclopentadienyl) zirconium dichloride,
(3) bis (dimethylcyclopentadienyl) zirconium dichloride,
(4) bis (trimethylcyclopentadienyl) zirconium dichloride,
(5) bis (tetramethylcyclopentadienyl) zirconium dichloride,
(6) bis (pentamethylcyclopentadienyl) zirconium dichloride,
(7) bis (i-propylcyclopentadienyl) zirconium dichloride,
(8) Bis (n-butylcyclopentadienyl) zirconium dichloride,
(9) Bis (n-butyl-methyl-cyclopentadienyl) zirconium dichloride,
(10) (cyclopentadienyl) (ethyl-methyl-cyclopentadienyl) zirconium dichloride,
(11) (cyclopentadienyl) (dimethyl-cyclopentadienyl) zirconium dichloride,
(12) (n-butylcyclopentadienyl) (dimethylcyclopentadienyl) zirconium dichloride (13) bis (indenyl) zirconium dichloride,
(14) bis (tetrahydroindenyl) zirconium dichloride (15) bis (2-methyltetrahydroindenyl) zirconium dichloride (16) bis (azulenyl) zirconium dichloride,
(17) Bis (fluorenyl) zirconium dichloride,
(18) bis (benzoindenyl) zirconium dichloride,
(19) Tris (benzoindenyl) zirconium chloride,
(20) bis (dibenzoindenyl) zirconium dichloride,
(21) (cyclopentadienyl) (indenyl) zirconium dichloride,
(22) (cyclopentadienyl) (fluorenyl) zirconium dichloride,
(23) (cyclopentadienyl) (azurenyl) zirconium dichloride,
(24) (Indenyl) (benzoindenyl) zirconium dichloride,
(25) (Indenyl) bis (benzoindenyl) zirconium chloride,
(26) (indenyl) (dibenzoindenyl) zirconium dichloride,
(27) (Indenyl) bis (dibenzoindenyl) zirconium chloride, etc.
Among them, a metallocene compound having at least one benzoindenyl ligand or dibenzoindenyl ligand is preferable.

(B) The case where the auxiliary ligands X and Y are chlorine is exemplified as the compound represented by the general formula [2].
(B) -1 First, as the bonding group Q ¹ having Q ¹ = alkylene group, for example,
(1) methylenebis (indenyl) zirconium dichloride,
(2) ethylenebis (indenyl) zirconium dichloride,
(3) ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride,
(4) ethylenebis (2-methylindenyl) zirconium dichloride,
(5) ethylenebis (2,4-dimethylindenyl) zirconium dichloride,
(6) ethylene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylcyclopentadienyl) zirconium dichloride,
(7) ethylene (2-methyl-4-tertbutylcyclopentadienyl) (3′-tertbutyl-5′-methylcyclopentadienyl) zirconium dichloride,
(8) ethylene (2,3,5-trimethylcyclopentadienyl) (2 ′, 4 ′, 5′-trimethylcyclopentadienyl) zirconium dichloride,
(9) ethylene-1,2-bis (4-indenyl) zirconium dichloride,
(10) ethylene 1,2-bis [4- (2,7-dimethylindenyl)] zirconium dichloride, (11) ethylene 1,2-bis (4-phenylindenyl) zirconium dichloride,
(12) isopropylidenebis (indenyl) zirconium dichloride,
(13) isopropylidene (2,4-dimethylcyclopentadienyl) (3 ′, 5′-dimethylpentadienyl) zirconium dichloride,
(14) methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride,
(15) methylenebis (2,5-methylfurylindenyl) zirconium dichloride,
(16) isopropylidene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride,
(17) isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride,
(18) methylene (3-butylcyclopentadienyl) (3′-butylindenyl) zirconium dichloride,
(19) Diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride,
(20) Cyclohexylidene (2,5-dimethylcyclopentadienyl) (3 ′, 4′-dimethyldimethylcyclopentadienyl) zirconium dichloride (21) Dichloro {1,1′-dimethylmethylenebis [2-methyl -4- (4-biphenylyl) -4H-azurenyl]} zirconium,
(22) dichloro {1,1′-trimethylenebis [2-methyl-4- (4-biphenylyl) -4H-azurenyl]} zirconium, etc.

(B) -2 Next, as Q ¹ = silylene group, for example,
(1) Dimethylsilylenebis (indenyl) zirconium dichloride,
(2) dimethylsilylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride,
(3) Dimethylsilylenebis (2-methylindenyl) zirconium dichloride,
(4) Dimethylsilylene bis (2-methyl-4,5,6,7-tetrahydroindenyl) zirconium dichloride,
(5) Dimethylsilylene bis (2-methyl-4,5-benzoindenyl) zirconium dichloride,
(6) Dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride,
(7) Dimethylsilylene bis (2-methyl-4,4-dimethyl-4,5,6,7-tetrahydro-4-sylinedenyl) zirconium dichloride,
(8) Dimethylsilylenebis [4- (2-phenylindenyl)] zirconium dichloride,
(9) Dimethylsilylenebis [4- (2-tertbutylindenyl) zirconium dichloride,
(10) Dimethylsilylenebis [4- (2-phenyl-3-methylindenyl)] zirconium dichloride,
(11) Dimethylsilylene (cyclopentadienyl) (indenyl) zirconium dichloride,
(12) Dimethylsilylene (cyclopentadienyl) [3-methylindenyl)] zirconium dichloride,
(13) Dimethylsilylene (cyclopentadienyl) [3-butylindenyl)] zirconium dichloride,
(14) Dimethylsilylene (3-methylcyclopentadienyl) (indenyl) zirconium dichloride,
(15) Dimethylsilylene (cyclopentadienyl) [4-phenyl-2-methylindenyl)] zirconium dichloride,
(16) Dimethylsilylenebis [4- (4-butylphenyl) -2,5-methylfurylindenyl)] zirconium dichloride,
(17) Dimethylsilylene (cyclopentadienyl) [4- (4-butylphenyl) -2,5-methylfurylindenyl)] zirconium dichloride,
(18) phenylmethylsilylenebis (indenyl) zirconium dichloride,
(19) Phenylmethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ′, 4 ′, 5′-trimethylcyclopentadienyl) zirconium dichloride,
(20) diphenylsilylenebis (indenyl) zirconium dichloride,
(21) Tetramethyldisilenebis (indenyl) zirconium dichloride,
(22) Dimethylsilylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride,
(23) Dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,
(24) Dimethylsilylene (3-tertbutyl-cyclopentadienyl) (fluorenyl) zirconium dichloride,
(25) Dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride,
(26) Dimethylsilylene (diethylcyclopentadienyl) (octahydrofluorenyl) zirconium dichloride,
(27) Dimethylsilylenebis [1- (2-methyl-4-phenyl-4H-azurenyl] zirconium dichloride,
(28) dichloro {1,1′-dimethylsilylenebis [2-i-propyl-4- (4-biphenylyl) -4H-azulenyl]} zirconium,
(29) dichloro {1,1′-dimethylsilylenebis [2-methyl-4- (2-fluoro-4-biphenylyl) -4H-azurenyl]} zirconium,
(30) dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (2-fluoro-4-biphenylyl) -4H-azurenyl]} zirconium,
(31) dichloro {1,1′-dimethylsilylenebis [2-methyl-4- (4-chlorophenyl) -4H-azurenyl]} zirconium,
(32) dichloro_ {1,1′-dimethylsilylenebis [2-methyl-4- (2 ′, 6′-dimethyl-4-biphenylyl) -4H-azurenyl]} zirconium,
(33) dichloro {1,1′-dimethylsilylenebis [2-methyl-4- (1-naphthyl) -4H-azulenyl]} zirconium,
(34) dichloro {1,1′-dimethylsilylenebis [2-i-propyl-4- (1-naphthyl) -4H-azulenyl]} zirconium,
(35) dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (2-naphthyl) -4H-azulenyl]} zirconium,
(36) dichloro {1,1′-dimethylsilylenebis [2-i-propyl-4- (4-tert-butylphenyl) -4H-azurenyl]} zirconium,
(37) dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (9-anthryl) -4H-azurenyl]} zirconium,
(38) dichloro {dimethylsilylene-1- [2-methyl-4- (4-biphenylyl) -4H-azurenyl] -1- [2-methyl-4- (4-biphenylyl) indenyl]} zirconium,
(39) Dichloro {1,1′-dimethylsilylenebis [2-methyl-4- (4-biphenylyl) -4H-5,6,7,8-tetrahydroazurenyl] -1- [2-methyl-4- (4-biphenylyl) indenyl]} zirconium and the like.
Among these, metallocene compounds each having one cyclopentadienyl ligand and one indenyl ligand each having a substituent are preferable.

(B) -3 Further, Q ¹ = germanium, phosphorus, nitrogen, boron or a hydrocarbon group containing aluminum, for example,
(1) Dimethylgermanium bis (indenyl) zirconium dichloride,
(2) Dimethylgermanium (cyclopentadienyl) (fluorenyl) zirconium dichloride,
(3) methylaluminum bis (indenyl) zirconium dichloride,
(4) phenylaluminum bis (indenyl) zirconium dichloride,
(5) phenylphosphinobis (indenyl) zirconium dichloride,
(6) ethyl foranobis (indenyl) zirconium dichloride,
(7) phenylaminobis (indenyl) zirconium dichloride,
(8) Phenylamino (cyclopentadienyl) (fluorenyl) zirconium dichloride (9) Dichloro {1,1'-dimethylgermylene [2-methyl-4- (4-biphenylyl) -4H-azurenyl]} zirconium, etc. .

(C) A compound represented by the general formula [3], that is, a transition metal compound having no linking group Q ² and having one conjugated five-membered ring ligand is, for example,
(1) pentamethylcyclopentadienyl-bis (phenyl) aminozirconium dichloride,
(2) indenyl-bis (phenyl) amidozirconium dichloride,
(3) pentamethylcyclopentadienyl-bis (trimethylsilyl) aminozirconium dichloride,
(4) pentamethylcyclopentadienylphenoxyzirconium dichloride,
(5) cyclopentadienylzirconium trichloride,
(6) pentamethylcyclopentadienylzirconium trichloride,
(7) cyclopentadienylzirconium benzyl dichloride,
(8) cyclopentadienylzirconium dichlorohydride,
(9) cyclopentadienylzirconium triethoxide, etc.

(D) A compound represented by the general formula [4], that is, a transition metal compound having one conjugated five-membered ring ligand bridged by a binding group Q ² is, for example,
(1) Dimethylsilylene (tetramethylcyclopentadienyl) phenylamidozirconium dichloride,
(2) dimethylsilylene (tetramethylcyclopentadienyl) tertbutyramide zirconium dichloride,
(3) Dimethylsilylene (indenyl) cyclohexylamide zirconium dichloride,
(4) Dimethylsilylene (tetrahydroindenyl) decylamidozirconium dichloride,
(5) Dimethylsilylene (tetrahydroindenyl) ((trimethylsilyl) amino) zirconium dichloride,
(6) Dimethylgermane (tetramethylcyclopentadienyl) (phenyl) aminozirconium dichloride and the like are exemplified.

(E) In addition, one or both of the chlorine atoms in the “dichloride” part of the compounds (a) to (d) above are hydrogen atoms, bromine atoms, iodine atoms, methyl groups, phenyl groups, diethylamide groups, methoxy groups, etc. Substituted compounds are also used.
Among the compounds (i) to (d) above, preferred specific examples are:
(A) Bis (dimethylcyclopentadienyl) zirconium dichloride, bis (n-butyl-methyl-cyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (dimethyl-cyclopentadienyl) zirconium dichloride, bis (benzoin) Denyl) zirconium dichloride, tris (benzoindenyl) zirconium hydride, tris (dibenzoindenyl) zirconium hydride, (b) ethylenebis (indenyl) zirconium dichloride, ethylenebis (4,5,6,7-tetrahydroindenyl) Zirconium dichloride, methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, methylene bis (2,5-methylfurylindenyl) zirconium dichloride, Isopropylidene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride, isopropylidene (2,5-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, methylene (3-butylcyclopentadienyl) (3 ' -Butylindenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (4,5,6,7 -Tetrahydroindenyl) zirconium dichloride, dimethylsilylene bis (2-methylindenyl) zirconium dichloride, dimethylsilylene bis (2-methyl-4,5,6,7-tetrahydroindenyl) Zirconium dichloride, dimethylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) [3-methylindenyl]] Zirconium dichloride, dimethylsilylene (cyclopentadienyl) [3-butylindenyl]] zirconium dichloride, dimethylsilylene (3-methylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) [4- Phenyl-2-methylindenyl]] zirconium dichloride, dimethylsilylenebis [4- (4-butylphenyl) -2,5-methylfurylindenyl]] zirconium dichloride, di Tylsilylene (cyclopentadienyl) [4- (4-butylphenyl) -2,5-methylfurylindenyl]] zirconium dichloride, phenylmethylsilylenebis (indenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, dimethyl Silylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) Zirconium dichloride, (d) dimethylsilylene (tetramethylcyclopentadienyl) phenylamide zirconium dichloride, dimethylsilylene (tetramethylcyclopentadi) Sulfonyl) tert-butyl amide zirconium dichloride, dimethylsilylene (indenyl) cyclohexyl amide zirconium dichloride, and more preferred embodiments are (i) tris (benzindenyl) zirconium hydride, tris (dibenzo indenyl) zirconium hydride,
(B) Ethylenebis (indenyl) zirconium dichloride, ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, methylenebis (2,5-methylfurylindenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium Dichloride, dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis (2-methylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4,5,6,7- Tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) [3-methylindenyl]] zyl Nium dichloride, dimethylsilylene (cyclopentadienyl) [3-butylindenyl]] zirconium dichloride, dimethylsilylene (3-methylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) [4- Phenyl-2-methylindenyl]] zirconium dichloride, dimethylsilylene bis [4- (4-butylphenyl) -2,5-methylfurylindenyl]] zirconium dichloride, dimethylsilylene (cyclopentadienyl) [4- ( 4-butylphenyl) -2,5-methylfurylindenyl]] zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclo Ntajieniru) (fluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride,
(D) dimethylsilylene (tetramethylcyclopentadienyl) tertbutyramide zirconium dichloride, dimethylsilylene (indenyl) cyclohexylamide zirconium dichloride,
Further preferred examples are tris (benzoindenyl) zirconium hydride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, methylenebis (2,5-methylfurylindene). Nyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis (2-methylindenyl) zirconium dichloride, dimethylsilylenebis ( 2-methyl-4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethyl Silylene (cyclopentadienyl) [3-methylindenyl)] zirconium dichloride, dimethylsilylene (cyclopentadienyl) [3-butylindenyl)] zirconium dichloride, dimethylsilylene (3-methylcyclopentadienyl) (indenyl) ) Zirconium dichloride, dimethylsilylene (cyclopentadienyl) [4-phenyl-2-methylindenyl)] zirconium dichloride, dimethylsilylene (cyclopentadienyl) [4- (4-butylphenyl) -2,5-methyl Furylindenyl)] zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) zirconium It is chloride.

  Furthermore, in this invention, the compound which changed the central metal of the zirconium compound illustrated to said (i)-(e) from zirconium to titanium and hafnium can also be used. Of these, preferred are zirconium compounds and hafnium compounds, and particularly preferred are zirconium compounds. In some cases, a mixture of a zirconium compound and a hafnium compound can be used.

In the above example, the disubstituted form of the cyclopentadienyl ring includes 1,2- and 1,3-substituted forms, and the trisubstituted form includes 1,2,3- and 1,2,4-substituted forms.
When an asymmetric carbon is generated in these metallocene transition metal compounds, one of stereoisomers or a mixture thereof (including a racemate) is shown unless otherwise specified.

The metallocene compound may be used by being supported on an inorganic or organic compound carrier. The support is preferably a porous oxide of an inorganic or organic compound, specifically, an ion-exchange layered silicate, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO. ZnO, BaO, ThO _{2 and the} like, or a mixture thereof.

(Ii) The co-catalyst used in the present invention is a component that can be activated to a stable ionic state by reacting with the metallocene compound. Specifically, an organoaluminum oxy compound (aluminoxane compound), an ion-exchange layered silicic acid Examples thereof include salts, Lewis acids, boron compounds, lanthanoid salts such as lanthanum oxide, and tin oxide.

(Iii) Examples of organoaluminum compounds include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum; dialkylaluminum halide; alkylaluminum sesquihalide; alkylaluminum dihalide; alkylaluminum hydride, organoaluminum alkoxide Side etc. are mentioned.

As the polymerization method, any method can be adopted as long as the catalyst component and each monomer come into efficient contact. Specific examples include a slurry method, a gas phase fluidized bed method and a solution method in the presence of these catalysts, or a high-pressure bulk polymerization method in which a pressure is 200 kg / cm ² or more and a polymerization temperature is 100 ° C. or more. . A preferable production method includes a high-pressure bulk polymerization method.
Such an ethylene polymer can be appropriately selected from those commercially available as single-site polyethylene.

The ethylene / α-olefin copolymer (A) in the present invention has (c) a measurement temperature of 190 ° C., a shear rate of 60 (sec ⁻¹ ) measured by a capillograph, and a shear rate of 1200 (sec ⁻¹ ). The ratio (η ₆₀ / η ₁₂₀₀ ) of the viscosity η (Pa · S) to VPR is in the range of 3.5 to 7.0. As a method for adjusting the VPR to this range, ethylene · α- Examples thereof include a method of introducing long chain branching into the olefin copolymer, a method of widening the molecular weight distribution of the ethylene / α-olefin copolymer, and a method of combining these.

The ethylene / α-olefin copolymer (A) having a long chain branch (referred to as LCB) is an ethylene / α-olefin copolymer having a long branch structure (long chain branch) in a polyethylene molecule, As shown in FIG. 1, an ethylene / α-olefin copolymer having a conventional short chain branching (also referred to as linear polyethylene) which shows a change with time of the extension viscosity as shown in FIG. 1 and does not show a change with time of the extension viscosity as shown in FIG. ).
Various attempts have been made to produce a resin having the long chain branch (referred to as LCB), and a method of directly copolymerizing ethylene and α-olefin using a Ziegler catalyst or a metallocene catalyst, or ethylene. And a method of introducing a long-chain branch by copolymerizing with a previously prepared macromonomer.

For example, JP-A-60-090203 and JP-A-10-298234 can be cited as examples using a Ziegler catalyst. In these methods, an ethylene / α-olefin copolymer (A) is selected by appropriately selecting the type and amount of the organoaluminum compound, the type of the catalyst, and the polymerization conditions to control the quality and amount of the long chain branching. ) VPR can be adjusted.
Examples of using a metallocene catalyst include JP-A-2002-544296, JP-A-2005-507961, etc., as examples of using a complex having a bridged biscyclopentadienyl ligand, As examples of using a complex having a bridged bisindenyl ligand, JP-A-2-276807, JP-A-2002-308933, JP-A-2004-292772, JP-A-8-311121, JP-A-8- No. 311260, JP-A-8-48711, and the like. Examples of using constrained geometric catalysts include JP-A-6-306121 and examples using a complex having a benzoindenyl ligand. JP, 2006-2098, A, etc. are mentioned. A method using a complex having a bridged (cyclopentadienyl) (indenyl) ligand is also preferable for the generation of long chain branching. In these methods, the VPR of the ethylene / α-olefin copolymer (A) is adjusted by appropriately selecting the type of complex, catalyst preparation conditions, and polymerization conditions to control the quality and amount of long-chain branching. Is possible.

  JP-A-10-512600 discloses a method of introducing a long chain branch into a polyethylene chain by copolymerizing a diene with ethylene as a comonomer, and JP-T-2008-505222 discloses a T-reagent. There is also disclosed a method for introducing long chain branching into a polyethylene chain using a chain transfer reagent. In these methods, by controlling the type and amount of dienes and chain transfer agents, and by appropriately selecting the type and polymerization conditions of the catalyst, the quality and amount of long chain branching are controlled. It is possible to adjust the VPR of the α-olefin copolymer (A).

  Further, JP-A-07-252311, JP-A-08-502303, International Publication No. WO95-11931, JP-T-2001-511215, JP-A-2006-321991, etc. A method is disclosed in which a macromonomer is produced in advance using a catalyst, and this macromonomer and ethylene are copolymerized to introduce long chain branching into a polyethylene chain. In these methods, an ethylene / α-olefin copolymer is obtained by controlling the quality and amount of long chain branching by appropriately selecting the type of complex, catalyst preparation conditions, polymerization conditions, macromonomer amount and molecular weight. It is possible to adjust the VPR of (A).

Moreover, as an index representing the ethylene / α-olefin copolymer (A) having such a long chain branch, generally, a melt flow rate ratio (MFR ratio: for example, Japanese Patent No. 2571280), melt tension, etc. (MT: for example, Japanese Patent No. 3425719, etc.), presence / absence of rising of extensional viscosity (strain hardening) (for example, Japanese Patent No. 4190638), activation energy (for example, Japanese Patent Application Laid-Open No. 07-062031, etc.) ) Etc., and is expressed by various measurement methods.
Moreover, as a resin actually marketed, brand name: AFFINITY (registered trademark) FM1570 (made by Dow Chemical Co., Ltd.), brand name: Excellen GMH (registered trademark) (made by Sumitomo Chemical Co., Ltd.), etc. .

In addition, the molecular weight distribution (MWD) of the ethylene / α-olefin copolymer can be expanded by a plurality of types of polymer blends, a multistage polymerization method, a multi-component complex or a polymerization method using a plurality of types of catalysts. Such a method can be used to adjust the VPR of the present invention to an optimum range.
In addition, a method in which both a method of introducing long chain branching into the ethylene / α-olefin copolymer and a method of extending the molecular weight distribution are used is also a desirable method.

<(III) Sealant layer>
Examples of the material constituting the sealant layer include an ethylene-α-olefin copolymer (B) having a density of 0.860 to 0.945 g / cm ³ and / or a high-pressure radical polyethylene (C).

<Ethylene / α-olefin copolymer (B)>
In the present invention, the ethylene / α-olefin copolymer (B) is an ethylene / α having a density in the range of 0.860 to 0.945 g / cm ³ and a density of less than 0.860 to 0.910 g / cm ^3. -An olefin copolymer (also referred to as ultra-low density polyethylene) and an ethylene / α-olefin copolymer (also referred to as linear low density polyethylene) having a density of 0.910 to 0.945 g / cm 3 are included.
The ultra-low density polyethylene and the linear low density polyethylene are produced with an ionic catalyst such as a Ziegler catalyst or a single site catalyst, preferably an ethylene / α-olefin copolymer produced with a single site catalyst. is there.

  The melt flow rate (MFR: 190 ° C., 21.18 N load) of the ethylene / α-olefin copolymer (B) is 0.1 to 100 g / 10 minutes, preferably 0.5 to 70 g / 10 minutes, more preferably. The range is 1.0 to 50 g / 10 min. When the MFR is less than 0.1 g / 10 minutes, the workability deteriorates, and when it exceeds 100 g / 10 minutes, the heat seal strength may be lowered.

  The α-olefin used as a comonomer of the ethylene / α-olefin copolymer (B) is an α-olefin having 3 to 20 carbon atoms, preferably 4 to 12 carbon atoms, and more preferably 4 to 8 carbon atoms. Specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4-methyl-pentene-1, 4-methyl-hexene-1, 4,4-dimethylpentene- 1 etc. can be mentioned. As specific examples of such ethylene / α-olefin copolymers, ethylene / 1-butene copolymers, ethylene / 1-hexene copolymers, ethylene / 1-octene copolymers and the like are particularly preferable.

  The α-olefin used as a comonomer is not limited to one type, and a multi-component copolymer using two or more types like a terpolymer is also preferable. Specific examples include an ethylene / propylene / 1-butene terpolymer and an ethylene / propylene / 1-hexene terpolymer.

  The ethylene / α-olefin copolymer (B) preferably has a structural unit derived from ethylene as the main component, and has an ethylene content of 50 to 99% by weight, more preferably 60 to 97% by weight, and still more preferably. Is selected from the range of 70 to 95% by weight. Therefore, the α-olefin content is preferably selected from the range of 1 to 50% by weight, more preferably 3 to 40% by weight, and still more preferably 5 to 30% by weight. The ethylene content is determined by 13C-NMR spectrum analysis in the same manner as shown in the ethylene / α-olefin copolymer (A).

In the ethylene / α-olefin copolymer (B) of the present invention, the same single-site catalyst as that shown in the ethylene / α-olefin copolymer (A) can be used.
The ethylene / α-olefin copolymer (B) used in the (III) heat seal layer of the present invention is essentially a linear chain including an ultra-low density polyethylene resin and a linear low density polyethylene resin. However, it does not preclude the use of (II) the heterogeneous ethylene / α-olefin copolymer (A) used in the intermediate layer. However, (II) the ethylene / α-olefin copolymer (A) used in the intermediate layer and (III) the ethylene / α-olefin copolymer of (A) and / or (B) in the sealant layer In the meantime, it is important to maintain the relationship of (II) intermediate layer> (III) heat seal layer at the melting point.
Commercial products manufactured with single-site catalysts include DuPont Dow “Affinity (registered trademark)”, Nippon Polyethylene “Kernel (registered trademark)”, “Harmolex (registered trademark)”, Mitsui “Evolue (registered trademark)” manufactured by Kagaku Co., “Escolen (registered trademark)” manufactured by Exxon Mobil, etc.

<High pressure radical polyethylene (C)>
In the present invention, the high-pressure radical method polyethylene (C) is a high-pressure radical method low-density polyethylene (HPLD), an ethylene-vinyl ester copolymer, a copolymer of ethylene and an α, β-unsaturated carboxylic acid or a derivative thereof. And at least one resin selected from the group consisting of:

The high-pressure radical process low-density polyethylene (HPLD) is a low-density polyethylene having a long-chain branched structure produced by a high-pressure radical polymerization process, and has a density of 0.900 to 0.940 g / cm ³ , preferably 0.910. It is selected from the range of ˜0.935 g / cm ³ , more preferably 0.912 to 0.930 g / cm ³ .
The melt flow rate (MFR) measured under a load of 190 ° C. and 21.18 N is 0.1 to 100 g / 10 minutes, preferably 0.3 to 70 g / 10 minutes, more preferably 0.5 to 50 g / 10. Selected in minutes range.
Examples of commercially available products, manufactured by Japan Polyethylene Corporation LC600A (density 0.919g ^/ cm 3, MFR7g ^/ 10 min), manufactured by Japan Polyethylene Corporation LC520 (density 0.924g ^/ cm 3, MFR3.5g ^/ 10 min), manufactured by Sumitomo Chemical L705 (density 0.919 g / cm ³ , MFR 7 g / 10 min) and the like are commercially available. HPLD has a high melt elasticity and has the effect of improving the extrusion laminate processability. If there is too much HPLD, the heat seal strength and pressure resistance when packaged will be weak, and if it is too small, neck-in in extrusion laminating will become large and it will be difficult to obtain a uniform molten film. As described above, the ethylene / α-olefin copolymer is the main component, and the HPLD content is preferably selected from the range of 10 to 40% by weight.
The melt tension is 1.5 to 25 g, preferably 3 to 20 g, more preferably 3 to 15 g.
Moreover, Mw / Mn is 3.0-15, Preferably it is 4.0-10. Melt tension, Mw / Mn is an elastic item of resin, and sheet molding is easy within the above range.

The ethylene-vinyl ester copolymer of the present invention is a vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate based on ethylene produced by a high-pressure radical polymerization method, It is a copolymer with a vinyl ester monomer such as vinyl trifluoroacetate.
Among these, vinyl acetate is particularly preferable. That is, 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 preferable. The vinyl ester content is in the range of 3 to 30% by weight, preferably 5 to 20% by weight. The MFR of these copolymers is 0.01 to 50 g / 10 minutes, preferably 0.1 to 40 g / 10 minutes, and the melt tension is 2.0 to 25 g, preferably 3 to 20 g.

The copolymer of ethylene-α, β-unsaturated carboxylic acid or a derivative thereof is a copolymer of ethylene and α, β-unsaturated carboxylic acid or a derivative thereof and optionally other unsaturated monomers. And their metal salts (ionomers), amides, imides and the like. Specific examples of the α, β-unsaturated carboxylic acid as the copolymer component include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid.
Specific examples of the derivatives include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, methacrylic acid. Examples thereof include n-butyl, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl acrylate, and glycidyl methacrylate.
Specific examples of these copolymers include ethylene- (meth) acrylic acid copolymers, ethylene-maleic anhydride copolymers, ethylene- (meth) acrylic acid ester copolymers, ethylene-acrylic acid-vinyl acetate. Binary or multi-component copolymers such as copolymers and ethylene ethyl acrylate-maleic anhydride copolymers may be mentioned.

Other unsaturated monomers in the above are olefins having 3 to 10 carbon atoms such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene, C ₂ -C ₃ vinyl esters of alkanecarboxylic acids, (meth) acrylate, (meth) acrylate, (meth) acrylate, propyl glycidyl (meth) (meth) acrylic acid esters such as acrylates, (meth) It is at least one selected from the group of ethylenically unsaturated carboxylic acids such as acrylic acid, maleic acid, fumaric acid and maleic anhydride, or anhydrides thereof.

  The copolymer is preferably a copolymer comprising 65 to 99.5% by weight of ethylene, 0.5 to 35% by weight of an unsaturated carboxylic acid or ester thereof, and 0 to 25% by weight of another unsaturated monomer. The MFR of these copolymers is selected in the range of 0.05 to 50 g / 10 minutes, preferably 0.1 to 40 g / 10 minutes.

The component (B) and the component (C) may be used alone with the ethylene / α-olefin copolymer (B) or the high-pressure radical polyethylene (C), and the components (A) and (B) The same can be used. The ethylene / α-olefin copolymer (B) is preferably an ultra low density polyethylene resin or a linear low density polyethylene resin prepared using a single site catalyst.
Furthermore, a mixture of a linear low density polyethylene resin and a high pressure method low density polyethylene resin is particularly preferable because a sealant layer exhibiting high heat seal strength can be formed.
The blending ratio (% by weight) of the component (B) and the component (C) is (B) / (C) = 5 to 95/95 to 5, preferably 10 to 90/90 to 10, more preferably 30 to 70. By selecting in the range of / 70-30, well-balanced performances such as heat seal strength, workability, and high-speed filling properties are exhibited.

  Various optional additives can be added to the resin composition used in the (II) intermediate layer and / or (III) sealant layer of the present invention, if necessary. These additives include antioxidants, slip agents such as higher fatty acid amides, antistatic agents such as polyglycerin fatty acids, antifogging agents, neutralizing agents such as zinc stearate and calcium stearate, silicon oxide, calcium sulfate, etc. Additives such as anti-blocking agents, fillers and the like can be added as necessary.

<Manufacture of laminates>
In the present invention, the polyethylene resin composition used for the intermediate layer and the sealant layer is separately or simultaneously melt-extruded, or the intermediate layer is melt-extruded on a base material to form a laminate, that is, a packaging material. To manufacture.
The molding temperature of the intermediate layer and the sealant layer is 150 to 320 ° C, and if it is out of this range, the adhesion between the base material and the intermediate layer and between the intermediate layer and the sealant layer is deteriorated, and exceeds 320 ° C. Also, it is not preferable from the viewpoint of processability and odor.
Moreover, when melt-extrusion molding an intermediate | middle layer to a base material, it is preferable from an adhesive point to perform an anchor-coat process to the surface by which the base material is extrusion-molded, and to perform ozone treatment in the said shaping | molding temperature range. Anchor coating treatment includes known anchor coating agents such as polyurethane, isocyanate compounds, urethane polymers, or mixtures and reaction products thereof, mixtures or reaction products of polyesters or polyols and isocyanate compounds, or solutions thereof, adhesives, etc. Is applied to the substrate surface.

In the laminated body of the present invention, the basic structure is indispensable to have a total of three layers, each of (I) base material layer, (II) intermediate layer and (III) sealant layer. Here, each of the (I) base material layer, (II) intermediate layer, and (III) sealant layer may be a single layer, but in some cases, each of the layers may be composed of a plurality of layers.
For example, a two-layer film obtained by dry laminating a polyester film and a ceramic-deposited polyester film can be used as the base material layer. In the case of laminating one intermediate layer and one sealant layer on a base material layer composed of a two-layer film, a total of four layers is formed. In addition, for example, when a total three-layer film in which a polyester film and an aluminum foil are dry-laminated and further a polyester film is dry-laminated on the aluminum foil surface is used as a base material layer, a five-layer structure is formed. The intermediate layer and the sealant layer are usually used as a single layer (only one layer).

Ozone treatment is performed by directing ozone-containing gas (air, etc.) from the nozzle or slit-shaped outlet in the air gap to the base material adhesion surface of the intermediate layer or the base material surface laminated with this. It is performed by spraying toward the crimping part. In addition, when extrusion laminating at a speed of 100 m / min or more, it is preferable to spray toward both the above-mentioned crimping portions. The concentration of ozone in the gas containing ozone is preferably 1 g / m ³ or more, and more preferably 3 g / m ³ or more.
The amount of spraying is preferably 0.03 liter / min / cm or more, more preferably 0.1 liter / min / cm or more with respect to the width of the adhesive layer.

The laminating speed is generally 100 to 150 m / min from the viewpoint of productivity. Further, the air gap of a known extrusion laminator is generally 100 to 150 mm. The laminate in the present invention is preferably subjected to an aging treatment immediately after molding from the viewpoint of adhesiveness. Aging is performed by leaving still for 12 to 24 hours in an atmosphere of a temperature of 23 to 45 ° C., preferably 35 to 45 ° C. and a humidity of 0 to 50% within 12 hours after the formation of the laminate.
As for the laminated body obtained in this way, it is common that the thickness of a base material layer is 10-50 micrometers, the thickness of an intermediate | middle layer is 10-50 micrometers, and the thickness of a sealant layer is 5-100 micrometers.

2. Liquid packaging bag The liquid packaging bag of the present invention is a bag filled with a liquid or a viscous body using the packaging material described above, and specifically comprises (I) base layer / (II) intermediate layer composed of the following materials: / (III) The laminated body laminated in the order of the sealant layer is formed into a bag shape by two-side seal, three-side seal or four-side seal with a conventional heat sealer.
(I) Base material layer: selected from polyamide resin, polyester resin, polyvinylidene chloride resin, saponified ethylene-vinyl acetate copolymer, polycarbonate resin, polystyrene resin or stretched product thereof, metal foil, and inorganic oxide vapor deposited film At least one substrate.
(II) Intermediate layer: ethylene / α-olefin copolymer (A) satisfying the following (a) to (c)
(A) Density (according to JIS K6992-2: 1997 appendix (23 ° C.)) is 0.860 to 0.970 g / cm ³
(B) Melt flow rate (according to JIS K6992-2: 1997 appendix (190 ° C., 21.18 N load)) is 0.5-100 g / 10 min. (C) Measured by a capillograph at a measurement temperature of 190 ° C. The ratio (η ₆₀ / η ₁₂₀₀ ) of the viscosity η (Pa · S) between the shear rate 60 (sec ⁻¹ ) and the shear rate 1200 (sec ⁻¹ ) is in the range of 3.5 to 7.0. (III) An ethylene / α-olefin copolymer (B) having a density of 0.860 to 0.945 g / cm ³ and / or a high-pressure radical polyethylene resin (C).

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited only to these examples. In addition, the basic physical property and processing evaluation in the following examples and comparative examples were implemented by the method shown below.

<Test method>
1. Density: Performed according to JIS-K6922-2: 1997 appendix (23 ° C.).
2. MFR: JIS-K6922-2: Performed according to 1997 appendix (190 ° C., 21.18 N load).
3. Measurement of long chain branching (λmax):
Measuring method:
・ Device: Ales manufactured by Rheometrics
-Jig: EXTENSIONAL VISUALITY FIXTURE, manufactured by TA Instruments
・ Measurement temperature: 170 ℃
-Strain rate: 2 / sec-Preparation of test piece: Press-molded to produce a sheet of 18 mm x 10 mm and thickness 0.7 mm.
Calculation method:
The elongational viscosity at 170 ° C. and a strain rate of 2 / second is plotted as a log-log graph of time t (second) on the horizontal axis and elongation viscosity η (Pa · second) on the vertical axis. On the logarithmic graph, the maximum elongation viscosity until strain is 4.0 after strain hardening is ηMax (t1) (t1 is the time when the maximum elongation viscosity is shown), and the elongation viscosity before strain hardening is When the approximate straight line is ηLinear (t), a value calculated as ηMax (t1) / ηLinear (t1) is defined as strain hardening degree (λmax). The presence / absence of strain hardening is determined by whether or not there is an inflection point at which the extensional viscosity changes from an upward convex curve to a downward convex curve over time. FIG. 1 shows a schematic diagram when the polymer has an extensional viscosity (long chain branching), and FIG. 2 shows a schematic diagram when the polymer does not have an extensional viscosity.

4). Processability Processability ◎ = Neck-in is small and can be processed by lamination
Processability ○ = Neck-in is large, but laminating is possible.
Workability x = Neck-in is very large and laminating is impossible.
5. Evaluation of liquid filling suitability (N = 5)
Using a viscous body automatic filling and packaging machine (NT-DANGAN TYPE-III, manufactured by Taisei Lamic Co., Ltd.), liquid was filled under the following conditions to obtain a liquid-filled sachet.
[Filling conditions]
Sealing temperature: (longitudinal) 190 ° C, (horizontal) in increments of 5 ° C in the range of 130-160 ° C Packaging style: Three-sided seal Bag dimensions: width 75mm x length 100mm pitch Filling: 30 ° C water Filling amount: about 30cc
Filling speed: 20 m / min. Appearance observation and pressure resistance test of the horizontal seal part of the liquid-filled sachet obtained were performed and evaluated according to the following criteria.
Seal temperature range and appearance of seal part: Evaluation of suitability for high-temperature filling (N = 5)
◯: No leakage, no appearance defect △: 1 to 4/5, leakage ×: 5/5 leakage, or appearance failure Pressure resistance test: criteria for low-temperature filling suitability (minimum pressure resistance temperature) A pressure resistance tester (manufactured by Komatsu) applies a load of 100 kg to the bag after filling for 3 minutes to perform a pressure resistance test, and no bag breakage or water leakage occurs. Evaluation was made at the lowest temperature. A lower minimum withstand temperature is desirable.
○: Pressure resistance 100kg, no problem for 3 minutes, clear 5/5 △: 1 to 4/5 clear
×: Leakage at 5/5

[Raw resin]
PE-1: linear low density polyethylene resin (density: 0.920 g / cm ³ , MFR: 2 g / 10 min, melting point: 105 ° C., trade name: Sumikasen GMH CB2001, manufactured by Sumitomo Chemical Co., Ltd.)

PE-2: Ethylene / α-olefin copolymer (1) Preparation of catalyst for production of PE-2:
(1-1) Synthesis of dimethylsilylene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride: Macromolecules 1995, 28, 3771- using cyclopentadienyl- (3-methylindenyl) dimethylsilane Synthesized according to the procedure described in 3778.

(1-2) Preparation of Solid Catalyst Under a nitrogen atmosphere, 5 g of silica fired at 600 ° C. for 5 hours was placed in a 200 ml two-necked flask and dried under reduced pressure with a vacuum pump for 1 hour while heating in an oil bath at 150 ° C. In a separately prepared 100 ml two-necked flask, 51.8 mg of dimethylsilylene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride synthesized in (1-1) above was placed in a nitrogen atmosphere, and dehydrated toluene 13. After dissolving in 4 ml, 8.6 ml of a 20% methylaluminoxane / toluene solution manufactured by Albemarle was further added at room temperature and stirred for 30 minutes. While heating and stirring the 200 ml two-necked flask containing the vacuum-dried silica in an oil bath at 40 ° C., the whole toluene solution of the reaction product of the complex and methylaluminoxane was added. After stirring at 40 ° C. for 1 hour, the toluene solvent was distilled off under reduced pressure while heating to 40 ° C. to obtain a solid catalyst.

(2) Polymerization of PE-2 (ethylene / 1-hexene copolymer) Ethylene / 1-hexene gas phase continuous copolymerization was carried out using the solid catalyst obtained in (1-2) above. That is, a gas phase continuous polymerization apparatus (internal volume 100 L, fluidized bed diameter 10 cm, bed prepared at a temperature of 75 ° C., a hexene / ethylene molar ratio of 1.32 mol%, a hydrogen / ethylene molar ratio of 0.312%, and an ethylene partial pressure of 0.64 MPa. Polymerization was carried out at a constant gas composition and temperature while intermittently supplying the solid catalyst at a rate of 0.22 g / hour to a weight of 1.8 kg. In order to maintain cleanliness in the system, 0.03 mol / L of hexane diluted solution of triethylaluminum (TEA) was supplied to the gas circulation line at 7 ml / hr. As a result, the average production rate of the produced polyethylene was 330 g / hour. The MFR and density of the ethylene / 1-hexene copolymer obtained after producing a cumulative amount of polyethylene of 5 kg or more were 7 g / 10 min and 0.916 g / cm ³ , respectively.

PE-3: Production of ethylene / α-olefin copolymer (1) Preparation of PE-3 catalyst:
Under a nitrogen atmosphere, 10 grams of silica baked at 600 ° C. for 5 hours was placed in a 200 ml two-necked flask and dried under reduced pressure with a vacuum pump for 1 hour while heating in a 150 ° C. oil bath. In a separately prepared 100 ml two-necked flask, under a nitrogen atmosphere, 46 mg (0.1 mmol) of trisindenylzirconium hydride and 118 mg (0.2 mmol) of trisbenzoindenylzirconium hydride were placed, dissolved in 20 ml of dehydrated toluene, Further, 14.0 ml of a 20% methylaluminoxane / toluene solution manufactured by Albemarle was added at room temperature and stirred for 30 minutes. While heating and stirring the 200 ml two-necked flask containing the vacuum-dried silica in an oil bath at 40 ° C., the whole toluene solution of the reaction product of the above two complexes and methylaluminoxane was added. After stirring at 40 ° C. for 1 hour, the toluene solvent was distilled off under reduced pressure while heating to 40 ° C. to obtain a solid catalyst.

(2) Polymerization of PE-3 (ethylene / 1-hexene / diene copolymer) Using the solid catalyst obtained in the above (1-2), ethylene / 1-hexene / 1,7-octadiene gas phase continuous copolymer Polymerization was performed. That is, a gas prepared at a temperature of 75 ° C., a hexene / ethylene molar ratio of 2.60 mol%, a 1,7-octadiene / 1-hexene ratio of 0.168 mol%, a hydrogen / ethylene molar ratio of 0.114%, and an ethylene partial pressure of 0.50 MPa. While supplying the solid catalyst intermittently at a rate of 0.49 g / hour to a phase continuous polymerization apparatus (internal volume 100 L, fluidized bed diameter 10 cm, bed weight 1.8 kg), polymerization is performed with a constant gas composition and temperature. went. In order to maintain cleanliness in the system, 0.03 mol / L of hexane diluted solution of triethylaluminum (TEA) was supplied to the gas circulation line at 7 ml / hr. As a result, the average production rate of the produced polyethylene was 320 g / hour. The MFR and density of the ethylene / 1-hexene / 1,7-octadiene copolymer obtained after producing a cumulative amount of 5 kg or more of polyethylene were 8 g / 10 min and 0.918 g / cm ³ , respectively.

PE-4: linear low-density polyethylene resin (density: 0.911 g / cm ³ , MFR: 8 g / 10 min, product name: Moretech 1018G, manufactured by Prime Polymer Co., Ltd.)

PE-5: Linear low density polyethylene resin (1) Preparation of catalyst for production of PE-5:
To a catalyst preparation apparatus equipped with an electromagnetic induction stirrer, 1000 ml of toluene purified under nitrogen, 22 g of tetraethoxyzirconium (Zr (OEt) 4), 75 g of indene and 88 g of methylbutylcyclopentadiene were added and tripropyl was maintained at 90 ° C. 100 g of aluminum was added dropwise over 100 minutes, 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, 2000 g of silica (Grace, # 952, surface area 300 m 2 / g) preliminarily baked at 450 ° C. for 5 hours is added, stirred for 1 hour at room temperature, blown with nitrogen at 40 ° C., and dried under reduced pressure. A good solid catalyst was obtained.

(2) Polymerization of PE-5 (ethylene / 1-hexene copolymer):
The molar ratio of 1-hexene / ethylene was 0.027, the molar ratio of hydrogen / ethylene was 7.5 × 10 ⁻⁴ , the nitrogen concentration was 30 mol%, the total pressure was 0.8 MPa, and the temperature was 75 ° C. A hexane solution (0.01 mmol / ml) of triethylaluminum was supplied at 25 ml / h to a gas phase continuous polymerization apparatus (internal volume 100 L, fluid bed diameter 10 cm, fluid bed seed polymer (dispersant) 1.5 kg). While maintaining the gas composition and temperature constant, polymerization was carried out by intermittently supplying a solid catalyst so that the production amount per hour was about 300 g. The activity was 410 g / (g catalyst MPa · h), and the physical properties of the obtained ethylene / 1-hexene copolymer (PE-5) were measured. As a result, the 1-hexene content was 11% by weight and the MFR was 12 g / 10 min. The density was 0.912 g / cm ³ .

PE-6: High pressure radical process low density polyethylene
(Density: 0.918 g / cm ³ , MFR: 7 g / 10 min, trade name: Novatec LD LC600A manufactured by Nippon Polyethylene Co., Ltd.)

<Base material>
Biaxially stretched nylon film (trade name: Harden N4142 manufactured by Toyobo Co., Ltd.) Thickness 15 μm

<Intermediate layer>
The resin and resin composition shown in the following Table 1 were supplied to the intermediate layer as a composition (S1 to S6) obtained by extrusion kneading and pelletizing at 190 ° C. in a single screw extruder.

<Sealant layer>
Linear low density polyethylene (density: 0.906 g / cm ³ , MFR: 11 g / 10 min) 80% by weight produced with a single site catalyst and linear low density polyethylene (density: A composition (melting point: 100 ° C.) consisting of 20% by weight (0.880 g / cm ³ , MFR: 3.5 g / 10 min).

<Examples 1-3>
[Preparation of laminate film]
The laminate film was produced under the following extrusion laminating conditions.
<Made by MODERN MACHINERY>
Extruder: T die diameter 90mmφ, die width 600mm, die lip opening 0.7mm
Processing resin temperature: 320 ° C., cooling roll surface temperature: 25 ° C.
Take-up processing speed: 100 m / min On a biaxially stretched nylon film (Toyobo Co., Ltd., Harden N4142) having a width of 500 mm and a thickness of 15 μm under the above conditions, an isocyanate anchor coating agent (Nihon Soda Co., Ltd., Titabond T120 solution) is applied. In Example 1, the polyethylene resin (S1) shown in Table 1 was taken out as an intermediate layer material while being coated with a bow roll and ozone sprayed at the laminating portion, and extruded at a coating speed of 25 μm at a take-up speed of 100 m / min. Lamination was performed. In Examples 2 and 3, polyethylene resin (S2) or (S3) shown in Table 1 was used as the intermediate layer material. Furthermore, using the same extrusion laminating apparatus, a linear low density polyethylene (density: 80% by weight: 0.906 g / cm ³ , MFR: 11 g / 10 min) as a sealant layer and a single-site catalyst (density: 0.880 g / cm ³ , MFR: 3.5 g / 10 min) A composition comprising 20% by weight is extruded and laminated at an extrusion resin temperature of 280 ° C., a take-off speed of 100 m / min, and a coating thickness of 25 μm. It was. The laminated film after processing was aged for 24 hours in an oven at 45 ° C., and then slit to a width of 130 mm to obtain a packaging film for evaluation.

  The packaging film was fed at a speed of 20 m / min. And 25 m / min. Then, vertical sealing and horizontal heat sealing were performed in a temperature range of 130 ° C. to 160 ° C., and the sealing portion was evaluated (N = 5). The results are shown in Table 2.

<Comparative Examples 1-3>
In Example 1, a packaging film for evaluation was obtained in the same manner except that any of polyethylene resins (S4) to (S6) was used instead of the polyethylene resin (S1) shown in Table 1 as the intermediate layer material.
Next, this packaging film was fed at a speed of 20 m / min. And 25 m / min. Then, the vertical seal and the horizontal seal were performed in the temperature range of 130 ° C. to 160 ° C., and the seal portion was evaluated (N = 5). The results are shown in Table 3.

<Evaluation results>
As is apparent from Table 1 above, Examples 1 to 3 all satisfy (a) to (c) of the present invention in the (II) intermediate layer (A) ethylene / α-olefin copolymer In Example 1, although a relatively large neck-in is feared at the time of laminating, the shear rate measured by a capillograph, the viscosity η at 60 (sec ⁻¹ ) and 1200 (sec ⁻¹ ) The ratio (η ₆₀ / η ₁₂₀₀ ) of (Pa · S) is as high as VSP = 4.9, so that the temperature width of the horizontal seal bar during liquid filling is 135 to 150 ° C. and 25 m / min at 20 m / min. Then, it is as wide as 145 to 155 ° C. In Examples 2 and 3, workability is good, the shear rate measured by a capillograph, the ratio of viscosity η (Pa · S) at 60 (sec ⁻¹ ) and 1200 (sec ⁻¹ ) (η ₆₀ / η _1200). ) Is as high as 4.6, and the temperature width of the horizontal seal bar during liquid filling is as wide as 140 to 150 ° C. at 20 m / min and 145 to 155 ° C. at 25 m / min.
On the other hand, Comparative Example 1 using a resin in which an ethylene / α-olefin copolymer polymerized using a Ziegler catalyst and a high-pressure low-density polyethylene were mixed as an intermediate layer, ethylene / polymerized using a single-site catalyst In Comparative Example 2 in which a resin obtained by mixing an α-olefin copolymer and a high-pressure process low-density polyethylene was used for the intermediate layer, (II) the resin of the intermediate layer does not satisfy (a) to (c) of the present invention. Therefore, the temperature width of the horizontal seal bar at the time of liquid filling is inferior to that of Example 1 and Example 2.
Furthermore, Comparative Example 3 using only the high-pressure method low-density polyethylene for the intermediate layer has good laminability, but the pressure resistance of the obtained liquid-filled sachet is low, and the bag breaks in the pressure test, It was impossible.

  The present invention uses an ethylene / α-olefin copolymer having a shear rate ratio (VPR) in a specific range as an intermediate layer as a packaging material such as a packaging bag for liquids and viscous bodies in an automatic filling machine, thereby providing a pressure resistance strength. It is used for various packaging materials because of its high heat seal strength and high heat sealability, and high-speed filling in a wide range of seal temperatures from low to high temperatures. It is particularly useful as a liquid packaging bag.

Claims (7)

(I) In a packaging material having at least a base material layer, (II) intermediate layer, and (III) sealant layer, the (II) intermediate layer contains an ethylene / α-olefin copolymer satisfying the following (a) to (c): A packaging material using the polymer (A).
(A) Density (according to JIS K6992-2: 1997 appendix (23 ° C.)) is 0.860 to 0.970 g / cm ³
(B) Melt flow rate (according to JIS K6992-2: 1997 appendix (190 ° C., 21.18 N load)) is 0.5-100 g / 10 min. (C) Measured by a capillograph at a measurement temperature of 190 ° C. The ratio (η ₆₀ / η ₁₂₀₀ ) of the viscosity η (Pa · S) between the shear rate 60 (sec ⁻¹ ) and the shear rate 1200 (sec ⁻¹ ) is in the range of 3.5 to 7.0. thing   The packaging material according to claim 1, wherein the ethylene / α-olefin copolymer (A) is an ethylene / α-olefin copolymer produced with a single site catalyst.   The packaging material according to claim 1, wherein the ethylene / α-olefin copolymer (A) is an ethylene / α-olefin copolymer having a long chain branch.   (I) The base material layer is a polyamide resin, a polyester resin, a polyolefin resin, a polyvinylidene chloride resin, a saponified ethylene-vinyl acetate copolymer, a polycarbonate resin, a polystyrene resin or a stretched product thereof, a metal foil, an inorganic oxide The packaging material according to any one of claims 1 to 3, wherein the packaging material is at least one selected from a product vapor deposition film, paper, or nonwoven fabric. The (III) sealant layer is an ethylene / α-olefin copolymer (B) having a density of 0.860 to 0.945 g / cm ³ and / or a high-pressure radical polyethylene (C), and the (III) sealant The packaging material according to any one of claims 1 to 4, wherein the layer is lower than the melting point of (II) the intermediate layer.   The liquid packaging bag using the packaging material in any one of Claims 1-5. The liquid packaging bag according to claim 6, wherein (I) the base material layer, (II) the intermediate layer, and (III) the sealant layer are made of the following materials.
(I) Base material layer: selected from polyamide resin, polyester resin, polyvinylidene chloride resin, saponified ethylene-vinyl acetate copolymer, polycarbonate resin, polystyrene resin or stretched product thereof, metal foil, and inorganic oxide vapor deposited film At least one substrate.
(II) Intermediate layer: ethylene / α-olefin copolymer (A) satisfying the following (a) to (c)
(A) Density (according to JIS K6992-2: 1997 appendix (23 ° C.)) is 0.860 to 0.970 g / cm ³
(B) Melt flow rate (according to JIS K6992-2: 1997 appendix (190 ° C., 21.18 N load)) is 0.5-100 g / 10 min. (C) Measured by a capillograph at a measurement temperature of 190 ° C. The ratio (η ₆₀ / η ₁₂₀₀ ) of the viscosity η (Pa · S) between the shear rate 60 (sec ⁻¹ ) and the shear rate 1200 (sec ⁻¹ ) is in the range of 3.5 to 7.0. (III) Sealant layer: ethylene / α-olefin copolymer (B) having a density of 0.860 to 0.945 g / cm ³ and / or high-pressure radical polyethylene resin (C).

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