JP5830859B2 - Packaging material and liquid packaging bag using the same - Google Patents

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 automatic filling machines. 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.) Polyethylene resin composition with high viscosity at shear rate and low viscosity at high shear rate, that is, the ratio of high shear rate to low shear rate measured at a temperature close to the actual filling in a specific range By using the product, the pressure resistance strength, heat seal strength, and foreign matter heat sealability are high, enabling high-speed filling in a wide sealing temperature range from low temperature to high temperature, and satisfying the above automatic filling suitability. As well as, which is an improvement to also satisfy simultaneously the extrusion processability of the reduction of mechanical load.

Conventionally, polyamide resins, polyethylene terephthalate resins, polypropylene resins, and the like 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

It is an object of the present invention to provide a low-shear as an intermediate layer in a packaging material for a liquid packaging bag having at least a base material layer, an intermediate layer and a sealant layer when used as a packaging bag for liquid or viscous body in an automatic filling machine. A specific material having a high viscosity at a speed and a low viscosity at a high shear rate, that is, a polyethylene-based resin composition in which a ratio between a high shear rate and a low shear rate measured at a temperature close to that during actual filling is in a specific range By using, high pressure resistance, heat seal strength and foreign matter heat sealability, high-speed filling is possible in a wide sealing temperature range from low temperature to high temperature, satisfying the above automatic filling suitability and mechanical load. An object of the present invention is to provide a packaging material for a liquid packaging bag and a liquid packaging bag using the same, which are capable of simultaneously satisfying extrusion processing aptitude such as reduction.

  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, a polyethylene resin composition with a specific ratio between the high shear rate and the low shear rate measured at a temperature close to the actual filling is used for the intermediate layer By Rukoto it and compressive strength of the seal temperature range expands filling 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 1st invention of this application, in the packaging material for liquid packaging bags which consists of (I) base material layer, (II) intermediate | middle layer, and (III) sealant layer comprised with the following material,
A packaging material for a liquid packaging bag is provided in which the (II) intermediate layer and (III) sealant layer are formed by a melt extrusion molding method.
(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: 5 to 95% by weight of ethylene-α-olefin copolymer (A) produced by ionic polymerization satisfying the following (a) to (b), and the density other than the component (A) is 0 .860g / cm ³ or more 0.940 g / cm ³ less than a is other polyolefin resin (B) a polyethylene resin composition comprising 95 to 5% by weight with (X), the polyethylene resin composition (X) Satisfies the following (c).
(A) Density (based on JIS K6992-2: 1997 appendix (23 ° C.)) is 0.860 to 0.945 g / cm ³ ,
(B) Melt flow rate (according to JIS K6992-2: 1997 appendix (190 ° C., 21.18 N load)) is 0.5 to 100 g / 10 min.
(C) Ratio (η ₆₀ / η ₁₂₀₀ ) of viscosity η (Pa · S) between a shear rate of 60 (sec ⁻¹ ) measured by a capillograph and a shear rate of 1200 (sec ⁻¹ ) at a measurement temperature of 190 ° C. (III) sealant layer: ethylene-α-olefin copolymer (C) having a density of 0.860 to 0.945 g / cm ³ and / or high-pressure radical process polyethylene Resin (D).

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 for a liquid packaging bag 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 packaging material for a liquid packaging bag is provided.

According to the fourth invention of the present application, in any one of the first to third inventions, the polyethylene-based resin composition (X) is an ethylene-α-olefin copolymer (A1) 5 having a long chain branch. A packaging material for a liquid packaging bag is provided, which is contained in an amount of 95 to 5% by weight and an ion polymerization method polyethylene resin and / or a high-pressure radical method polyethylene resin (B) in a range of 95 to 5% by weight.

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. There is provided a packaging material for a liquid packaging bag , which is (C) and / or a high-pressure radical polyethylene (D), and 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 liquid packaging bag packaging materials.

According to the present invention, in a packaging material for a liquid packaging bag having at least (I) a base material layer, (II) an intermediate layer, and (III) a sealant layer, such as a packaging bag for liquid or viscous body in an automatic filling machine, (II) As an intermediate layer, a material having a high viscosity at a low shear rate and a low viscosity at a high shear rate, particularly a ratio between a high shear rate and a low shear rate measured at a temperature close to that during actual filling is in a specific range. Polyethylene-based resin composition is used, so it has high pressure strength, heat seal strength, and contaminant heat sealability, enabling high-speed filling in a wide range of sealing temperatures from low to high temperatures, and satisfying the above automatic filling suitability At the same time, it also satisfies aptitude for extruding such as reduction of mechanical load.
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).

In the following, the packaging material for a liquid packaging bag having at least the (I) base material layer, (II) intermediate layer and (III) sealant layer of the present invention, each raw material constituting the packaging material, and the packaging material for the liquid packaging bag were used. The liquid packaging bag will be described.

1. Liquid packaging bag packaging material in liquid packaging bag packaging material the present invention comprises at least (I) a substrate layer, a material obtained by laminating (II) intermediate layer and (III) a sealant layer.
<(I) Base material layer>
In the present invention, (I) the base material constituting the base material layer is a material having a relatively large rigidity and strength that becomes one outer surface of the packaging material for liquid packaging bags . 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, (II) the intermediate layer comprises 95 to 5% by weight of an ethylene / α-olefin copolymer (A) produced by ionic polymerization satisfying the following (a) to (b): It is important to use a polyethylene resin composition (X) containing 5 to 95% by weight of other polyolefin resin (B) other than the above, and that the polyethylene resin composition (X) satisfies the following (c): is there.
(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. 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. about

<Ethylene-α-olefin copolymer (A) produced by ionic polymerization>
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.

  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 ethylene / α-olefin copolymer (A) of the present invention is not limited to a Ziegler catalyst, a single site catalyst or the like as long as it is produced by ionic polymerization, but preferably a single site system. An ethylene / α-olefin copolymer produced with a catalyst is desirable because heat sealing performance such as low temperature heat sealability and heat seal strength is exhibited.
An ethylene / α-olefin copolymer using a single-site catalyst has a narrow crystallinity distribution as a polymer obtained by a single reaction. The blended blend has an advantage that it is easy to obtain a composition that satisfies the above-mentioned physical property values. 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, Japanese Laid-Open Patent Publication No. 60-35008, Japanese Laid-Open Patent Publication No. 60-35209, Japanese Laid-Open Patent Publication No. 61-130314, Japanese Laid-Open Patent Publication No. 3-163088, 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) ethylene bis (indenyl) zirconium dichloride, ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, Methylenebis (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 Mudichloride, 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) (indenyl) zirconium dichloride, dimethylsilylene ( Cyclopentadienyl) [3-methylindenyl]] zirconium dichloride, dimethylsilylene (cyclopentadienyl) [3-butylindenyl]] zirconium dichloride, di Tylsilylene (3-methylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) [4-phenyl-2-methylindenyl]] zirconium dichloride, dimethylsilylenebis [4- (4-butylphenyl) ) -2,5-methylfurylindenyl]] zirconium dichloride, dimethylsilylene (cyclopentadienyl) [4- (4-butylphenyl) -2,5-methylfurylindenyl]] zirconium dichloride, phenylmethylsilylenebis (Indenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilyl Down (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (octahydrofluorenyl) zirconium dichloride,
(D) Dimethylsilylene (tetramethylcyclopentadienyl) phenylamide zirconium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) tertbutyramide zirconium dichloride, and dimethylsilylene (indenyl) cyclohexylamide zirconium dichloride.
More preferable specific examples are (i) tris (benzoindenyl) zirconium hydride, tris (dibenzoindenyl) zirconium hydride, (b) ethylenebis (indenyl) zirconium dichloride, ethylenebis (4,5,6,7-tetrahydro Indenyl) zirconium dichloride, methylenebis (2,5-methylfurylindenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene Bis (2-methylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis (2- Til-4-phenylindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) [3-methylindenyl]] zirconium dichloride, dimethylsilylene (cyclopentadienyl) [3-butylindenyl]] zirconium dichloride, dimethyl Silylene (3-methylcyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) [4-phenyl-2-methylindenyl]] zirconium dichloride, dimethylsilylenebis [4- (4-butylphenyl) ) -2,5-methylfurylindenyl]] zirconium dichloride, dimethylsilylene (cyclopentadienyl) [4- (4-butylphenyl) -2,5-methylfurylindenyl]] zirconium dichloride, di Tylsilylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (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.

In addition, the polyethylene resin composition (X) in the present invention is composed of the component (A) and the component (B) described later, and the resin composition (X) is (c) a measurement temperature of 190 ° C. and a capillograph. The ratio (referred to as VPR) of the viscosity η (Pa · S) between the shear rate of 60 (sec ⁻¹ ) and the shear rate of 1200 (sec ⁻¹ ) measured by the above is in the range of 3.5 to 7.0. It is important to be.
As a method for adjusting the VPR within this range, a method of introducing a long chain branch into an ethylene / α-olefin copolymer, a method of expanding the molecular weight distribution of the ethylene / α-olefin copolymer, or a combination of these, etc. These adjustments can be adjusted by the component (A) and / or the component (B), but the ethylene / α-olefin copolymer having a long chain branch of the component (A), particularly a single site catalyst Adjustment with an ethylene / α-olefin copolymer having a long chain branch produced in (1) is preferred.

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 branching (LCB). A method of directly copolymerizing ethylene and α-olefin using a Ziegler-based catalyst or a metallocene-based catalyst in recent years, Examples thereof include a method of introducing a long chain branch by copolymerizing with the produced 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-07-252231, JP-A-08-502303, International Publication No. WO95-11931, JP-T-2001-511215, JP-A-2006-321991 and the like include specific metallocene series. 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.

[Polyolefin resin (B)]
In the present invention, the polyolefin resin (B) is a resin other than the ethylene / α-olefin copolymer (A) produced by the ionic polymerization, and has a density of 0.86 to 0.97 g / cm ³ . ethylene polymer or ethylene · alpha-olefin copolymer, i.e., very low density polyethylene resin (B1) a density 0.86~0.91g / cm ^3, low density polyethylene 0.91~0.94g / cm ³ Resin (B2), a medium density of 0.94 to 0.97 g / cm ^3, a polyethylene resin produced by an ion polymerization method such as a high density polyethylene resin (B3), a low density polyethylene resin (B4), ethylene High pressure radical polyethylene resin such as vinyl ester copolymer (B5), copolymer with ethylene-α, β-unsaturated carboxylic acid or derivative thereof (B6), Selected from polypropylene-based resins (B8) such as len-α-olefin copolymer rubber (B7), propylene homopolymers or propylene and other α-olefin copolymers, and functional group-containing polyolefin resins (B9) And at least one polyolefin resin.

  The melt flow rate (MFR: 190 ° C., 21.18N load) of the polyolefin resin (B) is 0.1 to 100 g / 10 minutes, preferably 0.5 to 70 g / 10 minutes, more preferably 1.0. It is in the range of ˜50 g / 10 minutes. 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 that is the polyolefin resin (B) of the present invention has 3 to 20 carbon atoms, preferably 4 to 12 carbon atoms, and more preferably 4 to carbon atoms. 8 α-olefins. 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. Specific examples of such an ethylene / α-olefin copolymer include ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, and ethylene / 1-octene copolymer.

  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.

In the polyolefin-based resin (B) of the present invention, an ethylene-α-olefin copolymer having a density of 0.860 to 0.945 g / cm ³ is preferable, and a structural unit derived from ethylene is a main component. The ethylene content is selected from the range of 50 to 99% by weight, more preferably 60 to 97% by weight, and still more preferably 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).

Of the polyolefin resin (B) in the present invention, the linear polyethylene having a density of 0.86 to 0.94 g / cm ³ is preferably one produced by a single site catalyst, and the above-described ethylene-α-olefin. It can be produced using the same single site catalyst as used in the copolymer (A). Commercial products manufactured with the above single-site catalyst include DuPont Dow “Affinity” (registered trademark), Nippon Polyethylene “Kernel” (registered trademark), “Harmolex” (registered trademark), Mitsui Chemicals, Inc. “Evolue” (registered trademark) manufactured by the company, “Escolen” (registered trademark) manufactured by Exxon Mobil, and the like.

<Ultra low density polyethylene resin (B1), low density polyethylene resin (B2)>
Among these polyolefin resins (B), an ultra low density polyethylene resin (B1) and a linear low density polyethylene resin (B2) are preferable. The ultra-low density polyethylene resin (B1) has a density of 0.86 to 0.91 g / cm ³ , and the linear low density polyethylene resin (B2) has a density of 0.91 to 0.94 g / cm ³ . These are produced by an ionic catalyst such as a Ziegler catalyst, a Phillips catalyst, a single site catalyst, etc., preferably an ethylene homopolymer or an ethylene-α-olefin copolymer produced by a single site catalyst. .

<Medium / high density polyethylene (B3)>
In the present invention, the medium / high density polyethylene (B3) is selected in the range of density 0.94 to 0.97 g / cm ³ , preferably density 0.945 to 0.965 g / cm ³ . The melt flow rate (MFR) measured under a load of 190 ° C. and 21.18 N is 0.5 to 20 g / 10 minutes, preferably 1 to 15 g / 10 minutes, more preferably 1.5 to 10 g / MFR. It is selected in the range of 10 minutes.

In the present invention, the high-pressure radical polyethylene that can be used as the component (B) is a low-density polyethylene (HPLD), ethylene-vinyl ester copolymer, ethylene and an α, β-unsaturated carboxylic acid or its It includes at least one resin selected from copolymers with derivatives.
<High pressure low density polyethylene (B4)>
The high-pressure radical method low-density polyethylene (HPLD) is a low-density polyethylene having a long-chain branched structure produced by a high-pressure radical polymerization method, 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 the HPLD is too large, the heat seal strength and pressure resistance when used as a package will be weak, and if it is low, the neck-in in extrusion lamination will increase and it will be difficult to obtain a uniform molten film. Thus, it is preferable that the ethylene / α-olefin copolymer is a main component and the HPLD content is selected from a 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 and Mw / Mn are elastic items of the resin, and film forming is easy within the above range.

<Ethylene-vinyl ester copolymer (B5)>
In the present invention, the ethylene-vinyl ester copolymer (B5) refers to vinyl propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, stearin mainly composed of ethylene produced by a high-pressure radical polymerization method. It is a copolymer with vinyl ester monomers such as vinyl acid vinyl and 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.

<Copolymer with ethylene-α, β-unsaturated carboxylic acid or derivative thereof (B6)>
The above-mentioned copolymer (B6) with ethylene-α, β-unsaturated carboxylic acid or its derivative is a combination of ethylene with α, β-unsaturated carboxylic acid or its derivative and optionally other unsaturated monomers. Copolymers and their metal salts (ionomers), amides, imides and the like can be mentioned. 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, and n methacrylate. -Butyl, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl acrylate, glycidyl methacrylate, and the like. 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, C2 (Meth) acrylic acid esters such as vinyl esters of C3 alkanecarboxylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid , At least one selected from the group of ethylenically unsaturated carboxylic acids such as 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.

<Ethylene-α-olefin copolymer rubber (B7)>
In the present invention, the ethylene-α-olefin copolymer rubber (B7) includes a copolymer rubber of ethylene and an α-olefin having 3 to 10 carbon atoms, such as ethylene-propylene copolymer rubber, ethylene-propylene. -Diene (EPDM) copolymer rubber, ethylene-butene-1 copolymer rubber, etc. are mentioned.
These rubber components fulfill the effect of improving the performance of the sealant film such as impact strength and pinhole resistance.
Examples of the copolymer obtained by copolymerizing a diene monomer include ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / 5-ethylidene-2-norbornene copolymer, ethylene / propylene / 1,6-hexadiene. A copolymer etc. can be illustrated.

<Polypropylene resin (B8)>
In the present invention, the polypropylene resin (B8) means a polypropylene homopolymer such as a syndiotactic polypropylene resin or an isotactic polypropylene resin, a random copolymer of propylene and other α-olefin, a block copolymer, Examples thereof include crystalline polypropylene.
The propylene polymer has a melt flow rate (MFR) measured at 230 ° C. under a load of 2.160 kg of 0.5 to 100 g / 10 minutes, preferably 1 to 50 g / 10 minutes, more preferably 1.5 to 30 g. It is desirable to use a thing of / 10 minutes.

<Functional group-containing polyolefin resin (B9)>
Furthermore, in this invention, you may mix | blend a functional group containing polyolefin resin (B9) depending on necessity. The functional group-containing polyolefin resin (B9) according to the present invention is a copolymer of the following functional group-containing compounds (a) to (f) and an olefin, or a functional group in the presence of a radical generator in the polyolefin resin. It includes a functional group-modified polyolefin resin obtained by modifying and grafting the group-containing compounds (a) to (f).
The functional group-containing polyolefin resin (B9) may be a single type or a combination of two or more types.

(1) Functional group-containing compound The functional group-containing compound of the functional group-containing polyolefin resin (B9) according to the present invention includes an epoxy group-containing compound (a), an unsaturated carboxylic acid group-containing compound or a derivative thereof (b), and an ester. It is at least one compound selected from the group consisting of a group-containing compound (c), a hydroxyl group-containing compound (d), an amino group-containing compound (e), and a silane group-containing compound (f), and an epoxy group-containing compound ( a), or an unsaturated carboxylic acid group-containing compound or a derivative thereof (b) is preferred.

(A) Epoxy group-containing compound Examples of the epoxy group-containing compound include phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, adipic acid diglycidyl ester, methacrylic acid glycidyl ester, and trimethylolpropane triglycidyl ether. , Polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, butanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, phenol novolac polyglycidyl ether, epoxidized vegetable oil, and the like.

  Among these epoxy group-containing compounds, polyvalent epoxy compounds having a molecular weight of 3000 or less and containing at least two epoxy groups (oxirane groups) in the molecule are preferable. Since this epoxy compound contains two or more epoxy groups in the molecule, the adhesive strength is remarkably improved as compared with the case where there is one epoxy group in the molecule. The molecular weight of the epoxy compound is preferably 3000 or less, and particularly preferably 1500 or less. When the molecular weight exceeds 3000, there is a possibility that sufficient adhesive strength cannot be obtained when the composition is formed.

As the epoxy group-containing compound, an epoxidized vegetable oil can be selected from the viewpoint of ease of handling and safety. Epoxidized vegetable oil is an epoxidized unsaturated double bond of natural vegetable oil with peracid, for example, epoxidized soybean oil, epoxidized linseed oil, epoxidized olive oil, epoxidized safflower oil, epoxidized Examples include corn oil.
These epoxidized vegetable oils are commercially available as, for example, O-130P (epoxidized soybean oil), O-180A (epoxidized linseed oil), manufactured by Asahi Denka Kogyo Co., Ltd.
It should be noted that an oil component that is not epoxidized or is insufficiently epoxidized as a by-product when epoxidizing vegetable oil does not hinder the effects of the present invention even if it is present.

  In this invention, content of an epoxy-group containing compound is 0.01-5 weight% in a functional group containing polyolefin-type resin (B9), 0.01-3 weight% is preferable, 0.01-1 Weight percent is more preferred. If the content of the epoxy group-containing compound is within this range, problems such as insufficient adhesive strength with the substrate do not occur.

(B) Unsaturated carboxylic acid group-containing compound or derivative thereof The unsaturated carboxylic acid or derivative thereof used in the present invention is at least one compound selected from a carboxylic acid group or an acid anhydride group-containing compound. preferable.
Examples include monobasic unsaturated carboxylic acids, dibasic unsaturated carboxylic acids, and their metal salts, amides, imides, esters and anhydrides. The number of carbon atoms of the monobasic unsaturated carboxylic acid is 20 or less, preferably 15 or less, and the number of carbon atoms of the dibasic unsaturated carboxylic acid is 30 or less, preferably 25 or less. 30 or less, preferably 25 or less. Among these unsaturated carboxylic acid group-containing compounds and derivatives thereof, acrylic acid, methacrylic acid, maleic acid and its anhydride, 5-norbornene-2,3-dicarboxylic acid and its anhydride, and glycidyl methacrylate are particularly preferable. Maleic anhydride and 5-norbornene anhydride are preferred because of excellent adhesion performance of the resin composition.

  Preferred copolymers include ethylene / (meth) acrylic acid glycidyl copolymer, ethylene / (meth) acrylic acid copolymer, ethylene / maleic anhydride copolymer, ethylene / maleic anhydride / vinyl acetate copolymer. Examples thereof include a binary or ternary copolymer such as a polymer, an ethylene / maleic anhydride / methyl acrylate copolymer, and an ethylene / maleic anhydride / ethyl acrylate copolymer.

  The content of the unsaturated carboxylic acid group-containing compound or derivative thereof is preferably 0.05 to 5.0% by weight, more preferably 0.1 to 3% by weight, in the functional group-containing polyolefin resin (B9). Especially preferably, it is 0.2 to 2 weight%. If it is the range of this content, sufficient adhesive performance can be provided, without an unreacted monomer increasing.

(C) Ester group-containing compound Examples of the ester group-containing compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and the like. And ethyl acrylate.

Specific examples of the above products include ethylene-methyl methacrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd., ACLIFT (registered trademark) CM502), ethylene-ethyl acrylate copolymer (manufactured by Nihon Unicar, NUC (registered trademark)) 6570) is commercially available.
The content of the ester group-containing compound is preferably 5.0 to 40.0% by weight, more preferably 10 to 30.0% by weight, and particularly preferably 15.0% in the functional group-containing polyolefin resin (B9). ˜25.0% by weight. If it is content of this range, the softness | flexibility and adhesiveness of a functional group containing polyolefin resin (B9) will express.

The above ester group-containing compound and ethylene copolymer include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-octene, as other unsaturated monomers in addition to ethylene. olefins having 3 to 10 carbon atoms, such as _decene, C 2 -C ₃ vinyl esters of alkanecarboxylic acids, (meth) acrylate, (meth) acrylate, (meth) acrylate, propyl glycidyl (meth) At least one selected from the group of (meth) acrylic acid esters such as acrylate, ethylenically unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid and maleic anhydride, or anhydrides thereof. It is possible to use.

The ethylene 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 other unsaturated monomers. .
The MFR of these ethylene copolymers is selected in the range of 0.5 to 20 g / 10 minutes, preferably 1 to 15 g / 10 minutes, more preferably 1.5 to 10 g / 10 minutes.

(D) Hydroxyl group-containing compound Examples of the hydroxyl group-containing compound include hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.
The content of the hydroxyl group-containing compound is preferably 0.05 to 5.0% by weight, more preferably 0.1 to 3% by weight, and particularly preferably 0.2% in the functional group-containing polyolefin resin (B9). ~ 2% by weight. If it is content of this range, sufficient adhesive performance can be provided, without an unreacted monomer increasing.

(E) Amino group-containing compound Examples of the amino group-containing compound include aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, cyclohexylaminoethyl (meth) acrylate, and the like.
The content of the amino group-containing compound is preferably 0.05 to 5.0% by weight, more preferably 0.1 to 3% by weight, and particularly preferably 0.2% in the functional group-containing polyolefin resin (B9). ~ 2% by weight. If it is content of this range, sufficient adhesive performance can be provided, without an unreacted monomer increasing.

(F) Silane group-containing compound Examples of the silane group-containing compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetylsilane, vinyltrichlorosilane, vinyltriisopropoxysilane, vinyltrismethylethylketoximesilane, and vinyltriisopropenoxy. Vinyl silanes such as silane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane, acryloxymethylmethyldimethoxysilane, acryloxymethyldimethylmethoxysilane, γ-acryloxypropyltri Methoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropylmethyldi Acrylic silanes such as toxisilane, γ-acryloxypropyldimethylmethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethylmethyldimethoxysilane, methacryloxymethyldimethylmethoxysilane, γ-methacryloxypropyltri Methoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, methacrylsilanes such as γ-methacryloxypropyldimethylmethoxysilane, styryltrimethoxysilane, Styryltriethoxysilane, styrylmethyldimethoxysilane, N-vinylbenzyl-γ-aminopropyltrimethoxysilane, N-vinyl And unsaturated silane compounds such as styrylsilanes such as benzyl-γ-aminopropylmethyldimethoxysilane.
In addition, these unsaturated silane compounds can be used individually or in mixture of 2 or more types.
In the present invention, the content of the silane group-containing compound is 0.01 to 5% by weight in the functional group-containing polyolefin resin (B9). Preferably, it is 0.01 to 3 weight%, More preferably, it is 0.01 to 1 weight%. When the content is in this range, sufficient adhesion with a protective material such as glass can be obtained, and a decrease in the volume resistivity can be suppressed.

(2) Production of functional group-containing polyolefin resin (B9) The functional group-containing polyolefin resin (B9) is a copolymer of a functional group-containing compound and an olefin, or a polyolefin resin in the presence of a radical initiator. It can be produced by grafting reaction with the functional group-containing compound capable of grafting.

The functional group-containing polyolefin polymer (B9) is a copolymer of the functional group-containing compound and olefin which can be copolymerized.
Preferred copolymers include ethylene / (meth) acrylic acid glycidyl group-containing compound copolymers, ethylene-acrylic acid copolymers, ethylene / methacrylic acid copolymers, ethylene / maleic anhydride copolymers, ethylene / anhydrous copolymers. Examples thereof include binary or ternary copolymers such as a maleic acid / vinyl acetate copolymer, an ethylene / maleic anhydride / methyl acrylate copolymer, and an ethylene / maleic anhydride / ethyl acrylate copolymer. The amount of copolymerization varies depending on the type of the functional group-containing compound, but the functional group-containing compound unit is contained in an amount of 0.5 to 30% by weight in 100% by weight of the copolymer.

The functional group-modified polyolefin polymer (B9) is a functional group-modified polyolefin resin obtained by grafting a polyolefin resin with a functional group-containing compound. Specific examples thereof include maleic anhydride-modified ethylene / α-olefin copolymer. Examples include polymers, (meth) acrylic acid-modified ethylene-α-olefin copolymers, (meth) acrylic acid glycidyl-modified ethylene-α-olefin copolymers, and silane group-modified ethylene-α-olefin copolymers. it can.
The functional group-modified polyolefin polymer is prepared by melt-kneading a polyolefin polymer in the presence of a radical initiator, in the presence of a solvent or in a kneader such as an extruder, and grafting the functional group-containing compound capable of grafting. It is manufactured by modifying.

<Polyethylene resin composition (X)>
The polyethylene-based resin composition (X) used in the (II) intermediate layer of the present invention has (a) density (according to JIS K692-2: 1997 appendix (23 ° C.)) of 0.860 to 0.970 g. / Cm ³ , (b) ethylene flow produced by ionic polymerization of 0.5 to 100 g / 10 min with a melt flow rate (according to JIS K6992-2: 1997 appendix (190 ° C., 21.18 N load)) An α-olefin copolymer is a polyethylene resin composition containing 95 to 5% by weight (A) and 5 to 95% by weight of a polyolefin resin (B) other than the component (A). Preferably, the component (A) / component (B) is selected in the range of 90 to 10/10 to 90% by weight, more preferably 90 to 50/10 to 50% by weight, especially 85 to 60/15 to 40% by weight. It is desirable that
Since the ethylene / α-olefin copolymer (A) having a long chain branch can be adjusted with a Ziegler catalyst and / or a single site catalyst, it can be adjusted on the component (A) side or the component (B) side, or (A Although it may be adjusted on both the component side and the component side (B), among the ethylene / α-olefin copolymers (A) produced by ionic polymerization, a long-chain branch produced by a single site catalyst. By selecting the ethylene / α-olefin copolymer (A1) having a VPR, the VPR of the composition (X) can be easily adjusted.
In particular, 95 to 5% by weight of an ethylene-α-olefin copolymer (A) having a long chain branch produced by a single site catalyst and 5 to 95% by weight of a polyolefin-based resin (B) (A ) Component / (B) component is preferably a polyethylene-based resin composition (X) blended at 90 to 10/10 to 90% by weight, more preferably 90 to 50/10 to 50% by weight, and still more preferably 85 to 85%. 60/15 to 40% by weight.
Within the above range, the viscosity (η) of the shear rate 60 (sec ⁻¹ ) measured by a capillograph and the shear rate 1200 (sec ⁻¹ ) at (c) measurement temperature 190 ° C. of the composition (X). (Pa · S) ratio (η ₆₀ / η ₁₂₀₀ ), that is, the range of VPR can be easily adjusted to 3.5 to 7.0. Extrusion suitability (reduction of mechanical load, film workability, laminating workability, etc.), automatic filling suitability (heat seal strength, heat seal temperature range, seal speed, hot tack property, etc.), product characteristics (appearance, pressure strength, Various performances such as piercing strength and bag breaking strength can be maintained in a well-balanced manner.

  Moreover, the range of VPR = 3.5-7.0 of the composition (X) of this invention is an extrusion processability (of a mechanical load), when used as a packaging bag for liquids and mucilages in an automatic filling machine. Reduction, film workability, laminating workability, etc.) and automatic filling appropriateness (heat seal strength, heat seal temperature range, seal speed, hot tack property, etc.), product characteristics (appearance, pressure resistance, puncture strength, bag breaking strength, etc.) It is necessary to satisfy various performances. High shear measured at a temperature close to actual filling using a material with high viscosity at low shear rate and low viscosity at high shear rate, considering that filling suitability during automatic filling is an important factor. When the ratio between the speed and the low shear rate is in a specific range, the high-speed filling property is good, and the viscosity at the low shear rate affects when sealing while pushing away impurities, and if the viscosity at this time is low The flow of the resin is fast, and the filler entrains air and the sealing strength is lowered. Therefore, it is important that the viscosity at the low shear rate is high. However, a high viscosity at a relatively high shear rate during extrusion molding is not preferable because a large load is applied during actual molding. In the present invention, in consideration of the physical properties of the combination of both radically polymerized polyethylene with good extrusion processing characteristics and linear low density polyethylene with excellent automatic filling, product characteristics, etc., and expansion of the heat seal temperature range, It has a very good correlation with VPR.

The measurement method of VPR is shown below.
VPR was measured under the following conditions using a capillograph (CAPIROGRAPH 1B manufactured by Toyo Seiki Seisakusho Co., Ltd.).
[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 was set on a flat capillograph, and after confirming that it was stable at the measurement temperature, 12 g of resin pellets were charged into the barrel. After 6 minutes, the melt viscosity at each shear rate was measured in the order from low speed to high speed.

In the composition (X) of the present invention, (c) a viscosity η (Pa · S) between a shear rate of 60 (sec ⁻¹ ) measured by a capillograph and a shear rate of 1200 (sec ⁻¹ ) at a measurement temperature of 190 ° C. ) (VPR = η ₆₀ / η ₁₂₀₀ ) as a means for adjusting the range of 3.5 to 7.0, as described above, a method of introducing long chain branching into the ethylene / α-olefin copolymer The molecular weight distribution (MWD) of the ethylene / α-olefin copolymer can be adjusted by a method combining both, etc., but as described above, the ethylene / α-olefin copolymer of component (A) can be adjusted. The method of introducing a long-chain branch into the polymer is most preferable because it is simple and the various performance balances of the packaging bag are excellent.

The range of VPR = 3.5 to 7.0 depends on the blending amount of the ethylene-α-olefin copolymer having a long chain branch of the component (A) and / or the component (B). Viscosity η (Pa · S) ratio (η ₆₀ / η ₁₂₀₀ ) VSP in the range of 3.5 to 7.0 can be easily adjusted.

The polyethylene-based resin composition (X) in the present invention has (c) a viscosity η (at a measurement temperature of 190 ° C. and a shear rate of 60 (sec ⁻¹ ) measured by a capillograph and a shear rate of 1200 (sec ⁻¹ ). (Pa · S) ratio (η ₆₀ / η ₁₂₀₀ ) (ie VPR) is in the range of 3.5 to 7.0, preferably 3.7 to 6.8, more preferably 4.0 to 6 It is desirable that the range be .7. When the VPR is less than 3.5, the automatic filling suitability is not satisfied. Moreover, when VPR exceeds 7.0, there exists a concern that an industrially stable product cannot be obtained easily.

<(III) Sealant layer>
Examples of the material constituting the sealant layer include an ethylene-α-olefin copolymer (C) having a density of 0.860 to 0.945 g / cm ³ and / or a high-pressure radical polyethylene (D), and ( III) The melting point of the sealant layer is characterized by being lower than the melting point of (II) the intermediate layer. Preferably (C) component / (D) component is 95-30 / 70-5 weight%, More preferably, (C) component / (D) component is 90-50 / 10-50 weight%, More preferably, 80- It is selected in the range of 65/20 to 35% by weight. As a result, extrusion processability (reduction of mechanical load, film processability, laminate processability, etc.), automatic filling appropriateness (heat seal strength, heat seal temperature range, seal speed, hot tack property, etc.), product characteristics (appearance, Various performances such as pressure strength, puncture strength, bag breaking strength, etc. are satisfied.

In the present invention, the ethylene / α-olefin copolymer (C) 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 The same component as the component (B) can be used.
Further, the same high-pressure radical polyethylene resin (D) as the above component (B) can be used.

  The melt flow rate (MFR: 190 ° C., 21.18 N load) of the ethylene / α-olefin copolymer (C) 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.

  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>
The (II) intermediate layer and (III) sealant layer are formed by melt-extrusion of the polyethylene resin composition of the present invention separately or simultaneously, but the molding temperature is 150 to 320 ° C., which is out of this category. In addition, the adhesion between the base material and the intermediate layer, and between the intermediate layer and the sealant layer is deteriorated, and when it exceeds 320 ° C., it is not preferable from the viewpoints of workability 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: 5 to 95% by weight of an ethylene-α-olefin copolymer (A) having a long chain branch satisfying the following (a) and (b), an ion polymerization method polyethylene resin, or a high pressure radical method polyethylene resin A polyethylene resin composition (X) containing 95 to 5% by weight of any one of (B1) to (B4), and the polyethylene resin composition (X) satisfies the following (c).
(A) Density (based on JIS K6992-2: 1997 appendix (23 ° C.)) is 0.860-0.970 g / cm ³ ,
(B) Melt flow rate (according to JIS K6992-2: 1997 appendix (190 ° C., 21.18 N load)) is 0.5 to 100 g / 10 min.
(C) Ratio (η ₆₀ / η ₁₂₀₀ ) of viscosity η (Pa · S) between a shear rate of 60 (sec ⁻¹ ) measured by a capillograph and a shear rate of 1200 (sec ⁻¹ ) at a measurement temperature of 190 ° C. (III) Sealant layer: ethylene-α-olefin copolymer (C) having a density of 0.860 to 0.945 g / cm ³ and / or high pressure radical process polyethylene Resin (D).

  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 laminating is possible.
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: 75mm width × 100mm length
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: Judgment criteria for low temperature filling suitability (minimum pressure resistance temperature) A pressure resistance test is performed for 3 minutes on a bag after filling with a pressure resistance tester (manufactured by Komatsu Ltd.), 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: Ethylene / 1-hexene copolymer (1) Preparation of solid catalyst In a nitrogen atmosphere, 30 grams of silica calcined at 600 ° C for 8 hours was placed in a 500 ml two-necked flask and heated in an oil bath at 150 ° C. It dried under reduced pressure with the vacuum pump for 1 hour. In a separately prepared 200 ml two-necked flask, 483 mg (0.60 mmol) of trisbenzoindenylzirconium hydride-Al (iBu) ₃ complex was placed in a nitrogen atmosphere, dissolved in 40 ml of dehydrated toluene, and further manufactured at Albemarle at room temperature. 41.1 ml of 20% methylaluminoxane / toluene solution was added and stirred for 1 hour. While heating and stirring the 500 ml two-necked flask containing the vacuum-dried silica in a 40 ° C. oil bath, the total amount of the toluene solution of the reaction product of the above 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) Production of ethylene / 1-hexene copolymer (1) Ethylene / 1-hexene gas phase continuous copolymerization was carried out using the solid catalyst obtained in (1) above.
That is, a gas phase continuous polymerization apparatus (internal volume 100 L, fluidized bed diameter 10 cm, bed, prepared at a temperature of 65 ° C., a hexene / ethylene molar ratio of 2.75 mol%, a hydrogen / ethylene molar ratio of 0.210 mol%, and an ethylene partial pressure of 0.55 MPa. Polymerization was carried out at a constant gas composition and temperature while intermittently feeding the solid catalyst to a weight of 1.8 kg at a rate of 0.32 g / hour. 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 245 g / hour. As shown in Table 1 below, the MFR and density of the ethylene / 1-hexene copolymer obtained after producing a cumulative amount of 5 kg or more of polyethylene were 52 g / 10 min and 0.910 g / cm ³ , respectively. λmax is not measured because it is a high MFR.

PE-2: Production of ethylene / 1-hexene copolymer (2) Ethylene / 1-hexene gas phase continuous copolymerization was carried out using the solid catalyst obtained in (1) above.
That is, a gas phase continuous polymerization apparatus (internal volume 100 L, fluidized bed diameter 10 cm, bed, prepared at a temperature of 85 ° C., a hexene / ethylene molar ratio of 2.72 mol%, a hydrogen / ethylene molar ratio of 0.052 mol%, and an ethylene partial pressure of 0.54 MPa. Polymerization was carried out at a constant gas composition and temperature while intermittently supplying the solid catalyst at a rate of 0.38 g / hour to a weight of 1.8 kg. In order to maintain the cleanliness of the system, 0.03 mol / L of a hexane diluted solution of triethylaluminum (TEA) was supplied to the gas circulation line at 8 ml / hr. As a result, the average production rate of the produced polyethylene was 335 g / hour. As shown in Table 1 below, the MFR and density of the ethylene / 1-hexene copolymer obtained after producing a cumulative amount of 5 kg or more of polyethylene are 1.0 g / 10 min, 0.915 g / cm ³ , and λmax = 3. 6.

PE-3: Ethylene / 1-hexene copolymer (1) Synthesis of dimethylsilylene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride Using cyclopentadienyl- (3-methylindenyl) dimethylsilane And synthesized according to the procedure described in Macromolecules 1995, 28, 3771-3778.
(2) Preparation of solid catalyst Under a nitrogen atmosphere, 5 grams of silica calcined 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 milligrams of dimethylsilylene (cyclopentadienyl) (3-methylindenyl) zirconium dichloride synthesized in (1) above was placed in a nitrogen atmosphere, and 13.4 ml of dehydrated toluene. After dissolution, 8.6 ml of 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.
(3) Production of ethylene / 1-hexene copolymer Ethylene / 1-hexene gas phase continuous copolymerization was carried out using the solid catalyst obtained in (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. As shown in Table 1 below, the MFR and density of the ethylene / 1-hexene copolymer obtained after producing a cumulative amount of 5 kg or more of polyethylene are 7.2 g / 10 min, 0.9160 g / cm ³ , and λmax = 4. 3.

PE-4: Ethylene / 1-hexene copolymer (1) Preparation of PE-4 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) Production of PE-4: ethylene / 1-hexene copolymer Ethylene / 1-hexene / 1,7-octadiene gas phase continuous copolymerization was carried out using the solid catalyst obtained in (1) above. 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. As shown in Table 1 below, 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 are 8 g / 10 minutes, 0.918 g / cm ³ , respectively. λmax = 4.3.

PE-5: linear low density polyethylene resin (density: 0.898 g / cm ³ , MFR: 4 g / 10 min, metallocene catalyst, product name: kernel KNL KF360T manufactured by Nippon Polyethylene Co., Ltd.)
PE-6: linear low density polyethylene resin (density: 0.936 g / cm ³ , MFR: 2 g / 10 min, Ziegler catalyst, product name: Novatec C6 SF941 manufactured by Nippon Polyethylene Co., Ltd.)
PE-7: linear low-density polyethylene resin (density: 0.920 g / cm ³ , MFR: 2 g / 10 min, melting point: 105 ° C., metallocene catalyst, with long chain branching, trade name: Sumikasen GMH CB2001, Sumitomo Chemical Co., Ltd. (Made by company)

PE-8: 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-9: Ethylene-1-hexene copolymer resin (1) Preparation of PE-9 catalyst:
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 fired at 450 ° C. for 5 hours is added, stirred at room temperature for 1 hour, blown with nitrogen at 40 ° C., and dried under reduced pressure. A good solid catalyst was obtained.

(2) Production of PE-9: ethylene-1-hexene copolymer 1-hexene / ethylene molar ratio is 0.027, hydrogen / ethylene molar ratio is 7.5 × 10 ⁻⁴ , and nitrogen concentration is 30 mol%. And a total pressure of 0.8 MPa and a temperature of 75 ° C. were prepared. A hexane solution (0.01 mmol / ml) was supplied at 25 ml / h. 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-1) were measured. As shown in Table 1 below, the 1-hexene content was 11 % By weight, MFR 12 g / 10 min, density 0.912 g / cm ³ .

PE-10: High-pressure radical method 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.)
B: High pressure method low density polyethylene (using the above PE-10)

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

<Intermediate layer>
The compositions (S1 to S7) shown in Table 2 below were blended at a predetermined ratio, kneaded and extruded at 190 ° C., and pelletized.

<Sealant layer>
As a sealant, linear low-density polyethylene manufactured with a single-site catalyst and 55% by weight of linear low-density polyethylene (density: 0.898 g / cm ³ , MFR: 17 g / 10 min) manufactured with a single-site catalyst (Density: 0.880 g / cm ³ , MFR: 3.5 g / 10 min) 20% by weight and low density polyethylene produced by the high-pressure radical method (density: 0.918 g / cm ³ , MFR: 4 g / 10 min) A composition consisting of 25% (melting point: 100 ° C.) was used.

<Examples 1-4>
[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-based resin composition (S1) shown in Table 2 was taken up as an intermediate layer material while being coated with a bow roll and ozone sprayed in the laminating portion, and the coating thickness was 100 m / min. Extrusion laminating was performed at 25 μm. In Examples 2 to 4, the polyethylene resin composition (S2) (S3) or (S4) 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. 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.

<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. 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 4.

<Evaluation results>
As is apparent from Table 3 above, Examples 1 to 4 are all the ethylene / α-olefin copolymer (A) satisfying (a) to (b) of the present invention in the (II) intermediate layer. ) And a high-pressure radical method low-density polyethylene (B) in a specific amount mixed, a superior effect is obtained. That is, Example 1 shows that ethylene / 1-hexene copolymer (PE-1, PE-2) having two types of long chain branches in the intermediate layer, ethylene / 1-hexene copolymer produced by a single site catalyst. A composition comprising a polymer (PE-5), a Ziegler-catalyzed ethylene / α-olefin copolymer (PE-6) and a low-density polyethylene by high-pressure radical polymerization, and an ethylene / α-olefin having a long chain branch Since a copolymer is used, 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 ) VPR However, the processability at the time of laminating is good, and the temperature width of the horizontal seal bar at the time of liquid filling is 130 to 150 ° C. at 20 m / min, and 1 at 25 m / min. It spreads from 0 to 155 ° C, and when used as a packaging bag for liquids and mucilages in automatic filling machines, it is suitable for extrusion (reducing mechanical load, film workability, laminating workability, etc.) and automatic filling (heat) (Seal strength, heat seal temperature range, seal speed, hot tack property, etc.) and product characteristics (appearance, pressure resistance, puncture strength, bag breaking strength, etc.) were satisfied.
Further, in Example 2, an ethylene / 1-hexene copolymer (PE-3) having a long chain branch in the intermediate layer, an ethylene / 1-hexene copolymer (PE-5) produced with a single site catalyst. , A Ziegler-catalyzed ethylene / α-olefin copolymer (PE-6) and low-density polyethylene by high-pressure radical polymerization, using an ethylene / α-olefin copolymer having a long chain branch Therefore, the shear rate measured by the capillograph, the ratio (η ₆₀ / η ₁₂₀₀ ) VPR of the viscosity η (Pa · S) at 60 (sec ⁻¹ ) and 1200 (sec ⁻¹ ) is 4.3. Therefore, workability at the time of laminating is good, and the temperature width of the horizontal seal bar at the time of liquid filling is 130 to 150 ° C. at 20 m / min and 140 to 160 ° C. at 25 m / min. In addition, when used as a packaging bag for liquids and mucilages in automatic filling machines, it is suitable for extrusion (reducing mechanical load, film workability, laminating workability, etc.) and automatic filling (heat seal strength, heat seal) (Temperature range, sealing speed, hot tackiness, etc.) and product properties (appearance, pressure resistance, puncture strength, bag breaking strength, etc.) were satisfied.
Further, in Example 3, an ethylene / 1-hexene copolymer (PE-4) having a long chain branch in the intermediate layer, an ethylene / 1-hexene copolymer (PE-5) produced with a single site catalyst. , A Ziegler-catalyzed ethylene / α-olefin copolymer (PE-6) and a low-density polyethylene composition by high-pressure radical polymerization, and using an ethylene / α-olefin copolymer having a long chain branch , The shear rate measured by a capillograph, the ratio (η ₆₀ / η ₁₂₀₀ ) VPR of the viscosity η (Pa · S) at 60 (sec ⁻¹ ) and 1200 (sec ⁻¹ ) is 4.7, Processability at the time of laminating is good, and the temperature width of the horizontal seal bar at the time of liquid filling is 130 to 150 ° C. at 20 m / min, and 140 to 160 ° C. at 25 m / min, When used as a packaging bag for liquids and mucilages in dynamic filling machines, extrusion suitability (reducing mechanical load, film workability, laminating workability, etc.) and automatic filling suitability (heat seal strength, heat seal temperature range) , Sealing speed, hot tackiness, etc.) and product characteristics (appearance, pressure resistance, puncture strength, bag breaking strength, etc.) were satisfied.
Further, in Example 4, a commercially available linear low-density polyethylene having a long-chain branch, (Sumikacene GMH: PE-7), an ethylene / 1-hexene copolymer produced with a single-site catalyst ( PE-5), a Ziegler-catalyzed ethylene / α-olefin copolymer (PE-6) and a low-density polyethylene by high-pressure radical polymerization, and an ethylene / α-olefin copolymer having a long chain branch Therefore, 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 ) VPR is 4 .8, high workability during laminating, and the temperature range of the horizontal seal bar during liquid filling is 130 to 150 ° C. at 20 m / min, and 25 m / min. When spread as 40-155 ° C and used as a packaging bag for liquids and sticky bodies in automatic filling machines, it is suitable for extrusion processing (reduction of mechanical load, film workability, laminating workability, etc.) and automatic filling suitability (heat (Seal strength, heat seal temperature range, seal speed, hot tack property, etc.) and product characteristics (appearance, pressure resistance, puncture strength, bag breaking strength, etc.) were satisfied.
On the other hand, since all of Comparative Examples 1 to 3 do not use the polyethylene-based resin composition that satisfies the conditions of the present invention for the (II) intermediate layer, the desired effects are not obtained. That is, Comparative Example 1 using a resin obtained by mixing an ethylene-α-olefin copolymer polymerized using a Ziegler catalyst and a high-pressure low-density polyethylene as an intermediate layer, ethylene-α-olefin polymerized using a single site catalyst Since Comparative Example 2 using a resin in which a copolymer and a high-pressure method low-density polyethylene were mixed in the intermediate layer had VPR values of 3.3 and 3.4, which are below the claims of the present invention, The temperature range of the horizontal seal bar did not expand. In addition, 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 to measure the temperature of the horizontal seal bar.

  The present invention uses, as an intermediate layer, a polyethylene-based resin composition containing an ethylene-α-olefin copolymer having a specific long-chain branch as a packaging material such as a packaging bag for liquids and viscous bodies in an automatic filling machine. Therefore, it is used in various packaging materials because it has high pressure resistance, heat seal strength and contaminant heat sealability, and can be filled at high speed in a wide range of seal temperatures from low to high temperatures. It is particularly useful as a liquid packaging bag.

Claims (6)

In a packaging material for a liquid packaging bag composed of (I) a base material layer, (II) an intermediate layer and (III) a sealant layer composed of the following materials:
The packaging material for a liquid packaging bag, wherein the (II) intermediate layer and (III) sealant layer are formed by a melt extrusion molding method.
(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: 5 to 95% by weight of ethylene-α-olefin copolymer (A) produced by ionic polymerization satisfying the following (a) to (b), and the density other than the component (A) is 0 .860g / cm ³ or more 0.940 g / cm ³ less than a is other polyolefin resin (B) a polyethylene resin composition comprising 95 to 5% by weight with (X), the polyethylene resin composition (X) Satisfies the following (c).
(A) Density (based on JIS K6992-2: 1997 appendix (23 ° C.)) is 0.860 to 0.945 g / cm ³ ,
(B) Melt flow rate (according to JIS K6992-2: 1997 appendix (190 ° C., 21.18 N load)) is 0.5 to 100 g / 10 min.
(C) Ratio (η ₆₀ / η ₁₂₀₀ ) of viscosity η (Pa · S) between a shear rate of 60 (sec ⁻¹ ) measured by a capillograph and a shear rate of 1200 (sec ⁻¹ ) at a measurement temperature of 190 ° C. (III) sealant layer: ethylene-α-olefin copolymer (C) having a density of 0.860 to 0.945 g / cm ³ and / or high-pressure radical process polyethylene Resin (D).   The packaging material for a liquid packaging bag according to claim 1, wherein the ethylene / α-olefin copolymer (A) is an ethylene / α-olefin copolymer produced by a single site catalyst.   The packaging material for a liquid packaging bag according to claim 1 or 2, wherein the ethylene / α-olefin copolymer (A) is an ethylene / α-olefin copolymer having a long chain branch.   The polyethylene-based resin composition (X) comprises 5 to 95% by weight of an ethylene-α-olefin copolymer (A1) having a long chain branch, an ion polymerization method polyethylene resin and / or a high pressure radical method polyethylene resin (B). The packaging material for a liquid packaging bag according to any one of claims 1 to 3, wherein the packaging material is contained in a range of 95 to 5% by weight. The (III) sealant layer is an ethylene / α-olefin copolymer (C) and / or a high-pressure radical polyethylene resin (D) having a density of 0.860 to 0.945 g / cm ³ , and the (III) The packaging material for a liquid packaging bag according to any one of claims 1 to 4, wherein the sealant layer is lower than the melting point of the intermediate layer (II). The liquid packaging bag using the packaging material for liquid packaging bags in any one of Claims 1-5.

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