JP2000117914A - Multilayer film and sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multilayer film, a stretch multilayer film, a shrink multilayer film, a gas barrier multilayer film excellent in mechanical strength, transparency, stretchability, binding property, elastic recovery property, and chemical resistance. Provided is a heat-sealable multilayer film. SOLUTION: The aromatic vinyl compound content is 1 in mole fraction.
Less than 99.9%, comprising a resin composition containing 5% by weight or more of an aromatic vinyl compound-α-olefin random copolymer having a head-tail chain structure composed of two or more aromatic vinyl compound units. A multilayer film comprising at least one layer, a stretchable multilayer film,
Shrink multilayer film, gas barrier multilayer film and heat seal multilayer film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an aromatic vinyl compound having a head-tail chain structure comprising two or more aromatic vinyl compound units, wherein the content of the aromatic vinyl compound is from 1 to less than 99.9% by mole fraction. The present invention relates to a multilayer film containing at least one layer of a resin composition containing 5% by weight or more of a vinyl-α-olefin random copolymer, and a container obtained therefrom. More specifically, in the present invention, the alternating structure of the aromatic vinyl compound and ethylene has a constant ratio,
In addition, a stretchable multilayer film, a shrinkable multilayer film, a gas barrier multilayer film, and a heat layer containing at least one layer of a resin composition composed of an aromatic vinyl compound-ethylene random copolymer having a high isotactic property having an alternating structure. The present invention relates to a sealable multilayer film and a container formed therefrom.

[0002]

2. Description of the Related Art With respect to a film using a styrene-ethylene random copolymer, a so-called pseudo-random styrene-ethylene copolymer having no styrene chain in the head-tail and no stereoregularity derived from a styrene unit has been used. The film used is known. For example, USP
No. 5,703,187 describes a pseudorandom copolymer obtained using a so-called CGCT type catalyst and a film using the same. However, there is no specific description about the multilayer film. WO95 / 32095 describes a multilayer shrinkable film using a pseudo-random copolymer obtained using a similar CGCT catalyst. However, these pseudo-random copolymers are not sufficiently satisfactory in mechanical properties such as breaking strength and solvent resistance. Further, the copolymer obtained by using the CGCT catalyst has a relatively large styrene content composition distribution especially when the styrene content is 20 mol% or less, particularly 10 mol% or less, and the average styrene content Since it contains a copolymer component having a much lower styrene content, it has the drawback that its transparency is poor for film applications. The copolymer having a styrene content of 50 mol% or more has a glass transition point of 30 ° C.
Above, transparency, high initial elastic modulus, plastic film, particularly useful as a shrink film, but the pseudo-random copolymer, since there is no head-tail styrene chain, the styrene content is at most 50
Mol%, a copolymer having a styrene content higher than that is not obtained.

[0003] In recent years, due to the speeding up of packaging by automatic packaging machines and the diversification of articles to be packaged, the demand for packaging films has been steadily increasing in performance and function.

[0004] Stretch wrapping involves placing an object to be wrapped directly or on a lightweight tray, stretching the film appropriately, and overlapping the film, and is particularly frequently used for food packaging. Characteristics such as good packaging efficiency such as good packaging efficiency and clean packaging finish, elastic recovery properties that return to the original shape even after deformation after packing, good bottom sealing properties, and little peeling of the film during transportation and display. is necessary. For example, in the field of food packaging, polyvinyl chloride is mainly used.

Recently, due to environmental problems of polyvinyl chloride-based films, some non-polyvinyl chloride-based films are composed of low-density polyethylene, ethylene-vinyl acetate copolymer, or linear low-density polyethylene. Olefin-based films are used. Various films having a multilayer structure using a polyolefin resin have been devised. For example, ethylene-vinyl acetate copolymer (EV
A), a stretch film having a layer structure of EVA / 1-polybutene / EVA, EVA / linear ethylene-α-olefin copolymer / EVA, etc. Specifically, EVs are added to both sides of the hydrogenated ethylene-butadiene block copolymer.
A film laminated with A is disclosed in Japanese Examined Patent Publication No. 5-59822, and has the property of having a good elastic recovery property against deformation. Is canceled instantaneously, the packaging workability, the finish of the packaging, and the bottom sealing property cannot be sufficiently satisfied.

[0006] Shrink packaging is a method of rapidly and tightly packaging a plurality of products individually or simultaneously at the same time. For example, a method of thermally shrinking the film by hot air or the like after wrapping the film with a little margin and then primary wrapping, wrapping the conventional film with a certain degree of tension, folding the end of the film into the bottom of the packaged object, A method such as a stretch shrink method in which the folded portion is primarily packaged by self-adhesive force or thermal fusion between the films and then subjected to a heat shrink treatment to remove tarmi and wrinkles of the film. All packages are tight and beautiful in appearance, and the quality of the contents can be easily confirmed. Therefore, they are frequently used for packaging foods and miscellaneous goods. In particular, in stretch shrink wrapping, the film is pressed against the object to be wrapped with considerable tension, which may cause the film to be torn. Required. Specifically, this is a case where a tray having a hard or sharp edge or a packaged object having a sharp projection, for example, a crustacean, dried fish, crab, or the like is packaged. In addition, the distortion caused by the deformation applied to the film after packaging (thickness, wrinkles, local dents generated in the film due to deformation of the contents due to vibration, load, changes in environmental temperature, etc.) is related to the reduction in commercial value. However, there is a strong demand for a deformation recovery property in which the distortion can be quickly restored to the original state as much as possible.

Japanese Patent Publication No. 2-14898 discloses a polyolefin-based multilayer film for shrink packaging. This multilayer film is composed of at least four layers of both surface layers, a mixed resin layer containing a polyolefin elastomer and a layer made of a polypropylene resin.
The heat shrinkage at 0 ° C. is 20 to 50%. As a detailed description of the layer structure, the surface layer is for giving the multilayer film heat sealability, antifogging property, surface glossiness,
Specifically, ethylene-vinyl acetate copolymer (EVA),
Resins such as ethylene-ethyl acrylate copolymer (EEA) and ethylene-methyl methacrylate copolymer (EMMA) are exemplified. The polypropylene layer has a role of imparting heat resistance and mechanical strength to the multilayer film. Crystalline polypropylene and polybutene-1 are exemplified. The elastomer layer is composed of a resin mixture composition containing 5 to 90% by weight of a polyolefin elastomer having a Vicat softening point of 60 ° C or lower. The multilayer film synergistically improves the strength properties, flexibility, and adhesion to other layers, and plays a role in assisting the stretching of a layer that is difficult to stretch by itself. Specifically, a soft elastomer having a Vicat softening point of 60 ° C. or less, an ethylene-propylene copolymer elastomer, and an ethylene-butene-1 copolymer elastomer are used, and EVA, ethylene-α-olefin copolymer, polypropylene A layer in which a layer is formed by appropriately mixing a base resin, a polybutene-1 base resin, or the like is illustrated. By adjoining this layer and the polypropylene resin layer, the entire film can be stretched at a low temperature of 30 to 80 ° C. to an area stretching ratio of 4 to 30 times. As a result, a multilayer film having excellent heat resistance, shrinkage, and sealing properties was obtained, but was insufficient in terms of breakthrough resistance, tear resistance, and deformation recovery rate.

Japanese Patent Application Laid-Open No. 7-1680 discloses a blend resin of a terpolymer selected from ethylene, acrylic acid ester, maleic anhydride and glycidyl methacrylate and an ethylene-vinyl alcohol copolymer. A low oxygen permeable film having at least one oxygen barrier layer, in which a metallocene-catalyzed polyolefin is blended with one surface layer other than the seal layer, is disclosed.
However, a flexible multilayer film excellent in film formability and sealability has not been obtained, and there is room for improvement.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aromatic vinyl compound-α-olefin random copolymer which has improved the drawbacks of various conventional multilayer films or pseudo-random styrene-ethylene copolymer films. An object of the present invention is to provide a multilayer film comprising a resin composition containing a polymer.

More specifically, the disadvantages of the prior art are improved,
While maintaining the excellent heat resistance, shrinkage, heat sealability, transparency, and anti-fogging properties of the film, by laminating resin layers that provide various functions, self-adhesiveness and tear propagation resistance are further improved. , Piercing strength, mechanical strength such as elongation at break, stretchability, binding, elastic recovery, puncture resistance,
An object of the present invention is to provide various grades of multilayer films having excellent tear resistance, deformation recovery properties, and gas barrier properties. In addition, a novel aromatic vinyl compound-α-olefin random in which the drawbacks of a conventional pseudo-random styrene-ethylene copolymer film which can be used as a non-PVC-based stretch film and which can also be used in a handler wrapper or a stretch packaging machine, etc., is improved. It is an object of the present invention to provide a multilayer film containing a copolymer as a constituent component.

[0011]

According to the present invention, an aromatic vinyl compound content is from 1 to less than 99.9% by mole fraction,
Head comprising at least two aromatic vinyl compound units
A resin composition containing 5% by weight or more, particularly preferably 80% or more, of an aromatic vinyl compound-α-olefin random copolymer having a tail chain structure, or a multilayer film containing at least one layer composed of a single copolymer. Preferred are transparent films, and multilayer films and containers having stretchability or pallet stretchability, shrinkage, gas barrier properties, and heat sealing properties.

Aromatic vinyl compound used in the present invention
The α-olefin random copolymer will be described in detail using a styrene-ethylene random copolymer as a typical example. Its structure is nuclear magnetic resonance (NMR)
Is determined by

The copolymer used in the present invention shows main peaks at the following positions in ¹³ C-NMR based on TMS. Peaks derived from main chain methylene and main chain methine carbon were around 24 to 25 ppm, around 27 ppm, and 30 ppm.
around ppm, 34-37 ppm, 40-41 ppm
Near and around 42 to 46 ppm, and peaks derived from five carbons of the phenyl group which are not bonded to the polymer main chain were around 126 ppm and 128 ppm,
The peak derived from one carbon atom bonded to the polymer main chain among the phenyl groups is shown at around 146 ppm. Styrene-ethylene random copolymer used in the present invention,
The styrene content is 1 to less than 99.9%, preferably 5 to less than 99.9%, more preferably 10 to 99.9% by mole fraction.
A styrene-ethylene random copolymer having less than 9%, wherein the stereoregularity of a phenyl group having an alternating structure of styrene and ethylene represented by the following general formula (1) contained in the structure is an isotactic dye. 0.7 with add fraction m
And the alternating structure index λ given by the following formula (i) is smaller than 70 and larger than 1, preferably 7
It is a styrene-ethylene random copolymer smaller than 0 and larger than 5. λ = A3 / A2 × 100 Formula (i) Here, A3 represents three types of peaks a derived from a styrene-ethylene alternating structure represented by the following general formula (1 ′) and obtained by ¹³ C-NMR measurement, This is the sum of the areas b and c. A2 is the total area of peaks derived from main chain methylene and main chain methine carbon observed in the range of 0 to 50 ppm by ¹³ C-NMR based on TMS.

[0014]

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(In the formula, Ph represents a phenyl group, x represents the number of repeating units, and represents an integer of 2 or more.)

[0016]

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(In the formula, Ph represents a phenyl group, x represents the number of repeating units, and represents an integer of 2 or more.)

In the styrene-ethylene random copolymer used in the present invention, the isotactic structure in which the stereoregularity of the phenyl group in the alternating copolymerized structure of styrene and ethylene is the isotactic diad fraction m (Also called the meso diad fraction) is greater than 0.75,
Preferably, it refers to a structure exhibiting 0.85 or more, more preferably 0.95 or more. The isotactic diad fraction m of the alternating copolymerized structure of styrene and ethylene is 25 pp
The peak area Ar derived from the r structure of the methylene carbon peak appearing near m and the area Am of the peak derived from the m structure
From the following equation (ii). m = Am / (Ar + Am) Formula (ii) The appearance position of the peak may be slightly shifted depending on the measurement conditions and the solvent. For example, using deuterated chloroform as a solvent,
Based on TMS, the peak derived from the r structure is
The peak derived from the m-structure appears around 25.4 to 25.5 ppm, and around 25.2 to 25.3 ppm.

When heavy 1,1,2,2-tetrachloroethane is used as a solvent and the center of the triplet of heavy 1,1,2,2-tetrachloroethane (73.89 ppm) is used as a reference, r The peak derived from the structure is 25.3 to 2
Around 5.4 ppm, the peak derived from the m-structure was 25.
Appears around 1-25.2 ppm. Note that the m structure represents a meso diad structure, and the r structure represents a racemic diad structure.

In the styrene-ethylene random copolymer used in the present invention, a peak attributable to the r structure in the alternating copolymer structure of styrene and ethylene is not substantially observed.

Further, in the styrene-ethylene random copolymer used in the present invention, the stereoregularity of the phenyl group in the chain structure of the styrene unit is isotactic. Isotacticity of the stereoregularity of the phenyl group in the chain structure of the styrene unit means that the isotactic dyad fraction ms (or also referred to as the meso dyad fraction) is larger than 0.5, preferably 0.7 or more, and furthermore. It preferably refers to a structure showing 0.8 or more. The stereoregularity of the chain structure of the styrene unit is determined by a peak position of methylene carbon around 43 to 44 ppm observed by ¹³ C-NMR and a peak position of a main chain proton observed by ¹ H-NMR.

According to US Pat. No. 5,502,133,
The methylene carbon of the isotactic polystyrene chain structure appears at 42.9 to 43.3 ppm, whereas the methylene carbon of the syndiotactic polystyrene chain structure is 44.0.
Appears around ４４44.7 ppm. The appearance positions of the sharp methylene carbon of syndiotactic polystyrene and the broad peak of 43 to 45 ppm of atactic polystyrene are the peak positions where the other carbons of the styrene-ethylene random copolymer used in the present invention have relatively low intensity. It is close to or overlaps with. However, in the present invention, the methylene carbon peak is strongly observed at 42.9 to 43.4 ppm, compared with 44.0 to 44.7 pp.
No clear peak is observed near m.

Further, according to US Pat. No. 5,502,133, peaks attributed to the main chain methylene and methine protons in ¹ H-NMR are 1.5 to 1.6 ppm and 2.2 to 2 ppm in the case of isotactic polystyrene. .3pp
m is 1.3 for syndiotactic polystyrene
~ 1.4 ppm, 1.8-1.9 ppm.
In the copolymer used in the present invention, the peak is 1.
Observed in 5~1.6ppm and 2.2 ppm, the ¹
The result of the H-NMR analysis shows that the styrene chain in the copolymer of the present invention has isotactic stereoregularity.

The isotactic diad fraction ms of the chain structure of the styrene unit is calculated from the peaks of the methylene carbon of the styrene chain structure measured by ¹³ C-NMR or the main chain methylene and methine protons measured by ¹ H-NMR. It is derived by the formula. The peak area Ar ′ derived from the syndiotactic diad structure (r structure) of each peak and the peak area Am ′ derived from the isotactic diad structure (m structure) are determined by the following formula (iii). Can be. ms = Am ′ / (Ar ′ + Am ′) Formula (iii) The appearance position of the peak may be slightly shifted depending on the measurement conditions and the solvent.

The styrene-ethylene random copolymer used in the present invention includes a styrene-head-tail linked chain structure, an ethylene unit-linked chain structure, and a copolymer containing a styrene unit and an ethylene unit bonded structure. It is united. The proportion of these structures in the present copolymer varies depending on the styrene content or the polymerization conditions such as the polymerization temperature. The proportions of these structures and the distribution of the structures are not restricted by the structure distribution by a specific statistical calculation. The lower the styrene content, the lower the percentage of the head-tail linked chain structure of the styrene units (for example, a styrene content of about 20
In the case of a copolymer having a mole percent or less, it is difficult to directly observe a peak derived from the chain structure linked by the head-tail of the styrene unit by ordinary ¹³ C-NMR measurement.) However, using the transition metal compound of the present invention or by the production method of the present invention, a homopolymer having high activity and stereoregularity can be produced by polymerization of styrene alone, that is, a head-tail of essentially a styrene unit. Can form a linked structure, and in the copolymer, at least
^{According to the 13} C-NMR method, the proportion of the chain structure linked by the head-tail of the styrene unit continuously changes corresponding to the styrene content of 20 to 99 mol%.
It is clear that even if the amount is less than mol%, a small amount of a styrene unit head-tail linked chain structure may be present in the copolymer. ^The polymer copolymerized using the styrene monomer enriched with ¹³ C
Styrene content of 20 by means such as analysis by NMR.
Styrene unit head in the copolymer of not more than mol%
It is possible to observe chain structures linked by tails. The same applies to the chain structure of ethylene units.

The head of the styrene unit contained in the styrene-ethylene random copolymer used in the present invention
The chain structure linked by the tail is two or three or more chain structures that can be represented by the following structures.

[0027]

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[0028]

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Here, n is an arbitrary integer of 3 or more. Ph
Represents a phenyl group. On the other hand, in the case of a conventionally known so-called pseudo-random copolymer, a head-tail chain structure of styrene cannot be found even at a maximum styrene content of around 50 mol%. Further, even if homopolymerization of styrene is attempted using a catalyst for producing a pseudorandom copolymer, no polymer can be obtained. A very small amount of an atactic aromatic vinyl compound homopolymer may be obtained depending on polymerization conditions and the like. Should understand.

The peak of the methylene carbon of the structure derived from the hetero-bond of styrene in the conventional pseudorandom copolymer having no stereoregularity is 34.0 to 34.5 ppm and 34.5.
It is known to be in two regions of Ｐ35.2 ppm (eg, PolymerPreprints, Ja.
pan, 42 , 2292 (1993)). In the styrene-ethylene random copolymer used in the present invention, the peak attributed to the methylene carbon of the heterogeneous bond structure derived from styrene is observed in a region of 34.5 to 35.2 ppm, but 34.0 to 34 ppm. It is hardly observed at 0.5 ppm. This indicates one of the features of the copolymer of the present invention, and indicates that the phenyl group has a high stereoregularity even in a heterogeneous bond structure derived from styrene as shown in the following formula.

[0031]

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The weight average molecular weight of the styrene-ethylene random copolymer used in the present invention is 60,000 or more, preferably 80,000 or more when the styrene content is 1 mol% or more and less than 20 mol%, and is 20 mol% or more and 99. 3% for less than 9 mol%
It is 10,000 or more, preferably 40,000 or more. The upper limit of the weight average molecular weight is not particularly limited, but is preferably 3,000,000 or less, more preferably 1,000,000 or less. Molecular weight 30
If it exceeds 10,000, the melt viscosity will increase, and it will be difficult to mold by general molding methods such as injection molding and extrusion molding. Here, the weight average molecular weight (Mw) refers to a polystyrene-converted molecular weight determined by GPC using standard polystyrene. The molecular weight distribution (Mw / Mn) is 6 or less, preferably 4 or less, particularly preferably 3 or less. Note that Mn represents a number average molecular weight, which can be similarly measured by a GPC method. The styrene-ethylene random copolymer used in the present invention has a practically high molecular weight. Furthermore, the styrene-ethylene random copolymer of the present invention has an alternating structure of styrene and ethylene having high stereoregularity, and simultaneously various structures such as ethylene chains of various lengths, heterogeneous bonds of styrene, and styrene chains. It has the feature that it also has. Further, the styrene-ethylene random copolymer of the present invention can variously change the ratio of the alternating structure depending on the content of styrene in the copolymer in a range of greater than 1 and less than 70 in the λ value obtained by the above formula. is there. Since this stereoregular alternating structure is a crystallizable structure, the copolymer of the present invention can be made crystalline, non-crystalline, by controlling the degree of crystallinity by the content of styrene or by an appropriate method. It is possible to provide various properties such as a polymer having a partially crystalline structure. The λ value of less than 70 means that while being a crystalline polymer, in order to provide significant toughness and transparency, and to become a partially crystalline polymer, or It is important to become.

As described above, the aromatic vinyl compound -α-
A styrene-ethylene random copolymer has been described as a typical example of the olefin random copolymer. However, the above description is based on the aromatic vinyl compound -α-
Applicable to all olefin random copolymers. The aromatic vinyl compound-α-olefin random copolymer of the present invention has a head-tail chain structure of two or more aromatic vinyl compound units, and has a pseudo-random copolymer having no such chain structure. The values of the initial elastic modulus and the breaking strength are higher than those of the union. Further, it has a high alternating stereoregularity of an aromatic vinyl compound and an α-olefin, and is excellent in initial elastic modulus, breaking strength, elongation, and chemical resistance as compared with a copolymer having low stereoregularity. It has excellent transparency, rigidity, strength, impact resistance, weather resistance, chemical resistance and natural shrink resistance even as a heat shrink film.

The copolymer used in the present invention is different from a conventional pseudorandom aromatic vinyl compound-α-olefin random copolymer having no stereoregularity and having no aromatic vinyl compound chain. In the range of each aromatic vinyl compound content and various degrees of crystallinity, the performance such as initial tensile modulus, hardness, breaking strength, chemical resistance, etc. is improved, and new crystalline resins, thermoplastic elastomers, transparent soft resins It shows the characteristic physical properties. Further, by changing the content of the aromatic vinyl compound, the glass transition point can be changed in a wide range. Among the copolymers of the present invention,
A copolymer having an aromatic vinyl compound content higher than 50 mol%, which is mainly composed of a chain structure of aromatic vinyl compound units and an alternating structure of aromatic vinyl compound units and α-olefin units, has high transparency, Since the glass transition temperature is high and the number of α-olefin chains is small or very small, it has a high initial tensile modulus and exhibits good physical properties as a plastic. In addition, since the alternating structure and a small amount of α-olefin chains are relatively uniformly present in the chain structure, it has excellent impact resistance and exhibits excellent toughness. In the aromatic vinyl compound content region having a large amount of the aromatic vinyl compound-α-olefin alternating structure, the copolymer can have crystallinity due to the stereoregularity of the alternating structure, and is a copolymer having a partially crystalline structure. The properties as a thermoplastic elastomer can be exhibited at temperatures around and above the temperature. Further, the aromatic vinyl compound chain structure can be crystallized because of its isotactic stereoregularity, and can be crystallized by a general crystallization treatment.

The copolymer used in the present invention is approximately 1
In the aromatic vinyl compound content range of 0 mol% or more, a higher melting point than the conventional aromatic vinyl compound-α-olefin random copolymer having no stereoregularity and having no aromatic vinyl compound chain ( DSC).

The aromatic vinyl compound of the present invention -α-
By including a thermoplastic resin having a glass transition temperature (Tg) of 30 ° C. or higher in a resin composition containing an olefin random copolymer, it becomes possible to set Tg as a composition in a wide range, Temperature dependence of viscoelasticity such as storage elastic modulus, loss tangent (tan δ), etc. can be controlled. Further, in the aromatic vinyl compound-α-olefin random copolymer of the present invention, specifically, by changing the styrene content, the glass transition point is-
It can be varied over a wide range from 50 ° C to 90 ° C. In particular, when the styrene content is 50% or more, Tg is 30.
It will be close to ° C. Therefore, the aromatic vinyl compound of the present invention
The α-olefin random copolymer alone or mixed with a high Tg petroleum resin, a terpene resin, a coumarone-indene resin, a rosin-based resin, or a hydrogenated derivative thereof also raises the Tg to near room temperature. , It is easier to achieve specific viscoelastic properties.

The thermoplastic resin having a glass transition temperature (Tg) of 30 ° C. or higher includes petroleum resin derived from cyclopentadiene or a dimer thereof, and aromatic petroleum resin derived from C9 component. Examples thereof include terpene resins and terpene-phenol resins from β-pinene, and examples of the rosin-based resin include rosin resins such as gum rosin and wood rosin, and esterified rosin resins modified with glycerin or pentaerthritol. Some of these have various Tg depending on the molecular weight, but those having a Tg of 30 to 100 ° C, preferably 70 to 90 ° C are suitable for the present invention. When the Tg is 30 ° C. or lower, depending on the aromatic vinyl compound-α-olefin random copolymer to be mixed, it is necessary to mix a large amount in order to increase the Tg. It is easy to cause blocking,
In addition, a problem occurs in the mechanical strength of the entire film.

The copolymer used in the present invention includes an aromatic vinyl compound-α-olefin random copolymer obtained by using the following transition metal compound or by the following production method. Is not limited to the transition metal compound or the production method. The aromatic vinyl compound-α-olefin random copolymer used in the present invention employs a catalyst composed of a transition metal compound represented by the following general formula (2) and a co-catalyst, and comprises an aromatic vinyl compound and α-olefin.
Manufactured from olefins.

[0039]

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In the formula, A and B represent an unsubstituted or substituted cyclopentaphenanthryl group (Chemical Formulas 10 and 11 below) and an unsubstituted or substituted benzoindenyl group (Chemical Formulas 12 to 1).
4) an unsubstituted or substituted cyclopentadienyl group (Formula 15), an unsubstituted or substituted indenyl group (Formula 16),
Or a group selected from an unsubstituted or substituted fluorenyl group (Formula 17), and at least one of A and B is an unsubstituted or substituted cyclopentaphenanthryl group, an unsubstituted or substituted benzoindenyl group, or It is a group selected from a substituted or substituted indenyl group.
Preferably, at least one of A and B is a group selected from an unsubstituted or substituted cyclopentaphenanthryl group and an unsubstituted or substituted benzoindenyl group.

[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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(In the above chemical formulas 10 to 17, R1 to R
Each of the eight groups is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, a halogen atom, an OSiR ₃ group, a SiR ₃ group, or a PR ₂ group (R Each represents a hydrocarbon group having 1 to 10 carbon atoms), R1 and R2, R2 and R3,
4, R5, R6, R7, and R8 may be the same or different. A) When both A and B are an unsubstituted or substituted cyclopentaphenanthryl group, an unsubstituted or substituted benzoindenyl group or an unsubstituted or substituted indenyl group, they may be the same or different.

Specific examples of the unsubstituted cyclopentaphenanthryl group include a 3-cyclopenta [c] phenanthryl group and a 1-cyclopenta [l] phenanthryl group. As an unsubstituted benzoindenyl group,
4,5-benzo-1-indenyl group (also known as benzo (e) indenyl group), 5,6-benzo-1-indenyl group, and 6,7-benzo-1-indenyl group are substituted benzoindenyl groups. Is, for example, an α-acenaphth-1-indenyl group.

The unsubstituted cyclopentadienyl group is cyclopentadienyl, and the substituted cyclopentadienyl group is 4-aryl-1-cyclopentadienyl,
5-diaryl-1-cyclopentadienyl, 5-alkyl-4-aryl-1-cyclopentadienyl, 4-
Alkyl-5-aryl-1-cyclopentadienyl,
4,5-dialkyl-1-cyclopentadienyl, 5-
Groups such as trialkylsilyl-4-alkyl-1-cyclopentadienyl and 4,5-dialkylsilyl-1-cyclopentadienyl.

The unsubstituted indenyl group is 1-indenyl, and the substituted indenyl group is 4-alkyl-1-indenyl, 4-aryl-1-indenyl, 4,5-dialkyl-1-indenyl, 4,6-dialkyl -1-
Indenyl, 5,6-dialkyl-1-indenyl,
4,5-diaryl-1-indenyl, 5-aryl-
1-indenyl, 4-aryl-5-alkyl-1-indenyl, 2,6-dialkyl-4-aryl-1-indenyl, 5,6-diaryl-1-indenyl, 4,
Groups such as 5,6-triaryl-1-indenyl.

The unsubstituted fluorenyl group is 9-fluorenyl group, and the substituted fluorenyl group is 7-methyl-
Examples include a 9-fluorenyl group and a benzo-9-fluorenyl group.

In the above general formula (3), Y represents A, B
And a methylene group, a silylene group or an ethylene group having hydrogen or a hydrocarbon group having 1 to 15 carbon atoms. The substituents may be different or the same. Y may have a cyclic structure such as a cyclohexylidene group and a cyclopentylidene group. Preferably,
Y has a bond with A and B, and is hydrogen or a group having 1 to 15 carbon atoms.
Is a substituted methylene group substituted with a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, an aryl group, a cycloalkyl group, and a cycloaryl group. The substituents may be different or the same. Particularly preferably, Y
_{Is, -CH 2 -, - CMe 2} -, - CEt 2 -, - CPh 2
—, Cyclohexylidene, cyclopentylidene, and the like. Here, Me represents a methyl group, Et represents an ethyl group, and Ph represents a phenyl group.

X is hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms,
It is an alkylaryl group having 12 carbon atoms, a silyl group having a hydrocarbon substituent having 1 to 4 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a dialkylamide group having an alkyl substituent having 1 to 6 carbon atoms. Halogen is chlorine, bromine, etc., alkyl group is methyl group, ethyl group, etc., aryl group is phenyl group, etc., alkylaryl group is benzyl group, silyl group is trimethylsilyl group, etc., and alkoxy group is Examples of the group include a methoxy group, an ethoxy group and an isopropoxy group, and examples of the dialkylamide group include a dimethylamide group. In particular, when X is a dimethylamide group, if the production method described in WO 95/32979 is applied to the production of the transition metal compound of the present invention, there is an advantage that the production can be made very simply and inexpensively. That is, it can be produced by a one-step synthesis process of a ligand compound and zirconium tetrakisdimethylamide at a temperature that is easily controlled above room temperature. Strictly speaking, the transition metal compound produced in this step is a racemic form containing a considerable amount of a meso form as an impurity, but the incorporation of the meso form into the catalyst has little effect in the present invention. In the case where X is a transition metal complex of chlorine, it is more expensive because a complex reaction of a dimethylamide complex and dimethylamine hydrochloride must be performed at a high temperature at a low cost. Furthermore, when X is a dimethylamide group, the formation rate of the active species after contacting with a cocatalyst such as methylalumoxane is slightly slower than when X is chlorine. This is particularly true in batch liquid phase polymerization, where the cocatalyst is dissolved in the polymerization solution in advance, the transition metal compound is charged into the polymerization solution under predetermined conditions, and the polymerization is started. By gradually forming active species by the method described above, there is an important advantage in the production process that rapid generation of polymerization heat immediately after the introduction of the catalyst is suppressed and heat removal of the polymerization solution is facilitated.

M is a Group IV metal and is zirconium, hafnium, or titanium. Particularly preferred is zirconium. As for the complex in which a racemic body or a meso body exists, a racemic body is preferably used, but a racemic body, a mixture of meso bodies, or a meso body may be used. As for the complex in which a pseudo-racemic body or a pseudo-meso form is present, a pseudo-racemic form is preferably used, but a pseudo-racemic form, a mixture of the pseudo-meso form, or a pseudo-meso form may be used.

Examples of such transition metal compounds include the following compounds. For example, dimethylmethylenebis (1-indenyl) zirconium dichloride, diethylmethylenebis (1-indenyl) zirconium dichloride, di-n-propylmethylenebis (1-indenyl) zirconium dichloride, dii-propylmethylenebis (1-indenyl) zirconium Dichloride,
Cyclopentylidenebis (1-indenyl) zirconium dichloride, cyclohexylidenebis (1-indenyl) zirconium dichloride, diphenylmethylenebis (1-indenyl) zirconium dichloride, dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium Dichloride {also known as dimethylmethylenebis (benzo [e] indenyl) zirconium dichloride}, di-n-propylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride, dii-
Propylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride, cyclohexylidenebis (4,5-benzo-1-indenyl) zirconium dichloride, cyclopentylidenebis (4,5-benzo-1-indenyl) zirconium Dichloride, diphenylmethylenebis (4,5benzo-1-indenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (4,5-benzo-1-indenyl) zirconium dichloride, dimethylmethylene (1-indenyl) (4 5-benzo-1-indenyl) zirconium dichloride, dimethylmethylene (1-fluorenyl) (4,5-benzo-1-indenyl) zirconium dichloride, dimethylmethylene (4-phenyl-1-
Indenyl) (4,5-benzo-1-indenyl) zirconium dichloride, dimethylmethylene (4-naphthyl-1-indenyl) (4,5-benzo-1-indenyl) zirconium dichloride, dimethylmethylenebis (5,6-benzo -1-indenyl) zirconium dichloride, dimethylmethylene (5,6-benzo-1-indenyl) (1-indenyl) zirconium dichloride, dimethylmethylenebis (6,7-benzo-1-indenyl) zirconium dichloride, dimethylmethylene (6 , 7-benzo-1-indenyl) (1-indenyl) zirconium dichloride, dimethylmethylenebis (4,5-naphth-1-indenyl) zirconium dichloride, dimethylmethylenebis (α-acenaphth-1)
-Indenyl) zirconium dichloride, dimethylmethylenebis (3-cyclopenta [c] phenanthryl)
Zirconium dichloride, dimethylmethylene (3-cyclopenta [c] phenanthryl) (1-indenyl)
Zirconium dichloride, dimethyl methylene bis (1
-Cyclopenta [l] phenanthryl) zirconium dichloride, dimethylmethylene (1-cyclopenta [l] phenanthryl) (1-indenyl) zirconium dichloride, dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium bis (dimethylamide), etc. Is mentioned. Furthermore, dimethylmethylenebis (3
-Cyclopenta [c] phenanthryl) zirconium bisdimethylamide, di-n-propylmethylenebis (3-
Cyclopenta [c] phenanthryl) zirconium dichloride, dii-propylmethylenebis (3-cyclopenta [c] phenanthryl) zirconium dichloride, cyclohexylidenebis (3-cyclopenta [c]
Phenanthryl) zirconium dichloride, cyclopentylidenebis (3-cyclopenta [c] phenanthryl) zirconium dichloride, diphenylmethylenebis (3-cyclopenta [c] phenanthryl) zirconium dichloride, dimethylmethylene (4,5-benzo-1-indenyl) (3 -Cyclopenta [c] phenanthryl) zirconium dichloride, dimethylmethylene (5,6-benzo-1-indenyl) (3-cyclopenta [c] phenanthryl) zirconium dichloride,
Dimethylmethylene (6,7-benzo-1-indenyl)
(3-cyclopenta [c] phenanthryl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (3-cyclopenta [c] phenanthryl) zirconium dichloride, dimethylmethylene (1-fluorenyl) (3-cyclopenta [c] phenanthryl) zirconium dichloride Dimethylmethylene (4-phenyl-1-indenyl) (3-cyclopenta [c] phenanthryl) zirconium dichloride, dimethylmethylene (4-naphthyl-1-indenyl) (3-cyclopenta [c] phenanthryl) zirconium dichloride, dimethylmethylene ( 3-cyclopenta [c] phenanthryl) (4,5-naphth-1-indenyl) zirconium dichloride, dimethylmethylene (3-cyclopenta [c] phenane Lyl) (α-acenaphth-1-indenyl) zirconium dichloride, dimethylmethylenebis (1-cyclopenta [l] phenanthryl) zirconiumbisdimethylamide, di-n-propylmethylenebis (1-cyclopenta [l] phenanthryl) zirconium dichloride, i-propylmethylenebis (1
-Cyclopenta [l] phenanthryl) zirconium dichloride, cyclohexylidenebis (1-cyclopenta [l] phenanthryl) zirconium dichloride,
Cyclopentylidenebis (1-cyclopenta [l] phenanthryl) zirconium dichloride, diphenylmethylenebis (1-cyclopenta [l] phenanthryl)
Zirconium dichloride, dimethylmethylene (5,6
-Benzo-1-indenyl) (1-cyclopenta [l]
Phenanthryl) zirconium dichloride, dimethylmethylene (6,7-benzo-1-indenyl) (1-cyclopenta [l] phenanthryl) zirconium dichloride, dimethylmethylene (cyclopentadienyl)
(1-cyclopenta [l] phenanthryl) zirconium dichloride, dimethylmethylene (1-indenyl)
(1-cyclopenta [l] phenanthryl) zirconium dichloride, dimethylmethylene (1-fluorenyl) (1-cyclopenta [l] phenanthryl) zirconium dichloride, dimethylmethylene (4-phenyl-1-indenyl) (1-cyclopenta [l] phenanthryl ) Zirconium dichloride, dimethylmethylene (4-naphthyl-1-indenyl) (1-cyclopenta [l] phenanthryl) zirconium dichloride, dimethylmethylene (1-cyclopenta [l] phenanthryl) (4,5-naphth-1-indenyl) zirconium Dichloride, dimethylmethylene (1-cyclopenta [l] phenanthryl) (α-acenaphth-1-indenyl) zirconium dichloride, dimethylmethylene (1-cyclopenta [l Phenanthryl) (3-cyclopenta [c] phenanthryl) zirconium dichloride, dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride {also known as dimethylmethylenebis (benzo [e] indenyl) zirconium dichloride}, di-n-propyl Methylene bis (4,5-
Benzo-1-indenyl) zirconium dichloride,
Di-i-propylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride, cyclohexylidenebis (4,5-benzo-1-indenyl) zirconium dichloride, cyclopentylidenebis (4,5-
Benzo-1-indenyl) zirconium dichloride,
Diphenylmethylenebis (4,5benzo-1-indenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (4,5-benzo-1-indenyl) zirconium dichloride, dimethylmethylene (1
-Indenyl) (4,5-benzo-1-indenyl) zirconium dichloride, dimethylmethylene (1-fluorenyl) (4,5-benzo-1-indenyl) zirconium dichloride, dimethylmethylene (4-phenyl-1-indenyl) ( 4,5-benzo-1-indenyl) zirconium dichloride, dimethylmethylene (4
-Naphthyl-1-indenyl) (4,5-benzo-1-
Indenyl) zirconium dichloride, dimethylmethylenebis (5,6-benzo-1-indenyl) zirconium dichloride, dimethylmethylene (5,6-benzo-1-indenyl) (1-indenyl) zirconium dichloride, dimethylmethylenebis (6,7 -Benzo-
1-indenyl) zirconium dichloride, dimethylmethylene (6,7-benzo-1-indenyl) (1-indenyl) zirconium dichloride, dimethylmethylenebis (4,5-naphth-1-indenyl) zirconium dichloride, dimethylmethylenebis (α -Acenaphth-1-indenyl) zirconium dichloride, dimethylmethylenebis (4,5-benzo-1-indenyl)
Zirconium bis (dimethylamide), dimethylmethylene (1-indenyl) (4,5-benzo-1-indenyl) zirconium bis (dimethylamide) and the like can be mentioned. Although the zirconium complex has been exemplified above, the same compounds as described above are preferably used for the titanium and hafnium complexes. Further, a mixture of a racemic body and a meso body may be used.
Preferably, racemic or pseudo-racemic is used. In these cases, a D-form or an L-form may be used.

As the co-catalyst used in the present invention, a co-catalyst conventionally used in combination with a transition metal compound can be used. As such a co-catalyst, aluminoxane (or alumoxane) or boron is used. Compounds are preferably used. Further, in the present invention, an aluminoxane (or alumoxane) represented by the following general formulas (3) and (4) is suitably used as a co-catalyst at that time.

[0059]

Embedded image

In the formula, R is an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or hydrogen, and m is 2 to 10
It is an integer of 0. Each R may be the same or different.

[0061]

Embedded image

In the formula, R ′ is an alkyl group having 1 to 5 carbon atoms,
An aryl group having 6 to 10 carbon atoms or hydrogen, and n is 2 to 1
It is an integer of 00. Each R 'may be the same or different. As the aluminoxane, methylalumoxane, ethylalumoxane and triisobutylalumoxane are preferably used, and methylalumoxane is particularly preferably used. If necessary, a mixture of these different alumoxanes may be used. These alumoxanes may be used in combination with alkylaluminums, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, and alkylaluminums containing halogen, for example, dimethylaluminum chloride.

The addition of the alkyl aluminum is effective for removing a polymerization inhibitor such as a polymerization inhibitor in styrene, styrene, water in a solvent, and other substances that inhibit polymerization, and detoxifying the polymerization reaction. However, the amount of alumoxane used or the amount of alumoxane used should be reduced by a known method such as distillation of styrene or a solvent in advance, or bubbling with a dry inert gas or passing through a molecular sieve. It is not always necessary to add alkyl aluminum at the time of polymerization, if it is slightly increased or added.

In the present invention, a boron compound can be used as a promoter together with the above-mentioned transition metal compound. Boron compounds used as cocatalysts include triphenylcarbenium tetrakis (pentafluorophenyl) borate (also known as trityltetrakis (pentafluorophenyl) borate), lithium tetra (pentafluorophenyl) borate, and tri (pentafluorophenyl) borane , Trimethyl ammonium tetraphenyl borate,
Triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate,
Tri (n-butyl) ammonium tetra (p-tolyl)
Phenyl borate, tri (n-butyl) ammonium tetra (p-ethylphenyl) borate, tri (n-butyl) ammonium tetra (pentafluorophenyl) borate, trimethylammonium tetra (p-tolyl)
Borate, trimethylammonium tetrakis-3,5
-Dimethylphenylborate, triethylammoniumtetrakis-3,5-dimethylphenylborate, tributylammoniumtetrakis-3,5-dimethylphenylborate, tributylammoniumtetrakis-
2,4-dimethylphenyl borate, anilinium tetrakispentafluorophenyl borate, N, N'-dimethylanilinium tetraphenyl borate, N, N '
-Dimethylanilinium tetrakis (p-tolyl) borate, N, N'-dimethylanilinium tetrakis (m
-Tolyl) borate, N, N'-dimethylaniliniumtetrakis (2,4-dimethylphenyl) borate,
N, N'-dimethylanilinium tetrakis (3,5-
Dimethylphenyl) borate, N, N'-dimethylaniliniumtetrakis (pentafluorophenyl) borate, N, N'-diethylaniliniumtetrakis (pentafluorophenyl) borate, N, N'-2,4,5
-Pentamethylanilinium tetraphenylborate,
N, N'-2,4,5-pentaethylanilinium tetraphenylborate, di- (isopropyl) ammonium tetrakispentafluorophenylborate, di-cyclohexylammonium tetraphenylborate, triphenylphosphonium tetraphenylborate, tri (methylphenyl) ) Phosphonium tetraphenylborate, tri (dimethylphenyl) phosphonium tetraphenylborate, triphenylcarbenium tetrakis (p-tolyl) borate, triphenylcarbenium tetrakis (m-tolyl) borate, triphenylcarbenium tetrakis (2,4- Dimethylphenyl) borate, triphenylcarbeniumtetrakis (3,5-dimethylphenyl) borate, tropyliumtetrakispentafluorophenyl Borate, tropylium tetrakis (p-tolyl) borate, tropylium tetrakis (m-tolyl) borate, tropylium tetrakis (2,4-dimethylphenyl) borate, tropylium tetrakis (3,5-dimethylphenyl) borate and the like. . These boron compounds and the above-mentioned organoaluminum compounds may be used simultaneously. In particular, when a boron compound is used as a co-catalyst, the addition of an alkyl aluminum compound such as triisobutyl aluminum is effective for removing impurities such as water contained in the polymerization system that adversely affect the polymerization.

The aromatic vinyl compound used in the present invention includes styrene and various substituted styrenes such as p
-Methylstyrene, m-methylstyrene, o-methylstyrene, ot-butylstyrene, mt-butylstyrene, pt-butylstyrene, p-chlorostyrene,
Examples thereof include o-chlorostyrene, α-methylstyrene, and the like, and compounds having a plurality of vinyl groups in one molecule such as divinylbenzene. Industrially, styrene, p-methylstyrene and p-chlorostyrene are preferably used, and styrene is particularly preferably used.

The α-olefin used in the present invention is an α-olefin having 2 to 20 carbon atoms, that is, ethylene, propylene, 1-butene, 1-hexene,
Suitable are cyclic olefins such as -methyl-1-pentene, 1-octene, norbornene and norbornadiene. Two or more of these olefins may be used.
As the α-olefin, ethylene and propylene are preferable.

In producing the copolymer used in the present invention, the α-olefin, the aromatic vinyl compound, the transition metal compound which is a metal complex, and the cocatalyst are contacted as described above. As the method, any known method can be used. As the polymerization method, a method of polymerizing in a liquid monomer without using a solvent, or a saturated aliphatic or pentane, hexane, heptane, cyclohexane, benzene, toluene, xylene, chloro-substituted benzene, chloro-substituted toluene, methylene chloride, chloroform or the like There is a method using a single or mixed solvent of an aromatic hydrocarbon or a halogenated hydrocarbon. If necessary, a method such as batch polymerization, continuous polymerization, batch polymerization, preliminary polymerization, or gas phase polymerization can be used.

The polymerization temperature is suitably from -78 ° C to 200 ° C, preferably from -50 ° C to 160 ° C. -78
Polymerization temperatures below ℃ are industrially disadvantageous, and above 200 ℃ are not suitable because decomposition of the metal complex takes place. More preferably, it is 0 ° C to 160 ° C industrially.
When an organoaluminum compound is used as a cocatalyst, the ratio of aluminum atom to complex metal atom is 0.1 to 100,000, preferably 10 to 100, relative to the metal of the complex.
Used at a ratio of 00. If it is less than 0.1, the metal complex cannot be activated effectively, and if it exceeds 100,000, it is economically disadvantageous.

When a boron compound is used as a cocatalyst, it is used in a ratio of boron atom / complex metal atom of 0.01 to 100, preferably 0.1 to 10, particularly preferably 1. Can be If it is less than 0.01, the metal complex cannot be activated effectively, and if it exceeds 100, it is economically disadvantageous. The metal complex and the cocatalyst may be mixed and prepared outside the polymerization tank, or may be mixed in the tank during polymerization.

The aromatic vinyl compound used in the present invention
The α-olefin random copolymer does not necessarily have to be a copolymer consisting of only an aromatic vinyl compound and an α-olefin, and other structures are included as long as the structure and stereoregularity are within the above ranges. Or other monomers may be copolymerized. As other monomers to be copolymerized, α-olefins having 3 to 20 carbon atoms such as propylene other than those selected above, butadiene,
Examples thereof include diene compounds such as 1,4-hexadiene, 1,5-hexadiene, ethylidene norbornene, and vinylcyclohexene. Further, two or more aromatic vinyl compounds may be copolymerized. Depending on the polymerization conditions and the like, a small amount of an atactic homopolymer obtained by heat, radical or cationic polymerization of an aromatic vinyl compound may be contained, but the amount is 10% by weight or less of the whole. Such a homopolymer can be removed by solvent extraction, but if there is no particular problem in physical properties, the homopolymer can be used as it is. Further, for the purpose of improving the physical properties, blending with another polymer is also possible. Blends of the copolymers of the present invention having different styrene contents can also be used. Further, the aromatic vinyl compound of the present invention-
The α-olefin random copolymer can be modified by grafting, hydrogenation, addition of a functional group, and the like.

In the present invention, other polymers,
Elastomers, crosslinked rubbers and the like can be blended. Similarly, if necessary, fillers, stabilizers, anti-aging agents, weatherability improvers, ultraviolet absorbers, plasticizers, softeners, lubricants, processing aids, colorants, pigments, antistatic agents, flame retardants , An antifogging agent, an antiblocking agent, a crystal nucleating agent, a foaming agent, and the like. These can be used alone or in combination of two or more.

Among the above, there are no particular restrictions on the amounts of stabilizers, inhibitors, weatherability improvers, UV-absorbers, lubricants, coloring agents, pigments, antiblocking agents, crystal nucleating agents, etc. 10 parts by weight or less is preferable from the economical balance,
Particularly preferably, the content is 5 parts by weight or less. This does not apply to materials that exhibit an effect when added in a large amount.

The resin that can be blended in the present invention is not particularly limited. However, styrene resins, olefin resins, polycarbonates, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyphenylene ether (PPE), polyphenylene sulfide (P
Aromatic resins such as PS), polyamides such as 6.6 nylon and 6 nylon, methacrylic resins, acrylic resins, ethylene-vinyl acetate copolymer (EVA), and the like. Examples of the styrene resin include styrene / methacrylic ester copolymers such as polystyrene, rubber-reinforced polystyrene (high impact polyester), acrylonitrile / styrene copolymer (AS resin), and styrene / methyl methacrylate copolymer (MS resin). Acrylonitrile-butadiene-styrene terpolymer (ABS resin),
Rubber reinforced MS resin, maleic anhydride / styrene terpolymer, maleic anhydride / acrylonitrile / styrene copolymer terpolymer, acrylonitrile / α-methylstyrene terpolymer, methacrylonitrile / styrene copolymer,
Methyl methacrylate / acrylonitrile / styrene terpolymer can be used. As the olefin resin, polyethylene (PE), polypropylene (P
P) and the like, and blocks such as butene, hexene and octene, random copolymers, polymethylpentene, polybutene-1, propylene / butene-1 copolymer, chlorinated polyolefin, ethylene / methacrylic acid and the like Examples thereof include an ester copolymer, styrene / acrylic acid and its ester copolymer, and an ethylene / propylene copolymer (EPR). Examples of the methacrylic resin include polymethyl methacrylate (PMMA) and methyl methacrylate / methacrylic acid copolymer. Of the above, styrene resins and olefin resins are preferred.

The elastomers and crosslinked rubbers that can be blended with the multilayer film of the present invention are not particularly limited. Styrene-based, olefin-based thermoplastic elastomers and rubbers, natural rubber, isoprene rubber, chloroprene rubber, polyisobutylene, EPR, acrylic Examples thereof include thermoplastic elastomers such as rubber, neoprene rubber, polyester elastomer, and polyamide elastomer, and crosslinked rubber. These can be used alone or in combination of two or more.

Examples of styrene elastomers and crosslinked rubbers include styrene-butadiene block copolymer (SB
S), styrene-isoprene block copolymer (SI
S), and their hydrogenated products such as styrene-ethylene-butylene block polymer (SEBS), styrene-ethylene-propylene block polymer (SEP)
S), styrene-butadiene rubber (SBR), styrene-butadiene-methyl methacrylate terpolymer (MBS) and the like. Of the above, styrene-based, olefin-based elastomers and rubbers are preferred.

The aromatic vinyl compound-α-olefin random copolymer, preferably the aromatic vinyl compound-ethylene random copolymer, in the multilayer film of the present invention has excellent transparency because of having a uniform composition. When the copolymer is used alone as the main structural unit, a film having excellent transparency can be obtained. Specifically, it is preferable that the aromatic vinyl compound-α-olefin random copolymer of the present invention is composed of 80% by weight or more. Also,
In the case of the film containing the aromatic vinyl compound-α-olefin random copolymer of the present invention, a resin, an elastomer, a crosslinked rubber, and an additive having properties such as a close refractive index and excellent transparency. By blending with the above, a film having excellent transparency can be obtained. In this case, the difference in refractive index between the two is preferably 0.2 or less, more preferably 0.05 or less, and particularly preferably 0.1 or less.
02 or less. Further, in this case, if the difference between the values of the compatibility parameters is within a certain range, the transparency can be further improved. Specifically, 5 (cal / cm ³ ) ^1/2 or less is preferable, and 3 (cal / cm ³ ) ^1/2 or less is more preferable.
^{1 (cal / cm 3) 1} /2 or less is particularly preferred. The values of the refractive index and the compatibility parameter of the resins, elastomers, crosslinked rubbers, additives and the like to be blended are described in, for example, the third edition of Polymer Handbook issued by Willie Interscience, and are well known. Further, when the resin, elastomer, crosslinked rubber, additives, etc. are dispersed in fine particles, preferably 0.5 μm or less, more preferably 0.2 μm or less, particularly preferably 0.05 μm or less, excellent transparency is obtained. Film. In particular, the multilayer film of the present invention produced by an extrusion molding method has excellent transparency with a total light transmittance of usually 80% or more, preferably 88% or more, unless there is another factor that significantly impairs the transparency. The total light transmittance can be measured by, for example, a method described in JIS K-7361-1, K-7105, or the like. In addition,
The multilayer film of the present invention inherently has excellent transparency, but can also be used as an opaque film depending on the purpose of light-shielding properties, design properties, and the like.

The multilayer film of the present invention can be subjected to surface treatment such as corona, ozone, plasma, etc., antifogging agent application, lubricant application, printing, etc., as required. The multilayer film of the present invention can be subjected to uniaxial or biaxial stretching orientation as required. The multilayer film of the present invention, if necessary, can be bonded to each other by a method such as heat, ultrasonic waves, fusion by a method such as high frequency, or adhesion with a solvent, or to a material such as another thermoplastic resin. . When used as a stretch film for food packaging, it can be suitably packaged by an automatic packaging machine or a manual packaging machine. In order to produce the multilayer film of the present invention, a normal extrusion film forming method such as an inflation method or a T-die method can be employed.

The thickness of the multilayer film of the present invention is not particularly limited, but is preferably 3 μm to 1 mm, more preferably 10 μm to 0.5 mm. In order to use it suitably as a stretch film, it is preferable to use 5 to 100
μm, more preferably 10 to 50 μm. Further, it is preferable that the container has a thickness of 100 μm or more, and to provide packaging containers and trays for foods, electric appliances, etc. by a method such as thermoforming such as vacuum forming, compression molding, and pressure forming. Can be.

Further, in the multilayer film of the present invention, the aromatic vinyl compound-α-olefin random copolymer itself has a certain degree of self-adhesiveness and adhesiveness. A multilayer film having a self-adhesive pressure-sensitive adhesive layer can also be used. An appropriate amount of a tackifier may be added and used.
For the adhesive layer, an ethylene-vinyl acetate copolymer (EVA) resin is preferably used. The content of vinyl acetate is preferably 5 to 25% by weight, and the melt flow ratio (hereinafter referred to as MFR) is preferably 0.1 to 30 g / min when measured at 230 ° C. under a load of 2.16 kgf. Particularly preferably, the vinyl acetate content is 10 to 20% by weight and the MFR is 0.3 to 10 g / min. If the vinyl acetate content is less than 5%, it is hard and hard to elongate, and the transparency is lowered. If the vinyl acetate content is more than 25%, the strength is lowered and the film is easily broken during packaging. Also M
If the FR is less than 0.1, the extrudability deteriorates, and if it exceeds 30, the strength of the film is reduced and the film is easily broken.

The multilayer film of the present invention may be used in order to improve physical properties of other suitable films such as isotactic or syndiotactic polypropylene,
High density polyethylene, low density polyethylene (LDPE,
Or LLDPE), polystyrene, and polyethylene terephthalate films.

Examples of the polyolefin resin layer include isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene, linear low-density polyethylene (L-LDPE), low-density polyethylene (LDPE), high-density polyethylene (HDPE), and ethylene. , A block of propylene and an α-olefin such as butene, hexene and octene, a random copolymer, and polymethylpentene.

The heat-sealing layer constituting the multilayer film of the present invention is a resin layer for applying heat and applying pressure as necessary to express adhesion to other resins. Also,
If necessary, a seal auxiliary layer adjacent to the heat seal layer can be laminated. When the heat seal layer alone does not provide sufficient functions, there is a problem in extrusion workability and film formability, and when the range of the optimum seal conditions is narrow, it is desirable to arrange a seal auxiliary layer. . For the seal layer, a composition containing a polyolefin-based resin as a main component can be used, and the content thereof is preferably 50 to 100% by weight. As the polyolefin disposed in the seal layer, a polyethylene resin, a polypropylene resin, or a butene resin is used. Particularly, as the ethylene resin, an ethylene-α-olefin copolymer is contained, and as the α-olefin, From 3 to 10, for example, propylene, 1-butene, 1
-Pentene, 4-methyl-1-pentene, 1-hexene, 1-octene. Specifically, linear low density polyethylene (L-LDPE), linear medium density polyethylene (M
-LDPE), very low density polyethylene (VLDPE) and the like. The aromatic vinyl-α-olefin random copolymer of the present invention is also included. Further, other additives can be used to adjust the heat seal strength, the feeling of peeling, and the like. When heat resistance is required, a nylon-based resin and an ethylene-ester copolymer can be used. Examples thereof include an ethylene-vinyl acetate copolymer (EVA) and ethylene-ethyl acrylate. Copolymer (E
EA), ethylene-methyl methacrylate copolymer (EM
MA) and the like. When using a seal auxiliary layer,
It is preferable that the crystal melting point of the resin forming the seal layer is higher than the crystal melting point of the resin forming the seal auxiliary layer.

An adhesive layer may be disposed between layers when the adhesive strength is not sufficient. Desirable are thermoplastic polymers, copolymers, terpolymers, unsaturated carboxylic acid modified products of these resins or metal modified products of the acid modified products, and mixtures containing these. For example, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and olefin copolymer modified with maleic acid, acrylic acid, methacrylic acid, itaconic acid, or anhydride thereof,
There is a blend resin of a thermoplastic polyurethane elastomer. The normal thickness of this layer is not limited depending on the purpose and application, but is preferably 0.1 to 100 μm, more preferably 0.5 to 50 μm.

The gas barrier resin applicable to the present invention is, for example, formed into a film having a thickness of 25 μm at 23 ° C.
(Under 65% relative humidity) oxygen permeability 100cc / m
Is less than or equal to ² · 24hr · atm, preferably 50cc
/ M ² · 24 hr · atm. Examples of the gas barrier resin applicable to the present invention include aromatic nylon such as vinylidene chloride copolymer (PVDC), ethylene / vinyl alcohol copolymer (EVOH), and polyamide formed from meta-xylylenediamine. Examples thereof include copolymers containing acrylonitrile as a main component, such as crystalline nylon and polyacrylonitrile. A mixed resin such as a copolymer of ethylene and vinyl acetate, acrylic acid, methacrylic acid or an alkyl ester of an unsaturated acid thereof, or a copolymer of at least one kind of MBS resin, mainly containing a vinylidene chloride copolymer. Composition, mainly composed of ethylene and vinyl alcohol copolymer having a saponification degree of 95 mol% or more, polyester elastomer, polyamide elastomer, ethylene and vinyl acetate copolymer, ethylene and acrylate ester copolymer, saponification degree 95
A mixed resin composition of less than mol% of ethylene and a vinyl alcohol copolymer, and a mixed resin composition of the above-mentioned aromatic nylon, amorphous nylon and aliphatic nylon are also included. When flexibility is particularly required, an ethylene / vinyl alcohol copolymer system is selected.

The thickness of the gas barrier layer can be selected according to the object to be packaged and the purpose, and is not particularly limited.
Generally, it is preferably 0.1 to 500 μm, more preferably 1 to 100 μm, and particularly preferably 5 to 50 μm.
For example, when co-extruded with polyvinylidene chloride, the thickness of the layer is desirably 30% or less of the entire film from the viewpoint of thermal stability and low-temperature resistance. By using a gas barrier resin and a multilayered film and a container, to obtain an excellent multilayer film having both the features of the aromatic vinyl compound-α-olefin random copolymer of the present invention and oxygen barrier properties Can be. By imparting the oxygen barrier property, it is possible to reduce deterioration in quality such as deterioration, decay and oxidation of the contents of packaged foods, precision equipment and the like. When it is necessary to improve the adhesiveness between the gas barrier layer and the layer adjacent thereto, an adhesive resin layer can be interposed therebetween.

When the multilayer film of the present invention is a heat-shrinkable film, the heat shrinkage at a specific temperature of 40 to 100 ° C. is 20 to 200% in at least one of the vertical and horizontal directions. Is preferred. If it is less than 20%, the low-temperature shrinkage becomes insufficient, and after the shrink treatment,
It causes wrinkles and tarmi. On the other hand, if it exceeds 200%, dimensional shrinkage may occur during storage.

Examples of the specific layer constitution of the multilayer film of the present invention include a layer (A) composed of an ethylene-α-olefin random copolymer, a layer (B) composed of EVA, a gas barrier layer (C), and a heat seal. Layer (D) or the like,
Configuration, but not limited to this. Also,
For example, A / B, B / A /
B, B / C / A, B / C / A / B, B / D / C / A /
B, B / D / C / A / D, etc., but are not limited thereto. In addition, it is also possible to configure by laminating more layers.

The specific application of the film of the present invention is not particularly limited, but it can be used for packaging films, bags, pouches and the like. In the case of a multilayer film having a stretch property, it can be suitably used particularly as a stretch film for food packaging, a pallet stretch film, a protective film and the like. In the case of a barrier film, it can be used for packaging foods, beverages, precision instruments, pharmaceuticals and the like. In the case of a heat-shrinkable film, it can be used for shrink packaging, binding of shrink labels, and the like.

The method for obtaining the multilayer film raw material composition of the present invention is not particularly limited, but a kneader such as a kneader, a Brabender, a plast mill, an extruder such as a single screw or a twin screw, a mixer or the like can be used. . This can be performed under a nitrogen atmosphere as needed. Examples of the form of the obtained composition include a block, a pellet, a sheet, and a strand.

In order to produce the multilayer film of the present invention, techniques such as a co-extrusion method and an extrusion coating method (also referred to as an extrusion lamination method) using an inflation film production apparatus or a T-die film production apparatus are generally employed. can do. It is also possible to produce a desired multilayer film by a known technique such as a dry lamination method, a sand lamination method, or a hot melt lamination method using a multilayer or single-layer film obtained by using these apparatuses.

When the multilayer film of the present invention is a heat-shrinkable film, its production method is not particularly limited, and can be obtained by a known stretched film production method or the like. For example, a sheet or film extruded by a T-die method, a tubular method, an inflation method, or the like can be obtained by a stretching method such as uniaxial stretching, biaxial stretching, or multiaxial stretching. Examples of uniaxial stretching include a method of stretching an extruded sheet with a tenter in a direction perpendicular to the extrusion direction, a method of stretching an extruded tubular film in a circumferential direction, and the like. Examples of biaxial stretching include a method in which an extruded sheet is stretched by a roll in the extrusion direction, and then stretched by a tenter or the like in a direction perpendicular to the extrusion direction. A method of stretching separately and the like can be mentioned.

[0092] If necessary, post-processing such as heat setting, corona processing, and plasma processing may be performed.

Furthermore, at least one layer of the film of the present invention may be crosslinked. As the crosslinking treatment, a conventionally known method such as an electron beam, γ-ray, or peroxide is used. Lamination may be performed after the crosslinking treatment.

[0094]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but these Examples do not limit the present invention. In the following description, Ind represents a 1-indenyl group, BInd represents a 4,5-benzo-1-indenyl group,
Cp is a cyclopentaphenanthrene group, Flu is 9
-Represents a fluorenyl group, Me represents a methyl group, Et represents an ethyl group, tBu represents a tertiary-butyl group, and Ph represents a phenyl group.

The copolymers obtained in each of the experimental examples and comparative examples were analyzed by the following means. The ¹³ C-NMR spectrum was analyzed by α-500 or JNMGX-27 manufactured by JEOL Ltd.
0, deuterated chloroform solvent or deuterated 1,1,2,2
The measurement was performed using 2-tetrachloroethane solvent and TMS as a reference. Here, the measurement based on TMS is as follows. First, weight 1 based on TMS
Triplet ¹³ C-NMR of 1,2,2-tetrachloroethane
The shift value of the center peak of the peak was determined. Next, the copolymer is dissolved in heavy 1,1,2,2-tetrachloroethane.
¹³ C-NMR was measured, and each peak shift value was
It was calculated based on the triplet center peak of 1,2,2-tetrachloroethane. The shift value of the triplet center peak of heavy 1,1,2,2-tetrachloroethane is 73.89 pp.
m. The ¹³ C-NMR spectrum measurement for quantifying the peak area was performed by a proton gate decoupling method in which NOE was eliminated, and a pulse width of 45 ° pulse was used.
A repetition time of 5 seconds was used as a standard. Incidentally, the measurement was carried out under the same conditions except that the repetition time was changed to 1.5 seconds, and the quantitative value of the peak area of the copolymer coincided with the case of the repetition time of 5 seconds within the measurement error range. The determination of the styrene content in the copolymer was performed by ¹ H-NMR, and the equipment was α-500 manufactured by JEOL Ltd. and AC-500 manufactured by BRUCKER.
250 was used. Heavy chloroform solvent or heavy 1,
Using a 1,2,2-tetrachloroethane solvent, a peak derived from a phenyl group proton (6.5 to 6.5) was determined based on TMS.
7.5 ppm) and a proton peak (0.8 to 3 ppm) derived from an alkyl group.

The physical properties of the film were evaluated by the following methods. The measurement and evaluation methods used in the present invention and the resins used are as follows. <Tensile test> According to JIS K-6251, the film was cut into a No. 1 test piece shape, and Shimadzu AG
Using an S-100D type tensile tester, a tensile speed of 500 mm
/ Min. <Elastic recovery> The elastic recovery was measured by stretching a rod having a radius of curvature of 12.5 mm at the tip to a diameter of 45 after stretching 10% in the film width direction.
The film was pressed into a film surface of mm, and the critical depth at which the film was recovered within 1 minute was determined. Five tests were performed and expressed as the range between the maximum and minimum values (minimum to maximum) or the average of five experiments.

<Total light transmittance, haze> JIS-K-73
According to 61-1, the measurement was performed using a turbidity meter NDH-2000 from Nippon Denshoku Co., Ltd. at a test piece thickness of 2 mm. <Chemical resistance> For the chemical resistance evaluation, the sheet was strip-shaped (10 mm
x 50 mm) to make a test piece. After the test piece was immersed at room temperature for one week, it was evaluated by visual observation, tactile sensation, and weight measurement, and the results were shown in the table according to the following criteria. A: No change. Expansion coefficient: 10% or less ；: Expansion coefficient: 10 to 40% △: Slightly gelling, dissolving or solidifying ×: Gelling, dissolving or solidifying After being placed in a thermostatic chamber and treated for 10 minutes while freely shrinking, the shrinkage of the film was determined and expressed as a percentage of the value divided by the original dimension. In the case of uniaxial stretching, the value in the stretching direction, in the case of biaxial stretching, the length,
Each was measured in both the horizontal and horizontal directions. <Oxygen permeability> Method B based on JIS-K-7126
(Equal pressure method).

Synthesis Example <Synthesis A of Transition Metal Compound> 1-indenyl) zirconium dichloride, rac @ Bind-C (Me) _2- B
(Ind @ ZrCl ₂ ) was synthesized by the following synthesis method.

[0099]

Embedded image

4,5-Benzoindene is from Organom
et al., 13 , 964 (1994).

A-1 1,1-isopropylidene-4,
Synthesis of 5-benzoindene The synthesis of 1,1-isopropylidene-4,5-benzoindene is described in Can. J. Chem. , 62, 1751 (1
984), with reference to the synthesis of 6,6-diphenylfulvene. However, acetone was used as a starting material instead of benzophenone, and 4,5-benzoindene was used instead of cyclopentadiene.

A-2 Synthesis of isopropylidenebis 4,5-benzo-1-indene In an Ar atmosphere, 21 mmol of 4,5-benzoindene was dissolved in 70 ml of THF, and at 0 ° C., an equivalent amount of BuLi was added.
Was added and stirred for 3 hours. 1,1-isopropylidene-
THF in which 21 mmol of 4,5-benzoindene is dissolved
Was added and stirred at room temperature overnight. 100 ml of water and 150 ml of diethyl ether were added and the mixture was shaken. The organic layer was separated, washed with saturated saline, dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained yellow solid was washed with hexane and dried to obtain 3.6 g of isopropylidenebis 4,5-benzo-1-indene (yield: 46%). ^{By 1} H-NMR spectrum measurement, 7.2 to 8.0 ppm (m, 12
H), 6.65 ppm (2H), 3.75 ppm (4
H) It has a peak at 1.84 ppm (6H). The measurement was performed based on TMS using CDCl ₃ as a solvent.

A-3 Synthesis of rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride Under Ar atmosphere, 7.6 mmol of isopropylidenebis 4,5-benzo-1-indene and 7.2 mmol Of zirconium tetrakisdimethylamide, ｛Zr (NMe
2) Charge 4｝ together with 50 ml of toluene, 130 ° C
For 10 hours. Under reduced pressure, toluene was distilled off, 100 ml of methylene chloride was added, and the mixture was cooled to -78 ° C. Dimethylamine hydrochloride (14.4 mmol) was slowly added, and the mixture was slowly warmed to room temperature and stirred for 2 hours. After evaporation of the solvent, the resulting solid was washed with pentane, followed by a small amount of THF,
0.84 g (yield 21%) of rac-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride of yellow lantern represented by the following formula was obtained.

[0104]

Embedded image

According to ¹ H-NMR spectrum measurement, 8.
01 ppm (m, 2H), 7.75 ppm (m, 2H)
H), 7.69 ppm (d, 2H), 7.48-7.5.
8 ppm (m, 4H), 7.38 ppm (d, 2H),
7.19 ppm (d, 2H), 6.26 ppm (d, 2H)
H) It has a peak at 2.42 ppm (s, 6H). The measurement was performed based on TMS using CDCl3 as a solvent. Elemental analysis was performed using an elemental analyzer 1108 (manufactured by Fisons, Italy), and C63.86 was used.
%, H 3.98%. Theoretical value is C65.39.
%, H 4.16%.

<Synthesis B of Transition Metal Compound> rac-dimethylmethylene (4,5-benzo-1-indenyl) (1
-Indenyl) zirconium dichloride (also called r
ac-isopropylidene (1-indenyl) (4,5-
Benzo-1-indenyl) zirconium dichloride,
rac @ Ind-C (Me) ₂ -Bind @ ZrCl ₂ )
Was synthesized by the following synthesis method.

[0107]

Embedded image

B-1 Synthesis of isopropylidene (1-indene) (4,5-benzo-1-indene) Under Ar atmosphere, 14 mmol of indene was added to 50 ml of T
Dissolved in HF, added an equivalent of BuLi at 0 ° C., and stirred for 10 hours. 10 ml of THF in which 13 mmol of 1,1-isopropylidene-4,5-benzoindene was dissolved was added, and the mixture was stirred at room temperature overnight. 50 ml of water and 100 ml of diethyl ether were added and the mixture was shaken. The organic layer was separated, washed with saturated saline, dried over sodium sulfate, and the solvent was distilled off under reduced pressure. Further purification on a column, isopropylidene (1-
Indene) (4,5-benzo-1-indene) in 2.5
g (yield 59%).

B-2 rac-Dimethylmethylene (1-
Synthesis of indenyl) (4,5-benzo-1-indenyl) zirconium dichloride 6.5 mmol of isopropylidene (1
-Indene) (4,5-benzo-1-indene) and 6.
5 mmol of zirconium tetrakisdimethylamide,
{Zr (NMe ₂ ) ₄ } was charged together with 40 ml of toluene and stirred at 130 ° C. for 10 hours. Under reduced pressure, toluene was distilled off, 100 ml of methylene chloride was added, and the mixture was cooled to -78 ° C. 13 mmol of dimethylamine hydrochloride was slowly added, and the temperature was slowly raised to room temperature, followed by stirring for 2 hours. After evaporating the solvent, the obtained solid was washed with pentane and then with a small amount of methylene chloride, and rac-dimethylmethylene (1-
0.76 g (yield 24%) of indenyl) (4,5-benzo-1-indenyl) zirconium dichloride was obtained.

[0110]

Embedded image

According to ¹ H-NMR spectrum measurement, 7.
05 to 8.04 ppm (m, 10H, however, 7.17p
pm peak), 7.17 ppm (d, H),
6.73 ppm (d, H), 6.25 ppm (d,
H), 6.18 ppm (d, H), 2.41 ppm
(M, 3H) has a peak at a position of 2.37 ppm (m, 3H). The measurement was performed based on TMS using CDCl ₃ as a solvent.

<Synthesis C of Transition Metal Catalyst Component>
c-dimethylmethylenebis (3-cyclopenta [c] phenanthryl) zirconium dichloride (also called ra
_{c {CpPhen-CMe 2 -CpPhen}} ZrC
l ₂ ) was synthesized as follows. CpPhen represents 3-cyclopenta [c] phenanthryl).

[0113]

Embedded image

The ¹ H or 3H-cyclopenta [c] phenanthrene is described in the literature Organometallics, 1
6 , 3413 (1997).

C-1 isopropylidenebis (cyclopenta [c] phenanthrene) Under an Ar atmosphere, 32 mmol of 1H or 3H-cyclopenta [c] phenanthrene is added to 40 ml of dimethoxyethane in which 3.0 g of potassium hydroxide is suspended. After stirring at room temperature for 30 minutes, 15 mmol of acetone was added, and
For 2 hours. After neutralization by adding 10% phosphoric acid aqueous solution, the mixture was extracted with methylene chloride, the organic phase was washed with water and dried, and methylene chloride was distilled off. By recrystallization from methylene chloride-diethyl ether solution, 1.5 g of white crystalline isopropylidenebis (cyclopenta [c] phenanthrene) was obtained. ^{According to 1} H-NMR spectrum measurement, 1.93 pp
m (6H, s), 4.20 ppm (4H, d), 6.8
9 ppm (2H, t), 7.5-7.9 ppm (14
H, m) and 8.91 ppm (2H, d). The measurement was performed based on TMS using CDCl3 as a solvent.

C-2 Synthesis of rac-dimethylmethylenebis (3-cyclopenta [c] phenanthryl) zirconium dichloride 2.0 mmol of isopropylidenebis (cyclopenta [c] phenanthrene) and 2.0 mmol in an Ar gas flow
Of zirconium tetrakisdimethylamide, ｛Zr (N
Me ₂ ) _{4 4} was charged together with 20 ml of toluene and stirred under reflux for 7 hours. Under reduced pressure, the toluene is distilled off,
50 ml of methylene chloride was added, and the mixture was cooled to -50 ° C. Dimethylamine hydrochloride (4.0 mmol) was slowly added, and the mixture was slowly warmed to room temperature and further stirred for 2 hours. After evaporating the solvent, the obtained solid was washed with pentane and then a small amount of methylene chloride to remove the meso form and ligand, and to obtain rac-
0.36 g of yellow light yellow crystals of dimethylmethylenebis (3-cyclopenta [c] phenanthryl) zirconium dichloride were obtained. ^{By 1} H-NMR spectrum measurement,
2.55 ppm (6H, s), 6.49 ppm (2H,
7. d), 7.55-8.02 ppm (16H, m);
It has a peak at a position of 82 ppm (2H, d). The measurement was performed based on TMS using CDCl3 as a solvent.

<Resins Used in Examples and Comparative Examples>EVA; ethylene-vinyl acetate copolymer (NUNC-3)
753) EVOH; Ethylene vinyl alcohol copolymer PP; Grand Polymer polypropylene F-226D adhesive polyolefin; Mitsui Chemicals Admar NF500

<Synthesis of Styrene-Ethylene Random Copolymer><Experimental Example 1> Synthesis of Copolymer P-1 Polymerization was carried out using a polymerization vessel having a capacity of 150 L, a stirrer and a jacket for heating and cooling. 70 L of dehydrated cyclohexane and 2 L of dehydrated styrene were charged and heated and stirred at an internal temperature of 40 ° C. Triisobutyl aluminum 84mm
ol, methylalumoxane (MMAO manufactured by Tosoh Akzo)
-3A) was added in an amount of 84 mmol based on Al. Immediately after ethylene was introduced and the pressure was stabilized at 1 Mpa, the catalyst ra obtained in the above synthesis example was taken from the catalyst tank installed on the polymerization vessel.
About 100 mL of a toluene solution of 84 μmol of c-dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride was added to the polymerization vessel. Heat generation started immediately, and cooling water was introduced into the jacket. The internal temperature rises up to 66 ° C. Then descend gradually,
The temperature finally reached 70 ° C. The polymerization was carried out for 0.5 hour while maintaining the ethylene pressure at 1 MPa. Stir vigorously, 8
The polymerization liquid was fed over 1 hour into 150 L of heated water containing a dispersant heated to 5 ° C. Then at 97 ° C for 1
After stirring for a while, hot water containing crumb was fed into cold water to collect crumb. The obtained crumb was blow-dried at 50 ° C. The results of the polymerization are shown in Table 2. The dried crumbs were formed into pellets using a tandem extruder (Buss Co-Kneader PLK-46) with a hot cut pelletizer. The operation was performed under the following conditions. First extruder: cylinder temperature 80 ° C., screw rotation speed 120 rpm. Second extruder: cylinder temperature 120 ° C, die 135
° C, screw rotation speed 22 rpm.

<Comparative Experimental Example 1> The complex used was CGCT
(Restricted geometric structure) type Ti complex (tertiary butylamide) dimethyl (tetramethyl-η5-cyclopentadienyl)
Silane titanium dichloride (Me ₄ Cp-SiMe ₂ -N
Using tBuTiCl ₂ : CGCT type catalyst), polymerization was carried out under the conditions shown in Table 1.

<Experimental Examples 2 to 6> Copolymers P-2 to P-6
Under the conditions shown in Table 1, polymerization and post-treatment were performed in the same manner as in Experimental Example 1. Table 2 shows the styrene content of the copolymers obtained in each of the experimental examples and the comparative experimental examples determined by ¹ H-NMR measurement, the molecular weight obtained by GPC measurement, the molecular weight distribution, and the styrene content obtained by ¹³ C-NMR measurement. The tacticity, λ value, θ value, and melting point obtained by DSC measurement of the ethylene alternating structure are shown.

Experimental Example 7 Synthesis of Copolymer P-7 Polymerization was carried out using an autoclave having a capacity of 10 L, a stirrer and a jacket for heating and cooling. Dehydrated toluene 2
400 ml, 2400 ml of dehydrated styrene were charged,
The mixture was heated and stirred at an internal temperature of 50 ° C. About 100 L of nitrogen was bubbled through the system to purge the system, and 8.4 mmol of triisobutylaluminum (TIBA) and 8.4 mmol of methylalumoxane (PMAO, manufactured by Tosoh Akzo Co., Ltd.) based on Al.
l was added. Immediately introduce ethylene, pressure 10kg /
After being stabilized at cm ² G, the catalyst rac @ CpPhen-C (M
e) Approximately 50 ml of a toluene solution of 8.4 μmol of _2- CpPhen @ ZrCl ₂ and 8.4 mmol of triisobutylaluminum was added to the autoclave. The internal temperature was 50 ° C., and the ethylene pressure was 10 kg / cm ² G (1.1 M
The polymerization was carried out for 1 hour while maintaining Pa). During the polymerization, the temperature of the reaction solution and the consumption rate of ethylene were monitored by a flow integrator, and the polymerization was carried out until the polymerization reaction was substantially completed. After the completion of the polymerization, the resulting polymerization solution was poured little by little into excess methanol which was vigorously stirred to precipitate the produced polymer. After drying under reduced pressure at 60 ° C. until no change in weight was observed, the styrene content was 17.4.
409 g of mol% copolymer were obtained. The results are shown in Table 2.

<Examples 1 to 7, Comparative Example> A three-layer T-die and a single-screw extruder were combined to a thickness of 30 μm and a layer composition ratio EVA / P-1 / EVA (25% / 50% / 25%). )
Was prepared. For P-2 to 7 and CP-1, three-layer films with EVA were prepared in the same manner. The evaluation results of this film are shown in Tables 3 and 4. However, regarding chemical resistance, copolymers P-1 to P-7
And a test piece was prepared using CP-1 alone and evaluated.

<Embodiment 8> P-2 was used as both surface layers.
The two layers were extruded using a five-layer T-die so as to have five layers of 2 / adhesive polyolefin / EVOH / adhesive polyolefin / P-2. The thickness ratio of each layer is 35% /
It was adjusted to 7.5% / 15% / 7.5% / 35%. Oxygen gas permeability was measured and found to be 0.62 cc / m ^2.
The value was as good as 24 hr · atm.

<Embodiment 9> The layer composition ratio was changed to EVA / P-1.
A film was formed in the same manner as in Example 7 so that / PP = 25% / 50% / 25%. The obtained material is vertical 3.2
A film having a thickness of 60 μmm, which was simultaneously stretched 2.8 times and 2.8 times horizontally, was obtained. The heat shrinkage at 80 ° C. showed a good value of 45% vertical and 40% horizontal.

<Example 10> The layer composition ratio was LL / P-1.
= 30% / 70%, and a film was formed in the same manner as in Example 7 to obtain a film having a thickness of 60 μm. The two films were overlaid so that the heat seal layers were on the inside, and were heat-sealed at 120 ° C. with a width of 15 mm.
Further, as a result of a peeling test, a good sealing property of 3 kg was obtained.

[0126]

[Table 1]

[0127]

[Table 2]

[0128]

[Table 3]

[0129]

[Table 4]

[0130]

According to the present invention, transparency, self-adhesiveness,
Multilayer film, stretchable multilayer film, shrinkable multilayer, excellent in tear propagation resistance, piercing strength, breaking strength, mechanical strength such as breaking elongation, transparency, stretchability, binding, oil resistance, elastic recovery A film, a gas-barrier multilayer film, a heat-sealing multilayer film, and a package or container packaged with these films can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court II (Reference) C08F 210: 00) (72) Inventor Toru Arai 3-5-1 Asahicho, Machida-shi, Tokyo Electrochemicals F-term in Industrial Research Institute (reference) 4F100 AK01D AK01E AK03A AK03C AK03E AK03J AK04A AK04E AK04J AK07E AK11A AK11E AK11J AK11K AK16D BA46A AK48A AK68A EJ38 GB16 JA02 JB01 JD03D JK02 JK03 JK08 JL12E JL13B JN01 YY00A 4J028 AA01A AB00A AB01A AC01A AC10A AC28A BA01B BA02B BB00B BB01B BB02B BC15B BC25B EB02 EB03 EB04 EB05 EB07 EB09 EB10 EB18 EB21 FA01 FA02 FA04 GA14 GA26 4J100 AA02Q AA03Q AA04Q AA16Q AA18Q AA19Q AB02P AB03P AB04P AB08P AR11Q CA04 CA11 FA10 FA19 JA58

Claims (19)

[Claims] 1. The method according to claim 1, wherein the content of the aromatic vinyl compound is 1 in mole fraction.
Less than 99.9%, comprising a resin composition containing 5% by weight or more of an aromatic vinyl compound-α-olefin random copolymer having a head-tail chain structure composed of two or more aromatic vinyl compound units. A multilayer film comprising at least one layer. 2. The multilayer film according to claim 1, comprising at least one layer comprising a resin composition containing at least 80% by weight of an aromatic vinyl compound-α-olefin random copolymer. 3. The multilayer film according to claim 1, wherein the aromatic vinyl compound-α-olefin random copolymer is an aromatic vinyl compound-ethylene random copolymer. 4. An aromatic vinyl compound-ethylene random copolymer having the following general formula (1) contained in its structure:
3. The stereoregularity of the phenyl group having an alternating structure of an aromatic vinyl compound and ethylene represented by the formula: wherein the isotactic dyad fraction m is larger than 0.75.
The multilayer film according to any one of claims 1 to 3, wherein Embedded image (In the formula, Ph represents an aromatic group such as a phenyl group, and x represents the number of repeating units and represents an integer of 2 or more.) 5. An aromatic vinyl compound-α-olefin random copolymer whose alternating structure index λ given by the following formula (i) is smaller than 70 and smaller than 1. The multilayer film according to any one of claims 1 to 4, wherein the multilayer film is united. λ = A3 / A2 × 100 Formula (i) Here, A3 is obtained by ¹³ C-NMR measurement and is derived from an aromatic vinyl compound-ethylene alternate structure represented by the following general formula (1 ′): This is the sum of the areas of the peaks a, b, and c. A2 is ¹³ C- based on TMS.
It is the total sum of peak areas derived from main chain methylene and main chain methine carbon observed in the range of 0 to 50 ppm by NMR. Embedded image (In the formula, Ph represents an aromatic group such as a phenyl group, and x represents the number of repeating units and represents an integer of 2 or more.) 6. The aromatic vinyl compound-α-olefin random copolymer has a main chain methine and methylene peak derived from a chain structure of aromatic vinyl compound units of 40 as measured by ¹³ C-NMR measurement based on TMS. ~ 41pp
The multilayer film according to any one of claims 1 to 3, wherein the film is an aromatic vinyl compound-ethylene random copolymer which appears in m and / or 42 to 44 ppm. 7. A copolymer in which an aromatic vinyl compound-α-olefin random copolymer is produced by a catalyst comprising a transition metal compound for polymerization represented by the following general formula (2) and a co-catalyst: 4. The method according to claim 1, wherein
The multilayer film according to any one of the above. Embedded image In the formula, A and B represent an unsubstituted or substituted cyclopentaphenanthryl group, an unsubstituted or substituted benzoindenyl group,
A group selected from an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group, and an unsubstituted or substituted fluorenyl group;
One of the substituted or substituted cyclopentaphenanthryl group, an unsubstituted or substituted benzoindenyl group,
Or a group selected from an unsubstituted or substituted indenyl group. When both A and B are an unsubstituted or substituted cyclopentaphenanthryl group, an unsubstituted or substituted benzoindenyl group, or an unsubstituted or substituted indenyl group, the structures of both may be the same or different. Y has a bond with A and B, and additionally has hydrogen or a carbon number of 1 to 15;
A methylene group, a silylene group or an ethylene group having a hydrocarbon group. The substituents may be different or the same. X is hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms, an allyl group having 6 to 10 carbon atoms, an alkylaryl group having 8 to 12 carbon atoms, a silyl group having a hydrocarbon substituent having 1 to 4 carbon atoms, It is an alkoxy group having 1 to 10 carbon atoms or a diallylamide group having an alkyl substituent having 1 to 6 carbon atoms. M is Zr, Hf or Ti. 8. The resin composition according to claim 1, wherein the resin composition containing the aromatic vinyl compound-α-olefin random copolymer contains a thermoplastic resin having a glass transition temperature of 30 ° C. or higher. A multilayer film according to any one of the preceding claims. 9. The multilayer film according to claim 1, wherein at least one of the outermost layers is made of an adhesive resin. 10. The multilayer film according to claim 9, wherein the adhesive resin is an ethylene-vinyl acetate copolymer (EVA). 11. The multilayer film according to claim 1, wherein at least one layer is made of a polyolefin resin. 12. At least one layer is made of a gas barrier resin having an oxygen permeability of 100 cc / m ² · 24 hrs · atm or less measured under the conditions of a thickness of 25 μm, a temperature of 23 ° C., and a humidity of 65% RH. Claim 1
12. The multilayer film according to any one of 11 above. 13. The multilayer film according to claim 1, wherein at least one layer is made of a heat-sealing resin. 14. The multilayer film according to claim 1, wherein at least one of the layers other than the outermost layer comprises an adhesive resin layer. 15. The gas barrier resin comprises at least one resin selected from ethylene-vinyl alcohol copolymer (EVOH), polyvinylidene chloride (PVDC), and polyamide resin. The multilayer film according to the above. 16. The heat-sealing resin is polyethylene,
Polypropylene, nylon resin, ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl methacrylate copolymer (EMMA), α-olefin copolymer, aromatic The multilayer film according to claim 12, comprising at least one resin selected from a vinyl compound-α-olefin random copolymer. 17. A stretch film comprising the multilayer film according to claim 1. Description: 18. The multilayer film according to claim 1, wherein the multilayer film is a heat-shrinkable uniaxially stretched film or a biaxially stretched film. 19. A container formed from the multilayer film according to claim 1. Description: