JPH0952331A - Laminated material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily form an extrusion laminate by laminating a propylene polymer, in which the magnitude of non-linearity of elongational viscosity is specified, onto a substrate, whereby smell can be reduced and taste can be improved, while maintaining transparency of the laminate. SOLUTION: In a propylene polymer to be laminated onto a substrate, a λvalue indicating the magnitude of non-linearity of elongational viscosity is in the range of 2.0 to less than 6.0, where λ=λ1 /λ0 and λ0 is elongational viscosity at a transition point and λ1 is elongational viscosity when strain becomes twice the strain at a strain transition point. The transition point is a point at which a linear region of elongational viscosity (minute deformation region) transitions to a non-linear region (large deformation region). The propylene polymer is obtained by polymerization using catalysts comprising metallocene compounds and aluminoxan compounds as represented by formula I or II. In the formulas, M in formula I is any one of Ti, Zr, Hf, and X<1> , X<2> , R<1> -R<6> are H, a 1-10C hydrocarbon group, an alkylsilyl group, or a halogen, and Y is C or Si atom, and (n) is integer of 1-3.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate produced by an extrusion laminating method and having excellent transparency, low odor and low taste.

[0002]

2. Description of the Related Art Propylene-based polymers are excellent in transparency, rigidity, surface gloss and heat resistance as compared with other polyolefins, and have great utility value. However, since the melt tension was small, the extrusion laminate moldability was poor.

As a method of improving this drawback, a method of adding high-pressure low-density polyethylene is known. However, this method impairs the original transparency, rigidity, and heat resistance of polypropylene, and cannot be said to be a sufficient improvement.

As a method of improving extrusion laminate moldability and not impairing the original properties of the propylene polymer such as transparency and heat resistance, there are many examples of copolymers of non-conjugated diene and propylene. There is a report. Examples of the branched diene having one vinyl type double bond at the terminal include:
JP-A-4-173814, JP-A-4-170407, JP-A-3-177402, JP-A-2-281011, JP-A-4-28706, JP-A-4-25510, JP-A-2-
145611, JP-A-62-115007 and the like. Since these use Ziegler-Natta catalysts,
Low conversion of non-conjugated diene to polymer. in addition,
Since the non-vinyl type double bond is not introduced into the polymer, an effective crosslinked structure is not formed and the melt tension is not improved. Examples of non-conjugated dienes having vinyl type double bonds at both ends include JP-A-6-80729 and JP-A-3
-290416, JP-A-3-290417, etc., but since these also use a Ziegler-Natta type catalyst, the conversion rate of the non-conjugated diene to the polymer is small, and it cannot be said to be an effective means.

Recently, an example of a copolymer of a non-conjugated diene and propylene using a metallocene catalyst has been reported. For example, JP-A-5-222251 and JP-A-5-22
2121 etc. are mentioned. The metallocene-based catalysts used in these examples are not sufficiently large with mm% of less than 98% in ordinary polymerization, the molecular weight is insufficient, and in addition, the nonlinearity of melt tension and extensional viscosity is insufficient. It cannot be put to practical use.

In addition, as a method for producing a propylene-based polymer having an improved melt tension, a. Irradiation of radiation (high energy rays). b. Peroxide crosslinking. And the like, and these are also methods for improving melting characteristics by partially cross-linking after polymerization and introducing long chain branching. However, a requires large-scale equipment, and b
However, since kneading is required, the cost is not desirable.
In addition, both the methods a and b cause deterioration of the resin at the same time, so that there is a problem that a product manufactured by the extrusion laminating method tends to have a problem of odor or change the taste of the packaged food. As described above, in reality, there is still no laminate which is easily manufactured by the extrusion laminating method, retains the original transparency of the propylene-based polymer, and has excellent low odor and low taste.

[0007]

The object of the present invention is to solve the above-mentioned problems in the prior art, that is, it is easily produced by an extrusion laminating method and retains the original transparency of the propylene-based polymer. It is to provide a laminate having excellent low odor and low taste.

[0008]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that propylene obtained by copolymerizing propylene with a small amount of polyvalent ene using a metallocene compound. They have found that they can be obtained by extrusion-laminating a base polymer on a substrate, and arrived at the present invention.

The present invention will be described in detail below. The propylene-based polymer in the present invention means homopolypropylene or random polypropylene containing 0 to 10% by weight of ethylene or α-olefin. The propylene content contained in the random polypropylene is 90% by weight or more, and if it is less than 90% by weight, the original rigidity is impaired. Examples of the α-olefin used above include 1-butene, 1-hexene, 1-octene, 1-decene, 4-methyl-1-pentene and styrene.

The λ value in the present invention is an index of the degree of non-linearity of elongational viscosity, and represents the magnitude of strain hardening in various moldings by the elongational viscosity ratio before and after that. Here, λ = λ ₁ / λ ₀ [λ ₀ is the extensional viscosity at the displacement point, and λ ₁ is the extensional viscosity when the strain is twice the strain at the displacement point. The displacement point is a point at which the linear region (extreme deformation region) and the non-linear region (large deformation region) of extensional viscosity are displaced. The range of the λ value is preferably 2.0 or more and less than 6.0, and particularly preferably 3.0 or more and less than 5.0 when importance is attached to thickness uniformity. When the λ value is less than 2.0, sufficient strain hardening is not exhibited and the formability is not improved, and 6.0
If the above is the case, the melt fluidity of the polymer is lowered and actual molding becomes difficult. In addition, the generation of gel or the like becomes remarkable.

The polyvalent ene used in the present invention has a plurality of non-conjugated vinyl groups, has at least two vinyl type double bonds and has 5 to 80 carbon atoms and a molecular weight of 11
A polyvalent ene of 00 or less is effective. A more effective polyvalent ene has 8 to 20 carbon atoms. When the number of vinyl type double bonds is one, it is impossible to effectively increase the melt tension and the extensional viscosity at the time of strain hardening.

As a specific example, 1,4-pentadiene,
1,5-hexadiene, 1,6-heptadiene, 1,7
-Octadiene, 1,8-nonadiene, 1,9-decadiene, 1,13-tetradecadiene, 3-methyl-1,
4-pentadiene, 4-methyl-1,5-hexadiene, 3-methyl-1,5-hexadiene, 1,5,9-
Examples include decatriene.

In the present invention, the content of polyvalent ene introduced into the obtained polyolefin is 0.05 to 2% by weight.
It is. If it is less than 0.05% by weight, the effect of improving the melting property is not remarkable, and if it is 2% by weight or more, the generation of gel or the like is observed, which is a practical problem. It is preferably 0.05 to 1% by weight, and particularly preferably 0.05 to 0.2% by weight.

The metallocene compound used in the present invention is
It is represented by the general formula (1) having C ₁ symmetry or the general formula (2) having C ₂ symmetry. The general formula (1) is

Embedded image [M in Formula (1) means a transition metal selected from Ti, Zr, and Hf. X ¹ and X ² may be the same or different and each represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkylsilyl group or a halogen atom. R ¹ , R ² , R ⁵ and R ⁶ mean a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group, and ^one of R ¹ and R ² is not a hydrogen atom.
Further, R ³ and R ⁴ mean a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group, and may be bonded to each other to form a ring. Y means a carbon atom or a silicon atom. In the formula, n is an integer of 1 to 3. ]. The substituent on the cyclopentadienyl ring is a hydrocarbon group having 1 to 10 carbon atoms (alkyl group, aryl group, alkylaryl group, arylalkyl group, etc.) or alkylsilyl group (trialkylsilyl group, triarylsilyl group). Etc.), but preferably a substituent such as a tert-butyl group having a bulkiness of not less than a methyl group.

The general formula (2) is

Embedded image [M in Formula (2) means a transition metal selected from Ti, Zr, and Hf. X ¹ and X ² may be the same or different and each represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkylsilyl group or a halogen atom. R ¹ means a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group, and R ⁴ and R ⁵ mean a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group. Further, R ² and R ³ represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group, and may be bonded to each other to form a ring. Y means a carbon atom or a silicon atom. Where n is 1 to 3
Is an integer. ].

Specific examples of the metallocene compounds represented by the general formulas (1) and (2) in which M is Zr and X ¹ and X ² are chlorine atoms are shown below. As an example of the general formula (1), ethylene (4-methyl-cyclopentadienyl)
(3-methyl-indenyl) zirconium dichloride,
Ethylene (4-t-butyl-cyclopentadienyl) (3
-Methyl-indenyl) zirconium dichloride, ethylene (4-t butyl-cyclopentadienyl) (3-t
Butyl-indenyl) zirconium dichloride, ethylene (4-methyl-cyclopentadienyl) (3-tbutyl-indenyl) zirconium dichloride, ethylene (4-tbutyl-cyclopentadienyl) (3-trimethylsilyl-indenyl) zirconium dichloride , Ethylene (4-tbutyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (4-methyl-cyclopentadienyl) (3-methyl-
Indenyl) zirconium dichloride, isopropylidene (4-tbutyl-cyclopentadienyl) (3-methyl-indenyl) zirconium dichloride, isopropylidene (4-tbutyl-cyclopentadienyl) (3-
t-butyl-indenyl) zirconium dichloride, isopropylidene (4-t-butyl-cyclopentadienyl)
(Fluorenyl) zirconium dichloride, dimethylsilylene (4-tbutyl-cyclopentadienyl) (3-
Methyl-indenyl) zirconium dichloride, dimethylsilylene (4-tbutyl-cyclopentadienyl)
(3-t-Butyl-indenyl) zirconium dichloride, dimethylsilylene (4-tbutyl-cyclopentadienyl) (3-trimethylsilyl-indenyl) zirconium dichloride, dimethylsilylene (4-tbutyl-)
Cyclopentadienyl) (fluorenyl) zirconium dichloride and the like.

As an example of the general formula (2), ethylenebis (2-methyl-indenyl) zirconium dichloride,
Ethylenebis (2-ethyl-indenyl) zirconium dichloride, ethylenebis (2,4-dimethyl-indenyl) zirconium dichloride, ethylenebis (2-methyl-4-tbutyl-indenyl) zirconium dichloride, ethylenebis (2-methyl-) 4-trimethylsilyl-indenyl) zirconium dichloride, ethylenebis (2-methyl-benzindenyl) zirconium dichloride, isopropylidenebis (2-methyl-indenyl) zirconium dichloride, isopropylidenebis (2-ethyl-indenyl) zirconium dichloride,
Isopropylidene bis (2,4-dimethyl-indenyl) zirconium dichloride, isopropylidene bis (2-methyl-4-tbutyl-indenyl) zirconium dichloride, isopropylidene bis (2-methyl-4)
-Trimethylsilyl-indenyl) zirconium dichloride, isopropylidenebis (2-methyl-4-phenyl-indenyl) zirconium dichloride, isopropylidenebis (2-methyl-benzindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-)
Indenyl) zirconium dichloride, dimethylsilylenebis (2-ethyl-indenyl) zirconium dichloride, dimethylsilylenebis (2,4-dimethyl-indenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-tbutyl-indenyl) zirconium dichloride , Dimethylsilylene bis (2-methyl-
Examples thereof include 4-trimethylsilyl-indenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-benzindenyl) zirconium dichloride and the like.

The aluminoxane compound and the non-coordinating ionic compound used in the polymerization will be described below.
The aluminoxane compound used in the present invention is an organoaluminum compound represented by the general formula (3) or the general formula (4). General formula (3)

Embedded image General formula (4)

[Chemical 6] R ⁷ is a methyl group, an ethyl group, a propyl group, a butyl group,
It is a hydrocarbon group such as an isobutyl group, preferably a methyl group. m is an integer of 4 to 100, preferably 6 or more and particularly 10 or more. A method for producing a compound of this kind is known, and for example, a method obtained by adding a trialkylaluminum to a hydrocarbon solvent suspension of salts having crystal water (copper sulfate hydrate, aluminum sulfate hydrate) is exemplified. You can The aluminoxane compound can be used by supporting it on a carrier such as silica, alumina or magnesium chloride. It is also possible to modify it so as to be suitable for each process. For example, when used in a non-liquid phase polymerization method, it can be modified with water or an electron donating compound.

The non-coordinating ionic compound is represented by the following formula. (MX ¹ X ² X ³ X ⁴ ) ^(nm)-. C ^{(nm) +} (In the above formula, M is a metal selected from Groups 5 to 15 in the periodic table, X ¹ , X ² and X ³ , X ⁴ are each a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, a substituted alkyl group, A halogen-substituted aryl group, an organic metalloid group or a halogen atom is shown, and C is a counter cation such as carbonium or ammonium.
m is an valence of M and is an integer of 1 to 7, and n is an integer of 2 to 8. )

Specific examples of these compounds include triethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, tri (n-butylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) boron, tributylammonium tetrakis ( Pentafluorophenyl) borate, dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (3,5trifluoromethylphenyl) borate And the like, preferably triphenylcarbonium tetrakis (pentafluorophenyl) borate or dimethylanilinium tetrakis. Pentafluorophenyl) borate - a preparative.

The propylene polymer used in the present invention may be polymerized by liquid phase polymerization (solution polymerization using a solvent, for example, high temperature solution polymerization, and melt polymerization without solvent, for example, high pressure polymerization), slurry polymerization (using a solvent). Both system and solvent-free systems, eg bulk slurry polymerization), gas phase polymerization are possible. Further, multistage polymerization in which a plurality of the same or different processes are continuously performed is also possible.

When an aluminoxane compound is used in the polymerization, a mixture of both components of the metallocene compound and the aluminoxane compound may be supplied in advance to the reaction system, or both components may be supplied to the reaction system. In any case, the concentration molar ratio of both components in the polymerization system is not particularly limited, but preferably, the complex concentration is 10 ⁻³ to 10 ⁻¹⁰ mol / l, and the molar ratio of Al / complex is A ratio of 10 or more, particularly 100 or more is preferably used.

When a non-coordinating ionic compound is used in the polymerization, a mixture of the metallocene compound, the trialkylaluminum, and the non-coordinating ionic compound may be supplied to the reaction system. Each component may be supplied individually. In any case, the molar concentration of each component in the polymerization system is not particularly limited, but preferably, the complex concentration is 10 ⁻³ to 10 ⁻¹⁰ m 2.
The molar ratio of trialkylaluminum / complex is preferably in the range of 50 to 1000, and the molar ratio of non-coordinating ionic compound / complex is in the range of 0.5 to 10, particularly preferably in the range of 1 to 5. To be

The olefin pressure in the reaction system is not particularly limited, but is preferably in the range of normal pressure to 50 kg / cm ² G. The amount of polyvalent ene supplied is 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the olefin in the reaction system.
It is. The polymerization temperature is not limited, but preferably -30.
C. to 200.degree. C., particularly preferably 0.degree. C. to 80.degree. The molecular weight adjustment during polymerization is
It can be carried out by a known means such as selection of temperature or introduction of hydrogen.

For the propylene-based polymer used in the present invention, as additives such as stabilizers, lubricants, antiblocking agents, colorants, antistatic agents, nucleating agents and the like, those used in the relevant field can be applied. . Further, by mixing with other resins commonly known within the range not impairing the object of the present invention, for example, rubber such as high-pressure low-density polyethylene, linear low-density polyethylene, high-density polyethylene, polypropylene, EPR, EBR, and EPDM. Can be used.

The laminate of the present invention is produced by extrusion laminating a propylene polymer on a substrate. The conditions for extrusion lamination are not particularly limited, and conventionally-used methods can be applied, but in order to develop a low odor and low taste, molding is preferably performed at a temperature of 320 ° C or lower, and 290 ° C or lower. Is more preferable.

As the base material, a commonly used one is used. That is, biaxially oriented polypropylene film,
Examples thereof include biaxially stretched polyamide 6 film, biaxially stretched polyethylene terephthalate film, paper, aluminum foil and the like, but are not limited thereto. Corona treatment, imine-based, urethane-based anchor coat (adhesive) treatment can be applied to these base materials as required. Further, the laminated surface may be printed.

In using the laminate of the present invention,
Although it may be used alone, another resin may be extrusion-laminated on this laminate, or another resin film, paper, aluminum foil or the like may be further laminated and used by, for example, a dry lamination method or the like. .

[0029]

EXAMPLES Next, the present invention will be specifically described by way of examples. The analytical instruments used for measuring the physical properties are shown below. The content of the polyvalent ene, using a JEOL EX-400 ¹³
It was determined by C-NMR measurement. MFR is JIS K67
60 is a value measured under the conditions of a temperature of 230 ° C. and a load of 2.16 kg. The elongational viscosity was measured using a capillary rheometer manufactured by Toyo Seiki Co., Ltd., and a uniform strand with a diameter of 3 mm obtained at a molding temperature of 230 ° C. was used as a sample. It was measured at 0.1 s ^-1 .

In carrying out the examples and the comparative examples, the molding conditions and the physical property evaluation methods used are shown below. (1) Extrusion laminating molding In a laminating molding machine having a 40 mmφ extruder, a biaxially stretched polypropylene film or a biaxially stretched polyethylene terephthalate film is used as a substrate, and the temperature is 280.
Laminate molding was performed at a temperature of 110 ° C. and an air gap of 110 mm. The drawdown property was evaluated by increasing the take-up speed at the extruder rotation speed of 30 rpm and the speed at which film breakage occurred. Neck-in was a sample molded at a film thickness of 20 μm and a take-up speed of 200 m / min. It is expressed by the difference in the width of the laminate layer). The air gap during lamination molding was 110 mm. (2) Transparency Haze was measured according to JIS K7105. (3) Odor Extrusion lamination was performed on the uncorona-treated surface of the biaxially stretched polyethylene terephthalate film at a temperature of 280 ° C. and a thickness of 20 μm, and the base material of the obtained laminate was peeled off to obtain a propylene polymer film. 300g of this film 20g
After filling in a wide-mouthed glass bottle of ml and sealing with a lid, the mixture was heated at 60 ° C. for 1 hour, the lid was removed, and the odor was sensory evaluated. For comparison, polypropylene extruded laminate material (Show Allomer LR510 manufactured by Showa Denko KK) was used, and LR5
The odor level of 10 was designated as C, and compared with that, very little was A, little was B, and many was D, and relative evaluation was performed. (4) Taste A polypropylene polymer was extrusion-laminated on a biaxially oriented polypropylene film, and a pack was prepared so that the laminated resin layer was the inner layer. Mineral water was filled in this and stored at 60 ° C. for 4 days, then the mineral water was taken out and taste evaluation was performed. For comparison, the above-mentioned LR510 was used as a polypropylene-based polymer, and the taste level thereof was evaluated as C, the taste level having almost no taste was A, the level less than LR510 was B, and the level having more taste than LR510 was D.

The propylene-based polymers used in Examples and Comparative Examples are shown below. (MD1) Isopropylidene (4-tbutyl-cyclopentadienyl) (3-
Synthesis of t-butyl-indenyl) zirconium dichloride was performed. [Polymerization] S with an internal volume of 120 liters that has been sufficiently replaced with nitrogen
In a US autoclave, 150 ml of a 0.5 mmol / ml hexane solution of triisobutylaluminum and 1,7
-Adding 25 g of octadiene, 600 m of propylene
After adding ol, the temperature was kept at 25 ° C. Then, a solution of triisobutylaluminum in 0.5 mmol / ml hexane 10
0 ml, 1 μmol / ml toluene solution of isopropylidene (4-tbutyl-cyclopentadienyl) (3-tbutyl-indenyl) zirconium dichloride 100 m
1 and triphenylcarbonium tetrakis (pentafluorophenyl) borate 2 μmol / ml 75 ml of a toluene solution were mixed in a vessel previously purged with nitrogen, and a solution was introduced by pressurizing with nitrogen from an addition device to initiate polymerization. Polymerization was carried out for 30 minutes to obtain 8.0 kg of polymer.

(MD2) The procedure of preparing MD1 was repeated except that 1,9-decadiene was used instead of 1,7-octadiene to obtain 8.5 kg of a polymer.

The procedure of preparing MDE2 was repeated, except that the amount of (MD3) 1,9-decadiene used was 130 g, to obtain 8.5 kg of a polymer.

(MD4) The same operation as that for preparing MD1 was carried out except that 65 g of 1,13-tetradecadiene was used instead of 1,7-octadiene to obtain 4.2 kg of a polymer.

(MDR1) The same operation as that for preparing MD1 was carried out except that 1,7-octadiene was not used,
6.5 kg of polymer were obtained.

(MDR2) The procedure of preparing MD2 was repeated except that the amount of 1,9-decadiene used was 9.0 g, to obtain 7.0 kg of a polymer.

(MDR3) The same operation as that for preparing MD2 was carried out except that the amount of 1,9-decadiene used was 900 g and the amount of propylene supplied was 300 mol.
Was obtained.

(MDR4) Polypropylene with improved extrusion laminate moldability obtained by blending homopolypropylene obtained by using a conventional Ziegler-Natta catalyst and high-pressure polyethylene, Showallomer LR510 manufactured by Showa Denko KK .

(Examples 1 to 4) Lamination molding was performed using the propylene-based polymers of MD1 to MD4, but the drawdown property and neck-in were good, and the obtained products were also transparent and odorless. , Was excellent in taste.

Comparative Example 1 Propylene-based polymer (MDR
Laminate molding was carried out using 1), but surging occurred and molding was impossible.

(Comparative Example 2) Propylene polymer (MDR
Laminate molding was carried out using 2), but the drawdown property was insufficient and high speed molding was not possible.

(Comparative Example 3) Propylene polymer (MDR
Laminate molding was performed using 3), but the drawdown property was insufficient, and the obtained product also had many gels and fish eyes, and had poor transparency and odor.

(Comparative Example 4) Propylene polymer (MDR
Laminate molding was performed using 4), but the obtained product had poor transparency, odor and taste.

[0044]

[Table 1]

[0045]

According to the present invention, a laminate having excellent transparency and low odor can be obtained, and the laminate can be easily manufactured by an extrusion laminating method.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Minoru Minoru No. 2 in Oita City, Oita City, Oita Prefecture Showa Denko Co., Ltd. Oita Laboratory (72) Inventor Takamasa Tsuyuki No. 2 in Naka, Oita City, Oita Prefecture Showa Electric Works Co., Ltd. Oita Research Center

Claims (3)

[Claims] 1. A laminate comprising a layer made of a propylene-based polymer and a base material, which has a λ value showing the degree of nonlinearity of extensional viscosity of 2.0 or more and less than 6.0. Here, λ = λ ₁ / λ ₀ [λ ₀ is the extensional viscosity at the displacement point, and λ ₁ is the extensional viscosity when the strain is twice the strain at the displacement point. The displacement point is a point at which the linear region (extreme deformation region) and the non-linear region (large deformation region) of extensional viscosity are displaced. ] 2. A propylene-based polymer having a polyvalent ene content of 0.
The layered product according to claim 1, wherein the layered product is contained in an amount of 05 to 2% by weight. 3. A propylene-based polymer obtained by polymerization using a catalyst system comprising a metallocene compound represented by the general formula (1) or (2) and an aluminoxane compound or a non-coordinating ionic compound. The layered product according to claim 1 or 2 characterized by things. Embedded image [M in Formula (1) means a transition metal selected from Ti, Zr, and Hf. X ¹ and X ² may be the same or different and each represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkylsilyl group or a halogen atom. R ¹ , R ² , R ⁵ and R ⁶ are hydrogen atoms and have 1 carbon atom
To 10 hydrocarbon groups or alkylsilyl groups, and ^one of R ¹ and R ² is not a hydrogen atom.
Further, R ³ and R ⁴ mean a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group, and may be bonded to each other to form a ring. Y means a carbon atom or a silicon atom. In the formula, n is an integer of 1 to 3. ] [Chemical 2] [M in Formula (2) means a transition metal selected from Ti, Zr, and Hf. X ¹ and X ² may be the same or different and each represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkylsilyl group or a halogen atom. R ¹ means a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group, and R ⁴ and R ⁵ mean a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group. Further, R ² and R ³ represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group, and may be bonded to each other to form a ring. Y means a carbon atom or a silicon atom. Where n is 1 to 3
Is an integer. ]