JP2685262C - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTIONTECHNICAL FIELD OF THE INVENTION   The present invention relates to a heat sealant, and more particularly, has a low melting point
Propylene based with excellent blocking resistanceBothRegarding heat sealants made of polymer
You.Technical background of the invention and its problems   Polypropylene has excellent physical properties, so it is widely used
I have. For example, polypropylene is widely used as a packaging film,
Polypropylene has a relatively high melting point, so low temperatures
In order to improve heat sealability, propylene is generally ethylene or carbon number.
4-20 α-olefins are copolymerized to form a propylene / α-olefin copolymer.
It has been used.   Packaging foils made of such conventionally known propylene / α-olefin copolymers.
Films are more transparent and screen resistant than films made of low density polyethylene. Although excellent in latching property, heat sealing property at low temperature is still insufficient,
Furthermore, it has excellent heat sealing properties at low temperatures and can be used as a heat sealing agent.
It is desired that a propylene / α-olefin copolymer be produced.   Heat sealability of propylene / α-olefin random copolymer as described above
To improve propylene, ethylene or α-olefin having 4 to 20 carbon atoms
It is known that the copolymerization amount of the olefin should be increased, but if ethylene
Or by increasing the copolymerization amount of an α-olefin having 4 to 20 carbon atoms,
The propylene / α-olefin copolymer has a large amount of solvent-soluble components, and is resistant to blocking.
It becomes inferior in property and also inferior in rigidity.   Thus, a heat-sealable, blocking-resistant, and rigid
Lopylene seriesBothIn order to obtain a polymer, the amount of α-olefin
However, it is necessary to produce a propylene-based random copolymer having a low melting point.   By the way, to produce a conventional propylene / α-olefin random copolymer,
Generally consists of a titanium or vanadium compound and an organoaluminum compound
Olefin polymerization catalysts have been used, but in recent years new Ziegler-type olefins
Recently, catalysts composed of zirconium compounds and aluminoxanes have been used as polymerization catalysts.
Proposed.   JP-A-58-19309 discloses the following formula:   (Cyclopentadienyl)_TwoMeRHal [Where R is cyclopentadienyl, C₁~ C₆Alkyl, halogen,
Me is a transition metal, and Hal is a halogen.]
Compound and the following formula       Al_TwoOR_Four(Al (R) -O)_n Wherein R is methyl or ethyl, and n is a number from 4 to 20.
Linear aluminoxane or the following formula Wherein the definitions of R and n are the same as above. Ethylene and C in the presence of a catalyst comprising_Three~ C₁₂Α-olefin 1
A method of polymerizing a seed or two or more kinds at a temperature of −50 ° C. to 200 ° C. is described.
You. The publication discloses that in order to adjust the density of the obtained polyethylene, 10% by weight was used.
Of ethylene in the presence of small amounts of somewhat long-chain α-olefins or mixtures up to
Is described.   JP-A-59-95292 discloses the following formula: [Where n is 2 to 40 and R is C₁~ C₆] Linear aluminoki represented by
Sun and the following formula Wherein the definitions of n and R are the same as described above.
The invention relates to a method for producing a xanth. The same publication states that
Manufactured, for example, methylaluminoxane and titanium or zirconium bis
(Cyclopentadienyl) compound and the polymerization of olefin
25 g or more of polyethylene can be obtained per 1 g of transition metal and per hour.
It is described.   JP-A-60-35005 discloses the following formula:[Where R¹Is C₁~ C_TenAlkyl, R⁰Is R¹Or combined with-
Aluminoxane compound represented by the formula:
And then chlorinate the reaction product, and further react with Ti, V, Zr or Cr.
A method for producing a polymerization catalyst for olefins by treating with a compound is disclosed. same In the official gazette, the catalyst is ethylene and C_Three~ C₁₂Of α-olefin mixture
It is stated to be particularly suitable.   JP-A-60-35006 discloses a catalyst system for producing a reactor blend polymer.
The mono-, di- or tri-cyclopentadiamine of two or more different transition metals
Combinations of enyl or derivatives thereof (a) and aluminoxanes (b) are disclosed.
Example 1 of the publication discloses bis (pentamethylcyclopentadienyl) zirconium.
Polymerization of ethylene and propylene using dimethyl and aluminoxane as catalysts
The number average molecular weight of 15,300, the weight average molecular weight of 36,400 and
It is disclosed that a polyethylene containing 3.4% of a component was obtained. Also,
In Example 2, bis (pentamethylcyclopentadienyl) zirconium dichloride was used.
And bis (methylcyclopentadienyl) zirconium dichloride and
And aluminoxane as catalysts to polymerize ethylene and propylene to obtain a number average molecular weight
2,200, a weight average molecular weight of 11,900 and a propylene component of 30 mol%
Toluene-soluble part containing, number average molecular weight 3,000, weight average molecular weight 7,400 and
Average molecule consisting of a toluene-insoluble part containing 4.8 mol% of a propylene component
Propylene component having a weight average molecular weight of 8,300 and 7.1 mol% in an amount of 2,000
And a blend of polyethylene and an ethylene / propylene copolymer.Soluble fraction of 20.6% and a molecular weight distribution of 3.04 and a propylene component of 2.9 mol
% Insoluble part of LLDPE and ethylene-propylene copolymer blend
Product is listed.   JP-A-60-35007 discloses that ethylene alone or a compound having 3 or more carbon atoms is used.
Metallocene with α-olefin of formula [Where R is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 1 to about 20]
Or a cyclic aluminoxane represented by the following formula: [Wherein the definitions of R and n are the same as above]
A method for polymerizing in the presence of a catalyst system comprising xane is described. By the same method
According to the description of the publication, the obtained polymer has a weight average of about 500 to about 1.4 million.
It has a molecular weight and a molecular weight distribution of 1.5 to 4.0.   JP-A-60-35008 discloses that at least two kinds of metallocenes and
By using a catalyst system containing luminoxane, a polymer with a broad molecular weight distribution can be obtained.
Ethylene or ethylene and C_Three~ C_TenΑ-olefin copolymer is produced-50.   JP-A-61-130314 discloses a three-dimensionally fixed zircon key.
Polymerizes propylene in the presence of a catalyst system consisting of a rate compound and an aluminoxane.
Describes that a polypropylene with high isotacticity can be obtained.
.   In addition, J. Am. Chem. Soc.,109, 6544 (1987) include ethylene bis (indene).
Le) Catalyst consisting of hafnium dichloride or its hydride and aluminoxane
Polymerization of propylene in the presence of a system produces a high molecular weight isotactic polypropylene. Are listed.   On the other hand, Japanese Patent Application Laid-Open No. Sho 63-142005 discloses that
Clopentadienyl) catalyst system consisting of titanium chloride and aluminoxane Is described. The propylene obtained here is an isotactic chain
It is a short, rubbery polymer.   The present inventors have developed an olefin comprising a specific hafnium compound and an aluminoxane.
Propylene and ethylene and / or 4 to 20 carbon atoms in the presence of
Copolymerization with α-olefins of
Propylene based with lower melting point than polymerBothA polymer is obtained and the propyleneBoth
The present inventors have found that polymers have excellent properties as heat sealants and completed the present invention. Has come to fruition.Purpose of the invention   The present invention is intended to solve the above-mentioned problems in the prior art.
Therefore, it has low melting point, excellent heat sealing property, blocking resistance and rigidity.
Propylene type which is also excellentBothProvide a heat sealant made of a polymer
It is intended to be.Summary of the Invention   The heat sealant according to the present invention, (A) Propylene component is 90-990 to 10 moles of ethylene component in mole%
% And an α-olefin derived from an α-olefin having 4 to 20 carbon atoms
Component is present in an amount of 0 to 10 mol%, (B) The melting point [Tm] measured by a differential scanning calorimeter is   90<Tm <145-5.5 (100-P) (Where P isBothPropylene component content (mol%) in the polymer) in the range, (C) The intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.5 to 6 dl / g.
In the box, (D) The content of boiling trichlorethylene insolubles is 5% by weight or less. PropyleneBothIt is characterized by being composed of a polymer.Detailed description of the invention   Hereinafter, the heat sealant according to the present invention will be specifically described.   The heat sealant according to the present invention is a propylene-based heat sealant.BothIt is made of polymer,
Of propyleneBothIn the polymer, the propylene component is 90 to99Mole%, preferably 9
It is present in an amount of from 2 to 99 mol%, the ethylene component being from 0 to 10 mol%, preferably from 0.5 to
Derived from α-olefins having from 4 to 20 carbon atoms present in an amount of
The α-olefin component is present in an amount of 0 to 10 mol%, preferably 0.5 to 9.5 mol%.
Existing.   Propylene based with 0 mol% ethylene componentBothThe polymer is propylene and carbon number
Propylene / α-olefin random copolymer consisting of 4 to 20 α-olefins
It is. Α-olefin component derived from α-olefin having 4 to 20 carbon atoms Is 0 mol% propyleneBothPolymer is propylene / ethylene random copolymer
It is united.   Furthermore, neither the ethylene component nor the α-olefin component is 0 mol%.
PropyleneBothThe polymer is a propylene / ethylene / α-olefin random copolymer.
It is a polymer.   Propylene as aboveBoth90% by mole of propylene component in the polymer
When it is full, the blocking resistance and rigidity of the heat sealant tend to be inferior.
.   The α-olefin having 4 to 20 carbon atoms used in the present invention includes 1-butene and 1-butene.
Pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octane
Ten, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadece
And 1-eicosene are used. Of these, 1-butene is particularly preferred.   The propylene-based random copolymer according to the present invention is measured by a differential scanning calorimeter.
Melting point [Tm]   90 <Tm <145-5.5 (100-P) (Where P is the propylene component content (mol%) in the copolymer).   The melting point Tm of such a propylene-based copolymer and the propylene
The schematic relationship with the P content% is shown as a straight line A in FIG. Fig. 1 shows
The melting point Tm of the conventionally known propylene copolymer and the propylene component content P mol%
Is also shown as a straight line B.   As is clear from FIG. 1, the melting point of the propylene-based copolymer according to the present invention is
, Ethylene and / or α-olefin have the same copolymerization amount,
It is lower by 10 to 20 ° C. than the melting point of a conventionally known propylene random copolymer. But
The propylene series according to the present inventionBothFilms obtained from polymers, especially at low temperatures
Excellent heat sealability. And ethylene and / or α-olefin
Since the copolymerization amount shows at least excellent heat sealability, it also has
Excellent and also has excellent rigidity.   In the present invention, a propylene-based material is used by using a differential scanning calorimeter (DSC).BothPolymer
Is left at 200 ° C. for 5 minutes, cooled to 20 ° C. at a rate of 10 ° C./min.
After leaving at 20 ° C for 5 minutes, measure from 20 ° C to 200 ° C at a rate of 10 ° C / min. Temperature (Tm) of the maximum endothermic peak obtained byBothThe melting point of the polymer
Was.   In the present invention, such a propylene-basedBothThe polymer has excellent heat as described above
Shows sealability, blocking resistance and rigidity, and is used as a heat sealant
You.   In the present invention, the propylene-basedBothA heat sealant made of a polymer is
For example, it can be used in the form of a film and laminated with another film. Also above
Propylene-basedBothSince the polymer is also excellent in heat sealability,
Blended with other polyolefins and used as a heat sealant
it can.   Further, the propylene-based material according to the present inventionBothGel permeation chromatography of polymers It is particularly preferably in the range of 2.5 or less. Thus, the propyle according to the present invention
SystemBothPolymers have a narrow molecular weight distribution and have excellent blocking resistance in this respect as well.
doing. Raffy "was performed as follows. (1) Standard polystyrene with a known molecular weight (Toyo Soda Co., Ltd., monodisperse polystyrene)
Is used to determine the molecular weight M and its GPC (Gel Permeation Chromatograph) count.
It measures and prepares a calibration curve of the correlation diagram between the molecular weight M and the EV (Elution Volume). At this time
Is 0.02% by weight. (2) GPC chromatograph of the sample by GPC measurement,Ask for. The sample preparation conditions and GPC measurement conditions at that time are as follows.
. [Sample preparation] (A) Triangular filter with 0.1% by weight of o-dichlorobenzene solvent
Disperse in Lasco. (B) Heat the Erlenmeyer flask to 140 ° C. and stir for about 30 minutes to dissolve. (C) The solution is subjected to GPC. [GPC measurement conditions]   The test was performed under the following conditions. (B) Equipment Waters (150C-ALC / GPC) (B) Column made by Toyo Soda (GMH type) (C) Sample amount 400μl (D) Temperature 140 ° C (E) Flow rate 1 ml / min   The melting point was measured using a Perkin Elmer-7 type DSC device, and the sample amount was about 2.5 mg.
The temperature was measured at a heating rate of 10 ° C./min.   Further, the propylene-based material according to the present inventionBothThe polymer has a soluble part in boiling n-pentane of 5 parts.
% By weight or less, preferably 3% by weight or less, more preferably 2% by weight or less.
desirable.   Further, the propylene series according to the present inventionBothThe polymer reacts to boiling trichlorethylene
5% by weight or less, preferably 3% by weight or less, more preferably 1% by weight or less.
It is desirable to be below.   Finely pulverized boiling trichlorethylene insolubles and boiling n-heptane solubles
Approximately 3 g of the prepared sample was placed in a thimble filter paper, and a Soxhlet extractor was used using 180 ml of a solvent.
Extraction for 5 hours, and the extraction residue is dried in a vacuum drier to a constant weight to determine the weight.
It was calculated from the weight difference from the original sample.   Propylene system according to the present invention as described aboveBothThe polymer is (A) at least two members selected from a cycloalkadienyl group or a substituted product thereof
Having a multidentate coordination compound in which a group is bonded via a lower alkylene group as a ligand
Compound, and (B) Aluminoxane In the presence of a catalyst formed fromPropylene and ethylene and / or carbon number 4
~ 20 α-olefinsCan be produced by copolymerizing   The catalyst component [A] used in the present invention is a cycloalkadienyl group or
Substitutes thereof, specifically, an indenyl group, a substituted indenyl group and its partial hydrogen
At least two groups selected from the group consisting of A hafnium compound having a combined polydentate compound as a ligand. Hafnium conversion
The following compounds can be exemplified as the compound.   Ethylenebis (indenyl) dimethylhafnium,   Ethylenebis (indenyl) diethylhafnium,   Ethylenebis (indenyl) diphenylhafnium,   Ethylenebis (indenyl) methylhafnium monochloride,   Ethylenebis (indenyl) ethylhafnium monochloride,   Ethylenebis (indenyl) methylhafnium monobromide,   Ethylenebis (indenyl) hafnium dichloride,   Ethylene bis (indenyl) hafnium dibromide,   Ethylenebis (4,5,6,7-tetrahydro-1-indenyl) dimethylhafnium,   Ethylenebis (4,5,6,7-tetrahydro-1-indenyl) methylhafnium mono
Chloride,   Ethylene bis (4,5,6,7-tetrahydro-1-indenyl) hafnium dichloride
,   Ethylene bis (4,5,6,7-tetrahydro-1-indenyl) hafnium dibromide
,   Ethylenebis (4-methyl-1-indenyl) hafnium dichloride,   Ethylenebis (5-methyl-1-indenyl) hafnium dichloride,   Ethylenebis (6-methyl-1-indenyl) hafnium dichloride,   Ethylenebis (7-methyl-1-indenyl) hafnium dichloride,   Ethylenebis (5-methoxy-1-indenyl) hafnium dichloride,   Ethylenebis (2,3-dimethyl-1-indenyl) hafnium dichloride,   Ethylenebis (4,7-dimethyl-1-indenyl) hafnium dichloride,   Ethylene bis (4,7-dimethoxy-1-indenyl) hafnium dichloride.   The catalyst component [B] used in the method of the present invention is aluminoxane.
As the aluminoxane used as a catalyst component, general formula (I) and general formula (
II) Can be exemplified. The aluminum
In nooxane, R represents a carbon such as a methyl group, an ethyl group, a propyl group, and a butyl group.
A hydrogen group, preferably a methyl group, an ethyl group, particularly preferably a methyl group.
And m is an integer of 2 or more, preferably 5 or more. Production of the aluminoxane
As the method, for example, the following method can be exemplified. (1) Compounds containing adsorbed water, salts containing water of crystallization, such as magnesium chloride
Hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, salt
Trialkylaluminum is added to other hydrocarbon medium suspensions such as cerium iodide hydrate
A method of adding and reacting. (2) In a medium such as benzene, toluene, ethyl ether, and tetrahydrofuran
Method in which water, steam or ice is allowed to act directly on the trialkyl aluminum.   The aluminoxane may contain a small amount of an organic metal component.
I can't.   The hafnium compound as described above depends on the concentration of the hafnium atom in the polymerization reaction system.
And usually 10^-8-10^-2Gram atoms / l, preferably 10^-7-10^-3Gram Hara
Desirably, it is used in the amount of particles / l.   Aluminoxane as described above is converted to aluminum atoms in the reaction system.
Ten^-Four-10^-1Gram atoms / l, preferably 5 × 10^-Four~ 5 × 10^-2Gram Hara
Desirably, it is used in the amount of particles / l.   The polymerization temperature is usually 40 to 100 ° C, preferably 45 to 95 ° C, more preferably
It is desirable to be in the range of 50 to 90 ° C.   The polymerization of the olefin as described above is usually performed in a gas phase or a liquid phase.
In liquid phase polymerization, an inert hydrocarbon may be used as a solvent, or the olefin itself may be used as a solvent.
It can also be a solvent.   As the hydrocarbon medium, specifically, butane, isobutane, pentane, hexane
, Octane, decane, dodecane, hexadecane, octadecane, etc.
Hydrogen, cyclopentane, methylcyclopentane, cyclohexane, cyclooctane
Alicyclic hydrocarbons such as tan, and aromatic coals such as benzene, toluene, and xylene
Hydrogen fluoride, gasoline, kerosene,Light oilSuch as oil fractions are used.   The polymerization pressure is usually from normal pressure to 100 kg / cm^Two, Preferably normal pressure to 50 kg / c
m^TwoThe polymerization is carried out in a batch, semi-continuous, or continuous method.
Can also be performed. The molecular weight of the polymer depends on the hydrogen and / or polymerization temperature
Can be adjusted.The invention's effect   According to the present invention, conventionally known propylene-basedBothHas a lower melting point than polymers
PropyleneBothA heat sealability-imparting agent comprising a polymer is provided.
The sealant has excellent heat sealability, blocking resistance,
Excellent rigidity.   Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.
Not.Reference Example 1 (Preparation of methylaluminoxane) Polymer Commun.,29, 180 (1988). (Synthesis of ethylenebis (indenyl) hafnium dichloride)   Bis (indenyl) ethane (Bill) was placed in a 200 ml glass flask purged with nitrogen.
. Soc. Chim., 2954 (1967)), and 5.4 g and 50 ml of THF were charged.
The mixture was cooled to −30 to −40 ° C. with stirring. Add n-BuLi (1.6M solution)
) 31.5 ml was added dropwise, followed by stirring at −30 ° C. for 1 hour, followed by natural temperature rise to room temperature.
To anionize the bis (indenyl) ethane. Another nitrogen-substituted
A 200 ml glass flask was charged with 60 ml of THF and cooled to −60 ° C. or lower. HfCl_Four6.7 g was gradually added. Then, heat up to 60 ° C and stir for 1 hour
did. An anionized ligand was added dropwise thereto, and the mixture was stirred at 60 ° C. for 2 hours.
The mixture was filtered through a filter. The filtrate was concentrated to about the first 最初 volume at room temperature.
By this operation, a solid precipitates. This precipitated solid is filtered through a glass filter, and then
After washing with xanth / ethanol and drying under reduced pressure, the target compound was obtained. (polymerization)   In a 2-liter stainless steel autoclave sufficiently purged with nitrogen, toluene 75 was added at room temperature.
0 ml was charged and propylene gas was saturated. Next, methylaluminoxane is replaced with A
7.5 mg atom in terms of 1 atom, ethylene bis (indenyl) hafnium di
1.88 × 10 chloride^-3Mmol was added. Continuous supply of propylene gas
7kg / cm total pressure^TwoPolymerization was performed under G at 50 ° C. for 0.5 hour. Polymerization
Termination was performed by adding methanol to the polymerization system. The resulting polymer
-After pouring the slurry into a large amount of methanol,
The catalyst component was removed with a butyl alcohol / hydrochloric acid solvent. Then, at 80 ° C, 2 1.89 with a melting point of 132 ° C. by DSC in decalin at 135 ° C.
The measured [η] was 2.82 dl / g, and the boiling trichlorethylene insoluble content was 0%.
Isotactic, which has a boiling n-heptane soluble content of 0.2% by weight
107.1 g of polypropylene were obtained.Example 1 (polymerization)   In a 2-liter stainless steel autoclave sufficiently purged with nitrogen, toluene 50 was added at room temperature.
0 ml, 3 mol of propylene and 0.1 mol of 1-butene and methylaluminoxa
5 milligrams of Al atom were charged. Thereafter, the inside of the polymerization system was cooled to 45 ° C.
1.25x10 ethylene bis (indenyl) hafnium dichloride^-3Mi
The polymerization was carried out at 50 ° C. for 0.5 hour. Termination of the polymerization
Was added to the polymerization system.   After pouring the obtained polymer slurry into a large amount of methanol, the polymer slurry is recovered by filtration.
The catalyst component was removed with an isobutyl alcohol / hydrochloric acid solution. So After drying under reduced pressure overnight at 80 ° C. and 200 to 300 mmHg, the 1-butene content was
Is 2.2 mol%, and [η] measured in decalin at 135 ° C. is 3.02 dl /
g, the melting point by DSC is 124 ° C., and the boiling trichlorethylene insoluble matter
Amount is 0% by weight, boiling n-pentane soluble content is 0.3% by weight, Example 2   Propylene, 1-butene and ethylene gas compositions are 96.7, 2.1,
A mixed gas was prepared so as to be 1.2 mol%. 2 l of stainless steel sufficiently purged with nitrogen
500 ml of toluene was charged into an autoclave made by Reless and cooled to 0 ° C.
3 mol of the prepared mixed gas, and 5 mol of methylaluminoxane in terms of Al atom
Milligram atomic charge. Thereafter, the temperature of the polymerization system was raised to 45 ° C.
Ndenyl) hafnium dichloride 1.25 × 10^-3At 50 ° C
Polymerization was performed for 0.5 hour. To stop polymerization, add methanol to the polymerization system.
Performed by   After pouring the obtained polymer slurry into a large amount of methanol, the polymer slurry is recovered by filtration.
The catalyst component was removed with an isobutyl alcohol / hydrochloric acid solution. So
After drying under reduced pressure overnight at 80 ° C. and 200 to 300 mmHg, the 1-butene content was
Is 1.4 mol%, the ethylene content is 1.1 mol%, and the
[Η] was 3.32 dl / g, and the melting point by DSC was 121 ° C.
Yes, boiling trichlorethylene insoluble content is 0% by weight, boiling n-pentane soluble 51.3 g were obtained.Example 3   Example2, The molar ratio of propylene, 1-butene and ethylene is 95.1
Example except that /3.9/1.0 was used.2When polymerization was carried out in the same manner as in
Content is 2.7 mol%, ethylene content is 0.8 mol%, and [η] is 3 mol%.
. 29 dl / g, melting point 118 ° C, boiling trichlorethylene insoluble matter
But 48.5 g of 2.40 polymer were obtained. Example 4   Propylene and ethylene gas composition become 98.5 and 1.5 mol%, respectively
Was prepared as described above. Subsequent operation is an example2When I did the same as
The ethylene content is 1.3 mol%, [η] is 3.50 dl / g, and the melting point is 1
25 ° C., the boiling trichlorethylene insoluble content is 0% by weight, and the boiling n-pen3 g were obtained.Example 5 (Synthesis of ethylenebis (tetrahydroindenyl) hafnium dichloride)   referenceEthylene bis (indenyl) hafnium dichloro synthesized in the same manner as in Example 1.
Lido was purchased from Makromol. Chem.,190, 1177 (1989), The desired compound was obtained. (polymerization)   In a 2-liter stainless steel autoclave sufficiently purged with nitrogen, add toluene at room temperature.
500 ml, 3 mol of propylene and 0.12 mol of 1-butene and methylalumino
Oxane was charged at 5 milligrams in terms of Al atoms. Then, the polymerization system
The inside temperature was raised, and the hafnium compound synthesized above was^-3Mmol
At 50 ° C. for 0.5 hour. After polymerization,referencePerforming the same operation as in Example 1
At this time, the 1-butene content was 2.6 mol%, [η] was 2.8 dl / g,
Is 122 ° C., the boiling trichlorethylene insoluble content is 0% by weight, and the boiling n-
Pe 0 g was obtained.Example 6 (polymerization)   Propylene, 1-butene and ethylene gas composition are 97.0 mol%, 2
. A mixed gas was prepared so as to be 3 mol% and 0.7 mol%. Put enough nitrogen
500 ml of toluene was charged into the replaced 2 l stainless steel autoclave, and the temperature was reduced to 0 ° C.
After cooling, 3 mol of the mixed gas prepared above and further methylaluminoxane were added.
5 mg of atoms were charged in terms of Al atoms. Then, the temperature inside the polymerization system was raised to 45 ° C.
, Example51.5 × 10^-3Mmol, 50 ° C
For 0.5 hours. After polymerization,referenceWhen the same operation as in Example 1 was performed, 1-
The butene content is 1.7 mol%, the ethylene content is 0.6 mol%, and [η]
Is 3.1 dl / g, melting point is 122 ° C., boiling trichloroethylene Evaluation example   Propylene obtained in ExamplesBothThe heat sealability of the polymer was evaluated as follows.
It went to.Creating a film   0.1mm thick aluminum sheet and polyester sheet (Toray)
Co., Ltd., trade name Lumirror) and the thickness of 15cm x 15cm square
A 50 μm polyimide resin (manufactured by DuPont, Kapton trade name) sheet is placed in this order.
0.8 g of the sample was placed on the center (the cut-out portion). Then Lumi   Place the sample sandwiched between the above press plates in a hot press at 200 ° C for about 5 minutes
After preheating for a period of time, pressurization (20 kg / cm^Two・ G
) Repeat the depressurization operation three times. Then finally 150kg / cm^Two・ Pressurize to G for 5 minutes
Heat under pressure. After depressurization, the press plate was taken out of the press machine, and the crimped portion was kept at 30 ° C.
100kg / cm^TwoAfter pressurizing and cooling for 4 minutes with
And take out the sample. The obtained film has a uniform thickness of 50 to 70 μm.
The used film is used as the following measurement film.Measurement of heat seal strength   The film prepared by the method described above is placed in a constant-humidity layer at 50 ° C. for 2 days (Agent
G). When aging, be careful not to touch each other.
Put paper on the surface. Turn the aged film into a 15mm-wide chunk
Cut and stack the two pieces, and then add two pieces with a thickness of 0.1 mm to Teflon
Heat sealing is performed on the film. Heat seal is heat sealer heat
Keep the lower temperature of the plate constant at 70 ° C and change only the temperature of the upper part of the hot plate in 5 ° C increments as appropriate. Do it. Heat sealing pressure is 2kg / cm^TwoAnd the heat sealing time is 1 second.
The rule width is 5 mm (therefore, the sealing area is 15 mm × 5 mm).   Heat-sealing strength is a heat-sealed film at each of the above heat-sealing temperatures.
The peel strength of the rubber was determined by conducting a tensile test at a tensile speed of 30 cm / min.
You. (See FIG. 3).   The peel strength at each heat sealing temperature in increments of 5 ° C was determined by the method described above, and the heat
The blot of seal temperature vs. peel strength is connected by a curve. 800 g / 15 based on this curve
The heat-sealing temperature at which the peel strength is in cm is defined as the complete heat-sealing temperature.
).   Propylene system obtained in each exampleBothTable 1 shows the complete heat sealing temperature of the polymer.
did.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing the relationship between the propylene content and the melting point of the propylene copolymer according to the present invention. Note and straight line A shows the relationship between the propylene content and the melting point of the propylene copolymer according to the present invention in FIG. 1, line B is the relationship between the propylene content and the melting point of the conventional propylene copolymer Is shown. Yet a 2-4 is a diagram showing a heat-sealing property evaluation method of the propylene-based copolymer of the present invention. FIG. 5 is a flowchart in producing the propylene-based copolymer according to the present invention.

Claims (1)

Claims 1) (A) 90-99 mol% of a propylene component and 0-10
Α-olefin component derived from α-olefin having 4 to 20 carbon atoms in an amount of 0 to 10 mol%, and (B) a melting point [Tm measured by a differential scanning calorimeter. ] is, 90 <Tm <145 -5.5 in the range of (100-P) (P in the formula is a propylene component content in the co-polymer (mol%)), (C) of 135 ° C. in decalin in the range the intrinsic viscosity [eta] of 0.5~6dl / g measured, a heat-sealing material made of propylene copolymer is (D) a boiling trichlorethylene-insoluble content of 5 wt% or less.