JPH11279345A - Matte, crystalline propylene copolymer composition heat-sealable at low temperature - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a crystalline propylene copolymer compsn. which is heat- sealable and is useful for producing a matte film, sheet, or laminate thereof. SOLUTION: This compsn. comprises (A) 20-65 wt.% propylene/ethylene copolymer having an ethylene content of 1-5 wt.%, (B) 20-65 wt.% propylene/ ethylene/4-8C α-olefin terpolymer having an ethylene content of 1-5 wt.% and a 4-8C α-olefin content of 6-15 wt.%, and (C) 15-60 wt.% ethylene/4-8C α-olefin copolymer having a 4-8C α-olefin content of 6-50 wt.%, the sum of 4-8C α-olefin contents in the compsn. being 2.4-15 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a crystalline propylene polymer composition which is heat sealable and useful for producing matte films, sheets or laminates thereof, and to a process for producing this composition.

[0002]

2. Description of the Related Art A crystalline copolymer of propylene and another α-olefin (mainly ethylene, 1-butene or both) or a mixture of such a copolymer and another olefin polymer is heat-sealed. It is known in the art to use as a material having These crystalline copolymers can be used to convert propylene in the presence of a coordination catalyst in trace amounts of other α-
Obtained by polymerizing with an olefin comonomer. The polymerized comonomer units are statistically distributed in the resulting copolymer and the melting point of this copolymer is lower than that of crystalline propylene homopolymer. However, since these polymers form a homogeneous phase in a substantially molten state, films and sheets obtained from this polymer exhibit high gloss. On the other hand, for example, a composition of a propylene homopolymer and an ethylene-propylene copolymer obtained by copolymerizing a large amount of ethylene (a so-called propylene ethylene block copolymer) that does not form a homogeneous phase in a molten state was formed into a film. At times, the transparency of the film is significantly lost, which is inconvenient for the purpose of providing a film on which a printed surface can be displayed and contents can be confirmed. Furthermore, a composition (sequential copolymer) of a copolymer of propylene homopolymer and ethylene and butene is disclosed in Japanese Patent Publication No. 7-42366. Although this composition is an improvement in the transparency of the propylene-ethylene block copolymer, the low-temperature heat sealability is insufficient, and these compositions have a relatively low soluble content in cold xylene. Because of the large number, the use is limited from the viewpoint of hygiene, and it is considered that an undesirable result is given when printing is performed on the film surface.

Furthermore, preparing a mixture by mechanical melt blending is more expensive than preparing a mixture or blend in a polymerization in terms of time and energy to obtain a homogeneous dispersion of the components (eg, For melt extrusion and pelletization). In addition, preparation by mechanical melt blending is a process in which the polymer composition has a thermal history as indicated by some degree of pyrolysis (which is avoided in the case of polymer compositions prepared during polymerization). Can give things.

[0004]

SUMMARY OF THE INVENTION Accordingly, the present invention is directed to a crystalline propylene polymer composition which is heat sealable and useful for producing matte films, sheets or laminates thereof, and the preparation of such compositions. Give way.

[0005]

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a specific propylene / ethylene copolymer, a specific propylene / ethylene and C ₄ -C ₈ α- By blending a copolymer with an olefin, and a copolymer of a specific ethylene and a C _{4 to} C ₈ α-olefin, a low heat seal initiation temperature is exhibited,
Low content of the fraction soluble in n-hexane at 50 ° C.,
The inventors have found that a composition that gives a matte film can be obtained, and arrived at the present invention. That is, the present invention provides the following components (A) to (C): (A) a copolymer of propylene and ethylene containing 1 to 5% by weight of ethylene (component (A)),
20-65% by weight, (B) propylene,
A copolymer of ethylene and C ₄ -C ₈ alpha-olefin, the ethylene content is 1-5 wt%, C ₄ -C
_A copolymer having an 8α-olefin content of 6 to 15% by weight (component (B)); 20 to 65% by weight; and (C) a copolymer of ethylene and a C _{4 to} C ₈ α-olefin. hand,
C ₄ -C ₈ alpha-olefin content is 6 to 50 wt% copolymer (component (C)), 15 to 60 wt%, a crystalline propylene copolymer composition comprising, said composition The total content of C ₄ -C ₈ α-olefins in the mixture is 2.4 to 15
The present invention relates to a crystalline propylene copolymer composition characterized in that it is a weight percent.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The C ₄ -C ₈ α-olefin used in the crystalline propylene copolymer composition of the present invention includes a C ₄ -C ₈ α-olefin.
Various α-olefins can be used without particular limitation as long as they have eight α-olefins. As such an α-olefin, preferably, 1
-Butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like. As the α-olefin, 1-butene is particularly preferred. The component (A) used in the crystalline propylene copolymer composition of the present invention contains 1 to 5% by weight of ethylene, preferably 2 to 5% by weight.
Contains 4% by weight. The component (A) is blended in an amount of 20 to 65% by weight, preferably 25 to 50% by weight based on the weight of the composition.

[0007] The component (B) used in the crystalline propylene copolymer composition of the present invention comprises 1 to 5% by weight of ethylene,
Preferably, it contains 2 to 4% by weight. Also, component (B)
It is C ₄ -C ₈ alpha-olefins from 6 to 15% by weight, preferably contains 8 to 14 wt%. Component (B) comprises from 20 to 65% by weight, preferably based on the weight of the composition,
30 to 50% by weight is blended. Components used in the crystalline propylene copolymer composition of the present invention (C) is, C ₄ -C ₈
6 to 50% by weight of α-olefin, preferably 10 to 4%
It contains 0% by weight. The component (C) is blended in an amount of 15 to 60% by weight, preferably 20 to 35% by weight based on the weight of the composition. In the crystalline propylene copolymer composition of the present invention, preferably, the intrinsic viscosity of the cold xylene-soluble component at 25 ° C. is 0.8 dl / g or more, preferably 1.0 dl / g, and the upper limit is For example, it is appropriate to be 4.0 dl / g. If the intrinsic viscosity of the cold xylene-soluble component is less than 0.8 dl / g, it is not preferable from the viewpoints of productivity of the composition, transparency of the obtained product, bleeding of low molecular weight components, and the like. From the viewpoint of hygiene in use in the food field, the amount of the cold xylene-soluble component is, for example, 30% based on the weight of the composition.
It is suitable that the content is not more than 25% by weight, preferably not more than 25% by weight.

In the crystalline propylene copolymer composition of the present invention, the total content of C ₄ -C ₈ α-olefin is 2.4 to 15% by weight, preferably 5 to 15% by weight.
It is appropriate that The crystalline propylene copolymer composition of the present invention preferably has the following properties. (1) Melting point: about 126-147 ° C., (2) Sealing onset temperature: 90-114 ° C., (3) Fraction soluble in n-hexane at 50 ° C .: less than 5.5% by weight of the composition, particularly preferred Is 5.0% by weight
Less than is appropriate. The amount soluble in n-hexane is 5.5
When the amount is less than the weight%, it is preferable in terms of hygiene in use in the food field.

[0009] In the above characteristics, "seal start temperature" is abbreviated as SIT, and in some cases, is also referred to as "heat seal temperature". SIT is the minimum temperature required to seal one polypropylene film layer to one film layer made from the crystalline propylene copolymer composition of the present invention. Thus, when a load of 150 g is applied to this multilayer film, the seal does not break, ie,
The film layers do not separate at the seal. The crystalline propylene copolymer composition of the present invention can be prepared by sequentially polymerizing monomers in the presence of a stereospecific Ziegler-Natta catalyst. Stereospecific Ziegler-Natta catalysts are solid catalyst components comprising a titanium compound having at least one titanium-halogen bond and an electron donor compound, both supported on an active form of magnesium halide. In the stereospecific Ziegler-Natta catalyst, an organic aluminum compound such as an aluminum alkyl compound is used as a co-catalyst together with a solid catalyst component. The stereospecific Ziegler-Natta catalyst used in the present invention has an isotactic index of greater than 90%, preferably 95%
Polypropylene having a higher isotactic index can be produced. Said stereospecific Ziegler-Natta catalysts are well known in the patent literature. For example, US Pat. No. 4,339,054 and European Patent No. 45,9
Particular preference is given to the catalysts described in U.S. Pat.

Other examples of stereospecific Ziegler-Natta catalysts are described in US Pat. Nos. 4,472,524 and 4,473,660. In the solid catalyst component used in the stereospecific Ziegler-Natta catalyst, as the electron donor, ethers, ketones, lactones, compounds containing N, P and / or S atoms, and monocarboxylic acids, Compounds selected from the group consisting of dicarboxylic acid esters and the like can be mentioned. Particularly preferred electron donors are diisobutyl phthalate and phthalates such as dioctyl phthalate, diphenyl phthalate and benzyl butyl phthalate; diisobutyl malonate and malonates such as diethyl malonate; alkyl pivalates, Aryl pivalate; alkyl maleate, cycloalkyl maleate, aryl maleate; alkyl carbonate, aryl carbonate, for example, diisobutyl carbonate, ethylphenyl carbonate, diphenyl carbonate; succinic acid such as monoethyl succinate and diethyl succinate Esters and the like. Other electron donors that are particularly suitable are of the formula:

[0011]

Embedded image (Wherein, R ¹ and R ² are identical or different, located at C ₁ ~ ₁₈ alkyl, C ₃ ~ ₁₈ cycloalkyl or C ₇ ~ ₁₈ aryl group; R ³ and R ⁴ They are identical or different, are 1,3-diethers represented by a C ₁ ~ ₄ alkyl group.). Ethers of this type are described in published European patent application 361 493 corresponding to U.S. Pat. No. 5,095,153. As the diether compound,
Representative examples include, for example, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane ,
2-isopropyl-2-isoamyl-1,3-dimethoxypropane and the like.

The catalyst component is prepared according to various methods.
Can be done. For example, magnesium halide
(Anhydrous form containing less than 1% water), titanium compound and
Child-providing compounds produce magnesium halide activation
Can be ground together under shearing conditions. Next, the pulverized material is
For example, at temperatures of 80-135 ° C., excess TiCl
_FourAt least once, and then chloride ions are washed
Remove hydrocarbons (e.g. hexane) until
Wash repeatedly with recoat. According to another method,
Water magnesium halide is pre-activated according to known methods.
And then, for example, at 80-135 ° C., an electron donor.
Excess TiCl with compound dissolved_FourAnd react with. T
iCl_FourProcessing may be repeated in some cases.
And the solid is washed with hexane or another
Reaction TiCl_FourEliminate traces of According to another method,
MgCl_TwoNROH adducts (especially spheroidal particles)
Wherein n is generally 1-3 and ROH is ethanol
Solution, butanol or isobutanol) in a solution
Excess TiCl with electron donor compound in it_FourAnd anti
Respond. The temperature is generally between 80C and 120C.
The solid is then isolated and the excess TiCl_FourAgain
After reacting, separate and remove all chloride ions.
And wash with aliquots of hydrocarbons. In another way
For example, magnesium alcoholate and chloro alcoholate
(Especially, as described in US Pat. No. 4,220,554)
Chloroalcoholate) produced according to the method
Operate under appropriate conditions to include electron donor compound in solution
Excess TiCl_FourAnd react with.

[0013] In the solid catalyst component, the titanium compound expressed as Ti is generally present in an amount of 0.5 to 10% by weight.
The amount of electron donor compound that remains fixed on the solid catalyst component is generally between 5 and 20 mol%, based on the magnesium dihalide compound. Titanium compounds that can be used to prepare the solid catalyst component are titanium halides and halogen alcoholates. Titanium tetrachloride is the preferred compound. Satisfactory results have been obtained with titanium trihalides, especially H
-TiCl ₃ , AA-TiCl ₃ , and TiC
It can also be obtained in the case of halogen alcoholates such as l ₃ OR (where R is a phenyl group). The reaction produces an active form of the magnesium halide. In addition to these reactions, other reactions are known in the literature, starting from magnesium compounds other than halides, for example magnesium carboxylate, which result in the formation of active magnesium halides. The active form of the magnesium halide in the solid catalyst component is such that there is no longer a maximum intensity reflection which appears on the spectrum of the non-activated magnesium halide (having a surface area of less than 3 m ² / g) in the X-ray spectrum of the catalyst component, Due to the fact that at certain locations there is a halo having a maximum intensity shifted with respect to the position of the maximum intensity reflection of the non-activated magnesium dihalide, or of the maximum intensity reflection that appears in the non-activated Mg halide spectrum. At least 30% more than
It can be recognized by the fact that it shows a large half width. The most active form is where the halo appears in the X-ray spectrum of the solid catalyst component. Of magnesium halide,
Magnesium chloride is the preferred compound. In the case of the most active form of magnesium chloride, the X-ray spectrum of the solid catalyst component shows a halo instead of a reflection appearing at a distance of 2.56 Å in the spectrum of the unactivated chloride.

The Al-alkyl compound used as a co-catalyst includes, for example, Al-trialkyl such as Al-triethyl, Al-triisobutyl, Al-tri-n-butyl, O or N atom, SO ₄ or SO ₃ Mention may be made of linear or cyclic Al-alkyl compounds containing two or more Al atoms linked to one another via groups. Examples of these compounds include:

[0015]

Embedded image(Where n is a number from 1 to 20)
I can do it. Furthermore, AlR_TwoOR 'compound (formula
Wherein R ′ is an aryl group substituted at one or more positions.
R is an alkyl group having 1 to 6 carbon atoms);
lR_TwoH compound (where R has the above-mentioned meaning) is used
it can. Al-alkyl compounds are generally Al / Ti
It is used in such an amount that the ratio is between 1 and 1000. External offering
Examples of electron donor compounds that can be used as donors include Al
Aromatic acid esters such as kilbenzoate, especially
At least one Si-OR bond (R is a hydrocarbon group
Compound containing 2,2,6,6-tetra
Methyl piperidine or 2,6-diisopropylpiperidi
And the like. Examples of the silicon compound include (t-
Butyl)_Two-Si (OCH_Two)_TwoAnd (cyclohexyl
Le)_TwoSi (OCH_Three)_Two, (Phenyl)_TwoSi (OC
H_Three)_Two, (Cyclopentyl) _TwoSi (OCH_Three)_Twoetc
Is mentioned. 1,3-diethers having the above formula also
It can be used to advantage. An internal donor is used for these diethers.
If one, the external donor can be omitted.

The polymerization can be carried out, for example, in at least three sequential steps. In this case, components (A), (B) and (C) are separated in a separate subsequent step, except in the first step, operating in the presence of the polymer formed in the previous step and the catalyst used in the previous step. Generate. The catalyst is added only in the first step. However, the activity is such that it is still active in all subsequent steps. Thus, no catalyst is added in subsequent steps. Component (A),
The order of generating (B) and (C) is not particularly specified. The polymerization can be carried out in the liquid phase according to known techniques in the presence or absence of an inert diluent, or in the gas phase, or can be carried out continuously or batchwise by a mixed liquid-gas technique. Preferably, the process is performed in the gas phase. 3
The reaction time and reaction temperature in the process are not particularly limited. However, the temperature is preferably between 20 and 100C.
Regulation of the molecular weight can be effected by using known regulators, in particular hydrogen. The stereospecific Ziegler-Natta catalyst can be pre-contacted with a small amount of α-olefin (pre-polymerization).

Prepolymerization improves both the performance of the catalyst and the morphology of the resulting polymer. When the components (A), (B) and (C) are produced directly by sequential polymerization, the crystalline propylene copolymer composition of the present invention may be in the form of non-extruded particles or, in other words, as polymerized Particles, ie
In the form of particles from a polymerization reactor. The components (A) and (B) in these particles are optimally dispersed therein, and therefore the crystalline propylene copolymer composition of the present invention provides a better dispersion of the copolymer components. Can be used directly for the production of heat-sealable films, sheets or laminates without resorting to melt blending to obtain Preferred non-extruded compositions have a diameter of 0.5 to 4.5 mm and more preferably a narrow particle size distribution (i.e. at least 90% of said particles).
% Has a diameter of 0.5 to 3.5 mm) in the form of spherical or spheroidal particles. Such spherical particles are
For example, it can be obtained using a catalyst described in U.S. Pat. No. 4,472,524. The crystalline propylene copolymer composition of the present invention may contain additives such as an antioxidant, a light stabilizer, a heat stabilizer, a coloring agent, and a filler.

As mentioned above, the crystalline propylene copolymer composition of the present invention is particularly useful for producing films, sheets or laminates. In this specification, a film is defined as a sheet having a thickness of, for example, less than 100 μm. On the other hand, the sheet and the plate have, for example, a thickness of 100
μm or more. In the laminate of the present invention, at least one of the layers comprises the composition of the present invention alone or
For example, it is made by blending with polyethylene or propylene homopolymer. In the case of a laminate, each layer not containing the composition of the present invention comprises another polyolefin polymer,
For example, it can consist of polyethylene or other α-olefin homopolymer. Generally, the laminates of the present invention can be manufactured by known techniques such as extrusion, calendaring, and the like. Specific examples of films containing the composition of the present invention are described below in the SIT test.

[0019]

EXAMPLES The present invention will be described in more detail with reference to examples and the like, but these examples do not limit the scope of the present invention at all. Specific embodiments of the sequential polymerization method composition and specific embodiments of the sequential polymerization method for producing them are illustrated. Preparation of the solid catalyst component: 48 g of anhydrous magnesium chloride, 77 g of anhydrous ethyl alcohol and 830 ml of kerosene are introduced at room temperature under inert gas into a 2 liter autoclave equipped with a turbine stirrer and a drawing tube. The contents of the autoclave are heated to 120 ° C. with stirring, thus forming an adduct between MgCl ₂ and the alcohol, which adduct remains molten and dispersed in the kerosene. A nitrogen pressure of 15 atm is maintained in the autoclave. The autoclave draw tube is externally heated to 120 ° C. by means of a heating jacket, which has an inner diameter of 1 mm and is 3 m from one end of the heating jacket to the other. The dispersion is then flowed through the tube at a speed of about 7 m / sec. At the outlet of the tube, the dispersion is collected under stirring in a 5 liter flask (the flask contains 2.5 liters of kerosene and is externally cooled with a jacket maintained at an initial temperature of -40 DEG C.). . The final temperature of the dispersion is 0 ° C. The spherical solid product that makes up the dispersed phase of the dispersion is allowed to settle, then is filtered, and the solid is washed with an aliquot of hexane,
Separate by drying. All of these steps are performed in a nitrogen gas atmosphere. MgCl ₂ .3C ₂ H ₅ OH adduct 13 in the form of solid spherical particles with a maximum diameter of less than 50 μm
0 g are obtained. Drying the solid adduct under vacuum for 2 hours,
After the drying is completed, the weight is 105 g. The solid product is heated to a temperature of about 60 ° C. in a stream of nitrogen to partially remove the alcohol from the adduct, thereby reducing the MgCl ₂ .2C _2.
The H ₅ OH adduct is obtained. Then, using this adduct, a solid catalyst component is prepared as follows.

In a 1 liter glass flask equipped with a condenser, mechanical stirrer and thermometer, 625 ml of TiCl _{4 was} added.
Then, 25 g of MgCl ₂ .2C ₂ H ₅ OH adduct
Are introduced under stirring at 0 ° C. in an atmosphere of anhydrous nitrogen. The contents of the flask are heated to 100 ° C. in one hour. Temperature 40
When the temperature is reached, 9 mmol of diisobutyl phthalate are introduced into the flask. After maintaining the temperature at 100 ° C. for 2 hours, the contents are allowed to settle and then the liquid is siphoned. Add 550 ml of TiCl ₄ and heat to 120 ° C. for 1 hour. The contents are then allowed to settle and the liquid is siphoned. The solid residue is then dried at 60 ° C. in anhydrous hexane 200.
Wash 6 times with cc and 3 times at room temperature. The product is a solid catalyst component. Prior to introduction into the catalyst system and the prepolymerization polymerization reactor, the solid catalyst component is treated at about -5 ° C for about 5 hours.
Contact with TEAL and DCPMS in a weight ratio of aluminum triethyl (TEAL) / dicyclopentyldimethoxysilane (DCPMS) equal to and the TEAL / Ti molar ratio of the solid catalyst component is equal to 65 for 5 minutes. The catalyst system is then subjected to a prepolymerization by maintaining it in suspension in liquid propylene at 20 ° C. for about 20 minutes before introducing it into the first polymerization reactor.

Example 1 In a first gas phase polymerization reactor, a prepolymerization catalyst system, hydrogen (used as molecular weight regulator) and propylene and ethylene monomers in gaseous state are fed in a continuous, constant stream. A propylene / ethylene random copolymer [component (A)] was produced. Table 1 shows the polymerization conditions, the molar ratio of the reactants, and the composition of the obtained copolymer. 40 of the total composition
Wt% of the copolymer produced in the first reactor was discharged in a continuous stream and after unreacted monomers were expelled, the hydrogen and gaseous state were fed to the second gas phase reactor in the continuous stream. propylene,
It was introduced with a constant quantitative stream of ethylene and 1-butene monomer. The propylene / ethylene / 1-butene terpolymer [component (B)] produced in the second reactor was produced in an amount equal to 33% by weight, based on the total composition. Table 1 shows the conditions and the molar ratio of the reactants in each example. After discharging the copolymer composition produced in the second reactor in a continuous stream and expelling unreacted monomers, ethylene and hydrogen in a gaseous state were mixed with the third gas phase reactor in a continuous stream. -Introduced together with a quantitative, constant stream of butene monomer. The ethylene / 1-butene copolymer [component (C)] produced in the third reactor is produced in an amount equal to 27% by weight, based on the total composition. The polymer composition leaving the third reactor was subjected to a steam treatment to remove unreacted monomers and volatiles, and then dried. Table 1
Shows the composition of the resulting composition and some of its physical and chemical properties, which particularly indicate the application performance required for the composition of the present invention. From the data in Table 1, in the composition of Example 1, the component (A) was ethylene (C ₂ −).
2.9% by weight, and the component (B) is ethylene (C ₂ −).
It is estimated that the composition contains 3.23% by weight and 8.8% by weight of butene (C ₄ −), and the component (C) contains 33% by weight of butene (C ₄ −).

Comparative Example 1 Polymerization was carried out without using the third reactor. That is, Comparative Example 1 was conducted except that the ethylene-butene copolymer of the component (C) was not used.
Was prepared according to the method of Example 1 and thus in both the first reactor and the second reactor an amount of propylene / ethylene copolymer equal to 40% by weight each, 60% by weight Propylene / ethylene / 1 in an amount equal to
-A butene terpolymer was obtained. Table 1 shows the polymerization conditions, the molar ratio of the monomers, and the characteristics of the obtained composition. The data shown in Table 1 was obtained by using the following analytical method.

[Mole ratio of feed gas] Measured by gas chromatography. [Ethylene and 1-butene content of polymer] Measured by IR spectroscopy. [MFR] Measured in accordance with JIS K6758. [Melting temperature (Tm) and crystallization temperature (Tc)] DSC
(Differential scanning calorimetry). [N-Hexane Extractable] A 100 μm-thick film test piece of the composition was added to an excess of n-hexane in an autoclave for 5 minutes.
Suspend in excess n-hexane at 0 ° C. for 2 hours, evaporate n-hexane from the extract, and weigh dry residue.

[Intrinsic viscosity of cold xylene-soluble component] Excess o
After completely dissolving the composition in xylene at 135 ° C., stand at 25 ° C. Thereafter, the mixture is quickly filtered, the filtrate is recovered, and o-xylene is evaporated to obtain a dry residue.
The intrinsic viscosity of the obtained residue is measured at 135 ° C. of tetralin. [Seal Onset Temperature (SIT)] Production of Film Specimens Several films having a thickness of 30 μm are produced by extruding each test composition at about 250 ° C. For the measurement of SIT, a series of seal peeling tests were performed for each film test piece, and for each test, two test pieces of 10 cm side and 1.5 cm width were overlapped, and the stacked test pieces were tested by Tester Sangyo Co.
Seal using a heat sealer. The sealing time is 1 second at a pressure of ² kg / cm ² . The seal temperature is increased by 5 ° C. from one test sample to the next. In each test, the unsealed longitudinal end of the sample is attached to a tensile tester to determine the force required for peeling. 1
The minimum sealing temperature that did not break or separate under a load of 50 g is thus determined.

[Gloss] Gloss was measured at an incident angle of 60 degrees in accordance with JIS Z8741.

[0026]

Table 1 Example 1 Comparative Example 1 First reactor temperature, ° C 65 65 pressure, kg / cm ² 16 16 H ₂ / C _3- , mol 1.45 1.45 H ₂ / C _2- , mol 33.53 33.53 C _{^{2 - / C 2 - + C}} 3 -, mol _{^{0.04 0.04 C 4 - / C 4}} - + C 3 -, mol --- --- resulting polymer MFR / L, g / 10 min 5.9 5.9 C ₂ ^-, wt% 2.9 2.9 C ₄ ^-, wt% --- second reactor temperature, ° C. 65 65 ^{pressure, kg / cm 2 16 16 H} 2 / C 3 -, mol ^{_{0.10 0.01 H 2 / C 2 -}} , mol 2.73 2.73 C ₂ ⁻ / C ₂ ⁻ + C ₃ ⁻ , mol 0.04 0.04 C ₄ ⁻ / C ₄ ⁻ + C ₃ ⁻ , mol 0.14 0.14 Polymer obtained MFR / L, g / 10 min 5.9 5.9 C ₂ ⁻ , wt% 3.1 3.1 C ₄ ^-, wt% 5.3 5.3 third reactor temperature, ° C. 60 --- ^{pressure, kg / cm 2 7.7 --- H} 2 / C 2 -, mol _{^{0.04 --- C 2 - / C 2}} - + C ₄ ^-, mol 0.45 --- final composition MFR / L, g / 10 min 5.8 5.9 C ₂ ^-, wt% 19.7 3.1 C ₄ ^-, The amount% 12.0 5.3 Tm / Tc, (DSC) ℃ 139/93 143/91 SIT, ℃ 105 110 n- hexane extractables wt% 4.9 3.6 cold xylene-soluble component having an intrinsic viscosity of 1.3 1.1 Gloss 68 113

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 23/08 C08L 23/08 23/20 23/20

Claims (5)

[Claims] (A) a copolymer of propylene and ethylene containing 1 to 5% by weight of ethylene,
20 to 65 wt%, and (B) propylene, a copolymer of ethylene and C ₄ -C ₈ alpha-olefin, the ethylene content is 1-5 wt%, C ₄
Copolymer -C ₈ alpha-olefin content is 6 to 15% by weight, a copolymer of 20 to 65% by weight, and (C) ethylene and C ₄ -C ₈ alpha-olefin,
Copolymer C ₄ -C ₈ alpha-olefin content is 6 to 50 wt%, a crystalline propylene copolymer composition comprising 15 to 60 wt%, a, C ₄ -C in the composition ₈ α
-A crystalline propylene copolymer composition having a total olefin content of 2.4 to 15% by weight. 2. The method of claim 1, wherein the C ₄ -C ₈ α-olefin is selected from the group consisting of 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and 1-octene. Composition. 3. A film, sheet or laminate formed from the crystalline propylene copolymer composition according to claim 1. 4. A propylene and ethylene monomer is polymerized in a first step in the presence of a stereospecific catalyst supported on an active form of magnesium dihalide, and the propylene, ethylene and α-olefin monomer are polymerized. 2. The production of a crystalline propylene copolymer composition according to claim 1, characterized in that it is polymerized in at least one further successive step in the presence of the product formed in the previous step and the catalyst used. Method. 5. The method according to claim 4, wherein the polymerization step is performed in a gas phase.