JPH11263812A - Random propylene copolymer and film and metallized film made therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a copolymer which can give a film having a good balance between rigidity and heat sealability and a reduced content of solubles in a solvent by selecting a copolymer having a specified relationship between its melting point Tm and its flexural modulus FM and having a specifically arranged contiguous of two monomers comprising propylene and an α-olefin other than propylene. SOLUTION: This copolymer comprises 90.0-99.9 wt.% propylene and 10.0-0.1 wt.% α-olefin other than propylene, satisfies the relationship: 20,000>=218×Tm-FM (wherein Tm is the melting point as measured with a differential scanning colorimeter, and FM is the flexural modulus as measured according to JIS K 7203 and has a CSD of 3.5 or below (wherein CSD is represented by the equation: CSD=4[OO]×[PP]/[OP]<2> (wherein [OO] is the molar fraction of chains of an α-olefin other than propylene in the copolymer; [PP] is the molar fraction of propylene chains; and [OP] is the molar fraction of chains composed of propylene and an α-olefin other than propylene).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a film having excellent rigidity, heat sealability, blocking resistance and deposition strength.
The present invention relates to a metal-deposited film comprising the same, and a propylene random copolymer from which they can be obtained.

[0002]

2. Description of the Related Art Films made of a crystalline propylene polymer have been used in the fields of films and containers for food packaging because of their excellent strength, heat resistance, rigidity and transparency. However, when heat-sealing using a film made of a crystalline propylene-based polymer, a film made of a crystalline propylene-based polymer has a high heat-sealable temperature, and its application temperature range is narrow, and the heat-sealing property is poor. In addition, there arises a problem that workability such as sealing and packaging is deteriorated. For this reason, various methods for improving the heat sealing property of a film made of a crystalline propylene-based polymer have been conventionally proposed.

As one of the methods for improving such heat sealing properties, it is known to use a propylene random copolymer obtained by copolymerizing propylene and an α-olefin other than propylene such as ethylene. However, in such a propylene random copolymer, in order to facilitate heat sealing at low temperatures, it is necessary to copolymerize a large amount of α-olefins other than propylene, and accordingly, organic substances such as oils and fats and solvents are required. Ingredients that can be easily extracted increase, resulting in hygiene problems. Also,
There are problems such as a decrease in blocking resistance and difficulty in obtaining a film having high rigidity.

As described above, the conventional propylene random copolymer has insufficient heat sealing properties and blocking resistance, and it is difficult to control the balance between rigidity and heat sealing properties. In addition, since it contains components that can be extracted into fats and oils and solvents, there is a limitation on use in packaging materials such as food and medicine for hygiene.

As a propylene random copolymer which solves such problems, a propylene random copolymer characterized in that two consecutive monomer units composed of propylene and an α-olefin other than propylene have a specific sequence. A polymer is disclosed in JP-A-9-59321. However, the heat sealability and the blocking resistance are not yet sufficient, and there is room for improvement. In addition, the amount of solvent-soluble components has not been sufficiently reduced,
In particular, the drawback that a solvent-soluble component is large at room temperature or high temperature has not been solved. Also, the rigidity is insufficient.

[0006] Further, as a problem of the film made of the propylene random copolymer, there is a problem that the adhesion strength between the film and the deposition layer when metal deposition is performed (hereinafter referred to as deposition strength) is low. That is, the film may be used in a form in which a metal such as aluminum is vapor-deposited for the purpose of blocking light or oxygen, but if the vapor-deposition strength is insufficient, the metal is used in a vapor-deposited form. It becomes difficult. For this reason, to reduce the amount of additives used or to use specific additives in order to improve the vapor deposition strength, although some effects are seen, the vapor deposition strength is sufficiently improved It is hard to say that it is.

[0007]

Therefore, an object of the present invention is to provide a good balance between rigidity and heat sealing property.
Excellent blocking resistance, low solvent-soluble content, film with few restrictions on applications, good balance between rigidity and heat sealability, excellent blocking resistance, low solvent-soluble content, and excellent vapor deposition strength To provide a metal-deposited film and a propylene random copolymer from which the metal-deposited film can be obtained.

[0008]

In view of the above situation, as a result of intensive studies, it has been found that the melting point Tm and the flexural modulus FM satisfy a specific relationship, and that two consecutive monomers comprising propylene and an α-olefin other than propylene are used. Propylene random copolymer having a specific arrangement of body units has a good balance between rigidity and low-temperature heat sealability, has excellent blocking resistance, excellent vapor deposition strength, and has low solvent solubility. Thus, the present invention was completed.

That is, the propylene random copolymer of the present invention comprises 90.0 to 99.9% by weight of propylene,
Melting point T composed of 10.0 to 0.1% by weight of an α-olefin other than propylene and measured by a differential scanning calorimeter
m and curvature modulus FM measured according to JIS K7203
Satisfies the relationship of the following formula (1): 20,000 ≧ 218 × Tm-FM (1) and the following formula (2) (where [OO] is an α-olefin other than propylene in the propylene random copolymer) -Mole fraction of α-olefin chains other than propylene,
[PP] is the molar fraction of propylene-propylene chains in the propylene random copolymer, and [OP] is α- other than propylene in the propylene random copolymer.
A CSD value defined by an olefin (propylene) -propylene (which represents a mole fraction of an olefin other than propylene) chain is 3.5 or less. CSD = 4 [OO] × [PP] / [OP] ² (2)

[0010] The film of the present invention is characterized by comprising the above-mentioned propylene random copolymer. Also,
The metal-deposited film of the present invention is obtained by depositing a metal and / or an oxide thereof on the film.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The propylene random copolymer of the present invention is a random copolymer of propylene and an α-olefin other than propylene. As the α-olefin other than propylene, α-olefins such as ethylene, 1-butene, 1-pentene, 1-hexene and 1-octene can be used.

The propylene random copolymer of the present invention has a propylene content of 90.0 to 99.9% by weight.
, Preferably 93.0 to 99.5% by weight, more preferably 95.0 to 99.0% by weight, and particularly preferably 95.0 to 98.5% by weight. If the propylene content is less than 90.0% by weight, the heat resistance, rigidity and blocking resistance of the resulting film will be insufficient, and the solvent-soluble content will increase, thereby limiting the usable applications. Also,
When the propylene content exceeds 99.9% by weight, the heat sealability is reduced. Here, the propylene content is ¹³ C-
It can be measured according to a known method such as NMR.

The propylene random copolymer of the present invention comprises:
Melting point Tm (° C.) measured by a differential scanning calorimeter;
Flexural modulus FM (kg measured in accordance with IS K7203
/ Cm ² ) satisfies the above equation (1). When the melting point Tm and the flexural modulus FM do not satisfy this relationship, the solvent-soluble content increases, and further, the heat sealability and the blocking resistance of the obtained film decrease. In addition, when metal is deposited, the deposition strength is reduced. The value of 218 × Tm-FM on the right side of the above equation (1) is preferably 19,50.
0 or less, more preferably 19,000 or less, and most preferably 18,700 or less.

The flexural modulus FM measured according to JIS K7203 is 1000 kg / cm ² or more,
It is preferably at least 2000 kg / cm ² , more preferably at least 3000 kg / cm ² . Curvature modulus FM is 1
If it is less than 000 kg / cm ² , the resulting film has reduced blocking resistance and vapor deposition strength, and the solvent-soluble content increases.

The melting point Tm measured by a differential scanning calorimeter is 90 to 150 ° C., preferably 100 to 150 ° C.
It is 145 ° C, more preferably 110-140 ° C.
When the melting point Tm is less than 90 ° C., the blocking resistance decreases and the solvent-soluble content increases. When the melting point Tm exceeds 150 ° C., the heat sealability is reduced.

Further, the propylene random copolymer of the present invention has a CSD value defined by the above formula (2) of 3.5 or less, preferably 3.0 or less, more preferably 2.0 or less. . When the value of CSD exceeds 3.5, the solvent-soluble content of the obtained film increases, and the heat sealing property,
The blocking resistance decreases. In addition, when metal is deposited, the deposition strength is reduced. Here, the value of CSD is
This is a value indicating the copolymerizability of the propylene random copolymer, and the smaller the value, the better the copolymerizability.

In the above formula (2), [OO], [PP],
[OP] is an α-olefin other than propylene in the propylene random copolymer, an α-olefin chain other than propylene, a propylene-propylene chain, and an α-olefin other than propylene (propylene) -propylene (α other than propylene). -Olefin)
Represents the mole fraction of the chain. Here, [OO], [P
[P] and [OP] can be obtained from the measurement results of the ¹³ C-NMR spectrum. For example, “New Edition Polymer Analysis Handbook” (1995, published by Kinokuniya Bookstore) 616
Calculated according to the method described on page -619.

The weight average molecular weight Mw of the propylene random copolymer of the present invention is from 150,000 to 1,000,0.
00, preferably 170,000 to 70
0000, more preferably 190,000-500,
000, particularly preferably 220,000 to 440,00.
It is in the range of 0. Weight average molecular weight Mw of 150,000
If the amount is less than the above range, molding becomes difficult, and fumes and dust may occur. Weight average molecular weight Mw of 1,000,000
Exceeds, it becomes difficult to form a film, or
Molding at a higher temperature is required, which may result in coloration or reduction in strength of a molded article of the propylene random copolymer.

The xylene-soluble component Xs at 23 ° C. of the propylene polymer of the present invention is not particularly limited.
It is preferably at most 2.0% by weight. If the xylene-soluble content Xs exceeds 2.0% by weight, problems such as a decrease in blocking resistance, a decrease in rigidity, a decrease in heat sealability, and an increase in solvent-soluble content of the resulting film occur. The xylene-soluble content Xs is more preferably 1.6% by weight or less, further preferably 1.3% by weight or less, still more preferably 1.0% by weight or less, and particularly preferably 0.80% by weight or less. is there.

The boiling hexane soluble component Hs of the propylene polymer of the present invention is not particularly limited, but is preferably 5% by weight or less. Boiling hexane soluble Hs
If it exceeds 5% by weight, problems such as a decrease in blocking resistance of the obtained film, a decrease in rigidity, a decrease in heat sealability, and an increase in solvent-soluble components occur. The boiling hexane soluble content Hs is more preferably 4.0% by weight or less, and still more preferably 3.0% by weight or less.

Next, the method for producing the propylene random copolymer of the present invention will be described. The propylene random copolymer of the present invention can be produced by copolymerizing propylene with an α-olefin other than propylene in the presence of a metallocene catalyst comprising a metallocene compound and a cocatalyst component.

More specifically, the metallocene compound which can be used for producing the propylene random copolymer of the present invention is bis (2,3-dimethylcyclopentadienyl zirconium) dimethylsilane zirconium dichloride.
Bis (2,4-dimethylcyclopentadienyl zirconium) dimethylsilane zirconium dichloride, bis (2,3,5-trimethylcyclopentadienyl zirconium) dimethylsilane zirconium dichloride,
(Methylcyclopentadienyl) (η5-1-indenyl) dimethylsilane zirconium dichloride, (3-
t-butylcyclopentadienyl) (η5-1-indenyl) dimethylsilanezirconium dichloride, (3
-T-butylcyclopentadienyl) [4-t-butyl- (η5-1-indenyl)] dimethylsilanezirconium dichloride,

(Methylcyclopentadienyl) (η5-
9-fluorenyl) dimethylsilane zirconium dichloride, (3-t-butylcyclopentadienyl) (η
5-9-fluorenyl) dimethylsilane zirconium dichloride, bis (η5-1-indenyl) dimethylsilane zirconium dichloride, bis [2-methyl-
(Η5-1-indenyl)] dimethylsilane zirconium dichloride, bis [2,4,7-trimethyl- (η
5-1-indenyl)] dimethylsilane zirconium dichloride, bis [2,4-dimethyl- (η5-1-indenyl)] dimethylsilane zirconium dichloride, bis [2-ethyl- (η5-1-indenyl)] dimethylsilane zirconium Dichloride, bis [2-i
-Propyl- (η5-1-indenyl)] dimethylsilane zirconium dichloride,

Bis [2-methyl-4,5-benzo (η5
-1-indenyl)] dimethylsilane zirconium dichloride, bis [2-methyl-4-phenyl- (η5-
1-indenyl)] dimethylsilanezirconium dichloride, bis [2-methyl-4- (1-naphthyl)-
(Η5-1-indenyl)] dimethylsilane zirconium dichloride, bis [2-methyl-4- (2-naphthyl)-(η5-1-indenyl)] dimethylsilane zirconium dichloride, bis [2-methyl-4- (9 −
Anthracenyl)-(η5-1-indenyl)] dimethylsilane zirconium dichloride, bis [2-methyl-4- (9-phenanthryl)-(η5-1-indenyl)] dimethylsilane zirconium dichloride, bis [2-methyl-4 -(3,5-di-i-propylphenyl)-(η5-1-indenyl)] dimethylsilane zirconium dichloride,

Bis [2-methyl- (η5-1-indenyl)] methylphenylsilane zirconium dichloride, 1,2-bis (η5-1-indenyl) ethane zirconium dichloride, 1,2-bis [2-methyl-
(Η5-1-indenyl)] ethane zirconium dichloride, 1,2-bis [2,4-dimethyl- (η5-1
-Indenyl)] ethane zirconium dichloride,
1,2-bis [2,4,7-trimethyl- (η5-1-
Indenyl)] ethane zirconium dichloride, 1,
2-bis [2-ethyl- (η5-1-indenyl)] ethane zirconium dichloride, 1,2-bis [2-n
-Propyl- (η5-1-indenyl)] ethane zirconium dichloride, [2-ethyl- (η5-1-indenyl) [2-methyl- (η5-1-indenyl)] ethane zirconium dichloride,

1,2-bis (η5-9-fluorenyl)
Ethane zirconium dichloride, 2- (3-t-butylcyclopentadienyl) -2- (η5-1-indenyl) propane zirconium dichloride, 2- (3-t
-Butylcyclopentadienyl) -2- [4-t-butyl- (η5-1-indenyl)] propanezirconium dichloride, 2- (3-methylcyclopentadienyl) -2- (η5-9-fluorenyl) Propane zirconium dichloride, 2- (3-t-butylcyclopentadienyl) -2- (η5-9-fluorenyl) propane zirconium dichloride and the like can be used. Among them, at the 2-position and 4-position of the indenyl group, respectively, Those having an alkyl group and an aryl group are preferable, and in particular, [2-methyl-4,5-benzo (η5-1-indenyl)] dimethylsilane zirconium dichloride, [2
-Methyl-4-phenyl- (η5-1-indenyl)]
Dimethylsilane zirconium dichloride and [2-methyl-4- (1-naphthyl)-(η5-1-indenyl)] dimethylsilanezirconium dichloride are preferred.

The metallocene compound obtained by replacing zirconium with another metal such as titanium or hafnium;
Those obtained by replacing a chlorine atom with another halogen, a hydrogen atom, an amide group, an alkoxy group, a hydrocarbon group such as a methyl group or a benzyl group can be used without any limitation.

As the cocatalyst component used in the metallocene catalyst, any one can be used, and aluminoxane compounds such as methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and methylisobutylaluminoxane; Lewis acidic organic boron compounds; , −
Dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl)
Borate, triethyloxonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium [4- (trichlorosilyl) -2,3,5,6-
Tetrafluorophenyl] tris (pentafluorophenyl) borate, N, N-dimethylanilinium [4-
Non-coordinating anion-containing compounds such as (chlorodimethylsilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate. Among them, methylaluminoxane, N, N, -dimethylaniliniumtetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium [4- (chlorodimethylsilyl) -2, 3,5
[6-Tetrafluorophenyl] tris (pentafluorophenyl) borate is preferred. These can be used alone or in combination as needed.

As the metallocene catalyst, an organometallic compound such as an organoaluminum compound can be used for the purpose of activating the metallocene compound or removing impurities in the polymerization system. As the organic aluminum compound, trimethylaluminum, triethylaluminum, tri-n
Trialkylaluminums such as -propylaluminum, tri-n-butylaluminum, tri-i-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum; dialkylaluminum halides such as diethylaluminum dichloride and ethylaluminum dichloride; Alkyl aluminum dihalide; dialkyl aluminum hydride such as diisobutyl aluminum hydride; diethyl aluminum ethoxide, diethyl aluminum phenoxide and the like. Of these, trialkyl aluminum is preferred. These can be used alone or in combination as needed.

The amount of the co-catalyst component used with respect to the metallocene compound is not particularly limited. Usually, the amount of boron or aluminum contained in the co-catalyst component is 0 to 1 mol of the transition metal such as zirconium contained in the metallocene compound. .
0.1 to 100,000 mol, preferably 0.1
-10,000 mol, more preferably 1.0-3,
000 mol, particularly preferably 1.0 to 1,000 mo
1 range.

In the production of the propylene random copolymer of the present invention, a metallocene catalyst in which at least one of a metallocene compound and a cocatalyst component is supported on a fine particle carrier can be used. Examples of the fine particle carrier include metal oxides, metal halides, metal hydroxides, metal alkoxides, carbonates, sulfates, acetates, silicates, and organic polymer compounds. These can be used alone or in combination as needed.

Preferred among these fine particle carriers are silica, alumina, magnesium silicate such as mica and talc,
Silicates such as calcium silicate and sodium silicate; unsaturated polyhydric compounds containing hydroxyl groups, modified polyolefins graft-modified with unsaturated carboxylic acids and the like, ethylene-vinyl ester copolymer portions or completely saponified products.

The propylene random copolymer of the present invention comprises
It can be produced by copolymerizing propylene with an α-olefin other than propylene by an arbitrary polymerization method using the above catalyst or the like, specifically, bulk polymerization performed in liquid propylene, in the presence of an inert solvent. It can be produced by solution polymerization or slurry polymerization performed in a liquid phase, or gas phase polymerization performed in a gas phase monomer.

The polymerization temperature during the production of the propylene random copolymer of the present invention is not particularly limited, and is usually 35 to 35.
It is in the range of 95 ° C, preferably in the range of 50 ° C to 80 ° C. The pressure during polymerization is from normal pressure to 7 in polymerization in the liquid phase.
The range is generally 0 kg / cm ² , in the gas phase, normal pressure to 50 kg / cm ² , and an appropriate range can be selected in consideration of the properties of the propylene random copolymer to be obtained, productivity, and the like. . At the time of polymerization, the molecular weight can be adjusted by any means such as introduction of hydrogen and selection of temperature and pressure.

The propylene random copolymer of the present invention comprises
If necessary, antioxidants, chlorine supplements, heat stabilizers, antistatic agents, antifogging agents, ultraviolet absorbers, lubricants, antiblocking agents, nucleating agents, pigments, and other resins I don't care.

The propylene random copolymer of the present invention comprises
Films such as cast films and uniaxially or biaxially stretched films, packaging containers such as bottles, cups and trays, drawn yarns and fibers for non-woven fabrics, and various molded products such as sheets can be used. is there. Further, the film can be suitably used as a packaging material such as a heat sealant.

The film of the present invention may be either a non-stretched film or a stretched film. The stretched film may be uniaxially or biaxially stretched. The thickness of the film of the present invention is not limited.
１５０150 μm. Further, the film of the present invention may be subjected to a surface treatment such as a corona treatment, if necessary, or another film may be laminated.

The method for producing the film of the present invention is not particularly limited, and a known method can be employed without any limitation. For example, in the case of a non-stretched film, an additive such as an antioxidant, an ultraviolet absorber, and a heat stabilizer is added to a propylene random copolymer, and the mixture is kneaded with a single screw extruder or the like, and an extruder equipped with a T die or the like is attached. To form a film.
In the case of a stretched film, an additive such as an antioxidant, an ultraviolet absorber, and a heat stabilizer is added to the propylene random copolymer, and the mixture is kneaded with a single screw extruder or the like to produce a pellet. A film base is prepared using an extruder or the like, and the film base is subjected to continuous or simultaneous biaxial stretching using a stretching apparatus such as a tenter type or a pantograph type.

The metal-deposited film of the present invention can be obtained by depositing a metal and / or an oxide thereof on the film. There is no limitation on the method of vapor deposition, and a known method such as electrothermal heating, sputtering, ion plating, or ion beam can be used in a batch or continuous vacuum vapor deposition method. Examples of the metal used for vapor deposition include aluminum, gold, silver, copper, zinc, nickel, chromium, titanium, selenium, silicon, germanium, and tin, and preferably aluminum. The thickness of the deposited portion of the metal-deposited film thus obtained is usually in the range of several tens to several hundreds of angstroms.

If necessary, before the metal and / or its oxide is deposited, a known treatment for increasing the deposition strength can be performed on the film surface. Specifically, a method of performing a surface treatment such as a corona discharge treatment, a flame treatment, a plasma treatment, and an ozone treatment, and a method of applying a material having a high affinity for a metal such as a polyester-based, polyurethane-based, or epoxy-based resin to a film, Is mentioned.

[0041]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

The measurement and evaluation of the physical properties of the propylene random copolymer, the film comprising the same, and the metal-deposited film were performed by the following methods. (Measurement of propylene content) JNM-GSX manufactured by JEOL
The ¹³ C-NMR was measured by 400 and calculated from the result. (Measurement mode: proton decoupling method, pulse width: 8.0 μs, pulse repetition time: 3.0 s, number of integration: 20,000 times, measurement temperature: 120 ° C., internal standard: hexamethyldisiloxane, solvent: 1, 2, 2. 4-trichlorobenzene / benzene-d6 (volume ratio 3 /
1), sample concentration: 0.1 g / ml)

(Measurement of CSD) JNM-GS manufactured by JEOL Ltd.
The ¹³ C-NMR was measured by X400, and the results were calculated according to the method described in "New Edition of Polymer Analysis Handbook" (1995, published by Kinokuniya Publishing Co., Ltd.), pp. 616-619.

(Measurement of Curvature Modulus FM) Using a press molding machine, the propylene polymer was preheated at 230 ° C. for 5 minutes, pressurized at 60 kg / cm ² for 1 minute, and cooled at 30 ° C. for 5 minutes. Then, a test piece of 75 mm × 12.5 mm × 3 mm was prepared. After holding the test piece at 23 ° C. for 48 hours, Tensilon UTM250 manufactured by Toyo Baldwin Co., Ltd.
0, according to JIS K7203, distance between fulcrums 50.
The measurement was performed at a crosshead speed of 8 mm / min.

(Measurement of melting point Tm) PERKIN-ELM
It measured using the differential scanning calorimeter DCS7 made by ER. First, the temperature was raised to 230 ° C., and held for 5 minutes.
After cooling to −30 ° C. at 0 ° C./min, it was kept for 5 minutes. Thereafter, the melting peak when the temperature was raised again at 20 ° C./min was defined as the melting point Tm.

(Measurement of Weight Average Molecular Weight Mw) 1) Preparation of Calibration Curve 0.1% by weight of BHT (2,6-di-t-butyl-4-)
2 mg of each of three kinds of standard polystyrene samples (manufactured by Showa Denko KK) in 10 ml of 1,2,4-trichlorobenzene containing methylphenol) were dissolved in a dark place at room temperature for 1 hour. Thereafter, the elution time of the peak top was measured by GPC measurement. This measurement was repeated, and a calibration curve was prepared by a cubic approximation based on the molecular weights at a total of 12 points (molecular weight of 580 to 8.5 million) and the elution time at the peak top.

2) Measurement of weight average molecular weight Mw 5 ml of 1,2,2 containing 0.1% by weight of BHT was placed in a test tube.
4-Trichlorobenzene was taken, and about 2.5 mg of polypropylene (sample) was added thereto. After stoppering the test tube, the sample was dissolved in a constant temperature bath at 160 ° C. for 2 hours. After the obtained solution was filtered through a sintering filter, the filtrate was measured using a gel permeation chromatography device 150C manufactured by Waters, and Mw was determined from the obtained chromatogram. Other measurement conditions of GPC are as follows.

Detector: Differential refractometer Column: Shodex HT-G (1) manufactured by Showa Denko KK
Book) and Shodex HT-80 manufactured by Showa Denko KK
6M (two) connected in series.-Column temperature: 140 ° C-Solvent: 1,2,4-trichlorobenzene (BHT0.
1% by weight.・ Sample injection volume: 0.5 ml ・ Solvent flow rate: 1 ml / min ・ Sample injection waiting time in the apparatus: 30 minutes (5 minutes for polystyrene)

(Measurement of xylene solubles Xs) About 2 g of a propylene random copolymer was accurately weighed (this was
(G)) and dissolved in 250 ml of boiling xylene under a nitrogen stream. Thereafter, the solution was cooled to 25 ° C. and allowed to stand for 30 minutes, and the formed precipitate was promptly filtered. 100 ml of the obtained filtrate was collected and placed in an aluminum container whose constant weight was determined, and this was heated under a nitrogen stream to evaporate xylene. The weight of the evaporation residue was determined (m (g)), and the xylene-soluble portion Xs of polypropylene was determined by the following equation (3). Xs (% by weight) = mx250 / W (3)

[0050] (the boiling hexane soluble measurement of matter Hs) previously constant weight obtained thimble (w ₁ and (g)), placed propylene random copolymer (w ₂ and (g)), extraction solvent Was subjected to Soxhlet extraction using hexane for 6 hours under a nitrogen stream. Then, (a w ₃ (g)) of the propylene random copolymer remaining in the cylindrical filter paper was dried with the thimble to a constant weight. From the following formula (4), the boiling hexane-soluble component Hs of the propylene random copolymer is shown.
I asked. Hs (% by weight) = 100 × [(w ₂ − (w ₃ −w ₁ )] / w ₂ (4)

(Evaluation of Heat Sealing Property) Two 50 μm-thick films obtained from a propylene-based polymer were laminated, and a seal bar having a width of 5 mm was used at a predetermined temperature for 1 second at a pressure of 1.5 kg / cm ^2. Heat sealed. A test piece having a width of 15 mm was cut from this sample, and a peeling speed of 200 mm /
The peel strength was measured by T-type peeling. The temperature of the seal bar when the peel strength at this time was 300 g / 15 mm was defined as the heat sealing start temperature (SIT).

(Evaluation of Blocking Resistance) Two 50 μm-thick films obtained from a propylene-based polymer were stacked, sandwiched between press molding machines, and kept at 60 ° C. under a pressure of 10 kg-G for 24 hours. Then, this film was 100 × 1
The sheet was cut into a width of 00 mm, and a peeling test was performed at 200 mm / min. The value of the peel strength at that time was used as an index of blocking resistance. The smaller this value is, the better the blocking resistance is.

(Measurement of Vapor Deposition Strength) A polyurethane adhesive was applied at a thickness of ² g / m ^{2 on} the vapor deposition surface of the obtained metal vapor deposition film, and a 15 μm nylon film was laminated thereon. Hold for 48 hours. A test piece having a width of 15 mm and a length of 200 mm was cut from the metal-deposited film, and a peel test was performed at a peel speed of 300 mm / min.
The case where the deposition strength was 100 g / 15 mm width or more was evaluated as ○, and the case where it was less than that was evaluated as ×. The peeling proceeds between the deposited metal and the propylene random copolymer film.

Example 1 1) Preparation of Metallocene Catalyst 3 ml of purified toluene and 0.5 as an organometallic compound
mol / l tri-n-butylaluminum (hereinafter TN)
After mixing 0.1 ml of a toluene solution and stirring for 1 minute, methylaluminoxane supported on silica (methylaluminoxane content 26.6% by weight) as a co-catalyst component
Was added. Next, bis [2-methyl-4- (1-naphthyl)-(η5-1) is used as a metallocene compound.
-Indenyl)] 0.5 mmol / l of dimethylsilane zirconium dichloride (hereinafter abbreviated as 2MNIZ)
2 ml of a toluene solution was added, and at room temperature for 30 minutes at 65 ° C
For 30 minutes. After cooling to room temperature, toluene was distilled off under reduced pressure, a mixed solution of 5 ml of purified hexane and 0.1 ml of a TNBA hexane solution was added, and the mixture was stirred for 5 minutes. After removing the supernatant with a syringe, purified hexane 5
A solution obtained by mixing 0.1 ml of a TNBA hexane solution with 0.1 ml of a TNBA solution was added to obtain a slurry of a propylene polymerization catalyst.

2) Production of propylene random copolymer 0.5 mol / l TNB in 1.5 l autoclave
0.5 ml of A hexane solution, 330 g of propylene, 270 ml of hydrogen and 3.2 g of ethylene were added, and the temperature was raised to 60 ° C. Thereafter, the entire amount of the propylene polymerization catalyst was pressed into an autoclave and polymerization was performed for 10 minutes to obtain a propylene random copolymer. Propylene content, flexural modulus FM, melting point T of the obtained propylene random copolymer
Table 1 shows the measurement results of m, CSD, xylene solubles Xs, and boiling hexane solubles Hs, and FIG. 1 shows the relationship between the melting point Tm and the flexural modulus FM. As shown in FIG. 1, the propylene random copolymer of Example 1 satisfied the relationship of the above formula (1).

3) Production of Propylene Random Copolymer Film To the obtained propylene random copolymer was added 0.1 part by weight of calcium stearate as a chlorine scavenger and 0.1 part by weight of di-t-butylhydroxytoluene as an antioxidant. And kneaded at 200 ° C. for 5 minutes using a Brabender type mixer (Labo Plastmill, manufactured by Toyo Seiki Co., Ltd.). After kneading, a film having a thickness of about 50 μm was formed by press molding. Heat sealing start temperature SI of the obtained film
Table 1 shows the measurement results of T and blocking resistance.

4) Production of metal vapor deposition film The above film was set in a vacuum vapor deposition device, and 10 ^-4 Torr
Aluminum was evaporated under a vacuum of not more than r to obtain a metal evaporated film having a thickness of 500 Å.
Table 1 shows the measurement results of the vapor deposition strength of the obtained metal vapor-deposited film.
Shown in

Example 2 The amount of ethylene used was 5.3 g
Except having changed to, it carried out similarly to Example 1. Table 1 shows the evaluation results of the obtained propylene random copolymer, its film and metal-deposited film, and FIG. 1 shows the relationship between the melting point Tm and the flexural modulus FM. As shown in FIG.
Of the propylene random copolymer satisfied the relationship of the above formula (1).

Example 3 The amount of ethylene used was 6.7 g
Except having changed to, it carried out similarly to Example 1. Table 1 shows the evaluation results of the obtained propylene random copolymer, its film and metal-deposited film, and FIG. 1 shows the relationship between the melting point Tm and the flexural modulus FM. As shown in FIG.
Of the propylene random copolymer satisfied the relationship of the above formula (1).

Example 4 The amount of ethylene used was 9.6 g.
Except having changed to, it carried out similarly to Example 1. Table 1 shows the evaluation results of the obtained propylene random copolymer, its film and metal-deposited film, and FIG. 1 shows the relationship between the melting point Tm and the flexural modulus FM. As shown in FIG.
Of the propylene random copolymer satisfied the relationship of the above formula (1).

Comparative Example 1 1) Propylene Polymerization Catalyst A 200 ml three-necked flask equipped with a thermometer and a stirrer was sufficiently purged with nitrogen, and then diethoxymagnesium 1.1 was added.
1 g (9.47 mmol), 10 ml of toluene and 0.46 ml of di-n-butyl phthalate (1.73 mmol)
l) and stirred at 70 ° C. for 2 hours. Thereafter, the mixture was cooled to room temperature, and 50 ml of TiCl _{4 was} added dropwise from a dropping funnel over 1 hour. After completion of the addition, the temperature was raised to 110 ° C., and the mixture was reacted with stirring for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, washed three times with 200 ml of n-hexane,
For 30 minutes to obtain a solid titanium catalyst component.

To 7 mg of the above solid titanium catalyst component, 1.5 mmol of triethylaluminum, and 0.1 g of cyclohexylmethyldimethoxysilane as an electron donor component.
3 mmol was added to prepare a propylene polymerization catalyst.

2) Production of Propylene Random Copolymer 330 g of propylene, 2.4 g of ethylene and 700 ml of hydrogen (volume at normal pressure) were introduced into a 1.5-liter autoclave equipped with a magnetic stirrer. The internal temperature of the autoclave was raised to 70 ° C. Thereafter, the entire amount of the propylene polymerization catalyst was charged and polymerization was performed for 15 minutes. Table 1 shows the evaluation results of the obtained propylene random copolymer,
FIG. 1 shows the relationship between the melting point Tm and the curvature modulus FM. As shown in FIG. 1, the propylene random copolymer of Comparative Example 1
The relationship of the above formula (1) was not satisfied.

3) Production of Film and Metallized Film A film and a metallized film were produced from the obtained propylene random copolymer in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained film and the metallized film.
Shown in

(Comparative Example 2) The same operation as in Comparative Example 1 was carried out except that dicyclopentyldimethoxysilane was used as an electron donor component and the amount of ethylene used was changed to 1.3 g. Table 1 shows the evaluation results of the obtained propylene random copolymer, its film and metal-deposited film, and FIG. 1 shows the relationship between the melting point Tm and the flexural modulus FM. As shown in FIG. 1, the propylene random copolymer of Comparative Example 2 has the formula (1)
Was satisfied, but the value of CSD exceeded 3.5.

(Comparative Example 3) The same operation as in Comparative Example 1 was carried out except that dicyclopentyldimethoxysilane was used as the electron donor component and the amount of ethylene used was changed to 0.3 g. Table 1 shows the evaluation results of the obtained propylene random copolymer, its film and metal-deposited film, and FIG. 1 shows the relationship between the melting point Tm and the flexural modulus FM. As shown in FIG. 1, the propylene random copolymer of Comparative Example 3 has the above formula (1)
Was satisfied, but the value of CSD exceeded 3.5.

(Comparative Example 4) 1) Propylene polymerization catalyst The following procedure was carried out in accordance with the preparation and prepolymerization of the titanium compound in Example 1 of JP-A-9-59321. 0.95g of anhydrous magnesium chloride (10mmo
l), 10 ml of decane, and 4.7 ml (30 mmol) of 2-ethylhexyl alcohol were heated and stirred at 125 ° C. for 2 hours. 0.55 g of phthalic anhydride in this solution
(6.75 mmol) was added, and the mixture was further stirred at 125 ° C. for 1 hour to obtain a homogeneous solution. After cooling to room temperature,
40 ml of TiCl ₄ kept at 120 ° C. (0.36 m
ol) during 1 hour. Thereafter, the temperature of the mixed solution was raised to 110 ° C. over 2 hours, and 0.54 ml of diisobutyl phthalate was added.
For 2 hours. After completion of the stirring, a solid was collected by filtration, and the solid was resuspended in 140 ml of TiCl ₄ and then stirred at 110 ° C. for 2 hours. After completion of the stirring, the solid was collected by hot filtration, and sufficiently washed with decane and hexane until no free titanium compound was detected in the washing solution to obtain a solid titanium catalyst component.

In a 1-liter autoclave purged with nitrogen, 200 ml of purified n-hexane and triethylaluminum 5
0 mmol, diphenyldimethoxysilane 10 mmo
l, 50 mmol of methyl iodide and the above-mentioned solid titanium catalyst component (5 mmol in terms of titanium atoms), and the temperature was maintained at 15 ° C.
It was introduced into the autoclave continuously for 30 minutes so that the amount became 3 g per g. After 30 minutes, the reaction was stopped, and the inside of the autoclave was sufficiently replaced with nitrogen. The solid portion of the obtained slurry was washed four times with purified n-hexane to obtain a propylene polymerization catalyst (titanium-containing polypropylene). As a result of the analysis, 2.1 g of propylene was polymerized with respect to the solid titanium catalyst component.

2) Production of Propylene Random Copolymer The following procedure was used in accordance with the method described in the main polymerization in Example 1 of JP-A-9-59321. 330 g of propylene and 0.3 m of triethylaluminum were placed in a 1.5-liter autoclave equipped with a magnetic stirrer.
mol, t-butyl (ethyl) dimethoxysilane 0.1
5 mmol, 3.0 g of ethylene and 700 ml of hydrogen
(Volume at normal pressure) was introduced. The internal temperature of the autoclave was raised to 65 ° C. Thereafter, 5 mg of the above propylene polymerization catalyst was added in terms of solid titanium catalyst, and polymerization was performed for 30 minutes. Table 1 shows the evaluation results of the obtained propylene random copolymer, and FIG. 1 shows the relationship between the melting point Tm and the flexural modulus FM. As shown in FIG. 1, the propylene random copolymer of Comparative Example 4 did not satisfy the relationship of the above formula (1).

3) Production of Film and Metallized Film A film and a metallized film were produced in the same manner as in Example 1 from the obtained propylene random copolymer. Table 1 shows the evaluation results of the obtained film and the metallized film.
Shown in

(Comparative Example 5) The amount of ethylene used was 2.4 g.
The procedure was performed in the same manner as in Comparative Example 4 except for changing to. Table 1 shows the evaluation results of the obtained propylene random copolymer, its film, and metal-deposited film.
Is shown in FIG. As shown in FIG. 1, the propylene random copolymer of Comparative Example 5 did not satisfy the relationship of the above formula (1).

Comparative Example 6 2M as a metallocene compound
Example 1 was repeated except that 1,2-bis (η5-1-indenyl) ethanehafnium dichloride was used instead of NIZ. Table 1 shows the evaluation results of the obtained propylene random copolymer, its film and metal-deposited film, and FIG. 1 shows the relationship between the melting point Tm and the flexural modulus FM. As shown in FIG. 1, the propylene random copolymer of Comparative Example 6 did not satisfy the relationship of the above formula (1).

[0073]

[Table 1]

From the results of the examples, it can be seen that the propylene random copolymer of the present invention satisfies the above formula (1) and has a CSD value of 3.5 or less. It can be seen that the film obtained therefrom has a good balance between the heat sealability and the blocking resistance. Furthermore, it turns out that the metal vapor deposition film which vapor-deposited metal on the said film was excellent in vapor deposition strength.

On the other hand, a propylene random copolymer which does not satisfy the above formula (1) and has a CSD value of more than 3.5 as in Comparative Example 1 has a large amount of xylene-soluble components and boiling hexane-soluble components. And a film made of the same is inferior in heat sealability and blocking resistance. Further, the propylene random copolymer satisfying the above formula (1) as in Comparative Examples 2 and 3, but having a CSD value of more than 3.5, has a xylene-soluble component,
A film composed of a lot of boiling hexane solubles,
Poor heat sealability and blocking resistance.

As shown in Comparative Examples 4 and 5, the propylene random copolymer described in JP-A-9-59321 and the propylene random copolymer described in Comparative Example 6 had a CSD value of 3.0. Although it is 5 or less, since the above formula (1) is not satisfied, a xylene-soluble component and a boiling hexane-soluble component are large, and a film made of the same has poor blocking resistance. Further, the metal-deposited films made of the propylene random copolymers of Comparative Examples 1 to 6 have poor deposition strength.

[0077]

As described above, the film comprising the propylene random copolymer of the present invention has a good balance between rigidity and heat sealability, has excellent blocking resistance, and has a low solvent-soluble content. . Further, a metal vapor-deposited film obtained from this film has a good balance between rigidity and heat sealability, has excellent blocking resistance, has a low solvent-soluble content, and has excellent vapor deposition strength. Such a propylene-based polymer, a film made of the propylene-based polymer, and a metal-deposited film are particularly suitable as a packaging film in the food and pharmaceutical fields.

[Brief description of the drawings]

FIG. 1 is a plot showing the relationship between the melting point Tm and the flexural modulus FM of the present invention and the conventional propylene random copolymer.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI (C08F 210/06 210: 00) C08L 23:00 (72) Inventor Shintaro Inazawa 2nd Nakanosu, Oita, Oita, Oita Japan Polyolefin stock In company

Claims (3)

[Claims] 1. A melting point Tm of 90.0 to 99.9% by weight of propylene and 10.0 to 0.1% by weight of an α-olefin other than propylene as measured by a differential scanning calorimeter and JIS. The flexural modulus FM measured according to K7203 satisfies the relationship of the following formula (1), and 20,000 ≧ 218 × Tm-FM (1) and the following formula (2) (where [OO] is a propylene random copolymer Α-olefin other than propylene in the-mole fraction of α-olefin chain other than propylene,
[PP] is the molar fraction of propylene-propylene chains in the propylene random copolymer, and [OP] is α- other than propylene in the propylene random copolymer.
A propylene random copolymer, characterized by having a CSD value defined by olefin (propylene) -propylene (which represents a mole fraction of a propylene chain other than propylene) of 3.5 or less. CSD = 4 [OO] × [PP] / [OP] ² (2) 2. A film comprising the propylene random copolymer according to claim 1. 3. The film according to claim 2, wherein the film comprises metal and / or
Or a metal-deposited film obtained by depositing an oxide thereof.