JP5450917B2 - Propylene polymer composition for extrusion molding and film thereof - Google Patents

Description

  The present invention relates to a propylene polymer composition for extrusion molding and a film thereof. The present invention particularly relates to a film excellent in heat seal strength and a propylene polymer composition suitable for production thereof.

  Propylene polymers based on Ziegler-Natta catalysts are used in various fields because of their excellent characteristics. In a propylene polymer film, a propylene / ethylene copolymer having a low melting point is used in order to impart heat sealability. However, in order to obtain a sufficient heat seal property, that is, to lower the heat seal start temperature, a large amount of ethylene must be copolymerized, resulting in a decrease in rigidity and heat resistance, as well as a blocking property. There is a problem that a decrease occurs. Further, although the heat seal starting temperature is lowered, the heat seal strength is not always sufficient, and since it has a low melting point, heat resistance and rigidity are not necessarily sufficient.

  Propylene / ethylene copolymers are also used as a heat seal layer for laminated films. In this case, the heat seal strength can be improved by increasing the thickness of the heat seal layer. In the production of such a laminated film, the end portion trimmed at the time of film formation is mixed with the substrate of the laminated film and reused, and when the heat seal layer is thick, The amount of copolymer to be mixed increases. Therefore, when the heat seal layer is made thick in order to improve the heat seal strength, there arises a problem that the rigidity and heat resistance of the base material are lowered.

  Further, a propylene / butene copolymer is also used as a heat sealant, and low temperature heat sealability is imparted without impairing rigidity. However, the heat seal strength is not always sufficient, and the influence of molding conditions on optical properties such as transparency is large, and the optical characteristics may be impaired depending on the molding conditions.

  On the other hand, it has been proposed to improve heat sealability by using a propylene polymer based on a metallocene catalyst for the film. However, in this case, although the heat seal starting temperature is lowered, it is difficult to say that the heat seal strength is necessarily improved. In general, a metallocene catalyst requires a large amount of aluminoxane as a cocatalyst, so that the amount of aluminum remaining in the polymer increases. In a film obtained from such a polymer, transparency is lowered or a large amount of fish eyes are generated, so that the value as a product is significantly lowered.

Problems to be solved by the invention

  The objective of this invention is providing the propylene polymer composition with a small influence of the molding conditions with respect to optical properties, such as transparency, suitable for the film excellent in heat seal strength, and its manufacture.

Means for solving the problem

  As a result of intensive studies to solve the above problems, the present inventor, as a result, the propylene unit content and the peak temperature of the differential elution curve in temperature rising elution fractionation satisfy a specific relationship, and a propylene polymer having an aluminum content of a specific amount or less and It has been found that the above-mentioned problems can be solved by using a composition comprising an antiblocking agent having a specific particle size, and the present invention has been completed.

That is, the present invention has (A) (a) a melt flow rate measured at 230 ° C. and a load of 2.16 kg in the range of 0.01 to 20.0 g / 10 min, and (b) propylene unit content Cp (moles). %) And the peak temperature Tp (° C.) of the differential elution curve in temperature rising elution fractionation, the following formula (1),
Tp + 3.2 × (100−Cp) ≦ 110.0 (1)
(C) the aluminum content is 200 ppm or less, (d) the following 1) to 3),
1) The ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn is 2.0 or more. 2) The melting point Tm measured by a differential scanning calorimeter is in the range of 90.0 to 156.0 ° C. 3) 100 parts by weight of a propylene polymer satisfying one or more of the conditions that the peak temperature Tp (° C.) of the differential elution curve in the temperature rising elution fractionation is in the range of 60.0 to 105.0 ° C. and (B) average particles Provided is a propylene polymer composition for extrusion molding comprising 0.001 to 1.0 part by weight of an antiblocking agent having a diameter of 10 μm or less.

  The present invention also provides a film formed by extruding the propylene polymer composition.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

  The propylene polymer (A) useful in the present invention may be a homopolymer of propylene or a random copolymer of propylene and ethylene and / or α-olefin. The α-olefin is a linear, branched or cyclic α-olefin having 4 to 20 carbon atoms, and linear such as 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene. Examples thereof include olefins, branched olefins such as 4-methyl-1-butene and 4-methyl-1-pentene, and cyclic olefins such as vinylcyclohexane and vinylnorbornene. The content Co of these α-olefins may usually be in the range of 0.5 to 30 mol%, and preferably in the range of 1.0 to 25 mol%. Further, when the propylene polymer contains ethylene alone and an α-olefin unit at the same time, the contents of the ethylene unit and the α-olefin unit are 1.0 to 8.0 mol% and 1.0 to 5 respectively. A range of 0.0 mol% is preferred.

The propylene polymer used in the present invention is preferably a propylene random copolymer composed of propylene and ethylene, and its ethylene unit content C _E (mol%) is in the range of 0.5 to 10.0 mol%. is there. A preferred range of ethylene content C _E is from 1.0 to 8.0 mol%, more preferably 2.0 to 7.0 mol%, more preferably 2.6 to 6.2 mol%, still more preferably 2 The range is from 9.9 to 6.1 mol%, particularly preferably from 3.2 to 6.0 mol%, and most preferably from 3.5 to 5.8 mol%.

  The propylene polymer used in the present invention has a melt flow rate (hereinafter sometimes abbreviated as MFR) measured at 230 ° C. and a load of 2.16 kg in a range of 0.01 to 20.0 g / 10 minutes. Yes, preferably in the range of 0.05 to 18.0 g / 10 min, more preferably in the range of 0.1 to 15 g / 10 min, still more preferably in the range of 0.5 to 12.0 g / 10 min, and even more preferably Is in the range of 1.0 to 10.0 g / 10 min, particularly preferably in the range of 2.0 to 9.5 g / 10 min, and most preferably in the range of 3.0 to 9.0 g / 10 min. If the MFR is out of the range of 0.01 to 20.0 g / 10 min, the moldability is lowered and the heat seal strength is lowered.

The propylene polymer used in the present invention has a propylene unit content Cp (mol%) and a temperature elution fractionation (TREF: Temperature Rising Elution Fractionation, hereinafter referred to as TREF) peak temperature Tp ( ° C) is represented by the following formula (1),
Tp + 3.2 × (100−Cp) ≦ 110.0 (1)
Satisfy the relationship. When the propylene unit content Cp (mol%) and the peak temperature Tp (° C.) of the differential elution curve in TREF do not satisfy the above relationship, the heat seal strength and the blocking resistance are lowered.

  The peak temperature Tp of the differential elution curve in TREF depends on the stereoregularity distribution and copolymer composition distribution of the propylene polymer. Even if the propylene unit content Cp is the same value, a copolymer having a high Tp has a copolymer composition distribution. It is expected that a wide range, that is, a component having a high melting point and a component having a low melting point are mixed. The presence of such a low melting point component has an effect of improving the heat seal strength, but if the amount is too large, the cohesive strength of the film is lowered. For this reason, it is presumed that the heat seal strength is lowered, and further, blocking resistance and heat resistance are lowered. Accordingly, since the propylene copolymer used in the present invention has an appropriate distribution of the copolymer composition, the resulting film is considered to have high heat seal strength and excellent blocking resistance. .

  Cp and Tp preferably satisfy the following formula (3), more preferably satisfy the following formula (4), more preferably satisfy the following formula (5), still more preferably satisfy the following formula (6), Preferably the following formula (7) is satisfied, and most preferably the following formula (8) is satisfied.

70.0 ≦ Tp + 3.2 × (100−Cp) ≦ 108.0 (3)
73.0 ≦ Tp + 3.2 × (100−Cp) ≦ 106.0 (4)
76.0 ≦ Tp + 3.2 × (100−Cp) ≦ 104.0 (5)
78.0 ≦ Tp + 3.2 × (100−Cp) ≦ 102.0 (6)
79.0 ≦ Tp + 3.2 × (100−Cp) ≦ 101.0 (7)
80.0 ≦ Tp + 3.2 × (100−Cp) ≦ 100.0 (8)
Moreover, the peak temperature Tp of the differential elution curve in TREF of the propylene polymer may be usually 110.0 ° C. or less, preferably in the range of 60.0 to 105.0 ° C., more preferably 60.0. -100.0 ° C, more preferably 60.0-97.0 ° C, even more preferably 65.0-92.0 ° C, particularly preferably 68.0-88.0 ° C, most preferably 70.0- It is in the range of 85.0 ° C.

  The measurement of elution curve in temperature rising elution fractionation (TREF) is a well-known technique. For example, Journal of Polymer Science, Vol. 126, 4217-4231 (1981), Polymer Science Society Proceedings 2P1C09 (Showa 63) ) And the like. That is, the target propylene polymer is first completely dissolved in a solvent and then cooled to form a thin polymer layer on the surface of the inert carrier that has been present in the solvent. Next, the eluted components are collected by increasing the temperature continuously or stepwise, the concentration is continuously detected, and a graph created by the relationship between the amount of elution and the elution temperature is used as an elution curve. The peak temperature in the differential elution curve at this time is Tp.

  During the polymerization of propylene, the propylene monomer is 1,2-inserted (methylene side is bonded to the catalyst), but in some rare cases, 2,1-inserted. The 2,1-inserted monomer forms a regioregular unit with adjacent methyl groups as shown in the structure below in the chain.

  In the propylene polymer used in the present invention, the ratio P of the position irregular units based on 2,1-insertion of propylene adjacent to the methyl group is preferably in the range of 0.05 to 3.00 mol%. . When the ratio P of the position irregular units is in the above range, the heat seal strength, rigidity, and blocking resistance are not deteriorated.

  In addition, the position irregular unit based on 2,1-insertion of propylene may have a structure other than the above, that is, a structure adjacent to the ethylene chain, but these are adjacent to the ethylene unit having a large influence on crystallinity. ing. Therefore, since the influence on the crystallinity is not as great as that of the position irregularity unit, in the present invention, the P is considered to exhibit excellent properties at a specific ratio.

  When the propylene polymer used in the present invention is a propylene homopolymer, the ratio P of the position irregular units is more preferably 0.10 to 1.80 mol%, and still more preferably 0.20 to 1. 60 mol%, more preferably 0.30 to 1.40 mol%, even more preferably 0.40 to 1.30 mol%, particularly preferably 0.50 to 1.25 mol%, most preferably 0.60 It is in the range of ˜1.20 mol%.

  Further, when the propylene polymer used in the present invention is a propylene random copolymer, the ratio P of the position irregular units is more preferably 0.10 to 1.50 mol%, and still more preferably 0.15. To 1.20 mol%, more preferably 0.15 to 1.10 mol%, even more preferably 0.25 to 1.0 mol%, particularly preferably 0.25 to 0.90 mol%, most preferably It is in the range of 0.30 to 0.80 mol%.

In addition, the ratio P (mol%) of the position irregular unit based on 2,1-insertion of propylene with which the methyl group was adjacent can be calculated | required based on the measurement result of ¹³ C-NMR. The peak derived from the methyl group in (a) appears at 16.5 to 18.0 ppm based on tetramethylsilane (a plurality may appear). Therefore, it can be calculated according to the following formula (9) from the area of all peaks appearing in this range and the area of peaks derived from all methyl groups (appearing in the range of 15.0 to 22.5 ppm). It should be noted that when one unit of position irregular units based on 2,1-insertion adjacent to a methyl group is formed, two units of the peak derived from (a) are formed. Therefore,
P = (0.5 × I _a / I _t ) × Cp (9)
(Wherein, I _a is the area of a peak derived from the methyl groups of (a), I _t is the area of a peak derived from whole methyl groups, Cp is a propylene unit content (mol%))
In the propylene polymer useful in the present invention, the position irregular unit P and the propylene unit content Cp (mol%) usually satisfy the relationship of the following formula (10).

0.48 ≦ P + 0.058 (100−Cp) ≦ 0.83 (10)
When the position irregular unit P and the propylene unit content Cp (mol%) do not satisfy the above relationship, the blocking resistance and the heat seal strength may be lowered.

P and Cp more preferably satisfy the following formula (11),
0.53 ≦ P + 0.058 (100−Cp) ≦ 0.80 (11)
More preferably, the following formula (12) is satisfied,
0.57 ≦ P + 0.058 (100−Cp) ≦ 0.78 (12)
Particularly preferably, the following expression (13) is satisfied.

0.60 ≦ P + 0.058 (100−Cp) ≦ 0.76 (13)
The propylene polymer used in the present invention may have an aluminum content of usually 200 ppm or less, preferably 100 ppm or less, more preferably 80 ppm or less, still more preferably 60 ppm or less, still more preferably 50 ppm or less, and even more preferably. Is 40 ppm or less, particularly preferably 30 ppm or less, and most preferably 25 ppm or less. When aluminum content exceeds 200 ppm, the transparency of the film obtained may fall or a gel may generate | occur | produce. Furthermore, molding may be difficult, and heat seal strength may be reduced.

  Further, in order for the propylene polymer used in the present invention to have the above aluminum content, the content of transition metals such as zirconium derived from the polymerization catalyst may be usually 80 ppm or less, preferably 50 ppm or less, more preferably Is 20 ppm or less, more preferably 10 ppm or less, even more preferably 7 ppm or less, particularly preferably 5 ppm or less, and most preferably 3 ppm or less. If the transition metal content exceeds 80 ppm, the transparency of the resulting film may be reduced or a gel may be generated.

The propylene polymer used in the present invention has a propylene unit content Cp (mol%) and a melting point Tm (° C.) measured by a differential scanning calorimeter of the following formula (2):
135.0 <Tm + 4.7 × (100−Cp) <157.0 (2)
It is preferable to satisfy the relationship. When the propylene unit content Cp (mol%) and the melting point Tm (° C.) measured by the differential scanning calorimeter satisfy the above formula (2), the heat sealability is lowered, such as the heat seal strength is lowered. Does not decrease the blocking resistance.

  The propylene unit content Cp (mol%) and the melting point Tm (° C.) measured by a differential scanning calorimeter more preferably satisfy the following formula (14), more preferably satisfy the following formula (15), and more preferably The following formula (16) is satisfied, more preferably the following formula (17) is satisfied, and most preferably the following formula (18) is satisfied.

143.0 <Tm + 4.7 × (100−Cp) <155.0 (14)
144.0 <Tm + 4.7 × (100−Cp) <154.0 (15)
145.0 <Tm + 4.7 × (100−Cp) <153.0 (16)
146.0 <Tm + 4.7 × (100−Cp) <152.5 (17)
147.0 <Tm + 4.7 × (100−Cp) <152.0 (18)
Melting | fusing point Tm (degreeC) measured with the differential scanning calorimeter of the propylene polymer used by this invention may be the range of 80-156 degreeC normally. The melting point Tm is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, further preferably 110 ° C. or higher, still more preferably 115 ° C. or higher, particularly preferably 118 ° C. or higher, and most preferably 120 ° C. or higher. . If melting | fusing point Tm is 80 degreeC or more, heat seal intensity | strength will not fall or blocking resistance will not fall. Further, the melting point Tm is preferably 145 ° C. or lower, more preferably 140 ° C. or lower, more preferably 138.0 ° C. or lower, still more preferably 137.0 ° C. or lower, particularly preferably 136.0 ° C. or lower, most preferably Is 135.0 ° C. or lower. When the melting point Tm is 156 ° C. or less, the heat sealability is good.

  The propylene polymer used in the present invention may have a weight average molecular weight Mw usually in the range of 100,000 to 1,000,000. The weight average molecular weight Mw is preferably 150,000 or more, more preferably 190,000 or more, still more preferably 195,000 or more, and most preferably 200,000 or more. Further, the weight average molecular weight Mw is preferably 400,000 or less, more preferably 350,000 or less, more preferably 330,000 or less, even more preferably 310,000 or less, even more preferably 300,000 or less, and particularly preferably 290,000 or less, most preferably 280,000 or less. If the weight average molecular weight Mw is in the range of 100,000 to 1,000,000, the moldability is good.

  Further, the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn is not particularly limited, and is preferably in the range of 2.0 to 20.0, but usually the lower limit thereof may be 2.3 or more. Preferably it is 2.4 or more, more preferably 2.5 or more, still more preferably 2.6 or more, even more preferably 2.7 or more, particularly preferably 2.8 or more, Most preferably, it is 2.9 or more. Moreover, the upper limit may be 7.0 or less normally, Preferably it is 6.0 or less, More preferably, it is 5.5 or less, More preferably, it is 5.0 or less, More preferably, it is 4. It is 5 or less, particularly preferably 4.2 or less, and most preferably 4.0 or less. If the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn is 2.0 or more, the moldability is good.

  In the (A) propylene polymer used in the present invention, the xylene-soluble amount Xs at 25 ° C. may be usually 3.0% by weight or less, preferably 2.5% by weight or less, more preferably 2.0%. % By weight or less, more preferably 1.5% by weight or less, particularly preferably 1.0% by weight or less, and most preferably 0.8% by weight or less. When Xs is 3.0% by weight or more, rigidity, blocking resistance, and heat seal strength are not lowered.

  The propylene polymer used in the present invention is obtained by homopolymerizing propylene with a metallocene compound and a co-catalyst, preferably a co-catalyst excluding aluminoxane, so that the aluminum content is within the above range, or co-propylene and other olefins. It can be produced by polymerization.

  The metallocene compound can be used without particular limitation as long as it propylene is polymerized in a stereoregular manner. More specifically, bis (2,3-dimethylcyclopentadienyl) dimethylsilanezirconium can be used. Dichloride, bis (2,4-dimethylcyclopentadienyl) dimethylsilanezirconium dichloride, bis (2,3,5-trimethylcyclopentadienyl) dimethylsilanezirconium dichloride, (methylcyclopentadienyl) (1-indenyl) Dimethylsilane zirconium dichloride, (3-t-butylcyclopentadienyl) (1-indenyl) dimethylsilane zirconium dichloride, (3-t-butylcyclopentadienyl) [4-t-butyl- (1-indenyl)] Dimethylsilane Conium dichloride, (methylcyclopentadienyl) (9-fluorenyl) dimethylsilane zirconium dichloride, (3-t-butylcyclopentadienyl) (9-fluorenyl) dimethylsilane zirconium dichloride, bis (1-indenyl) dimethylsilane Zirconium dichloride, bis (2-methyl-1-indenyl) dimethylsilane zirconium dichloride, bis (2,4,7-trimethyl-1-indenyl) dimethylsilane zirconium dichloride, bis (2,4-dimethyl-1-indenyl) dimethyl Silane zirconium dichloride, bis (2-ethyl-1-indenyl) dimethylsilane zirconium dichloride, bis (2-i-propyl-1-indenyl) dimethylsilane zirconium dichloride Etc. it is.

  Furthermore, a metallocene compound having a structure in which a ring is further condensed to the indenyl skeleton described in JP-A-6-184179, JP-A-6-345809, and the like, that is, bis (2-methyl-4,5-benzo-1 -Indenyl) dimethylsilane zirconium dichloride, bis (2-methyl-α-acenaphtho-1-indenyl) dimethylsilane zirconium dichloride, bis (2-methyl-4,5-benzo-1-indenyl) methylphenylsilane zirconium dichloride Bis (2-methyl-α-acenaphtho-1-indenyl) methylphenylsilane zirconium dichloride, 1,2-bis (2-methyl-4,5-benzo-1-indenyl) ethane zirconium dichloride, bis (4,5 -Benzo-1-indenyl) dimethylsilane Such as benzalkonium dichloride can also be used.

  Further, metallocene compounds having an aryl group at the 4-position of the indenyl skeleton described in JP-A Nos. 6-100579 and 9-176222, that is, bis (2-methyl-4-phenyl-1) -Indenyl) dimethylsilanezirconium dichloride, (2-methyl-4-phenyl-1-indenyl) dimethylsilanezirconium dichloride, bis [2-methyl-4- (1-naphthyl) -1-indenyl] dimethylsilanezirconium dichloride, bis [2-Methyl-4- (2-naphthyl) -1-indenyl] dimethylsilanezirconium dichloride, bis [2-methyl-4- (9-anthracenyl) -1-indenyl] dimethylsilanezirconium dichloride, bis [2-methyl -4- (9-phenanthryl)- -Indenyl] dimethylsilane zirconium dichloride, bis [2-methyl-4- (3,5-di-i-propyl-phenyl) -6-i-propyl-1-indenyl] dimethylsilane zirconium dichloride, bis (2-methyl -4-phenyl-6-i-propyl-1-indenyl) dimethylsilanezirconium dichloride and the like can also be used.

  Metallocene compounds having an azulene skeleton as described in JP-A-10-226712 and JP-A-10-279588, that is, bis (2-methyl-4-phenyl-4-hydro-1-azurenyl) dimethylsilane zirconium dichloride Bis (2-ethyl-4-phenyl-4-hydro-1-azurenyl) dimethylsilane zirconium dichloride, bis [2-methyl-4- (chlorophenyl) -4-hydro-1-azurenyl] dimethylsilane zirconium dichloride, bis [2-Methyl-4- (fluorophenyl) -4-hydro-1-azurenyl] dimethylsilane zirconium dichloride, bis (2-methyl-4-phenyl-4-hydro-1-azurenyl) (chloromethyl) methylsilane zirconium Dichloride is also used Kill.

Further, bis [2-methyl- (η ⁵ -1-indenyl)] methylphenylsilane zirconium dichloride, 1,2-bis (η ⁵ -1-indenyl) ethane zirconium dichloride, 1,2-bis [2-methyl- (Η ⁵ -1-indenyl)] ethanezirconium dichloride, 1,2-bis [2,4-dimethyl- (η ⁵ -1-indenyl)] ethanezirconium dichloride, 1,2-bis [2,4,7- Trimethyl- (η ⁵ -1-indenyl)] ethanezirconium dichloride, 1,2-bis [2-ethyl- (η ⁵ -1-indenyl)] ethanezirconium dichloride, 1,2-bis [2-n-propyl- (eta ^{5-1-indenyl)]} ethane zirconium dichloride, [2-ethyl - (η ⁵ -1- indenyl) [2-methyl - (η ⁵ -1 Indenyl)] ethane zirconium dichloride, 1,2-bis (eta ^{5-9-fluorenyl)} ethane zirconium dichloride, 2- (3-t- butylcyclopentadienyl) -2- (η ⁵ -1- indenyl) propane zirconium Dichloride, 2- (3-t-butylcyclopentadienyl) -2- [4-t-butyl- (η ⁵ -1-indenyl)] propanezirconium dichloride, 2- (3-methylcyclopentadienyl)- 2- (η ⁵ -9-fluorenyl) propane zirconium dichloride, 2- (3-t-butylcyclopentadienyl) -2- (η ⁵ -9-fluorenyl) propane zirconium dichloride, and the like can also be used.

Among them, those having an aryl group at the 4-position of the indenyl skeleton described in JP-A-6-1005209, JP-A-9-176222, etc., JP-A-6-184179, JP-A-6-345809. A metallocene compound having a structure in which a ring is further condensed to an indenyl skeleton described in JP-A No. 10-267, and a metallocene compound having an azulene skeleton described in JP-A Nos. 10-226712 and 10-279588 are preferable. In particular bis [2-methyl-4,5-benzo (η ⁵ -1-indenyl)] dimethylsilane zirconium dichloride, bis [2-methyl-4-phenyl- (η ⁵ -1-indenyl)] dimethylsilane zirconium dichloride, bis [2-methyl-4- (1-naphthyl) - (eta ^5-1-indenyl) Dimethylsilane zirconium dichloride, bis (2-methyl-4-phenyl-4-hydro-1-azulenyl) dimethylsilane zirconium dichloride are preferred.

  These metallocene compounds with zirconium replaced with other metals such as titanium and hafnium, and chlorine atoms with other halogens, hydrogen atoms, amide groups, alkoxy groups, hydrocarbon groups such as methyl groups and benzyl groups. Can be used without any restrictions.

  Examples of the cocatalyst include a noncoordinating ion-containing compound and / or a Lewis acidic compound excluding organoaluminum supported on a fine particle carrier, an ion-exchange layered compound excluding silicate, and a solid coexisting compound such as inorganic silicate. Examples are catalysts.

  Non-coordinating ion-containing compounds include N, N, -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- (chlorodimethylsilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate and the like can be mentioned.

  Examples of Lewis acidic compounds excluding organic aluminum include triphenylborane, tris (pentafluorophenyl) borane, and tris (pentafluorophenyl) borate.

The ion-exchangeable layered compound excluding silicate is a compound having a crystal structure in which planes constituted by ionic bonds and the like are stacked in parallel with a weak binding force, and the contained ions can be exchanged. More specifically, there are γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O and the like described in JP-A-10-168111.

  Examples of the inorganic silicate include clay, clay mineral, zeolite, and diatomaceous earth. More specifically, examples include kaolinite, montmorillonite, vermiculite, hectorite, and the like described in JP-A-10-168111. These may be naturally produced or synthesized.

  The solid promoter component is preferably a solid promoter component containing a non-coordinating ion-containing compound. Among them, it is preferable that the non-coordinating ion-containing compound is bonded to the fine particle carrier by a chemical bond, and these are, for example, JP-T-7-501573, JP-A-8-143617, WO96. / 40796, WO96 / 41808, WO97 / 19959, JP2000-212225, and the like.

  The propylene polymer used in the present invention can be produced by bulk polymerization or gas phase polymerization of propylene and, if necessary, other olefins using the catalyst. In these polymerization methods, a small amount of an inert solvent used for introducing the catalyst into the polymerization reactor may be present, but the concentration in these polymerization reactors is usually 20% by weight or less, preferably It should be 10% by weight or less.

  In addition, in polymerization methods other than those described above, for example, slurry polymerization or solution polymerization in an inert solvent such as hexane or heptane, a part of the polymer produced in these solvents is eluted, so that the composition distribution and stereoregulation May affect the sex distribution and, as a result, the heat seal strength. In addition, these inert solvents remain in the polymer and may adversely affect moldability.

  In the present invention, the average particle size of the anti-blocking agent (B) may be usually 5.0 μm or less, preferably 3.8 μm or less, more preferably 3.3 μm or less, and even more preferably 2.8 μm or less. More preferably, it is 2.3 μm or less, particularly preferably 2.0 μm or less, and most preferably 1.8 μm or less. When the average particle size is 5.0 μm or less, the appearance of the film is not lowered due to the generation of fish eyes, and the optical characteristics such as heat seal strength and transparency are not lowered.

  The blending amount of the anti-blocking agent is preferably 0.001 to 1.0 part by weight, more preferably 0.005 to 0.9 part by weight, and still more preferably 100 parts by weight of the propylene polymer. 0.01 to 0.8 parts by weight, more preferably 0.03 to 0.7 parts by weight, still more preferably 0.05 to 0.6 parts by weight, particularly preferably 0.07 to 0.5 parts by weight, Most preferably, it is the range of 0.09-0.4 weight part. When the blending amount is in the range of 0.001 to 1.0 part by weight, the appearance and transparency of the film are good, and the heat seal strength does not decrease.

  As an antiblocking agent, an inorganic type or an organic type is used without particular limitation. Inorganic antiblocking agents include fused silica, synthetic silica, natural silica, silica, alumina, titania, composite oxides thereof, zeolites such as A-type zeolite, Pc-type zeolite, and X-type zeolite, talc, kaolin, alumino Examples include silicate, diatomaceous earth, and talc. Any of these may be subjected to treatment such as acid modification or ion exchange.

  Examples of the organic antiblocking agent include a crosslinked acrylate resin, a crosslinked polymethyl methacrylate, a crosslinked polystyrene, a non-melting silicone resin and a silicone rubber, a silicone copolymer, a polyamide, and a condensed resin having a triazine ring. Examples thereof include thermosetting resins such as melamine resin, guanamine resin, phenol resin, and urea resin. These are used in the form of powder, preferably spherical fine particles. These antiblocking agents may be used alone or in combination of two or more.

  There is no restriction | limiting in particular in the manufacturing method of the propylene polymer composition of this invention, It can manufacture by mixing the said propylene polymer (A) and antiblocking agent (B) by a well-known means. Specifically, after adding an antiblocking agent to the propylene polymer and further other additives as necessary, a kneading apparatus such as a single screw extruder, a twin screw extruder, a kneader, or a Banbury mixer is used. It can be carried out by kneading at a temperature of about ~ 300 ° C.

  The film of the present invention can be produced by extruding the propylene polymer composition, and specific examples include a method of extruding with an extruder equipped with a T die or the like. The film of the present invention may be either an unstretched film or a stretched film. In the case of a stretched film, it may be either uniaxial or biaxially stretched. In stretching, a known method can be adopted. After producing a film raw material using an extruder or the like, the film raw material is continuously or simultaneously used by using a tenter type, pantograph type stretching device or the like. Stretching can also be performed.

  In addition, other films may be laminated on the film of the present invention. There is no restriction | limiting in particular as another film, The propylene polymer film except the propylene polymer used by this invention, an ethylene (co) polymer film, a polyamide film, a polyester film, etc. can be used. The propylene polymer film excluding the propylene polymer used in the present invention may be any of a propylene homopolymer, a random copolymer, and a block copolymer film. Among these, a propylene polymer film is preferable, and a propylene homopolymer film is particularly preferable.

  There is no restriction | limiting in particular in the thickness of the film of this invention, Usually, the thickness of the range of 0.01-200 micrometers may be sufficient, Preferably it is the range of 0.05-100 micrometers, More preferably, it is the range of 0.1-80 micrometers, More preferably, it is the range of 0.1-60 micrometers, More preferably, it is the range of 0.3-50 micrometers, Most preferably, it is the range of 0.3-45 micrometers, Most preferably, it is the range of 0.5-40 micrometers.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited at all by these.

Measurement of melt flow rate It was measured at 230 ° C. and a load of 2.16 kg in accordance with JIS K7210.

Measurement of Elution Peak Temperature Tp in TREF Elution Curve The elution curve was measured using a cross fractionator (CFC T150A manufactured by Mitsubishi Oil Chemical Co., Ltd.) as follows. First, a sample to be measured is dissolved at 140 ° C. using a solvent (o-dichlorobenzene) so as to have a concentration of 4 mg / ml, and this is injected into a sample loop in the measuring apparatus. The following measurements are automatically performed according to the set conditions.

  0.4 ml of the sample solution held in the sample loop is injected into a TREF column (column filled with glass beads as an inert carrier) that is separated using the difference in dissolution temperature. The sample is then cooled to 140 ° C. to 0 ° C. at a rate of 1 ° C./min and coated on the inert carrier. At this time, a polymer layer is formed on the surface of the inert carrier in the order of the high crystalline component to the low crystalline component. After the TREF column is held at 0 ° C. for another 30 minutes, 2 ml of the component dissolved at 0 ° C. is injected into the infrared spectrophotometer at a flow rate of 1 ml / min. Thereafter, the temperature is raised to 2 ° C. and held for 30 minutes, and then 2 ml of similarly dissolved components are injected into the infrared spectrophotometer at a flow rate of 1 ml / min. Thereafter, the temperature is raised by 2 ° C. to 135 ° C., and the same operation is repeated. The concentration of the eluted polymer is detected with an infrared spectrophotometer, and a chromatogram is obtained for each elution temperature segment.

  The chromatogram at each elution temperature measured above is processed by a built-in data processing program, the area of each chromatogram is integrated, and an integrated elution curve is calculated. This integrated elution curve is differentiated with temperature, and a differential elution curve is calculated. The elution peak temperature Tp was determined from this differential elution curve.

Measurement of ¹³ C-NMR Measured with JNM-GSX400 manufactured by JEOL under the following conditions (measurement mode: proton decoupling method, pulse width: 8.0 μs, pulse repetition time: 3.0 s, integration number: 20000 times, measurement) Temperature: 120 ° C., internal standard: hexamethyldisiloxane, solvent: 1,2,4-trichlorobenzene / benzene-d6 (volume ratio 3/1), sample concentration: 0.1 g / ml).

Measurement of the proportion of regioregular units based on 2,1-insertion of propylene
Based on the measurement result of ¹³ C-NMR, it was calculated by the above formula (9).

Measurement of melting point Tm The melting point Tm was measured using a differential scanning calorimeter DCS7 manufactured by PERKIN-ELMER. First, the temperature was raised to 230 ° C. and held for 5 minutes, then cooled to −30 ° C. at 20 ° C./min and held 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 ratio of weight average molecular weight to number average molecular weight (Mw / Mn) 1) Preparation of calibration curve 1,2 containing 0.1% by weight of BHT (2,6-di-t-butyl-4-methylphenol) , 4-Trichlorobenzene 10ml, 3mg of standard polystyrene samples (manufactured by Showa Denko KK) with different molecular weights were added, dissolved in room temperature and dark place for 1 hour, and then the peak top elution time was measured by GPC measurement. Measurements were made. This measurement was repeated, and a calibration curve was prepared by approximation of a cubic equation from a total of 12 points (molecular weight: 580 to 8.5 million) and peak top elution time.

2) Measurement of weight average molecular weight (Mw), number average molecular weight (Mn) In a test tube, 5 ml of 1,2,4-trichlorobenzene containing 0.1% by weight of BHT was taken, and polypropylene (sample) was about 2 .5 mg was added. After plugging the test tube, the sample was dissolved in a constant temperature bath at 160 ° C. for 2 hours. After filtering the obtained solution through a sintered filter, the filtrate was measured using a water permeation chromatography apparatus 150C, Mw and Mn were determined from the obtained chromatogram, and the ratio of these molecular weights (Mw / Mn) was calculated. The other measurement conditions of GPC are as follows.
-Detector: differential refractometer-Column: Showa Denko Co., Ltd. Shodex HT-G (1) and Showa Denko Co., Ltd. Shodex HT-806M (2) connected in series-Column temperature: 140 ° C
Solvent: 1,2,4-trichlorobenzene (including 0.1% by weight of BHT)
・ Sample injection volume: 0.5ml
・ Solvent flow rate: 1 ml / min ・ Sample injection waiting time in the apparatus: 30 minutes (polystyrene is 5 minutes)
Measurement of Xylene-soluble content Xs About 2 g of a propylene polymer was accurately weighed (this is referred to as W (g)), and dissolved in 250 ml of boiling xylene under a nitrogen stream. Thereafter, this solution was cooled to 25 ° C. and allowed to stand for 30 minutes, and the produced precipitate was immediately 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 (this is referred to as m (g)), and the xylene-soluble part Xs of the propylene polymer was determined from the following formula (19).

Xs (% by weight) = m × 250 / W (19)
Measurement of aluminum content and ash content About 10 g of propylene polymer was accurately weighed and placed in a magnetic crucible whose constant weight was determined. Cover the crucible and incinerate it in a controlled electric furnace (10 minutes warming from room temperature to 200 ° C, hold for 30 minutes, then 10 minutes warming to 400 ° C, hold for 30 minutes, then 30 minutes The temperature was raised to 600 ° C. and held for 60 minutes, and finally the temperature was raised to 700 ° C. in 10 minutes and held for 30 minutes).

  2 g of potassium pyrosulfate was added to the crucible and heated and melted on a hot plate. After cooling and solidifying, 20 ml of 6N hydrochloric acid was added and dissolved by heating on a hot plate. After cooling, the contents of the crucible were filtered through filter paper (5B), and the filtrate was collected in a 100 ml volumetric flask. Further, the inner wall of the crucible and the filter paper were washed with pure water and added to the filtrate in the flask. Next, pure water was added to the volumetric flask containing the filtrate to make exactly 100 ml. The solution was subjected to ICP emission analysis (measurement wavelength: 396.152 nm, determined by a calibration curve prepared by measuring a standard solution containing potassium pyrosulfate and hydrochloric acid prepared according to the above), and the aluminum content was determined. .

Example 1
1) Production of cocatalyst component N, N-dimethylanilinium was added to a slurry in which 300 g of silica (SMR49 manufactured by Grace Davison, dried for 4 hours at 110 ° C. under a nitrogen stream) was added to 2.0 liter of dichloromethane. 300 ml of a dichloromethane solution containing 100 mmol of tris (pentafluorophenyl) [4- (chlorodimethylsilyl) -2,3,5,6-tetrafluorophenyl] borate was added over 10 minutes. The mixture was stirred at room temperature for 1 hour and stirred at reflux for 3 hours. The mixture was cooled to room temperature, 180 ml of trimethylchlorosilane was added by syringe, and the mixture was refluxed for 3 hours with stirring. Then, it cooled to room temperature, the supernatant liquid was removed, 2.0 liters of dichloromethane was newly added, and it stirred for 10 minutes at room temperature, and wash | cleaned. Thereafter, the supernatant liquid was removed, and this washing operation was repeated three more times, followed by drying under reduced pressure to obtain 289 g of a promoter component held on the white fine particle support.

2) Production of propylene polymer Propylene was supplied to a 150 liter loop polymerization reactor (first polymerization reactor) at a rate of 140 liters / hour. Next, a mixture of bis (2-methyl-4-phenyl-1-indenyl) dimethylsilanezirconium dichloride (hereinafter sometimes abbreviated as MPIZ), a promoter component and 0.5 M tri-n-octylaluminum as a metallocene compound Was fed with 30 liters / hour of hexane (corresponding to rates of 0.025 mmol / hour, 0.5 g / hour, and 0.1 liter / hour, respectively), and prepolymerization was carried out at 25 ° C. The reaction mixture discharged from the first polymerization reactor was fed to a 290 liter second loop polymerization reactor set at 70 ° C. Propylene was supplied to the second polymerization reactor at 100 liter / hour and ethylene was supplied at 3.0 kg / hour. Unreacted propylene and ethylene were removed from the reaction mixture discharged from the second polymerization reactor by a degassing apparatus, and a propylene random copolymer was obtained.

3) Production of propylene polymer composition By adding 0.2 parts by weight of silica (average particle size: 1.6 μm) as an antiblocking agent to 100 parts by weight of propylene polymer, and kneading at 200 ° C. by a single screw extruder. A propylene polymer composition was produced.

4) Production of film The propylene polymer composition obtained above was extruded by a single screw extruder equipped with a T die (T die temperature 230 ° C., chill roll temperature 30 ° C. or 50 ° C.), and the thickness was 30 μm. A stretched film was obtained.

5) Evaluation of heat-sealability Two obtained 30 μm-thick films were stacked and heat-sealed at a predetermined temperature for 1 second at a pressure of 1.5 kg / cm ² using a seal bar having a width of 5 mm. A specimen having a width of 15 mm was cut from this sample, and the peel strength was measured by T-peel at a peel rate of 200 mm / min. The maximum peel strength at this time was defined as the heat seal strength.

6) Evaluation of blocking resistance Two films obtained in 4) above were stacked and sandwiched between press molding machines, and held at 50 ° C. and a pressure of 10 kg-G for 24 hours. Thereafter, this film was cut to a width of 100 × 100 mm, and a peel test was performed at 200 mm / min. The peel strength at that time was used as an index of blocking resistance. It shows that blocking resistance is so favorable that this value is small.

Example 2
The procedure of Example 1 was repeated except that the amount of ethylene used was 2.4 kg / hour in the production of the propylene polymer.

Comparative Example 1
The procedure of Example 1 was repeated except that as the propylene polymer, a propylene / ethylene copolymer having the properties described in Table 1 below and produced using a catalyst comprising magnesium chloride, titanium chloride, and triethylaluminum was used.

Comparative Example 2
A 6-liter autoclave was charged with triethylaluminum and silica-supported methylaluminoxane and bis (2-methyl-4-phenyl-1-indenyl) dimethylsilanezirconium dichloride reacted at 60 ° C. for 20 minutes. Then, after introducing 32 mol of propylene, the temperature was rapidly raised to 50 ° C. while stirring. Next, ethylene was introduced until the partial pressure became 1.5 MPa, and polymerization was carried out for 1 hour to obtain a propylene copolymer.

Example 3
Using bis [2-methyl-4- (1-naphthyl) -1-indenyl] dimethylsilanezirconium dichloride instead of MPIZ, the amount of ethylene used in the production of propylene polymer was 1.8 kg / hour, and the presence of hydrogen The procedure of Example 1 was repeated except that the polymerization was performed below.

Example 4
The procedure of Example 1 was repeated except that bis (2-methyl-4,5-benzo-1-indenyl) dimethylsilanezirconium dichloride was used in place of MPIZ and ethylene was not used in the production of the propylene polymer.

Comparative Example 3
The procedure of Example 1 was repeated except that as the propylene polymer, a propylene / ethylene copolymer having the properties described in Table 1 below, produced with a catalyst comprising titanium trichloride and diethylaluminum chloride, was used.

Comparative Example 4
The operation of Example 1 was repeated except that the amount of the antiblocking agent used was 1.2 parts by weight.

Comparative Example 5
The procedure of Example 1 was repeated except that silica having an average particle size of 12 μm was used as the antiblocking agent.

Comparative Example 6
The procedure of Example 1 was repeated except that as the propylene polymer, a propylene / butene copolymer having the properties described in Table 1 below and produced using a catalyst comprising magnesium chloride, titanium chloride and triethylaluminum was used.

Claims (3)

(A) (a) Melt flow rate measured at 230 ° C. under a load of 2.16 kg is in the range of 0.5 to 12.0 g / 10 min. (B) Elution of propylene unit content Cp (mol%) and temperature The peak temperature Tp (° C.) of the differential elution curve in fractionation is the following formula (1),
Tp + 3.2 × (100−Cp) ≦ 100.0 (1)
(C) the aluminum content is 200 ppm or less, (d) the following 1) to 3),
1) The ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn is 2.3 or more. 2) The melting point Tm measured by a differential scanning calorimeter is in the range of 90.0 to 156.0 ° C. 3) 100 parts by weight of a propylene polymer satisfying the condition that the peak temperature Tp (° C.) of the differential elution curve in temperature rising elution fractionation is in the range of 60.0 to 97.0 ° C. and (B) an average particle size of 10 μm or less only contains the anti-blocking agent from 0.001 to 1.0 parts by weight,
The anti-blocking agent is one or more inorganic anti-blocking agents selected from the group consisting of silica, alumina, titania and composite oxides thereof, zeolite, kaolin, aluminosilicate, diatomaceous earth, and talc, and / or Or crosslinked acrylate resin, crosslinked polymethyl methacrylate, crosslinked polystyrene, non-melting silicone resin, silicone rubber, silicone copolymer, polyamide, condensed resin having triazine ring, melamine resin, guanamine resin, phenol resin, and urea A propylene polymer composition for extrusion molding , which is one or more organic antiblocking agents selected from the group consisting of resins .
2. The propylene polymer in which (f) regioregular units P based on 2,1-insertion of propylene adjacent to a methyl group are in the range of 0.05 to 3.0 mol%. Propylene polymer composition.
  A film formed by extruding the propylene polymer composition according to claim 1.