JP2013035604A - Packaging body obtained by using polypropylene-based resin composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a packaging body, which is excellent in mechanical strength thereof even when packing a liquid and/or powder being the material to be packed through the opening of a bag-shaped container formed by using a film having a heat seal layer and heat seal is performed while the material to be packed is held in at least a part of the opening thereof, and to provide a method for producing the packaging body.SOLUTION: The heat seal layer comprises a resin composition containing: a propylene-based resin (A) having ≥120°C melting point (Tm) when measured by a differential scanning calorimeter; and a propylene-1-butene copolymer (BB) having 60-100°C melting point (Tm) when measured by the differential scanning calorimeter. The packaging body is obtained, by packing a liquid and/or powder being the material to be packed through the opening of the bag-shaped container formed by using the film having the heat seal layer to perform the heat seal of the opening thereof.

Description

  The present invention relates to a package using a resin composition and a method for producing the same. More specifically, the present invention relates to a bag having a heat seal portion made of a resin composition containing a propylene-based resin (A) and a propylene / C2-C20 α-olefin copolymer (B). The present invention relates to a package in which an object to be filled is filled and a manufacturing method thereof.

  Polyethylene is excellent in mechanical properties such as tensile strength, rigidity, surface hardness, impact strength and cold resistance; optical properties such as glossiness and transparency; or food hygiene such as non-toxicity and odorlessness. Widely used in the packaging field.

  Patent Document 1 discloses a heat sealing property in the presence of interstices, in which a resin composition layer composed of propylene / ethylene / butene terpolymer, low density polyethylene and linear polyethylene is used as a heat sealing layer. An excellent bag-like container is disclosed. Patent Document 2 discloses a bag-like container having a heat seal layer made of a metallocene catalyst-based linear low-density polyethylene and an olefin-based elastomer.

  However, since both of them combine ethylene-based polymers, transparency and heat resistance are low, and it cannot be said that the heat resistance during heat sterilization is sufficient. Furthermore, the bag-like container described in Patent Document 2 has room for improvement in heat sealability in the presence of foreign matter.

JP 2001-219518 A JP-A-10-119207

  The present invention fills a liquid and / or powder as a filling material from an opening of a bag-like container formed by bag-making a film having a heat seal layer, and the filling is in at least a part of the opening. It is an object of the present invention to provide a package having excellent mechanical strength even when heat-sealed while being sandwiched, and a method for producing the same.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have excellent heat resistance in a bag-like container made of a resin composition containing a specific propylene resin and a specific propylene / α-olefin copolymer. And even if it heat-seals with the to-be-filled material pinched | interposed into at least one part of the opening part of this bag-shaped container, it discovered that there was little fall of heat seal intensity | strength and came to complete this invention.

That is, this invention is specified by the matter described below.
[1] A heat seal comprising a resin composition containing a propylene resin (A) having a melting point (Tm) measured by a differential scanning calorimeter of 120 ° C. or more and a propylene / 1-butene copolymer (BB). A package obtained by filling a liquid and / or powder as a filling material from an opening of a bag-like container formed by forming a film having a layer, and heat-sealing the opening,
The propylene / 1-butene copolymer (BB) is
(1) Containing a structural unit derived from propylene in an amount of 50 to 95 mol% and an amount of structural unit derived from 1-butene in an amount of 5 to 50 mol%,
(2) Based on ASTM D1238, the melt flow rate obtained by measuring at a temperature of 230 ° C. and a load of 2.16 kg is 0.01 to 1000 g / 10 minutes,
(3) The molecular weight distribution (Mw / Mn) obtained by gel permeation chromatography (GPC) is 3.0 or less,
(4) The melting point (Tm) measured with a differential scanning calorimeter is 60 to 100 ° C.
(5) The melting point (Tm) [° C.] measured by a differential scanning calorimeter and the constituent unit content (M) [mol%] derived from 1-butene are −2.6 M + 130 ≦ Tm ≦ −2.3 M + 155
Satisfies the relational expression
A package containing the propylene resin (A) and the propylene / 1-butene copolymer (BB) in an amount of 60 to 95% by weight and 5 to 40% by weight, respectively, in 100% by weight of the resin composition.

[2] The package according to [1], wherein the film is a laminate of the heat seal layer and the base material layer.
[3] The package according to [1] or [2], wherein the filling material is a liquid.

[4] The package according to [1] or [2], wherein the filling material is oil.
[5] A heat seal layer comprising a resin composition comprising a propylene resin (A) having a melting point (Tm) measured by a differential scanning calorimeter of 120 ° C. or higher and a propylene / 1-butene copolymer (BB). A method for producing a package including a step of filling a liquid and / or powder as a filling material from an opening of a bag-like container formed by bag-making a film having a film, and a step of heat-sealing the opening ,
The propylene / 1-butene copolymer (BB) is
(1) Containing a structural unit derived from propylene in an amount of 50 to 95 mol% and an amount of structural unit derived from 1-butene in an amount of 5 to 50 mol%,
(2) Based on ASTM D1238, the melt flow rate obtained by measuring at a temperature of 230 ° C. and a load of 2.16 kg is 0.01 to 1000 g / 10 minutes,
(3) The molecular weight distribution (Mw / Mn) obtained by gel permeation chromatography (GPC) is 3.0 or less,
(4) The melting point (Tm) measured with a differential scanning calorimeter is 60 to 100 ° C.
(5) The melting point (Tm) [° C.] measured by a differential scanning calorimeter and the constituent unit content (M) [mol%] derived from 1-butene are −2.6 M + 130 ≦ Tm ≦ −2.3 M + 155
Satisfies the relational expression
The production method wherein the propylene resin (A) and the propylene / 1-butene copolymer (BB) are contained in 60 to 95% by weight and 5 to 40% by weight, respectively, in 100% by weight of the resin composition.

[6] The method for manufacturing a package according to [5], wherein the filling material is a liquid.
[7] The method for manufacturing a package according to [5], wherein the object to be filled is oil.

  A bag having a heat seal layer made of a resin composition containing the propylene-based resin (A) used in the present invention and a propylene.multidot.2 or 4 to 20 α-olefin copolymer (B) is produced. The bag-shaped container is higher in heat resistance than conventional polyethylene-based bag-shaped containers, and has a lower heat seal temperature than a bag-shaped container made of polypropylene that does not contain propylene / 1-butene copolymer (BB). Therefore, it is excellent in high-speed moldability. Furthermore, the liquid and / or powder which is a to-be-filled material from the opening part of the bag-shaped container which consists of propylene-type resin (A) and a 2 or 4-20 alpha-olefin copolymer (B) of a carbon atom. Even if the body is filled and heat-sealed with the filling material sandwiched in at least a part of the opening, the heat-sealing strength decreases less than when the filling material does not exist in the heat-sealing layer. A package having excellent mechanical strength and a method for producing the same can be provided.

Hereinafter, the present invention will be specifically described.
The packaging body of the present invention has a melting point (Tm) measured with a differential scanning calorimeter of 120 ° C. or higher and a melting point (Tm) measured with a differential scanning calorimeter of less than 120 ° C. Or a film having a heat seal layer made of a resin composition containing propylene / α-olefin copolymer (B) having 2 or 4 to 20 carbon atoms, in which a melting point peak is not observed with a differential scanning calorimeter It is obtained by filling a liquid and / or powder which is an object to be filled from the opening of the bag-shaped container, and heat-sealing the opening.
The resin composition used in the present invention contains at least a propylene resin (A) and a propylene / α-olefin copolymer (B) having 2 or 4 to 20 carbon atoms.

[Propylene resin (A)]
The propylene resin (A) according to the present invention has a melting point measured by a differential scanning calorimeter of 120 ° C. or higher, preferably 120 to 170 ° C., more preferably 120 to 160 ° C., and particularly preferably 130 to 150 ° C. Then it is what you do. The propylene-based resin (A) according to the present invention has crystallinity and has an isotactic index I.V. I. It is desirable to use polypropylene having a (boiling n-heptane insoluble component) of preferably 75% by weight or more, more preferably 75 to 99% by weight. The density of the propylene-based resin (A) is 890 to 920 kg / m ³ , and the melt flow rate (ASTM D1238, temperature 230 ° C.) is 0.1 to 20 g / 10 minutes, preferably 1 to 10 g / 10 minutes. is there. It is preferable that the melt flow rate is in the range of 1 to 10 g / 10 min since the film can be molded at an appropriate resin pressure without causing drawdown from the die of the extruder during film forming.

  The propylene-based resin (A) may be homopolypropylene and is derived from propylene and a small amount of ethylene or an α-olefin other than propylene (for example, a composition derived from an α-olefin other than ethylene or propylene in the entire copolymer). And a copolymer of 10 mol% or less, preferably less than 5 mol%. Specific examples of the α-olefin include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, and 4-methyl-1-pentene. Α-olefins having 4 to 20 carbon atoms such as

  As the copolymer, random polypropylene or block polypropylene can be used, but random polypropylene is preferable. The block polypropylene is suitable for applications requiring higher heat resistance and bag breaking strength, for example, high retort applications.

As such a propylene-based resin (A), a conventionally known one can be used as a polypropylene for a film and can be easily obtained from the market. Examples thereof include “Prime Polypro F327” (trade name; manufactured by Prime Polymer Co., Ltd.) and “Prime Polypro F317” (trade name: manufactured by Prime Polymer Co., Ltd.).
The propylene-based resin (A) can be produced by a known method using a conventionally known solid titanium catalyst (Ziegler catalyst) component or metallocene compound catalyst component.

[Propylene / α-olefin copolymer having 2 or 4 to 20 carbon atoms (B)]
The propylene / C 2 -C 4 α-olefin copolymer (B) according to the present invention has a melting point (Tm) measured by a differential scanning calorimeter of less than 120 ° C., preferably 110 ° C. or less. Preferably it has 50-110 degreeC, More preferably, it has 60-100 degreeC, or a melting peak is not observed with a differential scanning calorimeter. Here, a melting point peak is not observed with a differential scanning calorimeter when a sharp melting point peak is not observed with a differential scanning calorimeter and the crystallinity (C) measured by the X-ray diffraction method is 10% or less. To do.

  Specific examples of the α-olefin of the propylene / carbon number 2 or 4 to 20 α-olefin copolymer (B) include 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene. 1-decene, 1-dodecene, 1-hexadecene, 4-methyl-1-pentene, and the like. Of these, 1-butene is preferred.

The propylene / 1-butene copolymer (BB), which is a preferred embodiment of the propylene / carbon number 2 or 4-20 α-olefin copolymer (B), is represented by the following requirements (1) to (4): It is preferable to satisfy at least one of them.
(1) The structural unit derived from propylene is contained in an amount of 50 to 95 mol%, and the structural unit derived from 1-butene is contained in an amount of 5 to 50 mol%.
(2) Based on ASTM D1238, MFR obtained by measuring at a temperature of 230 ° C. and a load of 2.16 kg is 0.01 to 1000 g / 10 min.
(3) The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is 3.0 or less.
(4) The melting point (Tm) measured with a differential scanning calorimeter is 110 ° C. or lower.

[Requirement (1)]
Requirement (1) is that propylene / 1-butene copolymer (BB) is an amount of 50 to 95 mol%, preferably 55 to 93 mol%, more preferably 60 to 90 mol% of structural units derived from propylene. Thus, the structural unit derived from 1-butene is contained in an amount of 5 to 50 mol%, preferably 7 to 45 mol%, more preferably 10 to 40 mol%. When the structural unit derived from propylene and the structural unit derived from 1-butene are within the above range, the heat seal temperature is low, and moreover, from the opening of a bag-like container made of polypropylene and a propylene / 1-butene copolymer. Even if it is filled with liquid and / or powder, which is to be filled, and heat-sealed while the filling is sandwiched in at least a part of the opening, there is little decrease in heat seal strength and excellent mechanical strength. In addition, the film blocking resistance is excellent.

  The propylene / 1-butene copolymer (BB) is a constituent unit derived from an α-olefin other than propylene and 1-butene in an amount not exceeding the object of the present invention, for example, an amount of 10 mol% or less. May be included.

[Requirement (2)]
Requirement (2) is that a melt flow rate (MFR) obtained by measuring propylene / 1-butene copolymer (BB) at a temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM D1238 is 0.01. ˜1000 g / 10 min, preferably 0.1 to 100 g / 10 min, more preferably 1 to 20 g / 10 min. When the MFR is 0.01 g / 10 min or more, a preferable thickness as a heat seal layer, more specifically, a thin layer of 50 μm or less can be formed. On the other hand, when the MFR is 1000 g / 10 min or less, It is preferable because good heat seal strength can be obtained.

[Requirement (3)]
Requirement (3) is a propylene / 1-butene copolymer (BB) having a molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) of 3 or less, preferably 2.0 to 3.0, more preferably 2.0 to 2.5. When the Mw / Mn in terms of polypropylene is within the above range, the content of low molecular weight components that have a low molecular weight and adversely affect heat sealability can be reduced.

[Requirement (4)]
Requirement (4) is that the melting point (Tm) of the propylene / 1-butene copolymer (BB) measured with a differential scanning calorimeter is 110 ° C. or less, preferably 50 to 110 ° C., more preferably 60 to 100. ° C, more preferably 65 to 90 ° C.

  If the melting point (Tm) is 50 ° C. or higher, the scratch resistance of the film will not be impaired, and the film will not block during storage and will not be practically used. In addition, when the melting point (Tm) is 100 ° C. or lower, the appropriate heat seal temperature of the film can be 100 ° C. or lower, and good low temperature heat sealability can be obtained.

The melting point was determined by using a differential scanning calorimeter (DSC). About 5 mg of a sample was packed in an aluminum pan, heated to 200 ° C., held at 200 ° C. for 5 minutes, and then −40 ° C. at 10 ° C./min. After cooling to −40 ° C. for 5 minutes, the temperature can be obtained from an endothermic curve when the temperature is increased at 10 ° C./min.
The propylene / 1-butene copolymer (BB) preferably further satisfies any of the following requirements (5) to (8).

[Requirement (5)]
Requirement (5) is that propylene / 1-butene copolymer (BB) has a melting point (Tm) measured by a differential scanning calorimeter of 50 to 110 ° C., and the melting point (Tm) [° C.] and 1 -Content of structural unit derived from butene (M) [mol%] is -2.6M + 130 ≦ Tm ≦ −2.3M + 155
It is assumed that the relational expression represented by When the melting point (Tm) and the structural unit content (M) derived from the 1-butene satisfy the above formula, the melting point (Tm) has a low melting point without impairing the blocking property of the propylene / 1-butene copolymer (BB). Therefore, it is suitable for heat sealable film applications.

[Requirement (6)]
Requirement (6) is that propylene / 1-butene copolymer (BB) has a parameter B value indicating the randomness of the copolymerization monomer chain distribution of 1.0 to 1.5, preferably 1.0 to 1.3. More preferably, it is 1.0 to 1.2. When the B value is within the above range, propylene and 1-butene are more uniformly copolymerized, and when the resin composition is constituted together with the propylene-based resin (A), a heat seal made of the resin composition The layer is excellent in low temperature heat sealability and heat seal strength retention when an object to be filled is present on the seal surface.

The parameter B value is proposed by Coleman et al. (BDCole-man and TGFox, J. Polym. Sci., Al, 3183 (1963)) and is defined as follows.
B = P ₁₂ / (2P ₁ · P ₂ )
In the formula, P ₁ and P ₂ are the first monomer and second monomer content fractions, respectively, and P ₁₂ is the ratio of (first monomer)-(second monomer) linkage in the chain in all two molecules. . The B value is in accordance with Bernoulli statistics when 1, and the copolymer is blocky when B <1, and is alternating when B> 1.

[Requirement (7)]
The requirement (7) is that the propylene / 1-butene copolymer (BB) has a crystallinity (C) [%] measured by an X-ray diffraction method and a structural unit content (M) [1] derived from 1-butene. Mol%] satisfies C ≧ −1.5M + 75. The crystallinity (C) of the propylene / 1-butene copolymer (BB) is 65% or less, preferably 15 to 65%, more preferably 20 to 60%. When the crystallinity (C) is 15% or more, a film having good scratch resistance and no blocking and stickiness can be obtained. On the other hand, when the crystallinity is 65% or less, good low-temperature heat is obtained. A sealing temperature can be obtained.

[Requirement (8)]
Requirement (8) is a configuration in which the propylene / 1-butene copolymer (BB) is derived from (i) three units of structural units derived from head-to-tail bonded propylene, or (ii) from propylene bonded to head-to-tail. A unit of propylene / butene consisting of a unit and a structural unit derived from butene and including a structural unit derived from propylene in the second unit, on the side of the structural unit derived from propylene of the second unit in the third chain When the chain methyl group was measured with a ¹³ C-NMR spectrum (hexachlorobutadiene solution, based on tetramethylsilane), when the total area of the peak expressed in 19.5 to 21.9 ppm was 100%, 21 The area of the peak appearing at 0.0 to 21.9 ppm is 90% or more, preferably 92% or more, more preferably 94% or more. When such a peak area is within the above range, the stereoregularity is low, that is, the content of the low melting point component that adversely affects the heat sealability can be reduced.

The stereoregularity of the propylene / 1-butene copolymer (BB) can be evaluated by triad tacticity (mm fraction). This mm fraction is defined as the ratio in which the branching directions of the methyl groups are the same when the three head-to-tail bonded propylene unit chains present in the polymer chain are represented by a surface zigzag structure. In ¹³ C-NMR spectrum.

When this mm fraction is determined from the ¹³ C-NMR spectrum, (i) three chains including propylene units present in the polymer chain, and (ii) The mm fraction is measured for a propylene unit / butene unit triple chain comprising propylene units and butene units bonded head-to-tail and the second unit being a propylene unit.

The mm fraction is determined from the peak intensity of the side chain methyl group of the second unit (propylene unit) in these three chains (i) and (ii). This will be described in detail below.
The ¹³ C-NMR spectrum of the propylene / 1-butene copolymer (BB) is completely in hexachlorobutadiene containing a small amount of deuterated benzene using the propylene / 1-butene copolymer (BB) as a lock solvent in the sample tube. And then dissolved at 120 ° C. by a proton complete decoupling method. Measurement conditions, a flip angle was 45 °, the pulse interval 3.4T ₁ or more (T ₁ is the longest value among spin-lattice relaxation time of methyl groups) and. Since T ₁ of the methylene group and methine group is shorter than the methyl group, the recovery of the magnetization of all the carbon in the sample is 99% or more under this condition. In the chemical shift, the methyl group carbon peak of the third unit of propylene units having 5 head-to-tail bonds (mmmm) based on tetramethylsilane was set to 21.593 ppm, and the other carbon peaks were based on this.

Of the ¹³ C-NMR spectrum of the propylene / 1-butene copolymer (BB) thus measured, the methyl carbon region (about 19.5 to 21.9 ppm) in which the side chain methyl group of the propylene unit is observed. Are classified into a first peak region (about 21.0 to 21.9 ppm), a second peak region (about 20.2 to 21.0 ppm), and a third peak region (about 19.5 to 20.2 ppm). .

  In each of these regions, a side chain methyl group peak of the second unit (propylene unit) in the trimolecular chain (i) and (ii) having head-to-tail bonds as shown in Table 1 is observed.

In Table 1, P represents a structural unit derived from propylene, and B represents a structural unit derived from 1-butene.
Of the head-to-tail three-linkage (i) and (ii) shown in Table 1, (i) methyl groups for PPP (mm), PPP (mr), and PPP (rr), in which all three chains are composed of propylene units The direction is illustrated in a surface zigzag structure below, but (ii) mm, mr, and rr bonds of three-chain (PPB, BPB) containing butene units conform to this PPP.

In the first region, the methyl group of the second unit (propylene unit) in the mm-bonded PPP, PPB, BPB3 chain resonates.
In the second region, the methyl group of the second unit (propylene unit) in the mr-bonded PPP, PPB, BPB3 chain and the methyl group of the second unit (propylene unit) in the rr-bonded PPB, BPB3 chain are resonant. To do.
In the third region, the methyl group of the second unit (propylene unit) of the rr-bonded PPP3 chain resonates.

Therefore, the triad tacticity (mm fraction) of the propylene / 1-butene copolymer (BB) is (i) a head-to-tail bonded propylene unit three-chain or (ii) a head-to-tail bonded propylene unit. 3 chain of propylene / butene consisting of a butene unit and containing a propylene unit in the second unit, and a ¹³ C-NMR spectrum (hexachlorobutadiene solution) for the side chain methyl group of the propylene unit of the second unit in the third chain 21.0-21.9 ppm (first region) when the total area of the peak appearing in 19.5-21.9 ppm (methyl carbon region) is taken as 100%. The ratio (percentage) of the area of the peak appearing in is obtained from the following formula.

In the propylene / 1-butene copolymer (BB), the mm fraction thus determined is 90% or more, preferably 92% or more, more preferably 94% or more.
The propylene / 1-butene copolymer (BB) has the following structures (iii), (iv), and (v) in addition to the above-described three-chain (i) and (ii) bonded to the head. And a peak derived from the side chain methyl group of the propylene unit by such other bonds is also in the above methyl carbon region (19.5 to 21). .9 ppm).

  Among the methyl groups derived from the structures (iii), (iv) and (v), the methyl group carbon A and the methyl group carbon B resonate at 17.3 ppm and 17.0 ppm, respectively. The peak based on B does not appear in the first to third regions (19.5 to 21.9 ppm). Furthermore, since carbon A and carbon B are not involved in the propylene trilinkage based on the head-to-tail bond, it is not necessary to consider them in the calculation of the triad tacticity (mm fraction).

  The peak based on the methyl group carbon C, the peak based on the methyl group carbon D, and the peak based on the methyl group carbon D ′ appear in the second region, and the peak based on the methyl group carbon E and the peak based on the methyl group carbon E ′ are Appears in the third region.

  Therefore, the 1st to 3rd methyl carbon regions include PPE-methyl group (side chain methyl group in propylene-propylene-erene chain) (around 20.7 ppm), EPE-methyl group (side in ethylene-propylene-ethylene chain). (Chain methyl group) (around 19.8 ppm), peaks based on methyl group C, methyl group D, methyl group D ′, methyl group E, and methyl group E ′ appear.

  Thus, in the methyl carbon region, peaks of methyl groups that are not based on the head-to-tail bond three linkages (i) and (ii) are also observed. It is corrected as follows.

  The peak area based on the PPE-methyl group can be obtained from the peak area of the PPE-methine group (resonant at around 30.6 ppm), and the peak area based on the EPE-methyl group is determined based on the EPE-methine group (around 32.9 ppm). Resonance) peak area. The peak area based on the methyl group C can be determined from the peak area of the adjacent methine group (resonance near 31.3 ppm). The peak area based on the methyl group D can be determined from ½ of the sum of the peak areas of the peaks based on the αβ methylene carbon of the structure (iv) (resonance at around 34.3 ppm and around 34.5 ppm). The peak area based on the group D ′ can be determined from the area of the peak (resonance around 33.3 ppm) based on the methine group adjacent to the methyl group of the structure (v) methyl group E ′. The peak area based on the methyl group E can be obtained from the peak area of the adjacent methine carbon (resonant at around 33.7 ppm), and the peak area based on the methyl group E ′ is determined at the adjacent methine carbon (around 33.3 ppm). Resonance) peak area.

  Therefore, by subtracting these peak areas from the total peak areas of the second region and the third region, it is possible to determine the peak area of the methyl group based on the head-to-tail three-linked propylene units (i) and (ii). .

  As described above, the peak area of the methyl group based on the three-chain (i) and (ii) propylene units bonded head-to-tail can be evaluated, and the mm fraction can be determined according to the above formula. Each carbon peak in the spectrum can be assigned with reference to literature (Polymer, 30, 1350 (1989)).

  The α-olefin copolymer (B) having 2 or 4 to 20 carbon atoms is composed of propylene, ethylene or an α-olefin having 4 to 20 carbon atoms and, if necessary, a small amount of other olefins. It can be suitably obtained by copolymerization in the presence of a Ziegler-Natta catalyst or a catalyst containing a metallocene compound. Examples of the Ziegler-Natta catalyst include JP-A-2-43242, JP-A-3-66737, JP-A-6-263935, and catalysts containing a metallocene compound include WO2004 / 088775 and WO01 / It can be produced by the method described in Japanese Patent No. 27124.

  More specifically, the α-olefin copolymer (B) having 2 or 4 to 20 carbon atoms (B) is a composite containing (a) at least magnesium, titanium and halogen as a Ziegler-Natta catalyst, b) Using a catalyst composed of a metal element of Group 1 to Group 3 of the periodic table and (c) an electron donor, propylene and an α-olefin having 2 or 4 to 20 carbon atoms It can be obtained by copolymerizing, preferably by copolymerizing propylene and 1-butene as an α-olefin. Part or all of the electron donor (c) may be fixed to part or all of the complex (a), or may be pre-contacted with the organometallic compound (b) prior to use. Also good. Particularly preferred is a form in which a part of the electron donor (c) is fixed to the complex (a), and the remainder is added to the polymerization system as it is or pre-contacted with the organometallic compound (b). It is a catalyst. In this case, the electron donor fixed to the composite (a) and the electron donor used in addition to the polymerization system as they are or preliminarily contacted with the organometallic compound (b) may be the same or different. It may be a thing.

  In addition, the α-olefin copolymer (B) having 2 or 4 to 20 carbon atoms as the propylene-carbon copolymer (B) is present as a metallocene catalyst containing a transition metal compound (1a) represented by the following general formula (1a) Below, it can obtain by copolymerizing propylene and a C2-C20 or alpha-olefin of 4-20, preferably copolymerizing 1-butene as propylene and alpha-olefin. Here, the catalyst containing the transition metal compound (1a) is (2a) an organometallic compound, (2b) an organoaluminum oxy compound, and (2c) a compound that forms an ion pair by reacting with the transition metal compound (1a). And a catalyst containing at least one compound selected from the above and the transition metal compound (1a).

（式中、Ｒ¹、Ｒ³は水素であり、Ｒ²、Ｒ⁴は炭化水素基、ケイ素含有基から選ばれ、それぞれ同一でも異なっていてもよい。Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³およびＲ¹⁴は水素、炭化水素基、ケイ素含有基から選ばれ、それぞれ同一でも異なっていてもよく、Ｒ⁵からＲ¹²までの隣接した置換基は互いに結合して環を形成してもよい。Ｒ¹³とＲ¹⁴はそれぞれ同一でも異なっていてもよく、互いに結合して環を形成してもよい。Ｍは第４族遷移金属であり、Ｙは炭素原子であり、Ｑはハロゲン、炭化水素基、アニオン配位子または孤立電子対で配位可能な中性配位子から同一または異なる組合せで選んでもよく、ｊは１〜４の整数である。）

(Wherein R ¹ and R ³ are hydrogen, and R ² and R ⁴ are selected from a hydrocarbon group and a silicon-containing group, and may be the same or different. R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are selected from hydrogen, hydrocarbon group, and silicon-containing group, and may be the same or different and are adjacent to R ⁵ to R ^12. The substituents may be bonded to each other to form a ring, and R ¹³ and R ¹⁴ may be the same or different from each other, and may be bonded to each other to form a ring, where M is a Group 4 transition metal Y may be a carbon atom, Q may be selected from the same or different combinations from halogen, hydrocarbon groups, anionic ligands or neutral ligands capable of coordinating with a lone pair, It is an integer of 4.)

  Examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and n-nonyl group. Linear hydrocarbon groups such as n-decanyl group; isopropyl group, tert-butyl group, amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl A branched hydrocarbon group such as a -1-propylbutyl group, a 1,1-propylbutyl group, a 1,1-dimethyl-2-methylpropyl group, and a 1-methyl-1-isopropyl-2-methylpropyl group; a cyclopentyl group Cyclic saturated hydrocarbon groups such as cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group; phenyl group, tolyl group, naphthyl group, biphenyl A cyclic unsaturated hydrocarbon group such as a group, a phenanthryl group or an anthracenyl group; a saturated hydrocarbon group substituted with a cyclic unsaturated hydrocarbon group such as a benzyl group, a cumyl group, a 1,1-diphenylethyl group or a triphenylmethyl group; Examples include heteroatom-containing hydrocarbon groups such as methoxy group, ethoxy group, phenoxy group, furyl group, N-methylamino group, N, N-dimethylamino group, N-phenylamino group, pyryl group, and thienyl group. it can.

Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylsilyl group, and a triphenylsilyl group. Moreover, the adjacent substituents of R ⁵ to R ¹² may be bonded to each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, octamethyloctahydrodibenzofluorenyl group, octamethyltetrahydrodicyclopentafluorenyl group, etc. Can be mentioned.

R ¹⁴ is an aryl group. Examples of the aryl group include the above-mentioned cyclic unsaturated hydrocarbon group, saturated hydrocarbon group substituted with the cyclic unsaturated hydrocarbon group, a heteroatom-containing cyclic unsaturated hydrocarbon group such as a furyl group, a pyryl group, and a thienyl group. be able to. R ¹³ and R ¹⁴ may be the same or different, and may be bonded to each other to form a ring.

In the general formula (1a), R ² and R ⁴ substituted on the cyclopentadienyl ring are preferably hydrocarbon groups having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the above hydrocarbon groups. Among these, R ² is more preferably a bulky substituent such as a tert-butyl group, an adamantyl group, or a triphenylmethyl group, and R ⁴ is R ² such as a methyl group, an ethyl group, or an n-propyl group. More preferably, the substituent is sterically smaller. The term “sterically small” as used herein refers to the volume occupied by the substituent.

In the general formula (1a), among R ⁵ to R ¹² substituted on the fluorene ring, any two or more of R ⁶ , R ⁷ , R ¹⁰ , and R ¹¹ are hydrocarbon groups having 1 to 20 carbon atoms. Preferably there is. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the above hydrocarbon groups. In particular, from the viewpoint of ease of synthesis of the ligand, it is preferable that R ⁶ and R ¹¹ and R ⁷ and R ¹⁰ are the same group. Among such preferred embodiments, R ⁶ and R ⁷ form an aliphatic ring (AR-1), and R ¹⁰ and R ¹¹ are the same aliphatic ring (AR-1). The case where (AR-2) is formed is also included.

In the said General formula (1a), Y which bridge | crosslinks a cyclopentadienyl ring and a fluorenyl ring is a carbon atom. R ¹³ and R ¹⁴ substituted for Y are preferably an aryl group having 6 to 20 carbon atoms at the same time. These may be the same as or different from each other, and may be bonded to each other to form a ring. Examples of the aryl group having 6 to 20 carbon atoms include the above-mentioned cyclic unsaturated hydrocarbon group, a saturated hydrocarbon group substituted with a cyclic unsaturated hydrocarbon group, and a heteroatom-containing cyclic unsaturated hydrocarbon group. R ¹³ and R ¹⁴ may be the same or different, and may be bonded to each other to form a ring. As such a substituent, a fluorenylidene group, a 10-hydroanthracenylidene group, a dibenzocycloheptadienylidene group, and the like are preferable.

  In the general formula (1a), M is a Group 4 transition metal, and specific examples thereof include Ti, Zr, and Hf. Q is selected from the same or different combinations from a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair. j is an integer of 1 to 4, and when j is 2 or more, Qs may be the same or different from each other. Specific examples of the halogen atom are fluorine, chlorine, bromine and iodine, and specific examples of the hydrocarbon group include the same as those described above. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxy. And ethers such as ethane. It is preferable that at least one Q is a halogen or an alkyl group.

  Examples of such a transition metal compound (1a) include dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) fluorenylzirconium dichloride, isopropylidene (3-tert-butyl-5-methylcyclohexane). Pentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-methylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (3-tert -Butyl-5-methylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-methylcyclopentadienyl) (octamethyloctahydride) Givens Fluore ) Zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (2,7- Di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3 -Tert-butyl-5-methylcyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride and the like, but are not limited thereto.

  Suitable catalysts for producing the propylene / carbon atom or α-olefin copolymer (B) having 4 to 20 carbon atoms (B) include (2a) organometallic compound and (2b) organic, together with the transition metal compound (1a). It contains at least one compound selected from an aluminum oxy compound and (2c) a compound that reacts with a transition metal compound (1a) to form an ion pair. These (2a), (2b), and (2c) compounds are not particularly limited, but preferred examples include the compounds described in WO2004 / 088775 or WO01 / 27124. It is done.

(2a) As the organometallic compound, the following Group 1, 2 and Group 12, 13 organometallic compounds are used.
(2a-1) General formula: R ^a _m Al (OR ^b ) _n H _p X _q
(In the formula, R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0. <M ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3). Specific examples of such compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, diisobutylaluminum hydride and the like.

(2a-2) General formula: M ² AlR ^a ₄
(Wherein M ² represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms) Complex alkylated product with aluminum. Examples of such a compound include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

(2a-3) General formula: R ^a R ^b M ³
(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ³ represents Mg, Zn or Cd. A dialkyl compound of a Group 2 or Group 12 metal represented by:

  Of these organometallic compounds (2a), organoaluminum compounds are preferred. Moreover, such an organometallic compound (2a) may be used individually by 1 type, and may be used in combination of 2 or more type.

(2b) The organoaluminum oxy compound may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound exemplified in JP-A-2-78687.
A conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally obtained as a solution of a hydrocarbon solvent.

  1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method in which an organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension and the adsorbed water or crystal water reacts with the organoaluminum compound.

  2) A method in which water, ice or water vapor is allowed to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, diethyl ether or tetrahydrofuran.

  3) A method of reacting an organotin oxide such as dimethyltin oxide or dibutyltin oxide with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.

  The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, it may be redissolved in a solvent or suspended in a poor aluminoxane solvent. Specific examples of the organoaluminum compound used when preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the above (2a-1). Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable. The organoaluminum compounds as described above are used singly or in combination of two or more.

  As the benzene-insoluble organoaluminum oxy-compound, an Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, that is, benzene Those that are insoluble or sparingly soluble are preferred. These organoaluminum oxy compounds (2b) are used singly or in combination of two or more.

  (2c) Examples of the compound that reacts with the transition metal compound (1a) to form an ion pair include JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, and JP-A-3- And Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A No. 179006, JP-A-3-207703, JP-A-3-207704, USP-5321106, and the like. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned. Such a compound of (2c) is used individually by 1 type or in combination of 2 or more types.

  In the production of the propylene / carbon atom 2 or 4 to 20 α-olefin copolymer (B), a catalyst in which an organic aluminum oxy compound (2b) such as methylaluminoxane is used together with the transition metal compound (1a) is used. And particularly preferable because of high polymerization activity.

  In addition, the polymerization catalyst used for the production of the propylene / carbon atom 2 or 4-20 α-olefin copolymer (B) may be one using a carrier as necessary, and other cocatalysts. A component may be included.

Such a catalyst may be prepared by mixing each component in advance or by supporting it on a carrier, or may be used by adding each component simultaneously or sequentially to the polymerization system.
Propylene / C2-C20 α-olefin copolymer (B) is preferably composed of propylene and a C2-C20 α-olefin in the presence of the catalyst, in particular. Preferably, it is obtained by copolymerizing 1-butene with a small amount of other olefin as required. In the copolymerization, each monomer may be used in such an amount that the amount of each constituent unit in the α-olefin copolymer (B) having 2 or 4 to 20 carbon atoms to be produced is a desired ratio. Specifically, it is 50/50 to 95/5, preferably 60/40 to 93/7, more preferably 70/30 to 90/10, in terms of a molar ratio of propylene / C2-α or α-olefin having 4 to 20 carbon atoms. Used at a ratio of

  The copolymerization conditions are not particularly limited. For example, the polymerization temperature is usually in the range of −50 to + 200 ° C., preferably 0 to 170 ° C., and the polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably normal. Pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be carried out in two or more stages having different reaction conditions. The molecular weight of the α-olefin copolymer (B) having 2 or 4 to 20 carbon atoms can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. It can also be adjusted by the amount of (2a), (2b) or (2c). When hydrogen is added, the amount is suitably about 0.001 to 100 NL per kg of monomer.

<Resin composition>
The resin composition according to the present invention contains at least a propylene-based resin (A) and a propylene / α-olefin copolymer (B) having 2 or 4 to 20 carbon atoms. More preferably, it is a resin composition containing at least a propylene resin (A) and a propylene / 1-butene copolymer (BB).

  In the resin composition of the present invention, the propylene-based resin (A) is preferably 50 to 95% by weight, more preferably 60 to 90% by weight, and particularly preferably 70 to 85% by weight in 100% by weight of the resin composition. %included.

The propylene / 1-butene copolymer (BB) is preferably contained in an amount of 5 to 50% by weight, more preferably 10 to 40% by weight, and particularly preferably 15 to 30% by weight.
When the content of the propylene / 1-butene copolymer (BB) is 5% by weight or more, flexibility can be imparted to the film, and the melting point (Tm) is lowered, so that the heat seal temperature is also lowered. The molding cycle can be shortened.

Further, when the content of the propylene / 1-butene copolymer (BB) is 50% by weight or less, the blocking resistance and scratch resistance of the film are not impaired.
When the content of the propylene / 1-butene copolymer (BB) is within the above range, the bag-like container obtained from the resin composition is excellent in heat resistance as compared with a conventional polyethylene-based bag-like container. It is suitable for heat sterilization after filling the filling material.

  In addition to the propylene resin (A) and the propylene / 1-butene copolymer (BB), the resin composition according to the present invention includes a heat resistance stabilizer, an ultraviolet absorber, an antiblocking agent, a slip agent, and an antistatic agent. Etc. can be mix | blended.

  Such an additive can be blended in an amount of 0.05 wt% or more and less than 5 wt%, preferably 0.1 wt% or more and less than 2 wt% in 100 wt% of the resin composition. Is within the above range, it is possible to obtain a resin composition having an excellent balance of slip property, heat seal property and economic efficiency.

  In the present invention, in order to prepare a resin composition containing a propylene-based resin (A) and a propylene / α-olefin copolymer having 2 to 4 or 20 carbon atoms (B), any conventionally known method is used. For example, a method of mixing with a mixer such as a V-type blender, ribbon blender or Henschel mixer, and / or a method of kneading with a kneader such as an extruder, mixing roll, Banbury mixer or kneader is combined. Alternatively, they may be used alone and the respective components may be mixed. The resin composition obtained by mixing may be prepared into pellets or granules using an extruder or the like, or may be directly formed into a film having a layer comprising the resin composition according to the present invention. Good.

<Filled material>
The filling material used in the present invention is liquid and / or powder, and specifically, may be water, oil, seasonings such as sugar, salt, and flour, foods, and the like. Not.

<Bag-like container>
The bag-like container used in the present invention is formed by bag-making a film having a heat seal layer made of the resin composition, and has an opening for filling the filling material. The opening has a heat seal portion and can be heat sealed. The temperature at the time of heat sealing is 80 to 220 ° C, preferably 100 to 200 ° C, more preferably 120 to 180 ° C. Since the resin composition can lower the heat seal temperature without greatly impairing the heat resistance of the propylene-based resin (A), the molding cycle time can be shortened. Moreover, the pressure at the time of heat-sealing is 0.05-1.0 MPa, Preferably it is 0.1-0.3 MPa. Furthermore, the time for heat sealing is 0.1 to 3 seconds, preferably 0.2 to 1 second.

  When filling a to-be-filled material into a bag-shaped container, the to-be-filled material may be clamped by at least one part of the heat seal part. That is, even if the object to be filled is heat-sealed while adhering to at least a part of the heat-sealing portion, the heat-sealing strength of the bag-like container is not greatly reduced.

After filling the object to be filled and heat-sealing, it is desirable that the bag-like container is sealed.
Depending on the type of filling, the sealed bag-like container may be sterilized by autoclaving (120 ° C., 2 atm, 4 minutes) as necessary. Since the package of this invention is excellent in heat resistance, it can be used conveniently also for the use which needs to sterilize by heat.

  Examples of the method for forming the resin composition into a film include extrusion lamination molding, T-die film molding, and inflation molding (air cooling, water cooling, multistage cooling, high-speed processing, etc.) and the like. The obtained film can be used as a single layer, but various functions can be imparted by forming a laminate.

The bag-like container is formed by bag-making the above film and can be molded by a conventionally known method. For example, general film molding, blow molding, injection molding, injection blow molding, extrusion molding , Stretching (uniaxial stretching, tubular simultaneous biaxial stretching, tenter method sequential biaxial stretching, tenter method simultaneous biaxial stretching, etc.) and the like can be processed into a desired bag shape.
The thickness of the bag-like container is desirably 3 to 500 μm, preferably 5 to 100 μm in order to support the weight of the contents and to withstand an external impact.

<Laminated body>
The film is preferably a laminate having the heat seal layer and at least one base material layer. The thickness of the laminate is preferably 5 to 1000 μm, more preferably in order to support the weight of the content while considering the economy, while depending on the type of the content and the type of the base material layer to be used. It has a thickness of 10 to 500 μm.

[Base material layer]
As a material used for the base material layer constituting the laminate, for example, resin, paper, barrier film (aluminum foil, vapor deposition film, coating film, etc.) and the like are used.

The resin constituting the base material layer preferably satisfies the performance as a container, and preferably has physical properties such as molecular weight, transparency, flexibility, and impact resistance that can be formed into a film.
Examples of the resin include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, and polyethylene-based copolymers of ethylene and long-chain olefin monomers such as 1-butene and 1-pentene. Resin: Polypropylene resin such as propylene homopolymer, high crystallinity propylene homopolymer, propylene / ethylene random copolymer, propylene / ethylene block copolymer; ethylene / ethyl acrylate copolymer, ethylene / n-butyl acrylate Examples thereof include a polymer, an ethylene / vinyl acetate copolymer, and an ionomer resin. These polyolefin resin may be used independently and 2 or more types may be used together. Furthermore, a conventionally well-known raw material can also be used.

The base material layer may be blended with an antioxidant, an antistatic agent, other additives, etc., if necessary, and these may be used alone or in combination of two or more.
Laminate molding methods include film molding, blow molding, injection molding, injection blow molding, extrusion molding, stretching (uniaxial stretching, tubular simultaneous biaxial stretching, tenter method sequential biaxial stretching, tenter method simultaneous biaxial stretching, etc.) And a co-extrusion method in the molding method. On the other hand, lamination with paper and barrier films (aluminum foil, vapor-deposited film, coating film, etc.) that are difficult to co-extrusion is possible by a lamination method such as extrusion lamination and dry lamination. The laminate can be formed by the co-extrusion method in blow molding, injection molding, and extrusion molding in the same manner as film molding.

<Manufacturing method of package>
The manufacturing method of the package of the present invention includes at least the following steps (1) and (2).
Step (1): A step of filling the filling liquid and / or powder from the opening of the bag-like container.
Step (2): a step of heat-sealing the opening filled with the filling material of the bag-like container.

Next, the packaging body of the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
The measuring method of each physical-property value of a propylene 1-butene copolymer (BB) is enumerated below.

[1-butene content (M)]
The 1-butene content (M) [mol%], which is the amount of structural units derived from 1-butene contained in the propylene / 1-butene copolymer (BB), was determined by ¹³ C-NMR.

[Melt flow rate (MFR)]
The melt flow rate (MFR) [g / 10 min] of the propylene / 1-butene copolymer (BB) was measured at a temperature of 230 ° C. and a load of 2.16 kg according to ASTM D1238.

[Molecular weight distribution (Mw / Mn)]
The molecular weight distribution (Mw / Mn) of the propylene / 1-butene copolymer (BB) was measured using GPC-150C manufactured by Millipore as follows.

  The separation column was TSK GNH HT, the column size was 27 mm in diameter and the length was 600 mm, the column temperature was 140 ° C., and o-dichlorobenzene (manufactured by Wako Pure Chemical Industries, Ltd.) and antioxidant were used as the mobile phase. BHT (manufactured by Takeda Pharmaceutical Co., Ltd.) is used at 0.025% by weight, moved at 1.0 ml / min, the sample concentration is 0.1% by weight, the sample injection amount is 500 μl, and a differential refractometer is used as a detector. Was used.

Standard polystyrenes manufactured by Tosoh Corporation were used for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and standard polystyrenes manufactured by Pressure Chemical Co., Ltd. were used for 1000 ≦ Mw ≦ 4 × 10 ⁶ .

[Melting point (Tm)]
The melting point (Tm) of the propylene / 1-butene copolymer (BB) was measured using a DSC-7 type apparatus (differential scanning calorimeter (DSC)) manufactured by PerkinElmer Co., Ltd.

About 5 mg of sample was packed in an aluminum pan, heated to 200 ° C., held at 200 ° C. for 5 minutes, cooled to −40 ° C. at 10 ° C./minute, held at −40 ° C. for 5 minutes, and then 10 ° C. / It was determined from the endothermic curve when the temperature was raised in minutes.
The measuring method of each physical property value of the package is listed below.

[Heat seal strength]
Using a brush on a part of the corona-treated surface of the corona-treated surface, salad oil ("Canola oil" manufactured by J-Oil Mills Co., Ltd.) as a filling material in a portion of 30 mm width x 250 mm length 0. 130g was apply | coated to the part of width 30mm x length 20mm using the brush. Similarly, a corona-treated film was laminated so that the corona-treated surfaces overlap each other, and a test body was prepared in which both surfaces of the overlapped film were sandwiched between Teflon (registered trademark) sheets having a thickness of 50 μm. Next, a heat seal bar of a heat seal tester (TB-701B type manufactured by Tester Sangyo Co., Ltd.) was set to 15 mm wide × 300 mm long, and the lower side of the seal bar was set to 70 ° C. The specimen (Teflon sheet / film (salad oil application) / film / Teflon sheet) was sandwiched between the heat seal bars and heat sealed at a pressure of 0.2 MPa for 1.0 second. The Teflon sheet was removed and the heat-sealed film part was left at room temperature of about 23 ° C. for 2 days. A slit having a width of 15 mm was inserted so as to include the heat seal portion of the film, and the unsealed portion was chucked by a tensile tester ("IM-20ST" manufactured by INTERSCO). The 180 ° peel strength of the film was measured at a speed of 300 mm / min. The said operation was performed 5 times and the average value was made into heat seal intensity | strength.

[Retention ratio]
The retention rate was calculated from the following equation.
Retention rate (%) = HS2 / HS1 × 100 (%)
HS1: Represents the heat seal strength (g / 15 mm) when no object to be filled is present on the corona-treated surface.
HS2: This represents the heat seal strength (g / 15 mm) when an object to be filled is interposed on the corona-treated surface.
Synthesis examples of Ziegler catalysts and metallocene catalysts are shown below.

[Synthesis Example 1: Ziegler catalyst]
200 g of anhydrous magnesium chloride, 46 ml of ethyl benzoate and 30 ml of methylpolysiloxane were put into a ball mill and kneaded in a nitrogen atmosphere, and then added to titanium tetrachloride to prepare a suspension. The suspension was filtered and dried to obtain a solid titanium catalyst supported on magnesium chloride.

[Synthesis Example 2: Metallocene catalyst]
(1) Preparation of 1-tert-butyl-3-methylcyclopentadiene Dehydrated diethyl ether (350 ml) in a tert-butylmagnesium chloride / diethyl ether solution (450 ml, 0.90 mol, 2.0 mol / l solution) under a nitrogen atmosphere A solution of 3-methylcyclopentenone (43.7 g, 0.45 mmol) in dehydrated diethyl ether (150 ml) was added dropwise to the solution to which was added while maintaining 0 ° C. under ice cooling, and the mixture was further stirred at room temperature for 15 hours. A solution of ammonium chloride (80.0 g, 1.50 mol) in water (350 ml) was added dropwise to the reaction solution while maintaining 0 ° C. under ice cooling. Water (2500 ml) was added to this solution and stirred, and then the organic layer was separated and washed with water. A 10% aqueous hydrochloric acid solution (82 ml) was added to the organic layer while maintaining 0 ° C. under ice cooling, and the mixture was stirred at room temperature for 6 hours. The organic layer of this reaction solution was separated, washed with water, saturated aqueous sodium hydrogen carbonate solution, water and saturated brine, and then dried over anhydrous magnesium sulfate. The desiccant was filtered and the solvent was distilled off from the filtrate to obtain a liquid. This liquid was distilled under reduced pressure (45-47 ° C./10 mmHg) to obtain 14.6 g of a pale yellow liquid. Analytical values are shown below.
¹ H-NMR (270 MHz, in CDCl ₃ , TMS standard) δ6.31 + 6.13 + 5.94 + 5.87 (s + s + t + d, 2H), 3.04 + 2.95 (s + s, 2H), 2.17 + 2.09 (s + s, 3H) 1.27 (d, 9H)

(2) Preparation of 3-tert-butyl-1,6,6-trimethylfulvene A solution of 1-tert-butyl-3-methylcyclopentadiene (13.0 g, 95.6 mmol) in dehydrated methanol (130 ml) under a nitrogen atmosphere Then, dehydrated acetone (55.2 g, 950.4 mmol) was added dropwise while maintaining 0 ° C. under ice cooling, and pyrrolidine (68.0 g, 956.1 mmol) was further added dropwise, followed by stirring at room temperature for 4 days. The reaction mixture was diluted with diethyl ether (400 ml), and water (400 ml) was added. The organic layer was separated, washed with 0.5N aqueous hydrochloric acid (150 ml × 4), water (200 ml × 3) and saturated brine (150 ml), and then dried over anhydrous magnesium sulfate. The desiccant was filtered and the solvent was distilled off from the filtrate to obtain a liquid. This liquid was distilled under reduced pressure (70 to 80 ° C./0.1 mmHg) to obtain 10.5 g of a yellow liquid. Analytical values are shown below.
¹ H-NMR (270 MHz, in CDCl ₃ , TMS standard) δ 6.23 (s, 1H), 6.05 (d, 1H), 2.23 (s, 3H), 2.17 (d, 6H), 1.17 (s, 9H)

(3) Preparation of 2- (3-tert-butyl-5-methylcyclopentadienyl) -2-fluorenylpropane To a solution of fluorene (10.1 g, 60.8 mmol) in THF (300 ml) under ice-cooling The n-butyllithium hexane solution (40 ml, 61.6 mmol) was added dropwise under a nitrogen atmosphere, and the mixture was further stirred at room temperature for 5 hours (dark brown solution). This solution was ice-cooled again, and a solution of 3-tert-butyl-1,6,6-trimethylfulvene (11.7 g, 66.5 mmol) in THF (300 ml) was added dropwise under a nitrogen atmosphere. The brown solution obtained after stirring at room temperature for 14 hours was ice-cooled and water (200 ml) was added. The organic phase extracted and separated with diethyl ether was dried over magnesium sulfate and filtered, and the solvent was removed from the filtrate under reduced pressure to obtain an orange-brown oil. This oil was purified by silica gel column chromatography (developing solvent: hexane) to obtain 3.8 g of a yellow oil. Analytical values are shown below.
¹ H-NMR (270 MHz, in CDCl ₃ , TMS standard) δ 7.70 (d, 4H), 7.34-7.26 (m, 6H), 7.18-7.11 (m, 6H), 6 .17 (s, 1H), 6.01 (s, 1H), 4.42 (s, 1H), 4.27 (s, 1H), 3.01 (s, 2H), 2.87 (s, 2H), 2.17 (s, 3H), 1.99 (s, 3H), 2.10 (s, 9H), 1.99 (s, 9H), 1.10 (s, 6H), 1. 07 (s, 6H)

(4) Preparation of dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) fluorenylzirconium dichloride 2- (3-tert-butyl-5-methylcyclopentadienyl) -2 under ice-cooling -A solution of n-butyllithium in hexane (5.0 ml, 7.7 mmol) was added dropwise to a solution of fluorenylpropane (1.14 g, 3.3 mmol) in diethyl ether (25 ml) under a nitrogen atmosphere. Stir for hours to obtain a pink slurry. Zirconium tetrachloride (0.77 g, 3.3 mmol) was added to this slurry at −78 ° C., and the mixture was stirred at −78 ° C. for several hours and then at room temperature for 65 hours. The resulting black-brown slurry was filtered, and the residue was washed with 10 ml of diethyl ether and extracted with dichloromethane to obtain a red solution. The solvent of this solution was distilled off under reduced pressure to obtain 0.53 g of a red-orange solid metallocene catalyst, dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) fluorenylzirconium dichloride. Analytical values are shown below.
¹ H-NMR (270 MHz, in CDCl ₃ , TMS standard) δ 8.11-8.02 (m, 3H), 7.82 (d, 1H), 7.56-7.45 (m, 2H), 7 .23-7.17 (m, 2H), 6.08 (d, 1H), 5.72 (d, 1H), 2.59 (s, 3H), 2.41 (s, 3H), 2. 30 (s, 3H), 1.08 (s, 9H)

[Production Example 1: Polymer 1 (Preparation of propylene / 1-butene copolymer (BB) with Ziegler catalyst)]
2,000 ml of hexane and 100 g of 1-butene are charged into a 2000 ml autoclave thoroughly purged with nitrogen, 1 mmol of triisobutylaluminum is added, the temperature is raised to 70 ° C., propylene is supplied to a total pressure of 0.7 MPa, and triethylaluminum 1 mmol, and the solid titanium catalyst supported on magnesium chloride obtained in Synthesis Example 1 was added to 0.005 mmol in terms of Ti atoms, and propylene was continuously supplied to keep the total pressure at 0.7 MPa. Polymerization was performed for 30 minutes, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 2 l of methanol and dried under vacuum at 130 ° C. for 12 hours.

  The obtained polymer 1 was 33.7 g. Polymer 1 has a 1-butene content (M) of 26.0 mol%, a melt flow rate (MFR) of 6.7 g / 10 min, a molecular weight distribution (Mw / Mn) of 4.0 and a melting point (Tm). : 110.0 ° C.

[Production Example 2: Polymerized polymer 2 (Preparation of propylene / 1-butene copolymer with metallocene catalyst)]
After charging 2,000 ml of hexane, 75 g of 1-butene and triisobutylaluminum (1.0 mmol) into a 2000 ml polymerization apparatus sufficiently purged with nitrogen at room temperature, the temperature inside the polymerization apparatus was raised to 65 ° C. and propylene was used. Pressurized to 0.7 MPa. Next, 0.002 mmol of dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) fluorenylzirconium dichloride, which is the metallocene catalyst obtained in Synthesis Example 2, and 0.6 mmol of methylaluminoxane (in terms of aluminum) ( A toluene solution brought into contact with Tosoh Finechem Co., Ltd. was added into the polymerization vessel, polymerized for 30 minutes while maintaining an internal temperature of 65 ° C. and a propylene pressure of 0.7 MPa, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 2 l of methanol and dried under vacuum at 130 ° C. for 12 hours.

  The obtained polymer 2 was 15.2 g. Polymerized polymer 2 had a 1-butene content (M) of 19.4 mol%, a melt flow rate (MFR) of 6.5 g / 10 min, a molecular weight distribution (Mw / Mn) of 2.11 and a melting point (Tm). : It was 83.2 degreeC. In addition, since M is 19.4 for the expression (2.6) + 130 ≦ Tm ≦ −2.3M + 155 of the requirement (5), the above expression becomes 79.6 ≦ Tm ≦ 110.4, and Tm: Satisfy 83.2.

[Production Example 3: Polymerized polymer 3 (Preparation of propylene / 1-butene copolymer with metallocene catalyst)]
Polymerization was carried out in the same manner as in Production Example 2, except that hexane was charged to 850 ml and 1-butene was changed to 90 g.
The obtained polymer 3 was 12.5 g. Polymerized polymer 3 has 1-butene content (M): 23.0 mol%, melt flow rate (MFR): 6.8 g / 10 min, molecular weight distribution (Mw / Mn): 2.1, and melting point (Tm): It was 75.6 ° C. In addition, since M is 23.0 for the expression (2.6) + 130 ≦ Tm ≦ −2.3M + 155 of the above requirement (5), the above expression becomes 70.2 ≦ Tm ≦ 102.1, and Tm: Satisfies 75.6.

[Reference Example 1]
As the propylene-based resin (A), “Prime Polypro F327” (manufactured by Prime Polymer Co., Ltd.), which is a propylene random copolymer having an MFR of 7 g / 10 min and a melting point of 138 ° C., and a polymer polymer 1 of 85 / Blended at a weight ratio of 15 and introduced into a cast molding machine manufactured by Sumitomo Heavy Industries Modern Co., Ltd., where the temperature of the cylinder part of the extruder was set to 190 to 230 ° C., so that the film thickness became 50 μm at a speed of 10 m / min. The melt resin was extruded into a film form from a T-die of a cast molding machine by adjusting the screw speed of the extruder, and the molten resin was brought into contact with a chill roll having a set temperature of 25 ° C. to continuously cool and solidify the film. Next, corona discharge was performed on the surface of the film so that the wetting index was 40 to 45 mN / m, and the film was wound up.

  Using a brush on a part of the corona-treated surface of the film, 0.130 g of salad oil (“Canola oil” manufactured by J-Oil Mills Co., Ltd.) was applied with a brush to a 30 mm wide × 250 mm long part. Similarly, a corona-treated film was laminated so that the corona-treated surfaces overlap each other, and a test body was prepared in which both surfaces of the overlapped film were sandwiched between Teflon sheets having a thickness of 50 μm. Next, a heat seal bar of a heat seal tester (manufactured by Tester Sangyo Co., Ltd .; TB-701B type) was installed at a width of 15 mm × a length of 300 mm, and the lower side of the seal bar was set at 70 ° C. The specimen was sandwiched between the heat seal bar portions, and heat sealed at a pressure of 0.2 MPa for 1.0 second. The Teflon sheet was removed and the heat-sealed film part was left at room temperature of about 23 ° C. for 2 days. A slit having a width of 15 mm was inserted so as to include the heat-sealed portion of the film, and the unsealed portion was chucked by a tensile tester (“IM-20ST” manufactured by INTESCO). The 180 ° peel strength of the film was measured at a speed of 300 mm / min. Table 2 shows each physical property value.

[Reference Example 2]
The physical properties were evaluated by preparing in the same manner as in Reference Example 1 except that the weight ratio of “Prime Polypro F327” and Polymerized Polymer 1 was changed to 70/30. Table 2 shows each physical property value.

[Example 1]
The physical properties were evaluated by preparing in the same manner as in Reference Example 1 except that the polymer 2 was used instead of the polymer 1. Table 2 shows each physical property value.

[Example 2]
The physical properties were evaluated by preparing in the same manner as in Example 1 except that the weight ratio of “Prime Polypro F327” and polymerized polymer 2 was changed to 70/30. Table 2 shows each physical property value.

Example 3
The polymerized polymer 3 was used in place of the polymerized polymer 1, and physical properties were evaluated by preparing in the same manner as in Reference Example 1 except that the weight ratio of “Prime Polypro F327” and polymerized polymer 3 was changed to 95/5. Table 2 shows each physical property value.

Example 4
The physical properties were evaluated by preparing in the same manner as in Reference Example 1 except that the polymer 3 was used instead of the polymer 1. Table 2 shows each physical property value.

Example 5
The physical properties were evaluated in the same manner as in Example 3 except that the weight ratio of “Prime Polypro F327” and polymerized polymer 3 was changed to 70/30. Table 2 shows each physical property value.

[Comparative Example 1]
The physical properties were evaluated in the same manner as in Reference Example 1 except that the polymer 1 was not used. Table 2 shows each physical property value.

[Comparative Example 2]
Instead of polymerized polymer 1, “Ultzex 20100J” (manufactured by Prime Polymer Co., Ltd.), which is a linear low density polyethylene having MFR: 8.5 g / 10 min, density: 916 kg / m ³ , melting point: 120 ° C. The properties were evaluated in the same manner as in Reference Example 1 except that was used. Table 2 shows each physical property value.

  The package of the present invention is excellent in transparency, scratch resistance, blocking resistance and the like, and can be packaged at high speed. As the package of the present invention, for example, a water package, a liquid soup bag, a liquid paper container, a laminated sheet, a special shape liquid package (such as a standing pouch), a standard bag, a heavy bag, a semi-heavy bag, a wrap film, It is suitable for various packaging films such as sugar bags, oil packaging, food packaging, and agricultural materials such as infusion bags and house films.

Claims (7)

It has a heat seal layer made of a resin composition containing a propylene resin (A) having a melting point (Tm) measured by a differential scanning calorimeter of 120 ° C. or higher and a propylene / 1-butene copolymer (BB). A package obtained by filling a liquid and / or powder as a filling material from an opening of a bag-like container formed by forming a film, and heat-sealing the opening,
The propylene / 1-butene copolymer (BB) is
(1) Containing structural units derived from propylene in an amount of 50 to 95 mol% and structural units derived from 1-butene in an amount of 5 to 50 mol%,
(2) Based on ASTM D1238, the melt flow rate obtained by measuring at a temperature of 230 ° C. and a load of 2.16 kg is 0.01 to 1000 g / 10 minutes,
(3) The molecular weight distribution (Mw / Mn) obtained by gel permeation chromatography (GPC) is 3.0 or less,
(4) The melting point (Tm) measured with a differential scanning calorimeter is 60 to 100 ° C.
(5) The melting point (Tm) [° C.] measured by a differential scanning calorimeter and the constituent unit content (M) [mol%] derived from 1-butene are −2.6 M + 130 ≦ Tm ≦ −2.3 M + 155
Satisfies the relational expression
A package containing the propylene resin (A) and the propylene / 1-butene copolymer (BB) in an amount of 60 to 95% by weight and 5 to 40% by weight, respectively, in 100% by weight of the resin composition.   The package according to claim 1, wherein the film is a laminate of the heat seal layer and the base material layer.   The package according to claim 1 or 2, wherein the filling material is a liquid.   The package according to claim 1 or 2, wherein the filling material is oil. Film having a heat seal layer made of a resin composition containing a propylene-based resin (A) having a melting point (Tm) measured by a differential scanning calorimeter of 120 ° C. or higher and a propylene / 1-butene copolymer (BB) A method for producing a package including a step of filling a liquid and / or a powder to be filled from an opening of a bag-like container formed by bag-making, and a step of heat-sealing the opening,
The propylene / 1-butene copolymer (BB) is
(1) Containing structural units derived from propylene in an amount of 50 to 95 mol% and structural units derived from 1-butene in an amount of 5 to 50 mol%,
(2) Based on ASTM D1238, the melt flow rate obtained by measuring at a temperature of 230 ° C. and a load of 2.16 kg is 0.01 to 1000 g / 10 minutes,
(3) The molecular weight distribution (Mw / Mn) obtained by gel permeation chromatography (GPC) is 3.0 or less,
(4) The melting point (Tm) measured with a differential scanning calorimeter is 60 to 100 ° C.
(5) The melting point (Tm) [° C.] measured by a differential scanning calorimeter and the constituent unit content (M) [mol%] derived from 1-butene are −2.6 M + 130 ≦ Tm ≦ −2.3 M + 155
Satisfies the relational expression
The production method wherein the propylene resin (A) and the propylene / 1-butene copolymer (BB) are contained in 60 to 95% by weight and 5 to 40% by weight, respectively, in 100% by weight of the resin composition.   The method for manufacturing a package according to claim 5, wherein the filling material is a liquid.   The method for manufacturing a package according to claim 5, wherein the filling material is oil.