JP2020196194A - Laminated film - Google Patents

Abstract

To provide a stretched laminated film for packaging which can produce a packaging bag without breaking of a sealed portion even in the case of using a high speed sealing and packaging means such as a vertical form fill seal machine (VFFS), and to provide a packaging bag storing contents.SOLUTION: The invention relates to a stretched laminated film comprising: a heat-sealable layer including a resin composition which contains 40 to 100 pts.mass of a 1-butene-based polymer (B) having a melting point (Tm) of lower than 120°C measured by differential scanning calorimetry (DSC), and comprising 10 to 90 mol% of a structural unit derived from 1-butene and 90 to 10 mol% of a structural unit derived from an α-olefin having 3 or 5 to 20 carbon atoms, wherein a sum of the unit derived from 1-butene and the unit derived from an α-olefin is 100 mol%, and 0 to 60 pts.mass of a propylene-based polymer (A) having a melting point (Tm) of 150°C or higher and 170°C or lower measured by differential scanning calorimetry (DSC), and 40 to 100 pts.mass of a 1-butene-based polymer (B) having a melting point (Tm) of lower than 120°C measured by differential scanning calorimetry (DSC), and comprising 10 to 90 mol% of a structural unit derived from 1-butene and 90 to 10 mol% of a structural unit derived from an α-olefin having 3 or 5 to 20 carbon atoms, wherein a sum of the unit derived from 1-butene and the unit derived from an α-olefin is 100 mol%, and wherein (AB)+(BA)=100 pts.mass; and a base layer.SELECTED DRAWING: None

Description

The present invention relates to a laminated film having excellent heat-sealing properties, and more particularly, a high-speed packaging in which a base material layer is laminated on a heat-sealing layer having excellent heat-sealing properties, low-temperature sealing properties and hot tack properties. The present invention relates to a laminated film preferably used in the above.

In order to improve the production speed of packages in the work of packaging processed edible products such as fish, ham and sausage, dairy products such as cheese and butter, and liquid soups used in instant foods. , While forming a packaging bag with a continuously supplied plastic film at high speed, the packaged object is filled and sealed at high speed using, for example, a vertical bag making filling machine (VFFS) in the packaging bag formed at almost the same time. Packaging means to be used is gradually permeating the industry (for example, Patent Documents 1 and 2).

Conventionally, resin films based on linear low-density polyethylene (L-LDPE) have been widely used, but they have higher heat-sealing properties and lower temperatures in response to the ever-increasing speed of filling and sealing. There is an increasing demand for laminated films for high-speed packaging that are provided with sealing properties and hot tack properties.

For example, even when a high-speed sealing / packaging means such as a vertical bag-making filling machine (VFFS) is used, a laminated film for packaging and contents that can manufacture a package without causing bag breakage of the sealed portion are available. It is intended to provide a stored package. When high-speed packaging is performed using such a vertical bag-making filling machine (VFFS), the packaged object falls in the vertical direction to the lower seal portion which is not sufficiently cooled immediately after the heat seal, so that the packaged object weight If the package is heavy, or if the shape of the packaged object has protrusions, the lower sealing surface may tear and the bag may break.

The main performances required for the heat seal layer to prevent such defects are high heat seal performance and low temperature sealability (that is, high heat seal strength is exhibited at a seal temperature lower than the current level, or the current temperature. However, it has high heat tack performance (that is, the ability to develop high heat seal strength in a shorter sealing time) and high hot tack performance (that is, the sealing part has strong adhesive force even in a high temperature state where the temperature of the sealing part is not sufficiently cooled). As a method for improving low-temperature heat-sealing properties and hot-tacking properties, the applicant has made a main component of a propylene-based polymer having a melting point in the range of 120 to 170 ° C. as a heat-sealing layer. It has been proposed to use a resin composition obtained by adding 3 to 50 parts by weight of a 1-butene polymer to (50 to 97 parts by weight) (Patent Document 3). In the examples of Patent Document 3, as the propylene-based polymer, a propylene random copolymer having a melting point of 138 ° C.: 85 parts by weight and a propylene / 1-butene copolymer having a melting point of 75.3 ° C. by 15 weights by weight. It is described that a partially added composition was used.

On the other hand, in recent years, the speed of the bag making machine has been further increased, and there is an increasing demand for a film having higher low temperature heat sealing property, heat sealing property and hot tack property.

JP-A-2009-051212 Japanese Unexamined Patent Publication No. 2013-18161 International Publication WO 2016/052326 Pamphlet

The present invention is to develop a laminated film having higher low temperature heat sealability, heat seal strength and hot tack performance.

That is, the present invention relates to [1] to [10].
[1] The melting point (Tm) measured by differential scanning calorimetry (DSC) is less than 120 ° C., contains a structural unit derived from 1-butene in an amount of 10 to 90 mol%, and has 3 carbon atoms or carbon. It contains 90-10 mol% of structural units derived from α-olefins having 5 to 20 atoms (however, the total of the units derived from 1-butene and the units derived from α-olefin is 100 mol%. A propylene-based polymer having a 1-butene-based copolymer (B) of 40 to 100 parts by mass and a melting point (Tm) of 150 ° C. or higher and 170 ° C. or lower as measured by differential scanning calorimetry (DSC). A) is 0 to 60 parts by mass [however, (B) + (A) = 100 parts by mass. ] Included in a heat-sealing layer and a base material layer containing the resin composition.
[2] The resin composition contains 50 to 95 parts by mass of the 1-butene copolymer (B) and 5 to 50 parts by mass of the propylene-based polymer (A) [provided that (B) + (A) = It is 100 parts by mass. ] The laminated film according to the item [1], which comprises.
[3] The resin composition further comprises 0 to 100 parts by mass of a propylene-based copolymer (C) having a melting point (Tm) of 120 ° C. or higher and lower than 150 ° C. measured by differential scanning calorimetry (DSC). B) + (A) = 100 parts by mass. ] The laminated film according to claim 1 or 2, wherein the laminated film comprises. The laminated film according to item [1] or [2].
[4] The 1-butene-based copolymer (B) contains a structural unit derived from 1-butene in an amount of 10 to 90 mol%, and a structural unit derived from propylene in an amount of 90 to 10 mol%. (However, the total of the unit derived from 1-butene and the unit derived from propylene is 100 mol%.) The term is characterized by being a 1-butene copolymer (B') [ The laminated film according to any one of 1] to [3].
[5] The 1-butene copolymer (B1) having a melting point (Tm) of 90 ° C. or higher and 110 ° C. or lower as measured by differential scanning calorimetry (DSC) for the 1-butene copolymer (B'). From the 1-butene copolymer (b2) having a melting point of 65 ° C. or higher and lower than 90 ° C. and the 1-butene copolymer (b3) having a melting point of less than 65 ° C. measured by the same method. Item 3. The laminated film according to Item [4], which comprises one or more selected ones.
[6] The laminated film according to Item [5], wherein the 1-butene copolymers (b1) and (b2) are polymers produced by a metallocene catalyst.
[7] The laminated film according to any one of Items [1] to [6], wherein the heat seal layer containing the resin composition is stretched.
[8] The laminated film according to any one of items [1] to [7], wherein the base material layer is stretched.
[9] A packaging bag sealed with the heat-sealing layer of the laminated film according to any one of items [1] to [8] inside.
[10] A packaging bag according to item [9], wherein the packaged object is stored in the packaging bag.

The laminated film of the present invention exhibits sufficient heat-sealing strength even when heat-sealed in the temperature range of 70 to 100 ° C. as well as 110 ° C. or higher, and at the same time, there is concern about a film having such low-temperature heat-sealing property. The decrease in hot tack strength at 110 ° C. or higher is reduced, and sufficient hot tack strength is exhibited at high temperatures. Therefore, it is suitably used as a packaging film when the object to be packed is filled and sealed at high speed by using a vertical bag-making filling machine (VFFS).

It is a schematic cross-sectional view which shows the laminated film of an Example.

Hereinafter, embodiments of the present invention will be described in detail.
[1-Butene copolymer (B)]
The 1-butene copolymer (B), which is the main component of the resin composition forming the heat seal layer of the laminated film of the present invention, has a melting point (Tm) of less than 120 ° C. as measured by differential scanning calorific value measurement (DSC). It contains a structural unit derived from 1-butene in an amount of 10 to 90 mol%, and contains a structural unit derived from an α-olefin having 3 carbon atoms or 5 to 20 carbon atoms in an amount of 90 to 10 mol%. 1-Butene-based copolymer contained in (however, the total of the units derived from 1-butene and the units derived from α-olefin is 100 mol%). [Hereinafter, it may be referred to as "component (B)". ]

As the α-olefin having 3 carbon atoms or 5 to 20 carbon atoms, an α-olefin having 3 carbon atoms, that is, propylene is preferably used from the viewpoint of versatility and availability (in the following description, α-olefin). The 1-butene copolymer when propylene is used as the olefin may be referred to as a component (B')). The melting point (Tm) of the component (B') when propylene is used as the α-olefin is preferably in the range of 40 ° C. to 115 ° C., more preferably 45 to 110 ° C.

The component (B) according to the present invention contains a structural unit derived from 1-butene in an amount of 10 to 80 mol%, and is derived from an α-olefin having 3 carbon atoms or 5 to 20 carbon atoms, preferably propylene. It is a particularly preferable embodiment to contain the constituent unit to be obtained in an amount of 90 to 20 mol%. By adopting such a preferred embodiment, the excellent heat-sealing performance and hot tackiness, which are the effects of the present invention, can be easily exhibited, and the handling property is also excellent.

In the present embodiment, the component (B') is a 1-butene copolymer (b1) having a melting point (Tm) of 90 ° C. or higher and 110 ° C. or lower as measured by differential scanning calorimetry (DSC). A 1-butene copolymer (b2) having a melting point (Tm) of 65 ° C. or higher and lower than 90 ° C. measured by the method and a 1-butene copolymer having a melting point (Tm) of less than 65 ° C. measured by the same method. It is mentioned as a preferable embodiment that it is composed of one or more selected from (b3).

The melting point (Tm) of the component (B) according to the present invention can be measured by the following method. That is, using a DSC manufactured by Seiko Instruments, a sample of about 5 mg was packed in an aluminum pan for measurement, the temperature was raised to 200 ° C. at 100 ° C./min, held at 200 ° C. for 5 minutes, and then-at 10 ° C./min. It can be obtained from the endothermic curve in which the temperature is lowered to 150 ° C. and then raised to 200 ° C. at 10 ° C./min.

The component (B) according to the present invention preferably has a molecular weight distribution (Mw / Mn) of 3.0 or less, more preferably 2.0 to 3.0, as determined by gel permeation chromatography (GPC). Yes, more preferably 2.0-2.5.

By setting Mw / Mn in the above range, the content of low molecular weight as the component (B) can be controlled, so that bleeding does not easily occur from the surface layer of the laminated film, and the surface layer becomes sticky and blocking during storage of the laminated film. Can be suppressed. As the method for measuring Mw / Mn, the same method as the method for measuring the propylene-based polymer (A) described later can be adopted.

The component (B) according to the present invention has a relationship between the melting point (Tm) measured by a differential scanning calorimeter and the 1-butene constituent unit content M (mol%).
-3.2M + 130 ≤ Tm ≤ -2.3M + 155
It is preferable to satisfy. By satisfying the above relationship between Tm and M, it is possible to obtain a laminated film having excellent low-temperature heat-sealing properties, high heat-sealing strength, and little decrease in sealing strength due to aging after stretching.

The melt flow rate (MFR; ASTM D1238, 230 ° C., under a 2.16 kg load) of the component (B) used in the present embodiment is preferably 0.1 to 30 g / 10 minutes, more preferably. Is 0.5 to 20 g / 10 minutes, particularly preferably 1.0 to 10 g / 10 minutes.

The 1-butene-propylene copolymer (B'), which is a preferred embodiment of the 1-butene copolymer (B) according to the present invention, is a copolymer of 1-butene and propylene in the presence of a catalyst containing a metallocene compound. It can be preferably obtained by polymerizing. In the present invention, among the 1-butene-propylene copolymers (B'), the 1-butene copolymer (b1) having a melting point (Tm) of 90 ° C. or higher and 110 ° C. or lower and the melting point (Tm) of 65 The 1-butene copolymer (b2) having a temperature of ° C. or higher and lower than 90 ° C. can be produced by a metallocene catalyst, preferably by the method described in WO2004 / 087775 or WO01 / 27124.

More preferably, the component (B) is 1-butene and an α-olefin having 3 carbon atoms or 5 to 20 carbon atoms in the presence of a catalyst containing a transition metal compound represented by the following general formula (1a). It is preferably obtained by copolymerizing with propylene. The transition metal compound (1a) is a compound in which a ligand in which a substituted cyclopentadienyl ring and a substituted fluorenyl ring are crosslinked with carbon is coordinated to a transition metal atom.

Here, the catalyst containing the transition metal compound (1a) is a compound that reacts with (2a) an organometallic compound, (2b) an organoaluminum oxy compound, and (2c) a transition metal compound (1a) to form an ion pair. It is desirable that the catalyst contains at least one compound selected from the above, together with the transition metal compound (1a).

(In the formula (1a), R ¹ and R ³ are hydrogen, and R ² and R ⁴ are selected from a hydrocarbon group and a silicon-containing group, which may be the same or different, respectively. R ⁵ , R ⁶ and R. ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are selected from hydrogen, hydrocarbon groups, silicon-containing groups, which may be the same or different, respectively, R ⁵ to R ¹² The substituents bonded to the adjacent carbons up to the above may be bonded to each other to form a ring. R ¹³ and R ¹⁴ may be the same or different from each other, or may be bonded to each other to form a ring. . M is a Group 4 transition metal, Y is a carbon atom, and Q is the same or different combination from halogens, hydrocarbon groups, anionic ligands or neutral ligands that can be coordinated with isolated electron pairs. Selected, j is an integer of 1-4.)

Examples of the above-mentioned 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. Linear hydrocarbon group such as group, n-decanyl group; isopropyl group, tert-butyl group, amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1- Branched hydrocarbon groups such as methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group; cyclopentyl Cyclic saturated hydrocarbon groups such as group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group; cyclic unsaturated hydrocarbons such as phenyl group, tolyl group, naphthyl group, biphenyl group, phenanthryl group and anthracenyl group. Group: Saturated hydrocarbon group substituted with cyclic unsaturated hydrocarbon group such as benzyl group, cumyl group, 1,1-diphenylethyl group, triphenylmethyl group; methoxy group, ethoxy group, phenoxy group, frill group, N- Examples thereof include heteroatom-containing hydrocarbon groups such as methylamino group, N, N-dimethylamino group, N-phenylamino group, pyryl group and thienyl group.

Examples of the above-mentioned silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylsilyl group, and a triphenylsilyl group.

Further, the substituents from R ⁵ to R ¹² bonded to adjacent carbons may be bonded to each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl groups, dibenzofluorenyl groups, octahydrodibenzofluorenyl groups, octamethyloctahydrodibenzofluorenyl groups, octamethyltetrahydrodicyclopentafluorenyl groups and the like. Can be mentioned.

R ¹³ and R ¹⁴ are preferably aryl groups. Examples of the aryl group include the above-mentioned cyclic unsaturated hydrocarbon group, a saturated hydrocarbon group substituted with a cyclic unsaturated hydrocarbon group, a heteroatom-containing cyclic unsaturated hydrocarbon group such as a frill group, a pyryl group, and a thienyl group. Can be mentioned. Further, R ¹³ and R ¹⁴ may be the same or different from each other, and may be combined with each other to form a ring.

In the general formula (1a), R ² and R ⁴ , which are substituents bonded to the cyclopentadienyl ring, are preferably hydrocarbon groups having 1 to 20 carbon atoms. As the hydrocarbon group having 1 to 20 carbon atoms, the above-mentioned hydrocarbon group can be exemplified. Among them, R ² is more preferably a bulky substituent such as a tert-butyl group, an adamantyl group and a triphenylmethyl group, and R ⁴ is more preferable than R ² such as a methyl group, an ethyl group and an n-propyl group. More preferably, it is a sterically small substituent. The term "sterically small" as used herein means that the volume occupied by the substituent is small.

In the general formula (1a), among R ⁵ to R ¹² which are substituents bonded to the fluorenyl ring, any two or more of R ⁶ , R ⁷ , R ¹⁰ and R ¹¹ have 1 to 20 carbon atoms. It is preferably a hydrocarbon group. As the hydrocarbon group having 1 to 20 carbon atoms, the above-mentioned hydrocarbon group can be exemplified. In particular, from the viewpoint of ease of synthesizing the ligand, it is preferable that R ⁶ and R ¹¹ and R ⁷ and R ¹⁰ are the same group. In such a preferred embodiment, R ⁶ and R ⁷ form an aliphatic ring (AR-1), and R ¹⁰ and R ¹¹ are the same aliphatic ring as the aliphatic ring (AR-1). The case where (AR-2) is formed is also included.

In the general formula (1a), Y for cross-linking the cyclopentadienyl ring and the fluorenyl ring is a carbon atom. The substituents R ¹³ and R ¹⁴ bonded to Y are preferably aryl groups having 6 to 20 carbon atoms at the same time. 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. Further, R ¹³ and R ¹⁴ may be the same or different from each other, and may be combined with each other to form a ring. As such a substituent, a fluorenylidene group, a 10-hydroanthrasenilidene 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.
In addition, Q is selected from halogens, hydrocarbon groups, anionic ligands or neutral ligands that can be coordinated with lone electron pairs in the same or different combinations. j is an integer of 1 to 4, and when j is 2 or more, a plurality of Qs may be the same or different from each other.

Specific examples of the halogen include fluorine, chlorine, bromine, and iodine, and specific examples of the hydrocarbon group include the same as described above. Specific examples of the anion ligand include an alkoxy group such as methoxy, tert-butoxy and phenoxy, a carboxylate group such as acetate and benzoate, and a sulfonate group such as mesylate and tosylate. Specific examples of the neutral ligand that can be coordinated with a lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxy. Examples include ethers such as ethane. It is preferable that at least one Q is a halogen or alkyl group.

Examples of such a transition metal compound (1a) include dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) fluorenyl zirconium dichloride and isopropylidene (3-tert-butyl-5-methylcyclopenta). Dienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) ) Zyroxide dichloride, isopropylidene (3-tert-butyl-5-methylcyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methylcyclopentadi) Enyl) (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) (octamethyloctahydridodibenz) Fluolenyl) zirconium dichloride and the like, but are not limited thereto.

The catalyst preferably used in producing the component (B), preferably the component (b1) and the component (b2) according to the present invention is the above-mentioned transition metal compound (1a) and the organometallic compound (2a). It preferably contains at least one compound selected from (2b) an organoaluminum oxy compound and (2c) a compound that reacts with a transition metal compound (1a) to form an ion pair. The compounds of (2a), (2b), and (2c) are not particularly limited, but the compounds described in WO2004 / 087775 pamphlet or WO01 / 27124 pamphlet are preferable, and examples thereof include the following. Can be mentioned.

As the (2a) organometallic compound, the following group 1, 2 and 12 and 13 organometallic compounds are used.
(2a-1) the 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, and represent hydrocarbon groups having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m is 0 <. An organic aluminum compound represented by 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 a Li, Na or K, R ^a is from 1 to 15 carbon atoms, preferably. Showing the 1-4 hydrocarbon group) and Group 1 metal and aluminum represented by Complex alkylated product.
Examples of such compounds include LiAl (C ₂ H ₅ ) ₄ , LiAl (C ₇ H ₁₅ ) _{4, and the} like.

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

Among these organometallic compounds (2a), organoaluminum compounds are preferable. Further, such an organometallic compound (2a) may be used alone or in combination of two or more.

(2b) The organoaluminum oxy compound may be a conventionally known aluminoxane, or may be a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687.

Conventionally known aluminoxane can be produced, for example, by the following method, and is usually 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, and first cerium chloride hydrate. A method in which an organic aluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension to cause the adsorbed water or water of crystallization to react with the organic aluminum 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 organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organometallic component other than the aluminoxane. Alternatively, the solvent or unreacted organoaluminum compound may be distilled and removed from the recovered solution of aluminoxane, and then redissolved in the solvent or suspended in a poor solvent of aluminoxane. Specific examples of the organoaluminum compound used when preparing alminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to (2a-1) above. Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable. The above-mentioned organoaluminum compounds are used alone or in combination of two or more.

As the benzene-insoluble organic aluminum oxy compound (2b), the amount dissolved in benzene at 60 ° C. (an organic aluminum oxy compound corresponding to 100 mg atom of aluminum is suspended in 100 ml of benzene and stirred at 60 ° C. After mixing for 6 hours, hot filtration was performed at 60 ° C. using a G5 glass filter with a jacket, and the solid separated on the filter was washed 4 times with 50 ml of benzene at 60 ° C. to collect the filtrate and put it in the filtrate. It is determined by measuring the abundance (mmol) of existing aluminum atoms.) Is usually 10 mmol or less, preferably 5 mmol or less, particularly preferably 2 mmol or less in terms of aluminum atoms, that is, that is, Those that are insoluble or sparingly soluble in benzene are preferred. These organoaluminum oxy compounds (2b) are used alone 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-3-179005. Lewis acid, an ionic compound, a borane compound, a carborane compound and the like described in JP-A-179006, JP-A-3-207703, JP-A-3-207704, and USP-5321106 can be mentioned. In addition, heteropoly compounds and isopoly compounds can also be mentioned. Such a compound (2c) is used alone or in combination of two or more.

In the production of the component (B) according to the present invention, it is preferable to use a catalyst in which an organoaluminum oxy compound (2b) such as methylaluminoxane is used in combination with the transition metal compound (1a) because particularly high polymerization activity can be achieved.

Further, the polymerization catalyst used for producing the component (B) according to the present invention may be a catalyst using a carrier, if necessary, or may contain other co-catalyst components.
Such a catalyst may be prepared by mixing each component in advance or supporting it on a carrier, or may be used by adding each component to the polymerization system simultaneously or sequentially.

The component (B) according to the present invention is preferably obtained by copolymerizing 1-butene and propylene in the presence of the above-mentioned catalyst. In the copolymerization, each monomer may be used in an amount such that the amount of each structural unit in the component (B) to be produced is a desired ratio. Specifically, the molar ratio of propylene / 1-butene is 50/50. It is used in a ratio of ~ 95/5, preferably 60/40 to 90/10, more preferably 70/30 to 90/10.

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 ~. It can be carried out under the condition of 5 MPa gauge pressure. Further, the polymerization reaction can be carried out by any of a batch type, a semi-continuous type and a continuous type. Further, it is also possible to carry out the polymerization in two or more stages having different reaction conditions.

The molecular weight of the component (B) can also be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature, and is adjusted by the amount of (2a), (2b) or (2c) in the catalyst. You can also do it. When hydrogen is added, the amount thereof is appropriately about 0.001 to 100 NL per 1 kg of the monomer.

[Propylene polymer (A)]
The propylene-based polymer (A), which is a subcomponent of the resin composition forming the heat seal layer of the laminated film of the present invention, has a melting point (Tm) of 150 ° C. or higher and 170 ° C. or lower as measured by differential scanning calorimetry (DSC). Is a propylene-based polymer [hereinafter, may be referred to as “component (A)”. ], And the propylene-based polymer is a random copolymer of propylene and α-olefin (excluding propylene) having 2 to 20 carbon atoms, even if it is a homopolymer of propylene (homo PP). Although it may be a propylene block copolymer, it is preferably a propylene homopolymer.

As the component (A) according to the present invention, from the viewpoint of imparting heat resistance and rigidity to the heat-sealing layer of the laminated film, it is preferable to use a propylene copolymer having a high melting point (Tm), particularly preferably a heat-sealing layer. From the viewpoint of imparting flexibility and transparency to the polymer, it is preferable to use a propylene / α-olefin random copolymer having a low melting point (Tm) and having 2 to 20 carbon atoms. As will be described later, a method of using a propylene homopolymer and a propylene random copolymer in combination is also one of the preferable specifications of the present invention.

Here, as the α-olefin to be copolymerized with propylene, ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1- Examples thereof include decene, 1-dodecene, 1-tetracene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. In the present embodiment, it is also preferable to use two or more kinds of α-olefins. Further, as the component (A) according to the present invention, an isotactic propylene-based polymer is preferably used.

The isotactic propylene-based polymer is a propylene-based polymer having an isotactic pentad fraction of 0.9 or more, preferably 0.95 or more, measured by an NMR method. The isotactic pentad fraction of this isotactic propylene polymer is expressed as a percentage of 90% or more, preferably 95% or more.

The isotactic pentad fraction (mmmm fraction) indicates the abundance ratio of the isotactic chain in the pentad fraction unit in the molecular chain measured using ¹³ C-NMR, and is a propylene monomer unit. Is the fraction of the propylene monomer unit at the center of the chain in which 5 consecutive mesobonds are formed. Specifically, it is a value calculated as a fraction of the mmmm peak in the total absorption peak of the methyl carbon region observed in the ¹³ C-NMR spectrum. The isotactic pentad fraction (mmmm fraction) is measured as follows.

The mmmm fractions are P _mmmm (absorption intensity derived from the third methyl group at the site where 5 units of propylene units are isotactically bonded consecutively) and P _w (total methyl of propylene units) in the ¹³ C-NMR spectrum. It is calculated by the following formula from the absorption strength (absorption strength derived from the group).
mm mm fraction = P _mmmm / P _w

The NMR measurement is performed, for example, as follows. That is, 0.35 g of the sample is dissolved by heating in 2.0 mL of hexachlorobutadiene. After filtering this solution with a glass filter (G2), 0.5 mL of deuterated benzene is added, and the solution is charged into an NMR tube having an inner diameter of 10 mm. Then, ¹³ C-NMR measurement is performed at 120 ° C. using a JNM GX-500 type NMR measuring device manufactured by JEOL Ltd. The total number of times is 10,000 or more.

The component (A) according to the present invention has a melting point (Tm) of 150 ° C. or higher and 170 ° C. or lower, preferably 155 ° C. or higher and 168 ° C. or lower, as obtained by differential scanning calorimetry (DSC). is there.

By using the component (A) having a melting point (Tm) in this range, excellent seal strength, hot tackiness, moldability, and heat resistance are imparted as a heat seal layer.
Further, the heat of fusion (ΔH) obtained at the same time is preferably 50 mJ / mg or more.

The melting point (Tm) and the amount of heat of fusion (ΔH) of the component (A) according to the present invention are measured as follows, for example.
That is, using DSC Pris 1 or DSC7 manufactured by PerkinElmer, a sample of about 5 mg is heated to 200 ° C. and held for 10 minutes under a nitrogen atmosphere (20 ml / min), and then cooled to 30 ° C. at 10 ° C./min. The melting point can be determined from the peak apex of the crystal melting peak when the temperature is raised to 200 ° C. at 10 ° C./min after holding at 30 ° C. for 5 minutes.

The melt flow rate (MFR; ASTM D1238, 230 ° C., under a load of 2.16 kg) of the component (A) according to the present invention is preferably 0.01 to 400 g / 10 minutes, more preferably 0.1 to 100 g / 10. Minutes. By using the component (A) having such an MFR value, the fluidity of the resin composition is improved, and even a relatively large sheet can be easily molded.

Further, the molecular weight distribution (Mw / Mn) of the component (A) according to the present invention determined by gel permeation chromatography (GPC) is preferably 3.0 or less, more preferably 2.0 to 3.0. It is more preferably 2.0 to 2.5.

This molecular weight distribution (Mw / Mn) can be measured as follows using, for example, a gel permeation chromatograph Alliance GPC-2000 manufactured by Waters Corp. The separation column has two TSKgel GNH6-HT and two TSKgel GNH6-HTL, the column size is 7.5 mm in diameter and 300 mm in length, the column temperature is 140 ° C., and the mobile phase is o. -Use 0.025 parts by mass of dichlorobenzene (manufactured by Wako Pure Chemical Industries, Ltd.) and BHT (manufactured by Takeda Pharmaceutical Co., Ltd.) as an antioxidant, move at 1.0 ml / min, set the sample concentration to 15 mg / 10 mL, and inject the sample. The amount is 500 microliters, and a differential refractometer is used as a detector. As the standard polystyrene, Tosoh Co., Ltd. is used for the molecular weights Mw <1000 and Mw> 4 × 106, and Pressure Chemical Co., Ltd. is used for 1000 ≦ Mw ≦ 4 × 106.

Further, as the component (A) according to the present invention, a component (A) having a tensile elastic modulus of 500 MPa or more can be preferably used. The tensile elastic modulus is a value measured at 23 ° C. using a JIS No. 3 dumbbell with a span spacing of 30 mm and a tensile speed of 30 mm / min in accordance with JIS K6301.

The component (A) according to the present invention can be produced by various methods, for example, it can be produced by using a stereoregular catalyst. Specifically, it can be produced by using a catalyst formed from a solid titanium catalyst component, an organometallic compound catalyst component, and, if necessary, an electron donor. Specific examples of the solid titanium catalyst component include a solid titanium catalyst component in which titanium trichloride or a titanium trichloride composition is supported on a carrier having a specific surface area of 100 m ² / g or more, or magnesium, halogen, or electrons. Examples thereof include a solid titanium catalyst component in which a donor (preferably an aromatic carboxylic acid ester or an alkyl group-containing ether) and titanium are essential components, and these essential components are supported on a carrier having a specific surface area of 100 m ² / g or more. ..

It can also be produced using a metallocene catalyst.
The organometallic compound catalyst component is preferably an organoaluminum compound, and specific examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, and alkylaluminum dihalide. The organoaluminum compound can be appropriately selected according to the type of titanium catalyst component used.

As the electron donor, an organic compound having a nitrogen atom, a phosphorus atom, a sulfur atom, a silicon atom, a boron atom and the like can be used, and an ester compound and an ether compound having the above-mentioned atoms are preferable. ..
In addition, such a catalyst may be further activated by a method such as co-grinding, or the α-olefin as described above may be prepolymerized.

[Propylene copolymer (C)]
A propylene-based copolymer (C) which is one of the components which may be contained in the resin composition forming the heat seal layer of the laminated film of the present invention [hereinafter, may be referred to as "component (C)". .. ] Is a propylene-based copolymer having a melting point (Tm) of 120 ° C. or higher and lower than 150 ° C. measured by differential scanning calorimetry (DSC), and the propylene-based copolymer is α- with propylene and 2 to 20 carbon atoms. It may be an olefin (excluding propylene) random copolymer or a propylene block copolymer, but is preferably a propylene / α-olefin random copolymer.

As the component (C) according to the present invention, it is preferable to use an α-olefin random copolymer having 2 to 20 carbon atoms of propylene from the viewpoint of imparting flexibility and low-temperature sealing property to the heat-sealing layer of the laminated film.

Here, as the α-olefin to be copolymerized with propylene, ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1- Examples thereof include decene, 1-dodecene, 1-tetracene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. In this embodiment, it is also one of the preferable embodiments to use an α-olefin of ethylene, 1-butene, 1-hexene and 1-octene.

Further, as the component (C) according to the present invention, an isotactic propylene-based copolymer is preferably used.
The isotactic propylene-based copolymer is a propylene-based copolymer having an isotactic pentad fraction of 0.9 or more, preferably 0.95 or more, measured by an NMR method. The isotactic pentad fraction of this isotactic propylene-based polymer is expressed as a percentage of 90% or more, preferably 95% or more.

The component (C) according to the present invention is a propylene-based polymer (a1) having a melting point (Tm) of 120 ° C. or higher and 150 ° C. or lower as measured by differential scanning calorimetry (DSC), preferably 0 to 45 parts by mass. A method using a propylene-based polymer composed of 30 parts by mass, more preferably 0 to 20 parts by mass is a preferred embodiment. The preferred melting point (Tm) of the component (C) is 120 ° C. to 150 ° C., and the more preferable melting point (Tm) is 120 to 140 ° C.

[Resin composition]
The resin composition for forming the heat seal layer of the laminated film of the present invention contains 40 to 100 parts by mass, preferably 50 to 100 parts by mass, and further of the 1-butene copolymer (B) "component (B)". Preferably, 75 to 95 parts by mass, and 0 to 60 parts by mass, preferably 0 to 50 parts by mass, and more preferably 5 to 30 parts by mass of the propylene-based polymer (A) "component (A)" [however, ( B) + (A) = 100 parts by mass. ] Included in the range.

As described above, the resin composition according to the present invention includes an embodiment in which the component (A) is 0, that is, does not contain the component (A), but even in that case, it is also referred to as a resin composition for convenience.
Since the resin composition according to the present invention contains the above component (B) as a main component, the heat seal layer containing the resin composition is excellent in low temperature heat seal property, heat seal strength, and hot tack property.

When a resin composition in which the amount of the component (A) contained in the resin composition exceeds 60 parts by mass is used for the heat seal layer, the low temperature heat seal property, the heat seal strength, and the hot tack property are not improved.

When the resin composition forming the laminated film of the present invention contains the above component (C), the above propylene-based copolymer is used with respect to the total amount of the above component (B) and the above component (A) = 100 parts by mass]. It contains 0 to 100 parts by mass of the polymer (C) [component (C)].
The lower limit of the blending amount of the component (C) is preferably usually 1 part by mass, preferably 5 parts by mass, more preferably 10 parts by mass, and further preferably 20 parts by mass.

The resin composition according to the present invention, or the component (B), the component (A) and the component (C) according to the present invention may contain a heat-resistant stabilizer, a weather-resistant stabilizer, an ultraviolet absorber, a lubricant, as necessary. Various additives usually used for polyolefins such as slip agents, nucleating agents, antiblocking agents, antistatic agents, antifogging agents, pigments and dyes may be added as long as the object of the present invention is not impaired.

[Laminated film]
The laminated film of the present invention is a laminated film containing a heat-sealing layer containing the above resin composition and a base material layer.

<Heat seal layer>
The heat-sealing layer constituting the laminated film of the present invention is a layer containing the above resin composition.
The thickness of the heat seal layer constituting the laminated film of the present invention can be appropriately determined depending on the application, but is usually in the range of 0.5 to 20 μm, preferably 1 to 15 μm, and more preferably 1 to 10 μm. ..

<Base layer>
As the base material layer constituting the laminated film of the present invention, conventionally known ones are appropriately adopted according to the intended use. Specific examples thereof include polyethylene terephthalate, a film made of polyester typified by polyethylene naphthalate, a polycarbonate film, a polyamide film made of nylon 6, nylon 66, etc., an ethylene / vinyl alcohol copolymer film, a polyvinyl alcohol film, and polychloride. Examples thereof include vinyl films, polyvinylidene chloride films, and thermoplastic resin films such as films made of polyolefins such as polypropylene, polyethylene, poly1-butene, and poly-4-methyl-1-pentene.

Further, the base material layer may be one layer or two or more layers depending on the purpose. Further, the thermoplastic resin film as the base material layer may be in the form of a laminated film with an inorganic substance such as aluminum, zinc, silica or a different inorganic material on which an oxide thereof is deposited.

The thickness of the base material layer constituting the laminated film of the present invention can be appropriately determined depending on the intended use, but is usually in the range of 5 to 100 μm, preferably 10 to 80 μm, and more preferably 10 to 50 μm.

In addition to the heat-sealing layer and the base material layer, the laminated film of the present invention is a gas barrier such as a layer made of another resin such as polyolefin or polyvinyl chloride, or a silica-deposited layer, as long as the object of the present invention is not impaired. An intermediate layer such as a layer may be interposed.

The laminated film of the present invention is usually in the range of 5 to 250 μm, preferably 10 to 120 μm.
The heat-sealing layer and / or the base material layer constituting the laminated film of the present invention may be unstretched (unstretched) or stretched.

[Manufacturing method of laminated film]
As the laminated film of the present invention, various known and known film forming methods can be adopted. For example, the composition resin composition or the component (B), which forms a heat-sealed layer prepared in advance in one extruder using at least two extruders having a multilayer die having a structure of two or more layers. A predetermined amount of the component (A) and the component (C) are weighed and charged, the above-mentioned thermoplastic resin or the like forming a base material layer is charged into another extruder, and the resin composition and the thermoplastic resin are melted. , Co-extrusion to obtain a laminated film in which a heat seal layer and a base material layer are laminated, or melt the resin composition and the thermoplastic resin with separate film molding machines to form a film. After obtaining, a method of laminating (laminating) a film made of a resin composition (heat seal layer) and a film made of a thermoplastic resin (base material layer), or a film made of a previously obtained thermoplastic resin (base). A method of extruding and laminating the above resin composition on the material layer) to form a laminated film can be mentioned.

In order to obtain a stretched laminated film, for example, a method of uniaxially or biaxially stretching the laminated film obtained by the above-mentioned production method by various known methods, a film made of the above-mentioned resin composition or a thermoplastic resin, respectively. The film obtained by uniaxial or biaxial stretching is laminated (lamination method), and the resin composition is extruded and laminated on a substrate layer made of a thermoplastic resin obtained by uniaxial or biaxial stretching in advance. Examples thereof include a method of forming a laminated film.

[Use of laminated film]
In the laminated film of the present invention, a packaging bag can be produced by heat-sealing the heat-sealing layers of the laminated film. Then, the contents (object to be packaged) are stored in the packaging bag, and a packaging bag can be obtained by further performing a heat seal sealing operation as needed.

The laminated film of the present invention exhibits sufficient heat-sealing strength and hot tack performance that surpasses the current strength even when sealing at the heat-sealing temperature generally used in the bag making industry from packaging films. In addition, sufficient heat seal strength and hot tack performance are exhibited even at temperatures below the heat seal temperature normally used in the industry.

Therefore, even when a high-speed sealing / packaging means such as a vertical bag-making filling machine (VFFS) is used, a durable packaging bag and a packaging stack that can provide a durable packaging bag that does not cause the seal portion to break are provided. It is preferably used as a film.

Next, the laminated film of the present invention and the packaging bag obtained from the laminated film will be described in more detail with reference to Examples, but the present invention is not limited thereto.
First, a method for measuring the physical property values of the component (A) and the component (B) is shown below.

[Molecular weight distribution (Mw / Mn)]
The molecular weight distribution (Mw / Mn) was measured as follows using a gel permeation chromatograph Alliance GPC-2000 manufactured by Waters Corp. The separation column has two TSKgel GNH6-HT and two TSKgel GNH6-HTL, the column size is 7.5 mm in diameter and 300 mm in length, the column temperature is 140 ° C., and the mobile phase is o. -Use 0.025 parts by mass of dichlorobenzene (manufactured by Wako Pure Chemical Industries, Ltd.) and BHT (manufactured by Takeda Pharmaceutical Co., Ltd.) as an antioxidant, move at 1.0 ml / min, set the sample concentration to 15 mg / 10 mL, and inject the sample. The amount was 500 microliters, and a differential refractometer was used as a detector. Standard polystyrene for molecular weights Mw <10 ³ and Mw> 4 × 10 ⁶ Using Tosoh Corp., was used Pressure Chemical Co. for ^{10 3 ≦ Mw ≦ 4 × 10} 6.

[Propylene and α-olefin content in polymer]
The propylene and α-olefin contents were quantified as follows using a JNM GX-500 type NMR measuring device manufactured by JEOL Ltd. 0.35 g of the sample is dissolved by heating in 2.0 ml of hexachlorobutadiene. After filtering this solution with a glass filter (G2), 0.5 ml of deuterated benzene is added, and the solution is placed in an NMR tube having an inner diameter of 10 mm, and ¹³ C-NMR measurement is performed at 120 ° C. The total number of times is 10,000 or more. The composition of propylene and α-olefin was quantified by the obtained ¹³ C-NMR spectrum.

[Melting point (Tm) of component (A)]
Using DSC Pris 1 or DSC7 manufactured by PerkinElmer, a sample of about 5 mg was heated to 200 ° C. and held for 10 minutes under a nitrogen atmosphere (20 ml / min), and then cooled to −100 ° C. at 10 ° C./min. The melting point was determined from the peak apex of the crystal melting peak when the temperature was raised to 200 ° C. at 10 ° C./min after holding at −100 ° C. for 1 minute.

[Melting points (Tm) of component (B) and component (C)]
Using a DSC manufactured by Seiko Instruments, fill an aluminum pan for measurement with a sample of about 5 mg, raise the temperature to 200 ° C at 100 ° C / min, hold at 200 ° C for 5 minutes, and then hold at -100 ° C at 10 ° C / min. The temperature was lowered to 200 ° C., and then the temperature was raised to 200 ° C. at 10 ° C./min.

[Melt flow rate (MFR) of component (A), component (B) and component (C)]
The melt flow rate (MFR) was measured in accordance with ASTM D1238 at 230 ° C. under a load of 2.16 kg.

[Heat seal strength]
Laminated films prepared by the method described later were laminated so that the heat-sealing layers overlap each other, and a test piece was prepared by sandwiching both sides of the laminated films with a Teflon (registered trademark) sheet having a thickness of 50 μm. Next, the heat seal bar of the heat seal tester (TB-701B type manufactured by Tester Sangyo Co., Ltd.) was installed at a width of 5 mm and a length of 300 mm, and the upper and lower seal bars were set to the same temperature. The test piece (Teflon (registered trademark) sheet / film / film / Teflon (registered trademark) sheet) was sandwiched between the heat seal bar portions, and heat sealing was performed at a pressure of 0.1 MPa for 0.5 seconds. The Teflon (registered trademark) sheet was removed, and the heat-sealed film portion was left at room temperature of about 23 ° C. for 1 day. A slit having a width of 15 mm was made so as to include the heat-sealed portion of the film, and the unsealed portion was chucked on a tensile tester (“IM-20ST manufactured by INTESCO”). The 180 ° peel strength of the film was measured at a speed of 300 mm / min. The above operation was performed 5 times, and the average value was taken as the heat seal strength.

[Hot tackiness]
A test piece was prepared by stacking strip-shaped films so that the heat-sealing layers overlap each other and sandwiching the laminated films prepared by the method described later with PET films (12 μm). The seal area of the hot tack tester (Model HT manufactured by Teller, USA Patent # 5,331,858 .; 5,847,284.) Is 25 mm in width and 12.7 mm in depth, and the upper and lower seal bars. The film was sealed at the same temperature and pressure of 0.1 MPa for 0.5 seconds, and then after 0.05 seconds, the peel strength of the film at 180 ° C. was measured at a rate of 400 mm / min. The above operation was performed 5 times, and the average of the maximum intensities of each was taken as the hot tack intensity.

Next, an example of synthesizing a metallocene-type complex which is a constituent component of the olefin polymerization catalyst, and an example of preparing propylene / 1-butene copolymer components (b2) and (b1) using the metallocene catalyst are shown.

[Synthesis example] -Synthesis of metallocene complex-
(1) Preparation of 1-tert-butyl-3-methylcyclopentadiene Dehydrated diethyl ether (350 ml) in tert-butyl magnesium chloride / diethyl ether solution (450 ml, 0.90 mol, 2.0 mol / L solution) under a nitrogen atmosphere. To the solution to which was added, a solution of 3-methylcyclopentenone (43.7 g, 0.45 mmol) in dehydrated diethyl ether (150 ml) was added dropwise 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 under ice-cooling while maintaining 0 ° C. 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 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. The analytical values are shown below.
^{1 1} H-NMR (270 MHz, 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. Dehydrated acetone (55.2 g, 950.4 mmol) was added dropwise to the mixture under ice-cooling while maintaining 0 ° C., and pyrrolidine (68.0 g, 956.1 mmol) was further added dropwise, and the mixture was stirred at room temperature for 4 days. The reaction mixture was diluted with diethyl ether (400 ml), and then water (400 ml) was added. The organic layer was separated, washed with 0.5 N aqueous hydrochloric acid solution (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. The analytical values are shown below.
^{1 1} H-NMR (270 MHz, CDCl ₃ , TMS standard) δ6.23 (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 in a solution of fluorene (10.1 g, 60.8 mmol) in THF (300 ml) under ice-cooling. A hexane solution of n-butyllithium (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-trimethylfluvene (11.7 g, 66.5 mmol) in THF (300 ml) was added dropwise under a nitrogen atmosphere. After stirring at room temperature for 14 hours, the obtained brown solution was ice-cooled and water (200 ml) was added. The organic phase extracted and separated with diethyl ether was dried over magnesium sulfate, 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 yellow oil. The analytical values are shown below.
^{1 1} H-NMR (270 MHz, CDCl ₃ , TMS standard) δ7.70 (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) fluorenyl zirconium 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, and the mixture was further added dropwise at room temperature. Stirring for hours gave 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 at room temperature for 65 hours. The obtained black-brown slurry was filtered, the filtrate was washed with 10 ml of diethyl ether, and then 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 dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) fluorenylzirconium dichloride, which is a red-orange solid metallocene catalyst. The analytical values are shown below.
^{1 1} H-NMR (270 MHz, CDCl ₃ , TMS standard) δ8.11-8.02 (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)

[Preparation Example 1] Preparation of Propylene 1-Butene Copolymer (b2) 875 ml of dry hexane, 75 g of 1-butene and triisobutylaluminum (1.0 mmol) were added to a sufficiently nitrogen-substituted 2000 ml polymerizer at room temperature. After charging, the temperature inside the polymerization apparatus was raised to 65 ° C. and pressurized to 0.7 MPa with propylene. Next, 0.002 mmol of dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) fluorenyl zirconium dichloride, which is a metallocene catalyst obtained in the above synthesis example, and 0.6 mmol of methylaluminoxane (0.6 mmol in terms of aluminum). A toluene solution in contact with Toso Finechem Co., Ltd.) was added into the polymerizer, 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 decompression, 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 polymerized polymer weighed 15.2 g. The polymerized polymer has a 1-butene content (M): 19.4 mol%, a melt flow rate (MFR): 6.5 g / 10 minutes, a molecular weight distribution (Mw / Mn): 2.11 and a melting point (Tm) :. It was 75.3 ° C. In the following description, the polymerized polymer may be abbreviated as PBR (1).

[Preparation Example 2] Preparation of propylene / 1-butene copolymer (b1) In Preparation Example 2, the amount of 1-butene used was changed to 45 g and the propylene pressure was changed to 0.7 MPa. A polymer was obtained in the same manner. Polymerized polymer, 1-butene content (M): 14.5 mol%, melt flow rate (MFR): 6.7 g / 10 min, molecular weight distribution (Mw / Mn): 2.25 and melting point (Tm) :. It was 85.7 ° C. In the following description, the polymerized polymer may be abbreviated as PBR (2).

[Example 1]
(Manufacturing of unstretched laminated film 1)
Using two extruders to which a T-die is connected, the resin composition for the heat seal layer and the thermoplastic resin for the base material layer shown below are supplied to each extruder, and the die and resin temperature are 230. The extrusion amount of each extruder was set at ° C. so that the thickness of the heat seal layer and the base material layer was 2/18, and an unstretched film 1 having a thickness of 800 μm was obtained by coextrusion molding.

The resin composition for the heat seal layer; the PBR (1) obtained in Preparation Example 1 was used alone as the component (B).
Thermoplastic resin for base material layer; propylene homopolymer [Product name Prime Polypro F-300SP manufactured by Prime Polymer Co., Ltd.]

(Manufacturing of Stretched Laminated Film 1)
The unstretched film 1 was stretched and laminated by a batch type biaxial stretching machine at a stretching temperature of 158 ° C. and a stretching speed of 238% in a length x width = 5 times x 8 times (stress relaxation after stretching for 30 seconds). Film 1 was obtained (base material layer thickness: 18 μm, heat seal layer thickness: 2 μm).

(Measurement of heat seal strength and hot tack strength)
Next, the stretched laminated films 1 were laminated so that the heat seal layers overlap each other, and a test piece was prepared in which both sides of the laminated films were sandwiched between Teflon (registered trademark) sheets having a thickness of 50 μm. The peel strength was measured according to the heat seal strength and hot tack test method described above. Table 1 shows each physical property value.

[Example 2]
A stretched laminated film was produced in the same manner as in Example 1 except that the following resin composition was used in place of the resin composition for the heat seal layer used in Example 1, and heat was performed by the same evaluation method as in Example 1. Seal strength and hot tack strength were measured. The results are shown in Table 1.

Resin composition for heat seal layer; as component (A), propylene homopolymer having MFR = 3 g / 10 minutes and melting point (Tm) = 160 ° C. (Homo PP) [trade name F-300SP manufactured by Prime Polymer Co., Ltd.] , A resin composition obtained by blending PBR (1) obtained in Preparation Example 1 as a component (B) at a mass ratio of 5/95.

[Example 3]
A stretched laminated film was produced in the same manner as in Example 1 except that the following resin composition was used in place of the resin composition for the heat seal layer used in Example 1, and heat was performed by the same evaluation method as in Example 1. Seal strength and hot tack strength were measured. The results are shown in Table 1.

Resin composition for heat seal layer; as component (A), propylene homopolymer having MFR = 3 g / 10 minutes and melting point (Tm) = 160 ° C. (Homo PP) [trade name F-300SP manufactured by Prime Polymer Co., Ltd.] , A resin composition obtained by blending PBR (1) obtained in Preparation Example 1 as a component (B) at a mass ratio of 10/90.

[Example 4]
A stretched laminated film was produced in the same manner as in Example 1 except that the following resin composition was used in place of the resin composition for the heat seal layer used in Example 1, and heat was performed by the same evaluation method as in Example 1. Seal strength and hot tack strength were measured. The results are shown in Table 1.

Resin composition for heat seal layer; as component (A), propylene homopolymer having MFR = 3 g / 10 minutes and melting point (Tm) = 160 ° C. (Homo PP) [trade name F-300SP manufactured by Prime Polymer Co., Ltd.] , A resin composition obtained by blending PBR (1) obtained in Preparation Example 1 as a component (B) at a mass ratio of 20/80.

[Example 5]
A stretched laminated film was produced in the same manner as in Example 1 except that the following resin composition was used in place of the resin composition for the heat seal layer used in Example 1, and heat was performed by the same evaluation method as in Example 1. Seal strength and hot tack strength were measured. The results are shown in Table 1.

Resin composition for heat seal layer; as component (A), propylene homopolymer having MFR = 3 g / 10 minutes and melting point (Tm) = 160 ° C. (Homo PP) [trade name F-300SP manufactured by Prime Polymer Co., Ltd.] , A resin composition obtained by blending PBR (1) obtained in Preparation Example 1 as a component (B) at a mass ratio of 30/70.

[Example 6]
A stretched laminated film was produced in the same manner as in Example 1 except that the following resin composition was used in place of the resin composition for the heat seal layer used in Example 1, and heat was performed by the same evaluation method as in Example 1. Seal strength and hot tack strength were measured. The results are shown in Table 1.

Resin composition for heat seal layer; as component (A), propylene homopolymer having MFR = 3 g / 10 minutes and melting point (Tm) = 160 ° C. (Homo PP) [trade name F-300SP manufactured by Prime Polymer Co., Ltd.] , A resin composition obtained by blending PBR (1) obtained in Preparation Example 1 as a component (B) at a mass ratio of 40/60.

[Example 7]
A stretched laminated film was produced in the same manner as in Example 1 except that the following resin composition was used in place of the resin composition for the heat seal layer used in Example 1, and heat was performed by the same evaluation method as in Example 1. Seal strength and hot tack strength were measured. The results are shown in Table 1.

Resin composition for heat seal layer; as component (A), propylene homopolymer having MFR = 3 g / 10 minutes and melting point (Tm) = 160 ° C. (Homo PP) [trade name F-300SP manufactured by Prime Polymer Co., Ltd.] , A resin composition obtained by blending PBR (1) obtained in Preparation Example 1 as a component (B) at a mass ratio of 45/55.

[Example 8]
A stretched laminated film was produced in the same manner as in Example 1 except that the following resin composition was used in place of the resin composition for the heat seal layer used in Example 1, and heat was performed by the same evaluation method as in Example 1. Seal strength and hot tack strength were measured. The results are shown in Table 1.

Resin composition for heat seal layer; as component (A), propylene homopolymer having MFR = 3 g / 10 minutes and melting point (Tm) = 160 ° C. (Homo PP) [trade name F-300SP manufactured by Prime Polymer Co., Ltd.] , A resin composition obtained by blending PBR (1) obtained in Preparation Example 1 as a component (B) at a mass ratio of 50/50.

[Example 9]
A stretched laminated film was produced in the same manner as in Example 1 except that the following resin composition was used in place of the resin composition for the heat seal layer used in Example 1, and heat was performed by the same evaluation method as in Example 1. Seal strength and hot tack strength were measured. The results are shown in Table 1.

Resin composition for heat seal layer; as component (A), propylene homopolymer having MFR = 3 g / 10 minutes and melting point (Tm) = 160 ° C. (Homo PP) [trade name F-300SP manufactured by Prime Polymer Co., Ltd.] , A resin composition obtained by blending PBR (1) obtained in Preparation Example 1 as a component (B) at a mass ratio of 60/40.

[Example 10]
A stretched laminated film was produced in the same manner as in Example 1 except that the PBR (2) obtained in Preparation Example 2 was used alone in place of the resin composition for the heat seal layer used in Example 1. The heat seal strength and the hot tack strength were measured by the same evaluation method as in Example 1. The results are shown in Table 1.

[Example 11]
A stretched laminated film was produced in the same manner as in Example 10 except that the following resin composition was used in place of the resin composition for the heat seal layer used in Example 10, and heat was performed by the same evaluation method as in Example 10. Seal strength and hot tack strength were measured. The results are shown in Table 1.

Resin composition for heat seal layer; as component (A), propylene homopolymer having MFR = 3 g / 10 minutes and melting point (Tm) = 160 ° C. (Homo PP) [trade name F-300SP manufactured by Prime Polymer Co., Ltd.] , A resin composition obtained by blending PBR (2) obtained in Preparation Example 2 as a component (B) at a mass ratio of 30/70.

[Example 12]
A stretched laminated film was produced in the same manner as in Example 10 except that the following resin composition was used in place of the resin composition for the heat seal layer used in Example 10, and heat was performed by the same evaluation method as in Example 10. Seal strength and hot tack strength were measured. The results are shown in Table 1.

Resin composition for heat seal layer; propylene copolymer (homo PP) having MFR = 3 g / 10 minutes and melting point (Tm) = 160 ° C. as component (A) [Prime Polymer Co., Ltd. trade name F-300SP]. The PBR (2) obtained in Preparation Example 2 as the component (B) is used as the component (C) as a propylene random copolymer having an MFR of 5.5 g / 10 min and a melting point (Tm) of 138 ° C. [lyondelbasell] A resin composition obtained by blending [trade name Addsyl5C30F] with a mass ratio of 30/50/30.

[Example 13]
A stretched laminated film was produced in the same manner as in Example 10 except that the following resin composition was used in place of the resin composition for the heat seal layer used in Example 10, and heat was performed by the same evaluation method as in Example 10. Seal strength and hot tack strength were measured. The results are shown in Table 1.

Resin composition for heat seal layer; propylene copolymer (homo PP) having MFR = 3 g / 10 minutes and melting point (Tm) = 160 ° C. as component (A) [Prime Polymer Co., Ltd. trade name F-300SP]. The PBR (1) obtained in Preparation Example 1 as the component (B) is used as the component (C) as a propylene random copolymer having an MFR of 5.5 g / 10 min and a melting point (Tm) of 138 ° C. [lyondelbasell] A resin composition obtained by blending [trade name Addsyl5C30F] with a mass ratio of 30/35/35.

[Example 14]
A stretched laminated film was produced in the same manner as in Example 10 except that the following resin composition was used in place of the resin composition for the heat seal layer used in Example 10, and heat was performed by the same evaluation method as in Example 10. Seal strength and hot tack strength were measured. The results are shown in Table 1.

Resin composition for heat seal layer; propylene copolymer (homo PP) having MFR = 3 g / 10 minutes and melting point (Tm) = 160 ° C. as component (A) [Prime Polymer Co., Ltd. trade name F-300SP]. The PBR (1) obtained in Preparation Example 1 as the component (B) is used as the component (C) as a propylene random copolymer having an MFR of 5.5 g / 10 min and a melting point (Tm) of 138 ° C. [lyondelbasell] A resin composition obtained by blending [trade name Addsyl5C30F] with a mass ratio of 30/20/50.

[Comparative Example 1]
A stretched laminated film was produced in the same manner as in Example 1 except that the following resin composition was used in place of the resin composition for the heat seal layer used in Example 1, and heat was performed by the same evaluation method as in Example 1. Seal strength and hot tack strength were measured. The results are shown in Table 1.

Resin composition for heat seal layer; It has PBR (1) obtained in Preparation Example 1 as component (B), and MFR = 5.5 g / 10 minutes and melting point (Tm) = 138 ° C. as component (C). A resin composition obtained by blending a propylene random copolymer [trade name Adsyl5C30F manufactured by lyondollbasell] at a mass ratio of 15/85.

As can be easily understood from Table 1, the laminated film of the present invention has excellent heat-sealing strength. For example, when the heat seal temperature is 110 ° C., the heat seal strength of Comparative Example 1 consisting of only the component (B) and the component (C) is 1.5 N, whereas the heat of Examples 1 to 11 The seal strength is about 4 times. The excellent heat-sealing strength characteristics of the laminated film of the present invention at such a low temperature are recognized in a wide heat-sealing temperature range of 70 to 120 ° C. On the other hand, Examples 1 to 4 also exhibit the strength of Comparative Example 1 or higher in the range of 80 to 120 ° C. in terms of hot tack strength.

Further, a film having a high heat-sealing strength at a low temperature as in Example 1 tends not to change the heat-sealing strength at 110 ° C. or higher, whereas the component (A) as in Examples 2 to 5 shows. In a laminated film containing such a propylene homopolymer (homo PP), sufficient heat seal strength of Example 1 or higher is exhibited at 90 to 100 ° C., and at the same time, hot tack strength is lowered at 100 ° C. or higher. It turns out that it can be suppressed. That is, it is recognized that the product of the present invention exhibits sufficient heat-sealing strength, low-temperature sealing property, and hot tack strength in a wide temperature range. Therefore, it is possible to handle a wide range of heat seal temperatures during high-speed packaging.

30 ... Laminated film 10 ... Heat seal layer 20 ... Base material layer

Claims (10)

It has a melting point (Tm) of less than 120 ° C. as measured by differential scanning calorimetry (DSC), contains 10-90 mol% of building blocks derived from 1-butene, and has 3 or 5 carbon atoms. It contains 90-10 mol% of the building blocks derived from ~ 20 α-olefins (where the sum of the units derived from 1-butene and the units derived from the α-olefin is 100 mol%. ) A propylene-based polymer (A) having a 1-butene copolymer (B) of 40 to 100 parts by mass and a melting point (Tm) of 150 ° C. or higher and 170 ° C. or lower as measured by differential scanning calorimetry (DSC). 0 to 60 parts by mass [However, (B) + (A) = 100 parts by mass. ] Included in a heat-sealing layer and a base material layer containing the resin composition. The resin composition contains 50 to 95 parts by mass of the 1-butene copolymer (B) and 5 to 50 parts by mass of the propylene-based polymer (A) [provided that (B) + (A) = 100 parts by mass. And. ] The laminated film according to claim 1, further comprising. The resin composition further comprises 0 to 100 parts by mass of a propylene copolymer (C) having a melting point (Tm) of 120 ° C. or higher and lower than 150 ° C. measured by differential scanning calorimetry (DSC) [however (B) + (A) = 100 parts by mass. ] The laminated film according to claim 1 or 2, wherein the laminated film comprises. The 1-butene copolymer (B) contains a structural unit derived from 1-butene in an amount of 10 to 90 mol% and a structural unit derived from propylene in an amount of 90 to 10 mol%. (However, the total of the unit derived from 1-butene and the unit derived from propylene is 100 mol%.) Claims 1 to 3 characterized by being a 1-butene copolymer (B'). The laminated film according to any one of the above items. The same method as the 1-butene copolymer (b1), wherein the 1-butene copolymer (B') has a melting point (Tm) of 90 ° C. or higher and 110 ° C. or lower as measured by differential scanning calorimetry (DSC). A type selected from a 1-butene copolymer (b2) having a melting point of 65 ° C. or higher and lower than 90 ° C. and a 1-butene copolymer (b3) having a melting point of less than 65 ° C. measured by the same method. The laminated film according to claim 4, further comprising the above. The laminated film according to claim 5, wherein the 1-butene copolymers (b1) and (b2) are polymers produced by a metallocene catalyst. The laminated film according to any one of claims 1 to 6, wherein the heat seal layer containing the resin composition is stretched. The laminated film according to any one of claims 1 to 7, wherein the base material layer is stretched. A packaging bag sealed with the heat-sealing layer of the laminated film according to any one of claims 1 to 8 inside. A packaging bag according to claim 9, wherein the packaged object is stored in the packaging bag.