JPH10338778A - Propylene-1-butene random copolymer composition for lamination and composite film using the same composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition useful for laminate molding a composite film excellent in low-containing sealability and blocking resistance by including a propylene-butene random copolymer and a low-density polyethylene therein. SOLUTION: This propylene-1-butene random copolymer composition for lamination is obtained by including (A) 50-97 wt.% propylene-1-butene random copolymer, containing 50-95 mol.% constituent unit derived from propylene and 5-50 mol.% constituent unit derived from 1-butene and having 0.1-40 g/10 min melt flow rate, <=3 molecular weight distribution determined by a gel permeation chromatography and 1.0-1.5 value of a parameter B indicating the randomness of the copolymer monomer chain distribution and (B) 50-3 wt.% low-density polyethylene having 1-30 g/10 min melt flow rate and <=0.940 g/cm<3> density.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene / 1-butene random copolymer composition for lamination suitable for a laminate layer of a composite film, and a composite film using the composition.

[0002]

BACKGROUND OF THE INVENTION Crystalline polypropylene film has mechanical properties such as tensile strength, rigidity, surface hardness, impact strength and cold resistance, optical properties such as gloss and transparency, and non-toxic and odorless properties. Excellent in food hygiene, etc.
In particular, it is widely used in the food field.

[0003] The crystalline polypropylene film has a high heat-sealable temperature and a narrow appropriate temperature range, and thus has problems such as poor welding of the heat-sealed portion and fusing. Therefore, in order to solve the above-described problem of the heat sealing property of the crystalline polypropylene film, a resin layer on which a heat-seal portion is conventionally formed is laminated on the surface of the crystalline polypropylene film. Is being done.

Many resins have been studied as such resin for forming a resin layer. The resins for forming a resin layer include (1) heat sealability at a considerably lower temperature than a base material, and (2) heat seal strength. (3) good adhesion to the substrate, (4) transparency equivalent to or higher than the substrate, (5) no blocking during storage (6) No sticking to bag making and filling / packaging jigs, (7) Good scratch resistance, and (8) Little change over time in heat seal strength.

A propylene / 1-butene random copolymer is a resin capable of forming a resin layer on which the heat seal portion is to be formed. It is known that this copolymer is excellent in transparency and low-temperature sealability, and has relatively good blocking resistance.

When this propylene / 1-butene random copolymer is laminated on the surface of a crystalline polypropylene film, increasing the laminating speed tends to cause surging (film shaking) and causes problems in molding such as an increase in neck-in. is there. As a method of solving the problem at the time of lamination, a method of blending a low-density polyethylene with a propylene / 1-butene random copolymer has been proposed (Japanese Patent Application Laid-Open No. 54-120656).

However, in recent years, the speeding up of packaging machines has been remarkable, and it is possible to seal at a lower temperature, that is, to laminate a composite film having excellent low-temperature sealing properties and excellent blocking resistance. The emergence of a suitable propylene / 1-butene random copolymer composition and its composite film is desired.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems associated with the prior art described above, and it is an object of the present invention to provide a propylene resin suitable for laminating a composite film having excellent low-temperature sealability and blocking resistance. It is intended to provide a 1-butene random copolymer composition and a composite film thereof.

[0009]

SUMMARY OF THE INVENTION Propylene for lamination according to the present invention
The 1-butene random copolymer composition is a composition comprising 50 to 97% by weight of a propylene / 1-butene random copolymer (A) and 50 to 3% by weight of a low-density polyethylene (B). The 1-butene random copolymer (A) is composed of (1) 50 structural units derived from propylene.
(2) a melt flow rate (ASTM D 1238, 230 ° C., 2.16 kg load) of 0.1 to 95 mol%, containing a structural unit derived from 1-butene in an amount of 5 to 50 mol%; ~ 40g
(3) molecular weight distribution (Mw / M) determined by gel permeation chromatography (GPC).
n) is 3 or less, (4) the parameter B value indicating the randomness of the copolymer monomer chain distribution is 1.0 to 1.5, and the low-density polyethylene (B) is obtained by (1) melt flow. Rate (ASTM D 1238, 190 ° C, 2.16kg load) 1-30
g / 10 minutes, and (2) the density is 0.940 g / cm ³ or less.

In the present invention, the propylene / 1-butene random copolymer (A) has a parameter B value which indicates the randomness of the monomer chain distribution of the copolymer (4) is 1.
0 to 1.3, and (5) a melting point Tm measured by a differential scanning calorimeter is 60 to 140 ° C, and
The melting point Tm and the 1-butene constituent unit content M (mol%) satisfy a relationship of -2.6M + 130 ≦ Tm ≦ −2.3M + 155. (6) Crystallinity measured by X-ray diffraction method C (%) and 1-butene constituent unit content M (mol%) are in a relationship satisfying C ≧ −1.5M + 75, and the low-density polyethylene (B) is (3) melt flow rate ( ASTM D 1238, 190
° C., 2.16 kg load) is 1 to 25 g / 10 min, (4) density is preferably 0.915~0.935g / cm ^3.

The propylene / 1-butene random copolymer (A) comprises [a] a transition metal compound represented by the following general formula [I]:

[0012]

Embedded image

[Wherein M is the periodic table IVa, Va, VI
a transition metal of group a, wherein R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, A silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, wherein R ³ is each independently
A secondary or tertiary alkyl group having 3 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms, and R ⁴ is each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. X ¹ and X ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
A halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group, and Y represents 1 to 2 carbon atoms.
0 divalent hydrocarbon group, divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, divalent silicon-containing group, divalent germanium-containing group, divalent tin-containing group, -O-, -CO
-, - S -, - SO -, - SO 2 -, - NR 5 -, - P
^{(R 5) -, - P} (O) (R 5) -, - BR 5 - or -A
lR ⁵ - is. (However, R ⁵ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
To 20 halogenated hydrocarbon groups. )], [B] an organoaluminum oxy compound [b-1], and / or a compound [b-2] that forms an ion pair by reacting with the transition metal compound [a], and [c] an organoaluminum It can be obtained by copolymerizing propylene and 1-butene in the presence of an olefin polymerization catalyst containing a compound.

In the composite film according to the present invention, the resin layer comprising the propylene / 1-butene random copolymer composition for lamination according to the present invention as described above has a resin layer having a thickness of 2 to 200 μm on at least one side of the base film. It is characterized by being laminated with a thickness.

[0015]

DETAILED DESCRIPTION OF THE INVENTION The propylene / 1-butene random copolymer composition for lamination according to the present invention and a composite film using the composition will be specifically described below.

The propylene / 1-for lamination according to the present invention
As described above, the butene random copolymer composition comprises the propylene / 1-butene random copolymer (A) and the low density polyethylene (B).

Propylene / 1-butene random copolymer
(A) The propylene / 1-butene random copolymer (A) used in the present invention has 50 structural units derived from propylene.
5 to 50 mol%, preferably 7 to 45 mol%, more preferably 7 to 95 mol%, preferably 55 to 93 mol%, more preferably 60 to 90 mol%, of the structural unit derived from 1-butene. Is contained in an amount of 10 to 40 mol%.

The propylene / 1-butene random copolymer (A) contains a small amount of structural units derived from olefins other than propylene and 1-butene, for example, 10 mol% or less, preferably 5 mol% or less. May be.

The propylene / 1-butene random copolymer (A) used in the present invention has a melt flow rate (MF)
R; ASTM D 1238, 230 ° C, load 2.16kg) 0.1-40
g / 10 minutes, preferably 0.5 to 30 g / 10 minutes, and more preferably 1 to 20 g / 10 minutes.

The propylene / 1-butene random copolymer (A) used in the present invention has a molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) of 3 or less, preferably 2.5 or less. It is as follows.

The propylene / 1-butene random copolymer (A) used in the present invention has a parameter B value indicating the randomness of the copolymer monomer chain distribution of 1.0 to 1.5,
Preferably 1.0 to 1.3, more preferably 1.0 to 1.3.
1.2.

This parameter B value is calculated according to Coleman et al.
D. Cole-man and TGFox, J. Polym. Sci., Al , 3183 (196
3)), and is defined as follows. B = P ₁₂ / (2P ₁ · P ₂ ) Here, P ₁ and P ₂ are a first monomer and a second monomer content fraction, respectively, and P ₁₂ is (first monomer) − in the entire bimolecular chain. (Second monomer) Chain ratio.

The B value is 1 according to Bernoulli statistics, and when B <1, the copolymer is blocky.
It is alternate when B> 1. Further, the propylene / 1-butene random copolymer (A) used in the present invention has, in addition to the above-mentioned properties, a melting point Tm measured by a differential scanning calorimeter of 60 to 140 ° C, preferably 80 to 140 ° C. 1
The melting point Tm is desirably 30 ° C.
It is desirable that the butene constituent unit content M (molar%) satisfy a relationship of -2.6M + 130 ≦ Tm ≦ −2.3M + 155.

When the melting point of the propylene / 1-butene random copolymer exceeds 140 ° C., the appropriate heat sealing temperature of the film becomes as high as 130 ° C. or higher. Although the sealing property is improved, the scratch resistance is reduced, and the film may be blocked during storage, which may make practical use difficult.

The propylene / 1-butene random copolymer (A) has a crystallinity C measured by an X-ray diffraction method.
(%) And 1-butene constituent unit content M (mol%) are desirably in a relationship satisfying C ≧ −1.5M + 75.

The propylene / 1-butene random copolymer (A) has a crystallinity of 15 to 65%, preferably 20 to 65%.
Desirably, it is 60%. When the propylene / 1-butene random copolymer (A) having a crystallinity within the above range is used, it is possible to provide a film having excellent scratch resistance and low-temperature heat sealability and also excellent blocking resistance. A composition is obtained.

Further, the propylene / 1-
Butene random copolymer (A) ¹³C-NMR spec
Of propylene in all propylene structural units determined from Torr
Position irregular units based on 2,1-insertion of monomer
It may be contained at a rate of 5% or more.

At the time of polymerization, the propylene monomer is 1,2-inserted (the methylene side is bonded to the catalyst), but rarely 2,1-inserted. The 2,1-inserted monomers form regiorandom units in the polymer.

The ratio of 2,1-insertion of the propylene monomer in all the propylene structural units was determined by using ¹³ C-NMR.
It can be determined from the following equation with reference to lymer, 30 (1989) 1350.

[0030]

(Equation 1)

The peaks are named according to the method of Carman et al. (Rubber Chem. Technol., 44 (1971), 781). Iαβ and the like indicate peak areas such as αβ peaks. If it is difficult to directly determine the area such as Iαβ from the spectrum due to overlapping peaks,
A carbon peak with the corresponding area can be substituted.

The propylene / 1-butene random copolymer (A) used in the present invention comprises a propylene monomer
The position irregularity unit based on 1,3-insertion may be 0.05% or less.

The tri-chain amount based on the 1,3-insertion of propylene can be determined from the βγ peak (resonance around 27.4 ppm). The propylene / 1-butene random copolymer (A) as described above comprises [a] a specific transition metal compound (metallocene compound), [b] an organic aluminum oxy compound [b-1], and / or Compound [b- which reacts with metal compound [a] to form an ion pair
2] and optionally [c] an organoaluminum compound, in the presence of an olefin polymerization catalyst (metallocene catalyst) in the presence of propylene and 1-butene.

Transition metal compound (metallocene compound)
[A] The transition metal compound [a] is represented by the following general formula [I].

[0035]

Embedded image

In the formula, M is a transition metal of Groups IVa, Va and VIa of the periodic table, and specifically, preferably, titanium, zirconium, and hafnium, and particularly preferably zirconium.

Substituents R ¹ and R ² R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
To 20 halogenated hydrocarbon groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups or phosphorus-containing groups.

The substituents R ³ R ³ are each independently a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom thereof, or a group substituted with a silicon-containing group. Desirably, it is a secondary or tertiary alkyl group or an aromatic group having 6 to 20 carbon atoms.

The substituents R ^{4 and} R ⁴ are each independently a hydrogen atom or a group having 1 to carbon atoms.
20 alkyl groups. This alkyl group may be substituted with a halogen atom or a silicon-containing group.

X ¹ and X ² X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a carbon atom having 1 carbon atom.
To 20 halogenated hydrocarbon groups, oxygen-containing groups or sulfur-containing groups.

[0041] Y Y is a divalent hydrocarbon group, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group , divalent tin-containing group, -O -, - CO -, - S -, - SO -, - SO 2
-And so on.

As Y, alkylsilylene, alkylarylsilylene and arylsilylene are particularly preferred.
As the transition metal compound [a] represented by the general formula [I], a compound in which R ¹ is a methyl group is particularly preferable.

Many specific examples of the transition metal compound [a] represented by the above general formula [I] are listed in JP-A-8-238729. The transition metal compound used in the present invention as described above is Journal of Organometallic Chem. 2
88 (1985), pp. 63-67, European Patent Application Publication No. 0,32.
It can be produced according to the specification of Japanese Patent No. 0,762 and examples.

Organoaluminum oxy compound [b-1] As the above - mentioned organoaluminum oxy compound [b-1], aluminoxane is preferably used. Specifically, methyl aluminoxane, ethyl aluminoxane, methyl ethyl aluminoxane having a repeating unit represented by the formula -Al (R) O- where R is an alkyl group is usually about 3 to 50. Are used. Such an aluminoxane can be prepared by a conventionally known production method.

Further, a benzene-insoluble organic aluminum oxy compound as exemplified in JP-A-2-78687 may be used. Reaction with a transition metal compound [a] to form an ion pair
Compound [b-2] a compound which reacts with the transition metal compound [a] used in the present invention to form an ion pair (ionized ionic compound)
As [b-2], for example, USP-5321106
No. 6,086,098, triphenylboron, MgCl ₂ ,
Lewis acids such as Al ₂ O ₃ and SiO ₂ —Al ₂ O ₃ are exemplified.

The ionized ionic compound [b-2] can be used alone or in combination of two or more. Organoaluminum Compound [c] Specific examples of the organoaluminum compound [c] used as required in the present invention include trialkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, and alkylaluminum dihalide. be able to.

These organoaluminum compounds can be used alone or in combination of two or more.
The catalyst for olefin polymerization used in the present invention includes the above-mentioned transition metal compound [a], organic aluminum oxy compound [b-1] and / or ionized ionic compound [b-2] and, if desired, organic aluminum compound [b]. c]. The catalyst for olefin polymerization comprises the transition metal compound [a], the organoaluminum oxy compound [b-1] and / or the ionized ionic compound [b-2] and, if desired, the component [c]. Or by mixing in an olefin solvent.

In the present invention, an olefin can be preliminarily polymerized and used for each component forming the olefin polymerization catalyst as described above. As the olefin used for the prepolymerization, propylene, ethylene, 1-butene and the like are preferable, but a mixture of these with another olefin may be used.

The propylene / 1-butene random copolymer (A) used in the present invention can be produced by copolymerizing propylene with 1-butene in the presence of the olefin polymerization catalyst. .

The polymerization can be carried out by any of liquid phase polymerization such as suspension polymerization and solution polymerization or gas phase polymerization. The molecular weight of the obtained propylene / 1-butene random copolymer (A) can be adjusted by allowing hydrogen to exist in the polymerization system or by changing the polymerization temperature and the polymerization pressure.

The method for producing the propylene / 1-butene random copolymer (A) is described in JP-A-8-23872.
No. 9 discloses this in detail. The propylene / 1-butene random copolymer (A) is 50 to 97% by weight based on 100% by weight of the total amount of the propylene / 1-butene random copolymer (A) and the low-density polyethylene (B). Preferably 55 to 96% by weight, more preferably 60 to 95% by weight.
Used in percentages by weight.

Low-density polyethylene (B) The low-density polyethylene (B) used in the present invention is an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. 0.94
0 g / cm ³ or less, preferably 0.915 to 0.935
g / cm ³ , more preferably 0.916 to 0.925
g / cm ³ .

As the above α-olefin, specifically, propylene, 1-butene, 1-pentene, 2-methyl-1-
Butene, 3-methyl-1-butene, 1-hexene, 3-methyl-1
-Pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-
Butene, 1-heptene, methyl-1-hexene, dimethyl-1
-Pentene, trimethyl-1-butene, ethyl-1-pentene, 1-octene, methyl-1-pentene, dimethyl-1-hexene, trimethyl-1-pentene, ethyl-1-hexene, methylethyl-1-pentene, Diethyl-1-butene,
Propyl-1-pentene, 1-decene, methyl-1-nonene,
Dimethyl-1-octene, trimethyl-1-heptene, ethyl-1-octene, methylethyl-1-heptene, diethyl
-1-hexene, 1-dodecene, 1-hexadodecene and the like.

These α-olefins can be used alone or in combination of two or more. The low-density polyethylene (B) used in the present invention has a melt flow rate (MFR; ASTM D 1238, 190 ° C., 2.16 kg load) of 1;
-30 g / 10 min, preferably 1-25 g / 10 min, more preferably 3-20 g / 10 min.

The low density polyethylene (B) as described above
Can be produced by a conventionally known method, for example, a high pressure method. Moreover, it can also be manufactured to have the above-mentioned physical properties using a metallocene catalyst.

The low-density polyethylene (B) is 50 to 3% by weight, preferably 45% by weight, based on 100% by weight of the total amount of the propylene / 1-butene random copolymer (A) and the low-density polyethylene (B). ~ 4% by weight, more preferably 4%
It is used at a ratio of 0 to 5% by weight. The propylene / 1-butene random copolymer (A) composition in which the low-density polyethylene (B) is blended in the above-described ratio is capable of surging even when the laminating speed is increased when laminating on a crystalline polypropylene film surface. There is no occurrence or neck-in increase, and the moldability is excellent.

Other Components In addition to the propylene / 1-butene random copolymer (A) and the low density polyethylene (B), the propylene / 1-butene random copolymer composition for lamination according to the present invention comprises
Within the range not impairing the object of the present invention, various additives such as an antioxidant, an ultraviolet absorber, a lubricant, a nucleating agent, an antistatic agent, a flame retardant, a pigment, a dye, and an inorganic or organic filler may be compounded. it can.

Propylene / 1-butenelander for laminating
Preparation of rubber copolymer composition The propylene / 1-butene random copolymer composition for lamination according to the present invention can be prepared by any known method, for example, a V-type blender, a ribbon blender,
It can be prepared by mixing the above components with a mixer such as a Henschel mixer, or can also be prepared by kneading the above components with a kneader such as an extruder, a mixing roll, a Banbury mixer, or a kneader. Can be. Further, the polypropylene resin composition according to the present invention can also be prepared by combining or kneading the above components by combining the above mixing method and kneading method.

Composite Film The composite film according to the present invention is characterized in that at least one side of the base film has two or more resin layers comprising the propylene / 1-butene random copolymer composition for lamination according to the present invention as described above. The layers are stacked at a thickness of 200 μm, preferably 10 to 60 μm.

Specific examples of the polymer used in the base film include polyolefins such as polypropylene and poly 1-butene, polyamides such as nylon 6 and nylon 66, and polyesters such as polyethylene terephthalate and polybutylene terephthalate. These unstretched films, uniaxially stretched or biaxially stretched films are used. Among them, a biaxially stretched polypropylene film is preferable.

The polypropylene used for forming the polypropylene film may be a homopolymer of propylene or a random or block copolymer of propylene with another α-olefin, for example, ethylene or 1-butene (usually propylene structural unit). (The content is 90 mol% or more)
It is desirable that the boiling n-heptane insoluble content is 90% or more, preferably 93% or more.

Such a polypropylene is typically produced using a catalyst formed from a solid titanium catalyst component and an organometallic compound catalyst component, or a catalyst formed from both components and an electron donor. Can be.

Examples of the solid titanium catalyst component include titanium trichloride or a titanium trichloride composition produced by various methods, magnesium, halogen, an electron donor (preferably an aromatic carboxylic acid ester or an alkyl group-containing ether). And a titanium catalyst component with a carrier containing titanium as an essential component. In particular, a titanium catalyst component with a carrier having a specific surface area of preferably 100 m ² / g or more is preferable.

As the organometallic compound catalyst component, an organoaluminum compound is preferable, for example, trialkylaluminum, dialkylaluminum halide,
Examples thereof include alkyl aluminum sesquihalide and alkyl aluminum dihalide. Whether or not these compounds are suitable as catalyst components depends on the type of titanium catalyst component. Therefore, it is preferable to select the organoaluminum compound to be used according to the type of titanium catalyst component to be used.

The electron donor is an organic compound containing nitrogen, phosphorus, sulfur, oxygen, silicon, boron and the like, and preferable examples thereof include esters and ethers.

The crystalline polypropylene can be produced by a known method using the above-mentioned conventionally known solid titanium catalyst component or metallocene compound catalyst component.

The polypropylene resin (A) can be used alone or in combination of two or more.
The composite film according to the present invention can be produced by, for example, a method in which the propylene / 1-butene random copolymer composition for laminating according to the present invention is extrusion-coated on a substrate with a T-die.

[0068]

The propylene for lamination according to the present invention
The 1-butene random copolymer composition is capable of forming a composite film having excellent laminate moldability and excellent low-temperature sealability, blocking resistance and hot tack properties.

The composite film according to the present invention is obtained by laminating the propylene / 1-butene random copolymer composition for lamination according to the present invention on at least one side of the base film, so that the low-temperature sealing property, blocking resistance, Excellent slip and hot tack properties.

[0070]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[Measurement of Physical Properties of Propylene / 1-Butene Random Copolymer] (1) Propylene content, 1-butene content Determined using ¹³ C-NMR. (2) MFR MFR is ASTM D 1238 (230 ° C, 2.16
kg).

(3) Molecular weight distribution (Mw / Mn) The molecular weight distribution (Mw / Mn) was measured by GPC-1 manufactured by Millipore.
It measured as follows using 50C. The separation column is TSK GNH HT, the column size is 27 mm in diameter, 600 mm in length, and the column temperature is 140
° C, and o-dichlorobenzene [manufactured by Wako Pure Chemical Industries, Ltd.] as a mobile phase and BHT [manufactured by Takeda Pharmaceutical Co., Ltd.] 0.025% by weight as an antioxidant were used at 1.0 ml / min. The sample was moved, the sample concentration was set to 0.1% by weight, the sample injection amount was set to 500 μl, and a differential refractometer was used as a detector.
For molecular weights Mw <1000 and Mw> 4 × 10 ⁶ , standard polystyrene manufactured by Tosoh Corporation was used, and 1000 <M
For w <4 × 10 ⁶ , standard polystyrene manufactured by Pressure Chemical Co. was used.

(4) B value The B value was obtained by measuring the ¹³ C-NMR spectrum of a sample obtained by uniformly dissolving about 200 mg of the copolymer in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube at a measuring temperature of 120 ° C.
° C, measurement frequency 25.05 MHz, spectrum width 150
0 Hz, a filter width of 1500 Hz, a pulse repetition time of 4.2 sec, and a total number of accumulations of 2000 to 5000 were measured, and P _E , P _o , P
_OE was calculated and calculated from the above equation.

(5) Melting Point (Tm) The melting point (Tm) was measured using a DSC-7 apparatus (Differential Scanning Calorimeter (DSC)) manufactured by PerkinElmer.
Specifically, about 5 mg of a sample was packed in an aluminum pan and 200
Temperature, and kept at 200 ° C for 5 minutes.
After cooling to −40 ° C. per minute and holding at −40 ° C. for 5 minutes, the temperature was determined from an endothermic curve when the temperature was raised at 10 ° C./min. (6) Crystallinity The crystallinity was determined by X-ray diffraction measurement of a 1.0 mm-thick pressed sheet that had passed at least 24 hours after molding.

The haze of the composite films obtained in the Examples and Comparative Examples, the change with time of the haze, the gloss, the slip property, the change with time of the slip property, the anti-blocking property, the anti-blocking property, and the interlayer The test methods performed for the adhesive strength, heat sealing property and hot tack property are as follows. (1) Cloudiness Measured according to ASTM D1003. (2) Temporal change in haze The composite film was kept at 80 ° C. for 3 days and allowed to cool, and then the haze was measured in the same manner as in (1) above. (3) Gloss The gloss was measured in accordance with ASTM D523. (4) Slip property (static friction coefficient, dynamic friction coefficient) After annealing the composite film at 40 ° C for 1 day, ASTM
The static friction coefficient and the dynamic friction coefficient of the surface of the propylene / 1-butene random copolymer composition layer were measured in accordance with D 1894. (5) Time-dependent change in slip property The composite film was kept at 40 ° C. for one week and allowed to cool, and then the static friction coefficient and the dynamic friction coefficient were measured in the same manner as in (4) above. (6) Blocking resistance (blocking force) Two composite films were superposed on each other on the propylene / 1-butene random copolymer composition layer surfaces, annealed at 50 ° C for 1 day, and then subjected to a blocking force according to ASTM D1893. Was measured. (7) Time-dependent change in blocking property The composite film was kept at 50 ° C. for one week and allowed to cool, and then the blocking force was measured in the same manner as in (6) above.

(8) Interlayer adhesion strength A test piece having a width of 15 mm was cut out from the composite film, and a layer at one end of the test piece was peeled off. Then, using an Instron tensile tester, a T-type peeling method was performed at a peeling speed of 300 mm / min. As a result, the interlayer adhesion strength (peel strength) between the base film layer and the propylene / 1-butene random copolymer composition layer was measured. (9) Heat sealability (heat seal adhesive strength) Two composite films were laminated on each other with the propylene / 1-butene random copolymer composition layers at 80 ° C, 90 ° C, and 1 ° C.
At a temperature of 00 ° C., 110 ° C., 120 ° C. and 130 ° C., a pressure of ² kg / cm ² for 1 second, the width of
After heat sealing in mm, it was allowed to cool. Next, 15 m from the composite film heat-sealed at each temperature
A test piece having a width of m was cut out, and the peel strength of the test piece when the heat-sealed portion was peeled off at a crosshead speed of 200 mm / min was measured. (10) Hot tack property The propylene / 1-butene random copolymer composition layers of the composite film are superimposed on each other, and the temperature is 80 ° C, 90 ° C, 100 ° C.
2kg at each temperature of ℃, 110 ℃, 120 ℃, 130 ℃
45 g after heat sealing at a pressure of 1 cm / cm ² for 1 second.
Was applied, and the distance at which the seal portion was peeled off was measured.

[0077]

[Production Example 1] [Propylene / 1-butene random copolymer (PBR-
Production of 1)] In a 2-liter autoclave sufficiently purged with nitrogen, 900 ml of hexane and 60 parts of 1-butene are added.
g, 1 mmol of triisobutylaluminum was added, the temperature was raised to 70 ° C., and propylene was supplied to give a total pressure of 7 g.
kg / cm ² G, 0.30 mmol of methylaluminoxane, 0.001 mmol of rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride in terms of Zr atom were added, Polymerization was carried out for 30 minutes while continuously supplying propylene and maintaining the total pressure at 7 kg / cm ² G. After the polymerization, the polymer was degassed, the polymer was recovered in a large amount of methanol, and dried under reduced pressure at 110 ° C. for 12 hours.

The yield of the polymer [propylene / 1-butene random copolymer (PBR-1)] obtained as described above was 39.7 g. The polymerization activity is 79k
g · polymer / mmol Zr · hr.

This polymer has a content of constituent units derived from 1-butene of 24 mol% and a melt flow rate (ASTM D 1238, 230 ° C., load 2.16 kg) of 20 g / 10 g.
And the molecular weight distribution (Mw / M
n) is 2.1, the B value is 1.00, and the melting point (T
m) was 91 ° C., and the crystallinity measured by X-ray diffraction was 40%.

[0080]

[Production Example 2] [Propylene / 1-butene random copolymer (PBR-
2) Production] In a 2-liter autoclave sufficiently purged with nitrogen, 830 ml of hexane and 10 parts of 1-butene were added.
After charging 0 g, adding 1 mmol of triisobutylaluminum and raising the temperature to 70 ° C., propylene was supplied to a total pressure of 7 kg / cm ² G, and 1 mmol of triethylaluminum was added.
Then, 0.005 mmol of a titanium catalyst supported on magnesium chloride in terms of Ti atoms was added, and propylene was continuously supplied to carry out polymerization for 30 minutes while keeping the total pressure at 7 kg / cm ² G. After the polymerization, the polymer was degassed, the polymer was recovered in a large amount of methanol, and dried under reduced pressure at 110 ° C. for 12 hours.

The yield of the polymer [propylene / 1-butene random copolymer (PBR-2)] obtained as described above was 33.7 g. The polymerization activity is 14 kg
Polymer / mmol Zr · hr This polymer has a content of structural units derived from 1-butene of 24 mol% and a melt flow rate (ASTM D 1238,230).
C., load 2.16 kg) was 20 g / 10 min, the molecular weight distribution (Mw / Mn) determined by GPC was 4.2, and B
Value is 0.92, melting point (Tm) is 110 ° C.,
The degree of crystallinity measured by the X-ray diffraction method was 48%.

[0082]

Example 1 [Preparation of propylene / 1-butene random copolymer composition] 90 parts by weight of the propylene / 1-butene random copolymer (PBR-1) obtained in Production Example 1 and low density polyethylene ( Density = 0.917 g / cm ³ , MFR = 7 g / 1
0 minutes, crystallinity = 4%, content of structural units derived from ethylene = 80 mol%, content of structural units derived from propylene = 20 mol%) and 10 parts by weight were melt-mixed at 280 ° C. Thus, a propylene / 1-butene random copolymer composition was obtained.

Next, this composition was extrusion coated on a biaxially oriented polypropylene film layer having a thickness of 20 μm under the following conditions to form a composite film. <Molding conditions> Film layer configuration and thickness of each layer: Biaxially stretched polypropylene film layer (base film layer)
/ Composition layer = 20 μm / 20 μm Molding speed: 80 m / min Table 1 shows the results of the above-mentioned tests of the composite film obtained as described above.

In the above-mentioned lamination molding, the molding speed was gradually increased to obtain the maximum lamination speed (m / min) as an index of the laminability, and
The neck-in (mm) at that time was determined. Here, the maximum laminating speed refers to a molding speed when a composition is extruded onto a biaxially stretched polypropylene film at a speed of 80 m / min at a thickness of 20 μm, and only the take-up speed is increased to cause surging. .

The results are shown in Table 1.

[0086]

Example 2 Example 1 was the same as Example 1 except that the blending amounts of the propylene / 1-butene random copolymer (PBR-1) and the low-density polyethylene were 80 parts by weight and 20 parts by weight, respectively. Thus, a propylene / 1-butene random copolymer composition was prepared.

Thereafter, a composite film was laminated and formed in the same manner as in Example 1. Table 1 shows the results of the above test of the obtained composite film.

In this lamination molding, the molding speed was gradually increased to determine the maximum lamination speed (m / min) as an index of the laminability, and the neck-in (mm) at that time. .

The results are shown in Table 1.

[0090]

Comparative Example 1 In Example 1, except that the propylene / 1-butene random copolymer (PBR-1) was used alone instead of the propylene / 1-butene random copolymer composition of Example 1, The composite film was laminated and formed in the same manner as in Example 1. Table 1 shows the results of the above test of the obtained composite film.

In this lamination molding, the molding speed was gradually increased to determine the maximum lamination speed (m / min) as an index of the laminability and the neck-in (mm) at that time. .

Table 1 shows the results.

[0093]

Comparative Example 2 The propylene / 1-butene random copolymer (PBR-2) obtained in Production Example 2 was replaced with 90 parts by weight of the propylene / 1-butene random copolymer (PBR-1) in Example 1. ) A propylene / 1-butene random copolymer composition was prepared in the same manner as in Example 1 except that 90 parts by weight was used.

Thereafter, the composite film was laminated and formed in the same manner as in Example 1. Table 1 shows the results of the above test of the obtained composite film.

In this lamination molding, the molding speed was gradually increased to find the maximum lamination speed (m / min) as an index of lamination moldability, and the neck-in (mm) at that time. .

The results are shown in Table 1.

[0097]

Comparative Example 3 The propylene / 1-butene random copolymer (PBR-2) obtained in Production Example 2 was replaced with 90 parts by weight of the propylene / 1-butene random copolymer (PBR-1) in Example 1. ) A propylene / 1-butene random copolymer composition was prepared in the same manner as in Example 1 except that 80 parts by weight and the amount of the low-density polyethylene were changed to 20 parts by weight.

Thereafter, the composite film was laminated and formed in the same manner as in Example 1. Table 1 shows the results of the above test of the obtained composite film.

In this lamination molding, the molding speed was gradually increased to determine the maximum lamination speed (m / min) as an index of the laminability and the neck-in (mm) at that time. .

Table 1 shows the results.

[0101]

[Table 1]

Claims (4)

[Claims] 1. A composition comprising 50 to 97% by weight of a propylene / 1-butene random copolymer (A) and 50 to 3% by weight of a low-density polyethylene (B). The polymer (A) is
(1) Structural units derived from propylene are contained in an amount of 50 to 95 mol%, and structural units derived from 1-butene are contained in an amount of 5 to 50 mol%. (2) Melt flow rate (ASTM D 1
(238, 230 ° C, 2.16 kg load) is 0.1 to 40 g / 10 min, and (3) the molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is 3
(4) The parameter B value indicating the randomness of the copolymer monomer chain distribution is 1.0 to 1.5, and the low-density polyethylene (B) is (1) a melt flow rate (ASTM D 1238, 190 ° C, 2.16kg load) 1-30g /
(2) A propylene / 1-butene random copolymer composition for lamination, which has a density of 0.940 g / cm ³ or less for 10 minutes. 2. The propylene / 1-butene random copolymer (A) has a parameter B value indicating the randomness of the monomer chain distribution of the copolymer (4) of 1.0 to 1.3,
And (5) a melting point Tm measured by a differential scanning calorimeter.
And the melting point Tm and the 1-butene constituent unit content M (mol%) satisfy the following relationship: -2.6M + 130≤Tm≤-2.3M + 155, and (6) X The crystallinity C (%) measured by the line diffraction method and the 1-butene structural unit content M (mol%) are in a relationship satisfying C ≧ −1.5M + 75, and the low-density polyethylene (B) is , (3) Melt flow rate (ASTM D 1238, 190 ° C, 2.16kg load) 1-25g
/ 10 minutes, and (4) the density is 0.915 to 0.935 g
2. The propylene / 1-butene random copolymer composition for a laminate according to claim 1, wherein the composition is / cm ³ . 3. The propylene / 1-butene random copolymer (A) comprises: [a] a transition metal compound represented by the following general formula [I]: Wherein M is a transition metal of Groups IVa, Va and VIa of the periodic table, and R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon having 1 to 20 carbon atoms. Group, 1 carbon atom
20 halogenated hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, R ³ are each independently secondary having 3 to 20 carbon atoms or A tertiary alkyl group or an aromatic group having 6 to 20 carbon atoms, R ⁴ is each independently a hydrogen atom or a C 1 to C
X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a carbon atom having 1
Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, and a divalent hydrocarbon group having 1 to 20 carbon atoms. group, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, -O -, - CO -, - S -, - SO -, - SO 2
—, —NR ⁵ —, —P (R ⁵ ) —, —P (O) (R ⁵ ) —,
—BR ⁵ — or —AlR ⁵ —. (However, R ⁵ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.)], [B] an organic aluminum oxy compound [b −
1] and / or propylene and 1-butene in the presence of an olefin polymerization catalyst containing a compound [b-2] which reacts with the transition metal compound [a] to form an ion pair. The propylene / 1-butene random copolymer composition for a laminate according to claim 1, which is obtained by: 4. A resin film comprising the propylene / 1-butene random copolymer composition for lamination according to claim 1 having a thickness of 2 to 200 μm on at least one surface of a substrate film. A composite film characterized by the above.