JP5094499B2 - Laminate and its use - Google Patents

Description

  The present invention relates to a laminate and its use. In detail, it is related with the laminated body suitably used for the container for packaging etc. which has the heat seal layer which consists of a specific resin composition, and its use.

  Polypropylene is excellent in mechanical properties such as tensile strength, rigidity, surface hardness, impact strength, cold resistance, optical properties such as glossiness and transparency, food hygiene such as non-toxicity and odorlessness, etc. It is widely used as a packaging material for packaging various articles.

  Since a polypropylene single layer film is usually excellent in heat resistance, the film alone shrinks when heated to a heat seal temperature, and it is difficult to heat seal. For this reason, many polypropylene films are provided with a heat seal layer.

  Many polypropylene composite films having a heat seal layer are known (for example, see Patent Document 1). Patent Document 1 discloses a composite film having a crystalline polypropylene layer and a layer (heat seal layer) containing crystalline propylene and a propylene / 1-butene random copolymer laminated on at least one surface of the layer. Has been. It is disclosed that an anti-blocking agent and a slip agent may be further added to the heat seal layer.

However, the composite film described in Patent Document 1 is a film that exhibits heat sealability at a temperature of 80 ° C. or higher, and has a large blocking force. For this reason, there was room for improvement in terms of heat sealability and blocking resistance at low temperatures.
JP-A-8-238731

  The present invention is suitable for packaging containers and the like that are excellent in heat sealability at low temperatures (hereinafter also referred to as low temperature heat sealability) and transparency, have a small coefficient of dynamic friction of the heat seal layer, and are excellent in handling during secondary molding. An object of the present invention is to provide a laminate for use in packaging and a packaging container comprising the laminate.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by providing a layer made of a specific propylene-based resin composition as a heat seal layer, thereby completing the present invention.

That is, the laminate of the present invention comprises a layer [I] composed of a polypropylene resin (i) and (A) (1) units derived from propylene in an amount of 50 to 95 mol% and 2 or 4 to 20 carbon atoms. The unit derived from α-olefin of 5 to 50 mol% is contained, and (2) the melting point (Tm) measured by differential scanning calorimetry (DSC) is 110 ° C. or lower, or DSC No melting point peak was observed in (3), the intrinsic viscosity measured in decalin at 135 ° C. was 0.1 to 12 dl / g, and (4) molecular weight determined by gel permeation chromatography (GPC) 100 to 40 parts by weight of a propylene / α-olefin copolymer having a distribution (Mw / Mn) of 3.0 or less, and (B) 0 to 60 parts by weight of a polypropylene resin having a melting point of 120 ° C. or more (provided that ( A) And (B) is 100 parts by weight) and (C) a poly (meth) acrylate ester antiblocking agent having an average particle diameter of 0.5 to 5 μm.
A heat seal layer [II] comprising a polypropylene resin composition comprising 01 to 0.3 parts by weight and (D) 0.1 to 3 parts by weight of a lubricant comprising a silicone oil having a viscosity of 500 to 250,000 mm ² / S. ].

The propylene / α-olefin copolymer (A) has (5) a melting point Tm measured by a differential scanning calorimeter of 50 to 110 ° C., and the melting point Tm and α-olefin structural unit content M ( Mol%)
It is preferable that −2.6M + 130 ≦ Tm ≦ −2.3M + 155.

  The propylene / α-olefin copolymer (A) is obtained by copolymerizing propylene and an α-olefin in the presence of a catalyst containing a transition metal compound (1a) represented by the following general formula (1a). It is preferable that

（式（１ａ）中、Ｒ¹、Ｒ³は水素であり、Ｒ²、Ｒ⁴は炭化水素基、ケイ素含有基から選ばれ、それぞれ同一でも異なっていてもよい。Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³およびＲ¹⁴は水素、炭化水素基、ケイ素含有基から選ばれ、それぞれ同一でも異
なっていてもよく、Ｒ⁵からＲ¹²までの隣接した置換基は互いに結合して環を形成しても
よい。Ｒ¹³とＲ¹⁴はそれぞれ同一でも異なっていてもよく、互いに結合して環を形成してもよい。Ｍは第４族遷移金属であり、Ｙは炭素原子であり、Ｑはハロゲン、炭化水素基、アニオン配位子または孤立電子対で配位可能な中性配位子から同一または異なる組合せで選んでもよく、ｊは１〜４の整数である。）
前記（Ｃ）ポリ（メタ）アクリル酸エステル系ブロッキング防止剤が、ポリメチルメタクリレートからなるブロッキング防止剤であることが好ましい。

(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, and may be the same or different. R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are selected from hydrogen, a hydrocarbon group, and a silicon-containing group, and may be the same or different, and R ⁵ to R ¹² R ¹³ and R ¹⁴ may be the same as or different from each other, and may be bonded to each other to form a ring, and M is the fourth. A transition metal, Y is a carbon atom, Q may be selected from the same or different combinations from halogens, hydrocarbon groups, anionic ligands or neutral ligands capable of coordinating with lone pairs, j Is an integer from 1 to 4.)
The (C) poly (meth) acrylic acid ester antiblocking agent is preferably an antiblocking agent comprising polymethyl methacrylate.

  The (B) polypropylene resin is preferably a propylene random copolymer having units derived from propylene and units derived from an α-olefin having 2 or 4 to 20 carbon atoms.

It is preferable that the thickness of the layer [I] is 10 to 60 μm, and the thickness of the layer [II] is 0.1 to 5 μm.
The packaging container of the present invention is formed from the laminate of the present invention.

According to the present invention, a laminate that is excellent in low-temperature heat sealability and transparency, has a small coefficient of dynamic friction of the heat seal layer, is excellent in handling during secondary molding, and is suitably used for a packaging container,
A packaging container comprising the laminate can be provided.

Hereinafter, the present invention will be specifically described.
The laminate of the present invention comprises a layer [I] composed of a polypropylene resin (i) and (A) (1) units derived from propylene in an amount of 50 to 95 mol% and having 2 or 4 to 20 carbon atoms. The unit derived from α-olefin is contained in an amount of 5 to 50 mol%, and (2) the melting point (Tm) measured by differential scanning calorimetry (DSC) is 110 ° C. or lower, or the DSC (3) The intrinsic viscosity measured in decalin at 135 ° C. is 0.1 to 12 dl / g, and (4) molecular weight distribution determined by gel permeation chromatography (GPC). 100 to 40 parts by weight of a propylene / α-olefin copolymer having (Mw / Mn) of 3.0 or less, and (B) 0 to 60 parts by weight of a polypropylene resin having a melting point of 120 ° C. or more (provided that (A ) And (B) And (C) 0.01 to 0.3 part by weight of a poly (meth) acrylate-based antiblocking agent having an average particle diameter of 0.5 to 5 μm, and (D) ) Lubricant 0 consisting of silicone oil with a viscosity of 500-250,000 mm ² / S
. And a layer [II] made of a polypropylene resin composition containing 1 to 3 parts by weight.

<Layer [I]>
Layer [I] which constitutes the layered product of the present invention is formed from polypropylene resin (i).

  The polypropylene resin (i) is not particularly limited, but a polypropylene resin having a melting point (Tm) measured by DSC of 140 ° C. or higher is usually used. In the present invention, conventionally known polypropylene can be widely used as the polypropylene resin (i).

  The polypropylene resin (i) may be a homopolypropylene, and includes a propylene-based resin containing units derived from propylene and a small amount (for example, 10 mol% or less, preferably less than 5 mol%) of an olefin other than propylene. A copolymer may also be used. The copolymer may be a random copolymer or a block copolymer. Specific examples of other olefins forming the propylene-based copolymer include α-olefins having 2 to 20 carbon atoms other than propylene, such as ethylene, 1-butene, 1-pentene, 1-hexene, 1 -Heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 4-methyl-1-pentene and the like.

In the present invention, a propylene homopolymer is preferably used as the polypropylene resin (i).
The polypropylene resin (i) used in the present invention can be produced by a known method using a conventionally known solid titanium catalyst component or metallocene compound catalyst component.

  The polypropylene resin (i) used in the present invention has a melting point (Tm) of 140 ° C. or higher, preferably 140 to 165 ° C., more preferably 150 to 165 ° C. When the melting point is in this range, the balance of rigidity, heat resistance and transparency is excellent. Polypropylene resin (i) usually has a higher melting point than (A) propylene / α-olefin copolymer and (B) polypropylene resin contained in layer [II] described later.

  The melt flow rate MFR (ASTMD 1238; 230 ° C., under a load of 2.16 kg) of the polypropylene resin (i) is usually 0.1 to 10 g / 10 minutes, preferably 0.5 to 8 g / 10 minutes. Is desirable.

The layer [I] may contain an additive. Examples of the additive include an antistatic agent, a heat stabilizer, an ultraviolet absorber, an antiblocking agent, and a lubricant.
When an additive is contained, it is usually used in the range of 0.01 to 5 parts by weight per 100 parts by weight of the propylene resin (i).

  The laminate of the present invention is usually in the form of a film or sheet (hereinafter collectively referred to as a film). The thickness of the layer [I] varies depending on the use of the laminate, but is usually 10 to 60 μm, preferably 15 to 50 μm. In the said range, since it is excellent in the handling at the time of packaging, it is preferable.

  The layer [I] is preferably stretched from the viewpoint of rigidity and heat resistance. The stretching may be uniaxial stretching in which stretching is performed in the vertical axis or horizontal axis direction, or biaxial stretching in which stretching is performed in the vertical axis and horizontal axis directions.

<Layer [II]>
The layer [II] constituting the laminate of the present invention comprises the following (A) propylene / α-olefin copolymer, (B) polypropylene resin, and (C) poly (meth) acrylate ester blocking inhibitor. And (D) a polypropylene resin composition containing a lubricant made of silicon oil.

(A) Propylene / α-olefin copolymer The propylene / α-olefin copolymer (A) according to the present invention satisfies the following characteristics (1) to (4), and preferably further: Satisfying at least one of the characteristics (5) and (6). Particularly preferably, all of the characteristics (1) to (6) are satisfied.

  (1) A unit derived from propylene is contained in an amount of 50 to 95 mol%, preferably 60 to 93 mol%, more preferably 70 to 90 mol%, and derived from an α-olefin having 2 or 4 to 20 carbon atoms. The unit to be removed is contained in an amount of 5 to 50 mol%, preferably 7 to 40 mol%, more preferably 10 to 30 mol%. When propylene is 50 mol% or less, handling becomes very worse because it becomes a veil, and when propylene is 95 mol% or more, it cannot be distinguished from the combined polypropylene resin (B). Absent.

The propylene / α-olefin copolymer (A) according to the present invention may contain a combination of structural units derived from α-olefins other than propylene.
The propylene / α-olefin copolymer (A) is preferably a propylene / 1-butene copolymer composed of units derived from propylene and 1-butene.

  (2) The melting point (Tm) measured by differential scanning calorimetry (DSC) is 110 ° C. or lower, or no melting point peak is observed by DSC. Preferably, the melting point (Tm) is 50 to 110 ° C, more preferably 60 to 100 ° C, and still more preferably 65 to 90 ° C. If the melting point is lower than 50 ° C., it tends to have tackiness at room temperature and tends to cause problems such as blocking, and if the melting point is higher than 110 ° C., the effect of the invention is diminished.

  (3) The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.1 to 12 dl / g, preferably 0.5 to 12 dl / g, more preferably 1 to 12 dl / g.

  (4) The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is 3.0 or less, preferably 2.0 to 3.0, more preferably 2.0 to 2. .5. When Mw / Mn is larger than 3.0, the amount of low molecular weight components that are considered to affect the blocking property of the laminate increases, which is not preferable.

(5) Melting | fusing point Tm measured by a differential scanning calorimeter is 50-110 degreeC normally, Preferably it is 60-100 degreeC, More preferably, it is 65-90 degreeC, and this melting | fusing point Tm and alpha-olefin structural unit content The relationship with M (mol%)
−2.6M + 130 ≦ Tm ≦ −2.3M + 155
Meet.

(6) Propylene / α-olefin comprising (i) a head-to-tail-bonded propylene unit three-chain, or (ii) a head-to-tail-bonded propylene unit and an α-olefin, wherein the second unit contains a propylene unit. When 3 chains were measured by ¹³ C-NMR spectrum (based on hexachlorobutadiene solution, tetramethylsilane) with respect to the side chain methyl group of the second propylene unit in the 3 chains, 19.5 to 21.9 ppm When the total area of the peak appearing in 100 is 100%, the peak area (triad tacticity) appearing in 21.0-21.9 ppm is 9
It is 0% or more, preferably 92% or more, more preferably 94% or more. If the triad tacticity showing stereoregularity is lower than 90%, the amount of low stereoregular component that is considered to affect the blocking property and dynamic friction coefficient of the laminate increases, which is not preferable.

The stereoregularity of the propylene / α-olefin copolymer (A) according to the present invention can be evaluated by triad tacticity (mm fraction).
For example, in the propylene / butene-1 random copolymer, this mm fraction is determined by the branching of the methyl group when the three head-to-tail bonded propylene unit chains existing in the polymer chain are represented by a surface zigzag structure. It is defined as the proportion of the same direction and is determined from the ¹³ C-NMR spectrum as follows.

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

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

Of the ¹³ C-NMR spectrum of the propylene / α-olefin copolymer thus measured, the methyl carbon region (about 19.5 to 21.9 ppm) in which the side chain methyl group of the propylene unit is observed is It is classified into 1 peak region (about 21.0 to 21.9 ppm), 2nd peak region (about 20.2 to 21.0 ppm), and 3rd peak region (about 19.5 to 20.2 ppm).

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

表１中、Ｐはプロピレンから導かれる単位、Ｂはブテンなどのα−オレフィンから導かれる単位を示す。

In Table 1, P represents a unit derived from propylene, and B represents a unit derived from an α-olefin such as butene.

  Of the three head-to-tail linkages (i) and (ii) shown in Table 1, (i) methyl groups for PPP (mm), PPP (mr), and PPP (rr), all of which are composed of propylene units. The direction is illustrated below in a surface zigzag structure. (Ii) The mm, mr, and rr bonds of the three-chain (PPB, BPB) containing α-olefin units conform to this PPP.

第１領域では、ｍｍ結合したＰＰＰ、ＰＰＢ、ＢＰＢ３連鎖中の第２単位（プロピレン単位）目のメチル基が共鳴する。

In the first region, the methyl group of the second unit (propylene unit) in the mm-bonded PPP, PPB, BPB3 chain resonates.

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

In the third region, the methyl group of the second unit (propylene unit) of the rr-bonded PPP3 chain resonates.
Therefore, the triad tacticity (mm fraction) of the propylene-based elastomer is (i) a head-to-tail-bonded propylene unit triple chain, or (ii) a head-to-tail-bonded propylene unit and α.
-A propylene / α-olefin triple chain composed of an olefin unit and containing a propylene unit in the second unit, with respect to a side chain methyl group of the propylene unit of the second unit in the third chain, a ¹³ C-NMR spectrum ( (Measured based on hexachlorobutadiene solution and tetramethylsilane) When the total area of the peak appearing in 19.5-21.9ppm (methyl carbon region) is 100%, the peak appearing in 21.0-21.9ppm (first region) It is calculated | required from a following formula as a ratio (percentage) of.

本発明に係るプロピレン・α−オレフィン共重合体（Ａ）は、このようにして求められるｍｍ分率が、９０％以上好ましくは９２％以上より好ましくは９４％以上である。

In the propylene / α-olefin copolymer (A) according to the present invention, the mm fraction thus determined is 90% or more, preferably 92% or more, more preferably 94% or more.

The propylene-based elastomer is composed of three chains (i) and (ii) having head-to-tail bonds as described above.
In addition, it has a small amount of a partial structure containing regioregular units as shown in the following structures (iii), (iv) and (v), and the side chain methyl of the propylene unit by such other bonds A peak derived from the group is also observed in the methyl carbon region (19.5 to 21.9 ppm).

上記の構造(iii)、(iv)および(v)に由来するメチル基のうち、メチル基炭素Ａおよびメチル基炭素Ｂは、それぞれ１７．３ ppm、１７．０ppmで共鳴するので、炭素Ａおよび炭
素Ｂに基づくピークは、前記第１〜３領域(19.5〜21.9ppm)内には現れない。さらにこの
炭素Ａおよび炭素Ｂは、ともに頭−尾結合に基づくプロピレン３連鎖に関与しないので、上記のトリアドタクティシティ（ｍｍ分率）の計算では考慮する必要はない。

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

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

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

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

The peak area based on the PPE-methyl group can be determined from the peak area of the PPE-methine group (resonant at around 30.6 ppm), and the peak area based on the EPE-methyl group is determined based on the EPE-methine group (around 32.9 ppm). Resonance) peak area. The peak area based on the methyl group C can be obtained from the peak area of the adjacent methine group (resonance at around 31.3 ppm). The peak area based on the methyl group D can be obtained from 1/2 of the sum of the peak areas of the peaks based on the αβ methylene carbon of the structure (iv) (resonance at resonance around 34.3 ppm and around 34.5 ppm). The peak area based on the methyl group D ′ can be determined from the area of the peak (resonance at around 33.3 ppm) based on the methine group adjacent to the methyl group of the structure (v) methyl group E ′. The peak area based on the methyl group E can be obtained from the peak area of the adjacent methine carbon (resonance at around 33.7 ppm), and the peak area based on the methyl group E ′ is calculated at the adjacent methine carbon (around 33.3 ppm). Resonance) peak area.

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

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

  The propylene / α-olefin copolymer (A) according to the present invention includes a metallocene compound containing propylene, an α-olefin having 2 or 4 to 20 carbon atoms, and a small amount of other olefin as necessary. It can be suitably obtained by copolymerization in the presence of a catalyst, and preferably can be produced by the method described in WO 2004/088775 or WO 01/27124.

  More preferably, the propylene / α-olefin copolymer (A) according to the present invention contains propylene and an α-olefin in the presence of a catalyst containing a transition metal compound (1a) represented by the following general formula (1a). It is desirable to be obtained by copolymerization of Here, the catalyst containing the transition metal compound (1a) is (2a) an organometallic compound, (2b) an organoaluminum oxy compound, and (2c) a compound that forms an ion pair by reacting with the transition metal compound (1a). And a catalyst containing at least one compound selected from the above and the transition metal compound (1a).

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

(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, and may be the same or different. R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are selected from hydrogen, a hydrocarbon group, and a silicon-containing group, and may be the same or different, and R ⁵ to R ¹² R ¹³ and R ¹⁴ may be the same as or different from each other, and may be bonded to each other to form a ring, and M is the fourth. A transition metal, Y is a carbon atom, Q may be selected from the same or different combinations from halogens, hydrocarbon groups, anionic ligands or neutral ligands capable of coordinating with lone pairs, j Is an integer from 1 to 4.)

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

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

Moreover, the adjacent substituents of R ⁵ to R ¹² may be bonded to each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, octamethyloctahydrodibenzofluorenyl group, octamethyltetrahydrodicyclopentafluorenyl group, etc. Can be mentioned.

R ¹³ and R ¹⁴ may be the same or different, and may be bonded to each other to form a ring.
In the general formula (1a), R ² and R ⁴ substituted on the cyclopentadienyl ring are preferably hydrocarbon groups having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the aforementioned hydrocarbon groups. Among these, R ² is more preferably a bulky substituent such as a tert-butyl group, an adamantyl group, or a triphenylmethyl group, and R ⁴ is more preferable than R ² such as a methyl group, an ethyl group, or an n-propyl group. It is more preferably 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 substituted on the fluorene ring, R ⁶ , R ⁷
, R ¹⁰ and R ¹¹ are each preferably a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the aforementioned hydrocarbon groups. In particular, from the viewpoint of ease of synthesis of the ligand, it is preferable that R ⁶ and R ¹¹ and R ⁷ and R ¹⁰ are the same group. Among such preferred embodiments, R ⁶ and R ⁷ form an aliphatic ring (AR-1), and R ¹⁰ and R ¹¹ are the same aliphatic ring (AR-1). The case where (AR-2) is formed is also included.

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

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

Examples of such a transition metal compound (1a) include dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) fluorenylzirconium dichloride, isopropylidene (3-tert-butyl-5-methylcyclopenta). Dienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (3-tert-butyl-5-methylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) ) Zirconium dichloride, isopropylidene (3-tert-butyl-5-methylcyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methylcyclopentadi) Enil) (full Oleenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5- Methylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) ) Zirconium dichloride and the like, but are not limited thereto.

  The catalyst suitably used for producing the propylene / α-olefin copolymer (A) according to the present invention includes (2a) an organometallic compound and (2b) organoaluminum oxy, together with the above-described transition metal compound (1a). And (2c) at least one compound selected from a compound that reacts with the transition metal compound (1a) to form an ion pair. These (2a), (2b), and (2c) compounds are not particularly limited, but preferred examples include the compounds described in WO2004 / 088775 or WO01 / 27124. It is done.

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

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

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

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

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

A conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally obtained as a solution of a hydrocarbon solvent.
1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method in which an organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension and the adsorbed water or crystal water reacts with the organoaluminum compound. 2) A method in which water, ice or water vapor is allowed to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, diethyl ether or tetrahydrofuran.
3) A method of reacting an organotin oxide such as dimethyltin oxide or dibutyltin oxide with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.

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

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

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

  In the production of the propylene / α-olefin copolymer (A) according to the present invention, when a catalyst using an organoaluminum oxy compound (2b) such as methylaluminoxane together with the transition metal compound (1a) is used, the polymerization is particularly high. It is preferable because it shows activity.

  Further, the polymerization catalyst used in the production of the propylene / α-olefin copolymer (A) according to the present invention may be a carrier using a carrier as necessary, and contains other promoter components. There may be.

Such a catalyst may be prepared by mixing each component in advance or by supporting it on a carrier, or may be used by adding each component simultaneously or sequentially to the polymerization system.
The propylene / α-olefin copolymer (A) according to the present invention is preferably propylene, an α-olefin having 2 or 4 to 20 carbon atoms, particularly preferably butene in the presence of the above-mentioned catalyst. If necessary, it can be obtained by copolymerizing with a small amount of other olefins. In the copolymerization, each monomer may be used in such an amount that each constituent unit amount in the produced propylene / α-olefin copolymer (A) is in a desired ratio, specifically, propylene / α-olefin. The molar ratio is 50/50 to 95/5, preferably 60/40 to 93/7, 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 5 MPa gauge pressure. The polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be carried out in two or more stages having different reaction conditions. The molecular weight of the propylene / α-olefin copolymer (A) can be adjusted by allowing hydrogen to be present in the polymerization system or changing the polymerization temperature, and (2a), (2b) or It can also be adjusted by the amount of (2c). When hydrogen is added, the amount is suitably about 0.001 to 100 NL per kg of monomer.

(B) Polypropylene resin As the polypropylene resin (B) used in the present invention, a polypropylene resin having a melting point (Tm) measured by DSC of 120 ° C. or more can be used without limitation. Conventionally known polypropylene can be widely used as the resin (B).

  The polypropylene resin (B) may be homopolypropylene, and includes a propylene-based resin containing units derived from propylene and a small amount (for example, 10 mol% or less, preferably less than 5 mol%) of an olefin other than propylene. A copolymer may also be used. The copolymer may be a random copolymer or a block copolymer. In the present invention, a propylene random copolymer is preferably used as the polypropylene resin (B).

  Specific examples of other olefins forming the propylene random copolymer include C2-C20 α-olefins other than propylene, such as ethylene, 1-butene, 1-pentene, 1-hexene, 1 -Heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 4-methyl-1-pentene and the like. The α-olefins as described above are used singly or in combination of two or more.

  The polypropylene resin (B) used in the present invention is preferably a polypropylene produced by a known method using a conventionally known solid titanium catalyst component. Polypropylene obtained using a metallocene compound catalyst component can also be used.

  The polypropylene resin (B) used in the present invention preferably has a melting point (Tm) of 120 ° C or higher, preferably 120 ° C or higher and lower than 160 ° C, more preferably 120 to 145 ° C. When the melting point is in this range, the balance between rigidity and low temperature heat sealability is excellent. As the polypropylene resin (B), a polypropylene having a melting point higher than that of the propylene / α-olefin copolymer (A) is used. The melting point of the polypropylene resin (B) is usually lower than that of the polypropylene resin (i).

  The difference (TmB-TmA) between the melting point (TmB) of the polypropylene resin (B) and the melting point (TmA) of the propylene / α-olefin copolymer (A) is 10 to 100 ° C., preferably 20 to 100 ° C. is there.

The polypropylene resin (B) has a melt flow rate MFR (ASTM D1238; 230 ° C., under a 2.16 kg load) of usually 0.1 to 400 g / 10 minutes, preferably 0.5 to 100 g / 10 minutes. Is desirable.
The propylene-based resin (B) used in the present invention usually has a higher hardness than the propylene / α-olefin copolymer (A).

(C) Poly (meth) acrylic acid ester-based antiblocking agent The poly (meth) acrylic acid ester-based antiblocking agent (C) used in the present invention is limited as long as the average particle diameter is 0.5 to 5 μm. In the present invention, a conventionally known poly (meth) acrylic acid ester blocking inhibitor can be used. In addition, a poly (meth) acrylic acid ester type | system | group antiblocking agent shows the antiblocking agent which consists of particle | grains of a poly (meth) acrylic ester.

  The average particle diameter of the poly (meth) acrylic acid ester-based antiblocking agent (C) is 0.5 to 5 μm, preferably 1 to 4 μm, more preferably 1 to 3 μm. In the said range, the film which is excellent in the balance of blocking resistance and transparency is obtained.

  Examples of the poly (meth) acrylic acid ester include polymethyl methacrylate (PMMA), polymethyl acrylate (PMA), and a crosslinked product thereof, and among them, polymethyl methacrylate (PMMA) and a crosslinked product thereof are preferable.

  A commercially available product may be used as the poly (meth) acrylic acid ester blocking inhibitor (C) used in the present invention. Examples of commercially available products include MX-180TA (PMMA beads, average particle size 1.8 μm, Soken Chemical Co., Ltd.), Art Pearl J-4P (PMMA beads, average particle size 2.2 μm, Negami Kogyo Co., Ltd.) can be used. The average particle diameter is a particle diameter measured by a laser diffraction method.

(D) Lubricant made of silicone oil The lubricant (D) made of silicone oil used in the present invention can be used without limitation as long as the viscosity is 500 to 250,000 mm ² / S. Silicon oil can be used as a lubricant.

The viscosity of the lubricant (D) made of silicone oil is 500 to 250,000 mm ² / S, preferably 800 to 100,000 mm ² / S, more preferably 1000 to 80,000 mm ² / S. In the said range, a film with favorable slip property can be obtained. The viscosity of the lubricant (D) can be measured by the method described in JIS K2283 (crude oil and petroleum products-kinematic viscosity test method and viscosity index calculation method).

  As the lubricant (D) made of silicone oil used in the present invention, a commercially available product may be used. Examples of the commercially available product include Shin-Etsu Chemical Co., Ltd., KF-96H-1000CS, KF-96H-6000CS, KF-96H- 60000CS or the like can be used.

Polypropylene Resin Composition The polypropylene resin composition according to the present invention contains (A) to (D), and the content thereof is (A) 100 to 40 parts by weight of a propylene / α-olefin copolymer, preferably Is 100 to 50 parts by weight, (B) 0 to 60 parts by weight of polypropylene resin, preferably 0 to 50 parts by weight (provided that the total of (A) and (B) is 100 parts by weight), (C ) 0.01-0.3 parts by weight, preferably 0.02-0.2 parts by weight of a poly (meth) acrylic acid ester-based antiblocking agent, (D) 0.1-3 parts by weight of a lubricant composed of silicone oil, Preferably it contains 0.2-2 weight part.

  When the polypropylene resin composition contains (A) to (D) in the above range, the layer [II] constituting the laminate of the present invention is excellent in low-temperature heat sealability and has a small dynamic friction coefficient. Moreover, the laminated body of this invention which has layer [II] is excellent in transparency, and is excellent in the handling in the case of secondary shaping | molding. For this reason, it can use suitably for a package container etc.

The layer [II] may contain an additive. Examples of the additive include an antistatic agent, a heat stabilizer, and an ultraviolet absorber.
When an additive is included, the total of (A) and (B) is usually used in the range of 0.01 to 5 parts by weight per 100 parts by weight.

The laminate of the present invention is usually a film, and the thickness of the layer [II] is usually 0.1 to 5 μm, preferably 0.5 to 3 μm, although it varies depending on the use of the laminate. In the said range, since the balance of heat-sealability and transparency is excellent, it is preferable.

  Moreover, since the bleeding to the film surface of a slip agent and an antiblocking agent is not accelerated | stimulated when not extending | stretching, it is preferable from the point of slip property and the anti-blocking expression that layer [II] is extended | stretched. The stretching may be uniaxial stretching in which stretching is performed in the vertical axis or horizontal axis direction, or biaxial stretching in which stretching is performed in the vertical axis and horizontal axis directions.

  In the present invention, (A) a propylene / α-olefin copolymer, (B) a polypropylene resin, (C) a poly (meth) acrylate ester antiblocking agent, and (D) a lubricant comprising a silicone oil. For example, the following methods can be used to prepare the resin composition, for example, a method of mixing with a mixer such as a V-type blender, a ribbon blender, or a Henschel mixer, and / or an extruder, a mixing roll, or a Banbury. A method of kneading with a kneader such as a mixer or a kneader may be used in combination or independently, and the components may be mixed. The polypropylene-based resin composition obtained by mixing may be prepared in the form of pellets or granules, or directly into a molded body such as a film or sheet that becomes the layer [II] composed of the polypropylene-based resin composition. You may shape | mold.

<Laminated body>
The laminate of the present invention is a laminate having a layer [I] composed of the polypropylene resin (i) and a heat seal layer [II] composed of the polypropylene resin composition. As a layer structure of the laminate, at least one surface layer is a heat seal layer [II]. Specific examples of the layer structure include a laminate composed of two layers [I] / [II] and a laminate composed of three layers [II] / [I] / [II]. .

The laminate of the present invention is usually a film, and is preferably a stretched film that has been stretched.
In the laminate of the present invention, when the layer [I] and the layer [II] are formed by coextrusion using a T die such as a single-many hold method or a multi-many hold method, the layer [I] And layer [II] are adjacent.

  On the other hand, for example, a film made of a polypropylene resin (i) and a film made of the polypropylene resin composition are produced separately, and a film made of a polypropylene resin (i) and a film made of a polypropylene resin composition When a laminated body is obtained by bonding together, an adhesive layer may be provided between the layer [I] and the layer [II] of the obtained laminated body.

The laminate of the present invention can be produced, for example, by the following method.
(1): The polypropylene resin (i) and the polypropylene resin composition are coextruded using a T die such as a single-many hold method or a multi-many hold method to form a laminate. Method. In addition, after the said coextrusion, it is preferable to give uniaxial or biaxial stretching to the laminated body obtained by coextrusion.

  (2): The polypropylene resin (i) is melt-extruded to form a film made of the polypropylene resin (i), and uniaxially or biaxially stretched as necessary, and the polypropylene resin (i) A method of obtaining a laminate by melt-extruding the polypropylene resin composition or laminating a preformed film made of the polypropylene resin composition on a film comprising the above. The laminate is preferably subjected to uniaxial or biaxial stretching. When extending | stretching the said laminated body especially, it is preferable to extend | stretch in the unstretched direction of the film which consists of polypropylene resin (i).

  Moreover, when laminating | stacking the film which consists of a polypropylene resin composition on the film which consists of the said polypropylene resin (i), it laminates | stacks by usually bonding together with an adhesive agent.

  Moreover, it is preferable that the laminated body of this invention is a laminated body by which the extending | stretching was given from the point of slip property and blocking resistance expression. Examples of the stretching method of the laminate include a tenter method.

  When biaxial stretching is performed by the tenter method, the laminate before stretching is heated to a temperature suitable for stretching (for example, 80 to 130 ° C.), and between the slow (front) roll and the fast (rear) roll Is stretched in the machine direction. Next, the film enters the tenter part, is heated (for example, 140 to 180 ° C.) while holding both ends of the film, and is stretched in the transverse direction. Next, the laminated body is heat treated to stabilize the physical properties of the laminated body, and wound up by a winder to obtain a stretched laminated body. Moreover, you may use the biaxial tenter method which performs the extending | stretching of the vertical direction and a horizontal direction simultaneously.

  As a draw ratio, both the layer [I] and the layer [II] are usually 4 to 6 times in the longitudinal direction and 7 to 11 times in the transverse direction. The range of the draw ratio is preferable because of the mechanical properties, heat seal performance, blocking property, and slip property of the film.

<Packaging container>
The packaging container of this invention is formed from the said laminated body.
The packaging container of the present invention may be obtained by molding the film-like or sheet-like laminate into a desired shape, or may be obtained by producing the laminate so as to have a desired packaging container shape. Good.

  The packaging container of the present invention is formed from a laminate that is excellent in low-temperature heat sealability and transparency, has a small dynamic friction coefficient of the heat seal layer, and is excellent in handling during secondary molding. It is suitably used for packaging and the like.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
In the following examples and comparative examples, the physical properties of the polymers were evaluated by the following methods.

[1-butene content]
^It calculated | required using < ¹³ > C-NMR.
(Molecular weight distribution)
The molecular weight distribution (Mw / Mn) was determined by measurement by GPC (gel permeation chromatography). For the measurement, a gel permeation chromatograph Alliance GPC-2000 manufactured by Waters was used. As separation columns, two TSKgel GNH6-HT and two TSKgel GNH6-HTL were used, both of which had a diameter of 7.5 mm and a length of 300 mm, a column temperature of 140 ° C., and a mobile phase. Was transferred at 1.0 ml / min using o-dichlorobenzene (Wako Pure Chemical Industries) and BHT (Takeda Pharmaceutical) 0.025% by weight as an antioxidant, and the sample concentration was 15 mg / 10 ml. The amount was 500 microliters, and a differential refractometer was used as a detector. As the standard polystyrene, those manufactured by Tosoh Corporation were used for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and those manufactured by Pressure Chemical Co. were used for 1000 ≦ Mw ≦ 4 × 10 ⁶ . Mw represents a weight average molecular weight, and Mn represents a number average molecular weight.

[Melting point]
The melting point (Tm) of the polymer was determined by differential scanning calorimetry (DSC), after the polymer sample held at 240 ° C. for 10 minutes was cooled to 30 ° C. and held for 5 minutes, the temperature was raised at 10 ° C./min. It was calculated from the crystal melting peak at that time.

[Intrinsic viscosity [η]]
Measurements were taken at 135 ° C. decalin and expressed in dl / g.
[Melt flow rate (MFR)]
It measured by the method of ASTM D1238 on condition of 230 degreeC and a 2.16kg load.

[Catalyst Preparation Example 1] Synthesis of dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) fluorenylzirconium dichloride (A) propylene / α-olefin copolymer used in the following Examples and Comparative Examples Dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) fluorenylzirconium dichloride used for the synthesis of the polymer was synthesized by the following method.

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

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

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

4) Synthesis of dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) fluorenylzirconium dichloride Under ice-cooling, 2- (3-tert-butyl-5-methylcyclopentadienyl) -2- To a solution of 1.14 g (3.3 mmol) of fluorenylpropane in diethyl ether (25 ml) was added dropwise 5.0 ml (7.7 mmol) of a hexane solution of n-butyllithium under a nitrogen atmosphere, and the mixture was further stirred at room temperature for 14 hours. To obtain a pink slurry. To this slurry, 0.77 g (3.3 mmol) of zirconium tetrachloride was added at −78 ° C., stirred at −78 ° C. for several hours, and stirred at room temperature for 65 hours. The resulting black-brown slurry was filtered, and the residue was washed with 10 ml of diethyl ether and extracted with dichloromethane to obtain a red solution. The solvent of this solution was distilled off under reduced pressure to obtain 0.53 g of a reddish orange solid. Analytical values are shown below.
¹ H-NMR (270 MHz, in CDCl ₃ , TMS standard) δ 8.11-8.02 (m, 3H), 7.82 (d, 1H), 7.56-7.45 (m, 2H), 7 .23-7.17 (m, 2H), 6.08 (d, 1H), 5.72 (d, 1H), 2.59 (s, 3H), 2.41 (s, 3H), 2. 30 (s, 3H), 1.08 (s, 9H)
FD-MS: m / z = 500, 502, 504 (M ⁺ )

[(A) Production of propylene / α-olefin copolymer]
Into a 2000 ml polymerization apparatus sufficiently purged with nitrogen, 866 ml of dry hexane, 90 g of 1-butene and triisobutylaluminum (1.0 mmol) were charged at room temperature, and then the temperature inside the polymerization apparatus was raised to 65 ° C. Pressurized to 0.7 MPa. Next, 0.002 mmol of dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) fluorenylzirconium dichloride obtained above was contacted with 0.6 mmol of methylaluminoxane (produced by Tosoh Finechem) in terms of aluminum. The toluene solution was added to the polymerization vessel, polymerized for 30 minutes while maintaining an internal temperature of 65 ° C. and a propylene pressure of 0.7 MPa, and 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 2 L of methanol and dried under vacuum at 130 ° C. for 12 hours. The obtained polymer was 12.5 g.

The resulting polymer was a propylene copolymer (intrinsic viscosity [η]: 1.63 dl / g, melting point: 76 ° C., MFR (230 ° C.): 7.0 g / 10 min, propylene / 1-butene random copolymer. Combined (A), Mw / Mn = 2.1, butene content 28.0 mol%).

[(B) Polypropylene resin]
As a polypropylene resin (B), a propylene / ethylene / butene copolymer (the molar ratio of each olefin is propylene / ethylene / butene = 96.3 / 2.2 / 1.5, MFR (ASTM D 1238, 230 ° C., 2.16 kg) = 7.0 g / 10 min, melting point = 138 ° C.).

[Polypropylene resin (i)]
Propylene homopolymer (trade name: F113G (MFR (ASTM D 1238, 230 ° C., 2.16 kg)) = 3.0 g / 10 min, melting point: 163 ° C. as polypropylene resin (i) ) Was used.

〔Evaluation methods〕
[Heat sealability (HS property)]
A heat sealer (manufactured by Toyo Seiki Co., Ltd.) having a seal bar with a width of 10 mm heated to a predetermined temperature of 60 to 140 ° C., with the surfaces (heat seal layers) of a strip-shaped film having a length of 200 mm and a width of 15 mm overlapped. Heat sealing was performed by pressing with a load of ² kg / cm ² for 1 second. The sample was conditioned at 23 ° C. and 50% humidity all day and night, and the peel resistance when peeled at 23 ° C. and 50% humidity at a peel rate of 200 mm / min and a peel angle of 180 degrees was determined.

〔Coefficient of friction〕
The dynamic friction coefficient of the heat seal layer was measured according to ASTM D1894.
[All HAZE (transparency)]
The overall HAZE of the laminates obtained in the examples was measured according to ASTM D1003.

[Blocking properties]
Evaluation was performed according to ASTM D1893. The stretched films obtained in the following examples and comparative examples were cut into a width of 10 cm and a length of 15 cm, and the heat seal layers were overlapped with each other, sandwiched between two glass plates, loaded with a load of 20 kg, and placed in a 50 ° C. air oven. Leave it alone. After 3 days, the sample was taken out, the peel strength was measured with a universal testing machine, and the peel strength (N / m) was taken as the blocking value.

[Example 1]
Propylene / 1-butene random copolymer (A): 100 parts by weight, PMMA beads (average particle size 2.2 μm, manufactured by Negami Kogyo Co., Ltd., Art Pearl J-4P): 0.12 parts by weight, silicon oil ( Shin-Etsu Chemical Co., Ltd., KF-96H-1000CS, viscosity 1000 mm ² / S): A composition comprising 1 part by weight is blended and kneaded using a single screw extruder, and a polypropylene resin composition (propylene / 1) -Butene random copolymer resin composition) was prepared as pellets.

  Next, the obtained pellets and the polypropylene resin (i) are composed of a propylene / 1-butene random copolymer resin composition using a two-type three-layer T-die molding machine equipped with a die having a width of 300 mm. A laminate (film) having a three-layer structure was obtained in which the layer was a surface layer (heat seal layer) and the layer made of polypropylene resin (i) was a core layer. The layer configuration of this film was: surface layer: 60 μm / core layer: 900 μm / surface layer: 60 μm.

  A 9 cm square sheet is cut out from the film thus obtained, preheated at 160 ° C. for 1 minute using a batch type biaxial stretching machine manufactured by Bruckner, and then biaxially stretched 5 times in length and 8 times in width. Thus, a stretched film having a surface layer: 1.5 μm / core layer: 22 μm / surface layer: 1.5 μm was obtained.

[Examples 2 to 6]
Surface layer in the same manner as in Example 1 except that the formulation of propylene / 1-butene random copolymer (A), PMMA beads, silicone oil and polypropylene resin (i) was changed to the amounts shown in Table 2. A stretched film of 1.5 μm / core layer: 22 μm / surface layer: 1.5 μm was produced.

Example 7
The propylene / 1-butene random copolymer (A): 50 parts by weight, the polypropylene resin (B): 50 parts by weight, PMMA beads (average particle size 2.2 μm, manufactured by Negami Kogyo Co., Ltd., Art Pearl J- 4P): 0.12 parts by weight, silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF-96H-6000CS): blending a composition consisting of 1 part by weight, kneading using a single screw extruder, and polypropylene resin A composition (propylene / 1-butene random copolymer resin composition) was prepared as pellets.

  Next, the obtained pellets and the polypropylene resin (i) are composed of a propylene / 1-butene random copolymer resin composition using a two-type three-layer T-die molding machine equipped with a die having a width of 300 mm. A laminate (film) having a three-layer structure was obtained in which the layer was a surface layer (heat seal layer) and the layer made of polypropylene resin (i) was a core layer. The layer configuration of this film was: surface layer: 60 μm / core layer: 900 μm / surface layer: 60 μm.

  A 9 cm square sheet is cut out from the film thus obtained, preheated at 160 ° C. for 1 minute using a batch type biaxial stretching machine manufactured by Bruckner, and then biaxially stretched 5 times in length and 8 times in width. Thus, a stretched film having a surface layer: 1.5 μm / core layer: 22 μm / surface layer: 1.5 μm was obtained.

Example 8
The propylene / 1-butene random copolymer (A): 40 parts by weight, the polypropylene resin (B): 60 parts by weight, PMMA beads (average particle size 2.2 μm, manufactured by Negami Kogyo Co., Ltd., Art Pearl J- 4P): 0.12 parts by weight, silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF-96H-1000CS): blended with 1 part by weight, kneaded using a single screw extruder, and polypropylene resin A composition (propylene / 1-butene random copolymer resin composition) was prepared as pellets.

  Next, the obtained pellets and the polypropylene resin (i) are composed of a propylene / 1-butene random copolymer resin composition using a two-type three-layer T-die molding machine equipped with a die having a width of 300 mm. A laminate (film) having a three-layer structure was obtained in which the layer was a surface layer (heat seal layer) and the layer made of polypropylene resin (i) was a core layer. The layer configuration of this film was: surface layer: 60 μm / core layer: 900 μm / surface layer: 60 μm.

  A 9 cm square sheet is cut out from the film thus obtained, preheated at 160 ° C. for 1 minute using a batch type biaxial stretching machine manufactured by Bruckner, and then biaxially stretched 5 times in length and 8 times in width. Thus, a stretched film having a surface layer: 1.5 μm / core layer: 22 μm / surface layer: 1.5 μm was obtained.

[Comparative Example 1]
The propylene / 1-butene random copolymer (A) and the polypropylene resin (i) are mixed with a propylene / 1-butene random copolymer using a two-type three-layer T-die molding machine equipped with a die having a width of 300 mm. A three-layer film was obtained in which the layer made of the polymer (A) was the surface layer (heat seal layer) and the layer made of the polypropylene resin (i) was the core layer. The layer configuration of this film was: surface layer: 60 μm / core layer: 900 μm / surface layer: 60 μm.

  A 9 cm square sheet is cut out from the film thus obtained, preheated at 160 ° C. for 1 minute using a batch type biaxial stretching machine manufactured by Bruckner, and then biaxially stretched 5 times in length and 8 times in width. Thus, a stretched film having a surface layer: 1.5 μm / core layer: 22 μm / surface layer: 1.5 μm was obtained.

[Comparative Example 2]
The propylene / 1-butene random copolymer (A): 100 parts by weight and silica (manufactured by Fuji Silysia, Silicia 430): 0.2 part by weight are blended and kneaded using a single screw extruder, propylene / 1. -The butene random copolymer resin composition was produced as a pellet.

  Subsequently, the obtained pellet and the polypropylene resin (i) are composed of a propylene / 1-butene random copolymer (A) using a two-type three-layer T-die molding machine equipped with a die having a width of 300 mm. A three-layer film was obtained in which the layer was a surface layer (heat seal layer) and the layer made of polypropylene resin (i) was the core layer. The layer configuration of this film was: surface layer: 60 μm / core layer: 900 μm / surface layer: 60 μm.

  A 9 cm square sheet is cut out from the film thus obtained, preheated at 160 ° C. for 1 minute using a batch type biaxial stretching machine manufactured by Bruckner, and then biaxially stretched 5 times in length and 8 times in width. Thus, a stretched film having a surface layer: 1.5 μm / core layer: 22 μm / surface layer: 1.5 μm was obtained.

[Comparative Examples 3 to 8]
Surface layer in the same manner as in Example 1 except that the formulation of propylene / 1-butene random copolymer (A), PMMA beads, silicone oil and polypropylene resin (i) was changed to the amounts shown in Table 2. A stretched film of 1.5 μm / core layer: 22 μm / surface layer: 1.5 μm was produced.

In Tables 2 and 3, PMMA (1.8 μm) represents MX-180TA manufactured by Soken Chemical Co., Ltd., and PMMA (2.2 μm) manufactured by Negami Kogyo Co., Ltd., Art Pearl J-4P, average particle size 2. 2 μm, PMMA (6.6 μm) is manufactured by Negami Kogyo Co., Ltd., Art Pearl J-7P, average particle size is 6.6 μm, silica is manufactured by Fuji Silysia, Silicia 430, silicone oil 100 mm ² / S is KF-96H-100CS, manufactured by Shin-Etsu Chemical Co., Ltd.
Silicone oil 1000 mm ² / S is manufactured by Shin-Etsu Chemical Co., Ltd., KF-96H
Indicates -1000CS, silicone oil 6000 mm ² / S is manufactured by Shin-Etsu Chemical Co., Ltd., shows a KF-96H-6000CS, silicone oil 60,000 mm ² / S is manufactured by Shin-Etsu Chemical Co., Ltd., shows a KF-96H-60000CS , Silicone oil 500,000 mm ² / S
Represents Shin-Etsu Chemical Co., Ltd., KF-96H-500000CS, and EBSA represents Nippon Oil & Fats Co., Ltd., Alflow H-50S.

ブロッキング防止剤および滑剤を含有しない比較例１、ブロッキング防止剤としてシリカを含有し、滑剤を含有しない比較例２、本発明と異なる滑剤を含有する比較例３〜５、および本発明よりも小さな粒径を有するブロッキンブ防止剤および本発明とは異なる滑剤を含有する比較例７では、動摩擦係数が大きくまた、ブロッキング性にも劣る。このため、二次成形の際のハンドリングに劣る傾向がある。

Comparative Example 1 containing no anti-blocking agent and lubricant, Comparative Example 2 containing silica as an anti-blocking agent and no lubricant, Comparative Examples 3 to 5 containing a lubricant different from the present invention, and particles smaller than the present invention In Comparative Example 7 containing a blocking agent having a diameter and a lubricant different from the present invention, the dynamic friction coefficient is large and the blocking property is also inferior. For this reason, there exists a tendency to be inferior to the handling in the case of secondary molding.

In Comparative Example 6 containing an anti-blocking agent having a particle size larger than that of the present invention, the dynamic friction coefficient is small and the blocking property is excellent, but the overall HAZE, that is, the transparency is inferior. For this reason, the packaging container using the laminated body of the comparative example 6 is inferior to the visibility of the contents.

Moreover, in the comparative example 8 which does not contain a propylene * alpha-olefin copolymer (A), heat seal property is inferior.
On the other hand, Examples 1 to 8 are excellent in low-temperature heat sealability, transparency and blocking properties, and also have a small dynamic friction coefficient, and are therefore excellent in handling during secondary molding.

  The laminate of the present invention is excellent in low temperature heat sealability and transparency, has a small dynamic friction coefficient of the heat seal layer, and is excellent in handling during secondary molding. For this reason, the packaging container formed from this laminated body can be utilized suitably for food packaging, filling packaging, fiber packaging and the like.

Claims (7)

A layer [I] made of polypropylene resin (i);
(A) (1) containing units derived from propylene in an amount of 50 to 95 mol% and units derived from an α-olefin having 2 or 4 to 20 carbon atoms in an amount of 5 to 50 mol%,
(2) The melting point (Tm) measured by differential scanning calorimetry (DSC) is 110 ° C. or lower, or the melting point peak is not observed by DSC,
(3) The intrinsic viscosity measured in decalin at 135 ° C. is 0.1-12 dl / g,
(4) 100 to 40 parts by weight of a propylene / α-olefin copolymer having a molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) of 3.0 or less,
(B) 0 to 60 parts by weight of a polypropylene resin having a melting point of 120 ° C. or higher (provided that the total of (A) and (B) is 100 parts by weight);
(C) 0.01 to 0.3 parts by weight of a poly (meth) acrylate ester antiblocking agent having an average particle size of 0.5 to 5 μm;
(D) A laminate having a heat seal layer [II] made of a polypropylene resin composition containing 0.1 to 3 parts by weight of a lubricant made of silicon oil having a viscosity of 500 to 250,000 mm ² / S. The propylene / α-olefin copolymer (A) is
(5) The melting point Tm measured by a differential scanning calorimeter is 50 to 110 ° C., and the relationship between the melting point Tm and the α-olefin structural unit content M (mol%) is
It is -2.6M + 130 <= Tm <=-2.3M + 155, The laminated body of Claim 1 characterized by the above-mentioned. The propylene / α-olefin copolymer (A) is
It is obtained by copolymerizing propylene and an α-olefin in the presence of a catalyst containing a transition metal compound (1a) represented by the following general formula (1a). 2. The laminate according to 2.

(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, and may be the same or different. R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are selected from hydrogen, a hydrocarbon group, and a silicon-containing group, and may be the same or different, and R ⁵ to R ¹² R ¹³ and R ¹⁴ may be the same as or different from each other, and may be bonded to each other to form a ring, and M is the fourth. A transition metal, Y is a carbon atom, Q is a halogen, a hydrocarbon group,
You may choose in the same or different combination from the neutral ligand which can be coordinated by an anion ligand or a lone pair, and j is an integer of 1-4. )   The laminate according to any one of claims 1 to 3, wherein the (C) poly (meth) acrylic acid ester-based antiblocking agent is an antiblocking agent comprising polymethyl methacrylate.   The (B) polypropylene resin is a propylene random copolymer having a unit derived from propylene and a unit derived from an α-olefin having 2 or 4 to 20 carbon atoms. The laminate according to any one of 4 above.   The layered product according to any one of claims 1 to 5, wherein the layer [I] has a thickness of 10 to 60 µm, and the layer [II] has a thickness of 0.1 to 5 µm.   A packaging container formed from the laminate according to any one of claims 1 to 6.