JP2011102367A - Film having silvery metallic luster and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin film excellent in decorativeness such as luster, water vapor barrier properties, light reflecting performance and heat resistance. <P>SOLUTION: The resin film includes 51-99 pts.mass syndiotactic polypropylene (A) and 1-49 pts.mass resin (B) selected from among a petroleum resin, a terpene resin, a rosin-based resin and hydrogenated materials thereof (on condition that the total of the syndiotactic polypropylene (A) and the resin (B) is 100 pts.mass). The resin film has ≥80% total reflectance R1 when measured on the surface of the resin film and 5-20% weight fraction ψ (ψ=R3/R1×100) of the regular reflectance R3 to the total reflectance R1, wherein the regular reflectance R3 is obtained by using the total reflectance R1, the diffuse reflectance R2 and expression (1): R3=R1-R2. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a film having a silver metallic luster and a method for producing the film.

In recent years, the demand for resin films is increasing in various fields such as foods, pharmaceuticals, electronic parts, and electronic devices.
For example, regarding a film for food packaging, Patent Document 1 attempts to produce a film having gloss and excellent cosmetic properties. Specifically, in Patent Document 1, a void-containing resin film containing voids therein is produced using a polymer having crystallinity such as isotactic polypropylene, polybutylene terephthalate, or nylon.

  In addition, the reflective film used in the liquid crystal display is required to have high reflective performance so that as much light as possible can be supplied to the liquid crystal to improve the performance of the backlight unit. Patent Document 2 discloses that according to a propylene resin composition containing a propylene random block copolymer and an inorganic filler, a film suitable as a reflective film can be produced.

JP 2009-190744 A JP 2009-84303 A

  However, for films for food packaging, since the demand for films having gloss and excellent water vapor barrier properties is increasing, the conventional food packaging films have a balance between gloss and water vapor barrier properties. There is room for further improvement.

Moreover, the reflective film obtained from the conventional propylene-based resin composition has room for further improvement in terms of a balance between reflective performance, heat resistance, and weight reduction.
In addition, as for resin films used in other fields, there is an increasing demand for films having excellent water vapor barrier properties and heat resistance in addition to cosmetic properties such as gloss and reflection performance.

  Accordingly, an object of the present invention is to provide a resin film having excellent cosmetic properties such as gloss and water vapor barrier properties. Moreover, it is providing the resin film excellent in reflective performance and heat resistance.

The film according to the present invention comprises 51 to 99 parts by mass of syndiotactic polypropylene (A), 1 to 49 parts by mass of a resin (B) selected from petroleum resins, terpene resins, rosin resins, and hydrogenated products thereof ( The total amount of syndiotactic polypropylene (A) and resin (B) is 100 parts by mass), and the total reflectance R1 measured on the surface of the film is 80% or more. The weight fraction φ (φ = R3) of the regular reflectance R3 obtained by the following formula (1) from the total reflectance R1 and diffuse reflectance R2 measured on the surface of the film and the total reflectance R1 / R1 × 100) is 5 to 20%.
R3 = R1-R2 (1)

  The film according to the present invention has a silvery metallic luster and is excellent in water vapor barrier properties. For this reason, the said film is used suitably for package bodies, such as a foodstuff and a pharmaceutical. In addition, the film according to the present invention is excellent in reflection performance and heat resistance. For this reason, the said film is used suitably for a reflective film.

FIG. 1 is an SEM image of the cross section of the stretched film obtained in Example 1.

Hereinafter, the present invention will be described in detail.
The film according to the present invention comprises 51 to 99 parts by mass of syndiotactic polypropylene (A), 1 to 49 parts by mass of a resin (B) selected from petroleum resins, terpene resins, rosin resins, and hydrogenated products thereof ( The total amount of syndiotactic polypropylene (A) and resin (B) is 100 parts by mass), and the total reflectance R1 measured on the surface of the film is 80% or more. The weight fraction φ (φ = R3) of the regular reflectance R3 obtained by the following formula (1) from the total reflectance R1 and diffuse reflectance R2 measured on the surface of the film and the total reflectance R1 / R1 × 100) is 5 to 20%.

R3 = R1-R2 (1)
The total reflectance R1 and the weight fraction φ in the above range mean that the film has a silvery metallic luster.

  The film is preferably produced by stretching an unstretched film obtained from a resin composition containing a specific component in a specific amount. This stretching forms a specific film structure, that is, a structure in which pores are present in the interior and pores are not present in the surface, so that the total reflectance R1 and the weight fraction φ are within the above ranges, and the silver metal It is thought that gloss develops.

<Resin composition>
The resin composition includes syndiotactic polypropylene (A) and a resin (B) selected from petroleum resins, terpene resins, rosin resins, and hydrogenated derivatives thereof.

  The syndiotactic polypropylene (A) used in the present invention may be a homopolypropylene, a propylene / α-olefin (excluding propylene) random copolymer having 2 to 20 carbon atoms, or a propylene block copolymer. A homopolypropylene or a propylene / α-olefin having 2 to 20 carbon atoms (excluding propylene) random copolymer is preferable. More preferred are homopolypropylene, a copolymer of propylene and ethylene or an α-olefin having 4 to 10 carbon atoms, and a copolymer of propylene, ethylene and an α-olefin having 4 to 10 carbon atoms. From the viewpoint of surface roughness, surface glossiness, and heat resistance in the obtained film, homopolypropylene is particularly preferable.

  Here, the α-olefin having 2 to 20 carbon atoms other than propylene includes ethylene, 1-butene, 3-methyl-1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1 -Octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like.

  In addition, when the syndiotactic polypropylene (A) is a propylene / α-olefin having 2 to 20 carbon atoms (excluding propylene) random copolymer or propylene block copolymer, the α having 2 to 20 carbon atoms is used. -The structural unit derived from propylene is usually more than 90 mol% and less than 100 mol%, preferably 91 mol% or more and 100 mol% with respect to the total 100 mol% of the structural units derived from olefins (including propylene) Contained in less than. The structural unit derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene) is usually contained in an amount of more than 0 mol% and less than 10 mol%, preferably more than 0 mol% and not more than 9 mol%. It is.

  When syndiotactic polypropylene (A) is a propylene / α-olefin (excluding propylene) random copolymer, the total number of structural units derived from α-olefin (including propylene) having 2 to 20 carbon atoms is 100. The structural unit derived from propylene is more preferably 93 to 99.7 mol%, still more preferably 94 to 99.7 mol%, particularly preferably 95 to 99.7 mol% relative to mol%. The structural unit derived from an α-olefin having 2 to 20 atoms (excluding propylene) is more preferably 0.3 to 7 mol%, still more preferably 0.3 to 6 mol%, particularly preferably 0.3 to 5 It is preferably contained in an amount of mol%.

  The syndiotactic polypropylene (A) used in the present invention has a syndiotactic pentad fraction (rrrr fraction, pentad syndiotacticity) measured by NMR method of usually 85% or more, preferably 90% or more. The syndiotactic polypropylene (A) having a rrrr fraction in this range, preferably 93% or more, more preferably 94% or more, is excellent in moldability, heat resistance, mechanical properties and transparency, and is a crystalline polypropylene. Since the characteristic as is favorable, it is preferable. The upper limit of the rrrr fraction is not particularly limited, but is 100% or less, and usually 99% or less, for example.

This syndiotactic pentad fraction (rrrr fraction) is measured as follows.
The rrrr fraction is expressed in terms of Prrrr in the ¹³ C-NMR spectrum (absorption intensity derived from the methyl group of the third unit at the site where 5 units of propylene units are continuously syndiotactically bonded) and Pw (total methyl groups of propylene units). (Absorption intensity derived from the above) is determined by the following formula (1).

rrrr fraction (%) = 100 × Prrrr / Pw (1)
The NMR measurement is performed as follows, for example. That is, 0.35 g of a sample is dissolved by heating in 2.0 ml of hexachlorobutadiene. After this solution is filtered through a glass filter (G2), 0.5 ml of deuterated benzene is added and charged into an NMR tube having an inner diameter of 10 mm. And ¹³ C-NMR measurement is performed at 120 degreeC using the JEOL GX-500 type | mold NMR measuring apparatus. The number of integration is 10,000 times or more.

  Syndiotactic polypropylene (A) has an intrinsic viscosity [η] measured in decalin at 135 ° C. of usually 0.1 to 10 dL / g, preferably 0.5 to 10 dL / g, more preferably 0.50 to 8. It is desirable to be in the range of 00 dL / g, more preferably 0.95 to 8.00 dL / g, particularly preferably 1.00 to 8.00 dL / g, and most preferably 1.40 to 8.00 dL / g. In particular, it is preferably in the range of 1.40 to 5.00 dL / g. Syndiotactic polypropylene (A) having such an intrinsic viscosity [η] tends to exhibit a good fluidity, is easy to be blended with other components, and has excellent mechanical strength.

The intrinsic viscosity [η] is measured by the method described in Examples described later.
Further, the syndiotactic polypropylene (A) has a melting point (Tm) obtained by differential scanning calorimetry (DSC) measurement of usually 145 ° C. or higher, preferably 147 ° C. or higher, more preferably 150 ° C. or higher, particularly preferably 155. It is at least 156 ° C, most preferably 156 ° C or higher. The upper limit of Tm is not particularly limited, but is usually 170 ° C. or lower, for example. Further, the heat of fusion (ΔH) is usually 40 mJ / mg or more, preferably 45 mJ / mg or more, more preferably 50 mJ / mg or more, particularly preferably 52 mJ / mg or more, and most preferably 55 mJ / mg or more. The upper limit of ΔH is not particularly limited, but is usually 90 mJ / mg or less, for example.

Differential scanning calorimetry is performed by the method described in the examples described later.
Syndiotactic polypropylene (A) having a melting point (Tm) in this range is excellent in moldability, heat resistance, transparency and mechanical properties, and has good properties as crystalline polypropylene. By using a catalyst and polymerization conditions as described later, syndiotactic polypropylene (A) having a melting point (Tm) in this range can be produced.

Moreover, as for a syndiotactic polypropylene (A), the glass transition temperature (Tg) obtained by a differential scanning calorimeter (DSC) measurement is -10-10 degreeC normally.
A glass transition temperature is calculated | required by the method as described in the Example mentioned later.

In addition, syndiotactic polypropylene (A) has an isothermal crystallization temperature determined by differential scanning calorimetry (DSC) measurement as T _iso , and a half crystallization time at isothermal crystallization temperature T _iso is t _1/2 . In the range of 110 ≦ T _iso ≦ 150 (° C.), the following formula (Eq-1) is usually satisfied, preferably the following formula (Eq-2) is satisfied, more preferably the following formula (Eq-3) is satisfied.

The half crystallization time (t _1/2 ) determined by isothermal crystallization measurement is the time when 50% heat is reached when the area between the DSC heat curve and the baseline in the isothermal crystallization process is defined as the total heat. (See Physical Properties of New Polymer Experiment 8 Polymers (Kyoritsu Shuppan Co., Ltd.)).

The half crystallization time (t _1/2 ) is measured as follows. About 5 mg of a sample is packed in a special aluminum pan, heated from 30 ° C. to 200 ° C. at 320 ° C./min using DSCPyris 1 or DSC 7 manufactured by PerkinElmer, and held at 200 ° C. for 5 minutes, then the temperature (200 ° C. ) To each isothermal crystallization temperature at a rate of 320 ° C./min and obtained from a DSC curve obtained by maintaining the isothermal crystallization temperature. Here, the half crystallization time (t _1/2 ) is obtained as isothermal crystallization process start time (time when the isothermal crystallization temperature is reached from 200 ° C.) t = 0. For the syndiotactic polypropylene (A) used in the present invention, t _1/2 can be determined as described above. However, when it is not crystallized at a certain isothermal crystallization temperature, for example, 110 ° C., it is conveniently 110 ° C. Several measurements are carried out at the following isothermal crystallization temperature, and the half crystallization time (t _1/2 ) is obtained from the extrapolated value.

  The syndiotactic polypropylene (A) satisfying the above (Eq-1) has remarkably superior moldability as compared with existing ones. Here, excellent formability means that when a film is produced, the time until solidification from a molten state is short. Moreover, such syndiotactic polypropylene (A) is excellent in high-speed moldability, shape stability, long-term production stability, and the like. By using a catalyst and polymerization conditions as described later, syndiotactic polypropylene (A) satisfying the above (Eq-1) can be produced.

  The syndiotactic polypropylene (A) has an n-decane soluble part amount of usually 1 wt% or less, preferably 0.8 wt% or less, more preferably 0.6 wt% or less. The amount of the n-decane soluble part is an index closely related to the blocking property of the syndiotactic polypropylene (A) and the film obtained therefrom, and the fact that the amount of the n-decane soluble part is usually small means that the amount of low crystalline component and It means that there are few low molecular weight components. That is, the syndiotactic polypropylene (A) having an n-decane soluble part amount in the above range has very good blocking resistance.

The syndiotactic polypropylene (A) satisfies ΔH ≧ 40 mJ / mg and preferably satisfies the above (Eq-1), but the n-decane soluble part amount is preferably 1 wt% or less. Further, the syndiotactic polypropylene (A) is a homopolypropylene, or a propylene / α-olefin (excluding propylene) random copolymer or propylene block copolymer having 2 to 20 carbon atoms, which is formed from propylene. A copolymer containing the derived structural unit in an amount exceeding 90 mol%, the syndiotactic pentad fraction (rrrr fraction) is 85% or more, and the melting point (Tm) is 145 ° C. or more; It is desirable that the heat of fusion (ΔH) is 40 mJ / mg or more, satisfies the above formula (Eq-1), and the amount of n-decane soluble part is 1 wt% or less. Syndiotactic polypropylene (A) satisfying the above properties can be produced by appropriately adjusting the catalyst and polymerization conditions as described below.
Syndiotactic polypropylene (A) may be used alone or in combination of two or more.

In producing the syndiotactic polypropylene (A) used in the present invention,
(I) a bridged metallocene compound represented by the following general formula [1];
(II) (II-1) organoaluminum oxy compounds,
(II-2) a polymerization catalyst (cat-) comprising: a compound that reacts with the bridged metallocene compound (I) to form an ion pair; and (II-3) at least one compound selected from organoaluminum compounds. 1) or a polymerization catalyst (cat-2) in which the catalyst (cat-1) is supported on a particulate carrier is preferably used. However, the catalyst used for the production of syndiotactic polypropylene (A) is not particularly limited as long as the polymer to be produced satisfies the requirements as syndiotactic polypropylene (A).

In the above general formula [1], R ¹ , R ² , R ³ and R ⁴ are selected from a hydrogen atom, a hydrocarbon group and a silicon-containing group, and R ² and R ³ are bonded to each other to form a ring. R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹¹ and R ¹² are selected from hydrogen, hydrocarbon groups and silicon-containing groups, and the two groups R ⁷ and R ¹⁰ are not hydrogen atoms, Selected from hydrocarbon groups and silicon-containing groups, which may be the same or different from R ⁵ and R ⁶ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁹ and R ^10, and R ¹¹ and R ^12. In the combination of one or more selected adjacent groups, the adjacent groups may be bonded to each other to form a ring.

R ¹⁷ and R ¹⁸ are a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a silicon atom-containing group, which may be the same or different from each other, and the substituents may be bonded to each other to form a ring. Good.

  M is Ti, Zr or Hf, Y is carbon, Q is selected from halogen, a hydrocarbon group, an anionic ligand, and a neutral ligand capable of coordinating with a lone pair in the same or different combinations However, j is an integer of 1 to 4.

Bridged metallocene compound (I)
Specific examples of the bridged metallocene compound (I) represented by the general formula [1] (also referred to as “component (I)” in the present specification) are shown below.

  Cyclopropylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, Cyclopentylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, Cycloheptylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride Dibenzylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, Di-n-butylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl (2,7-di ( 2,4,6-trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert- Butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-di (3,5-dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di n-butylmethylene (cyclopentadienyl) (2,3,6,7-tetratert-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-di (4- Methylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di-n-butyl Tylene (cyclopentadienyl) (2,7-dinaphthyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-di (4-tert -Butylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride,

  Diisobutylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl (2,7-di (2,4,6- Trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutyl Methylene (cyclopentadienyl) (2,7-di (3,5-dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (2,3, 6,7-tetra-tert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (2,7-di (4-methylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride , Sobutylmethylene (cyclopentadienyl) (2,7-dinaphthyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diisobutylmethylene (cyclopentadienyl) (2,7-di (4-tert- Butylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride ( Also known as 1,3-diphenylisopropylidene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride. Methylene (cyclopentadienyl (2,7-di (2,4,6-trimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2, 7-diphenyl-3,6-ditert-butyl (Luolenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-di (3,5-dimethylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopenta Dienyl) (2,3,6,7-tetra-tert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-di (4-methylphenyl) -3,6-di tert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dinaphthyl-3,6-ditert-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-di (4-tert-butylphenyl) -3,6-ditert-butylfluorenyl) zirconium dichloride,

  Diphenethylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenethylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6 -Ditert-butylfluorenyl) zirconium dichloride, di (benzhydryl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (benzhydryl) methylene (Cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6- Ditert-butylfluorenyl) zirconium dichloride, di (cumyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-phenyl-) Ethyl) methylene Clopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-phenyl-ethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3 , 6-Ditert-butylfluorenyl) zirconium dichloride, di (cyclohexylmethyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di ( (Cyclohexylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (cyclopentylmethyl) methylene (cyclopentadienyl) (2,7-dimethyl) -3,6-ditert-butylfluorenyl) zirconium dichloride, di (cyclopentylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, J Tilmethyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl- 3,6-ditert-butylfluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (Biphenylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride,

  (Benzyl) (n-butyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, (benzyl) (n-butyl) methylene (cyclopentadiene) Enyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, (benzyl) (cumyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert -Butylfluorenyl) zirconium dichloride, (benzyl) (cumyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cyclopropylidene (cyclopenta Dienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cyclopropylidene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluoride) Oleenyl) zirconium dichloride, cyclobutylidene ( Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cyclobutylidene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert- (Butylfluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (2 , 7-Diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride Cyclohexylidene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-dimethyl-3 , 6-Ditert-butylfull Oleenyl) zirconium dichloride, cycloheptylidene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride,

  Dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-dimethyl-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-dimethyl-3, 6-dimethyl-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-dicumyl-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopenta Dienyl) (2,7-dimethyl-3,6-dicumyl-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-di (trimethylsilyl) -butyl Fluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-di (trimethylsilyl) -butylfluorenyl) zirconium dichloride, dibenzyl Methylene (cyclopentadienyl) (2,7-dimethyl-3,6-diphenyl-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6- Diphenyl-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-dibenzyl-butylfluorenyl) zirconium dichloride, di-n-butylmethylene (cyclopentadienyl) ) (2,7-dimethyl-3,6-dibenzyl-butylfluorenyl) zirconium dichloride, dibenzylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-dimethyl-butylfluorenyl) zirconium Dichloride, di-n-butylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-dimethyl-butylfluorenyl) zirconium dichloride,

  Diphenylmethylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-diphenyl-3,6-di tert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) ) Methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-dimethyl- 3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, Di (m-chlorophenyl) methylene Lopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-chlorophenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert -Butylfluorenyl) zirconium dichloride, di (p-bromophenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-bromo Phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2 , 7-Dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert -Butylfluorenyl) zirconium dichloride, (p-trifluoromethyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-trifluoromethyl-phenyl) methylene ( Cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl -3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butyl-phenyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorene) Nyl) zirconium dichloride, di (pn-butyl-phenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (pn-butyl-phenyl) Methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butyl Rufuruoreniru) zirconium dichloride,

  Di (p-biphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-biphenyl) methylene (cyclopentadienyl) (2 , 7-Diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorene) Nyl) zirconium dichloride, di (1-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopenta Dienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (2-naphthyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-di tert-butylfluorenyl) zirconium dichloride, di (naphthylmethyl) methylene Lopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (naphthylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert- Butylfluorenyl) zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-isopropylphenyl) ) Methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (2,7-dimethyl-3) , 6-Ditert-butylfluorenyl) zirconium dichloride, di (biphenylmethyl) methylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylsilyl (Cyclopentadienyl) (2,7-dimethyl-3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (2,7-diphenyl-3,6-ditert -Butylfluorenyl) zirconium dichloride.

  In addition, the compound in which “zirconium” in the above compound is changed to “hafnium” or “titanium”, “dichloride” is a metallocene compound in which “difluoride”, “dibromide”, “diaiodide”, “dichloride” is “dimethyl” Examples include metallocene compounds that have become “methyl ethyl”.

The bridged metallocene compound (I) can be produced by a known method, and the production method is not particularly limited. As a known production method, for example, the production methods described in WO2001 / 27124 and WO2004 / 087775 by the present applicant can be mentioned.
The bridged metallocene compound (I) may be used alone or in combination of two or more.

Organoaluminum oxy compound (II-1)
As the organoaluminum oxy compound (II-1) (also referred to as “component (II-1)” in the present specification) used in the production of syndiotactic polypropylene (A), a conventionally known aluminoxane can be used as it is. Specific examples include compounds represented by the following general formula [2] and / or general formula [3].

(In the above formula [2], R is independently a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 2 or more.)
(In the above formula [3], R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more.)

  In particular, methylaluminoxane in which R is a methyl group and n is 3 or more, preferably 10 or more is preferably used. These aluminoxanes may be mixed with some organoaluminum compounds.

  In the present invention, a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687 can be used. Further, organoaluminum oxy compounds described in JP-A-2-167305, aluminoxanes having two or more kinds of alkyl groups described in JP-A-2-24701, JP-A-3-103407, and the like are also included. It can be suitably used. The “benzene-insoluble” organoaluminum oxy compound means that the 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 atoms. An organoaluminum oxy compound that is insoluble or sparingly soluble.

  Examples of the organoaluminum oxy compound include modified methylaluminoxane represented by the following general formula [4].

(In the above formula [4], R represents a hydrocarbon group having 1 to 10 carbon atoms, and m and n each independently represents an integer of 2 or more.)

  This modified methylaluminoxane is prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. Such modified methylaluminoxane [4] is generally called MMAO. Such MMAO can be prepared by the methods described in US4960878 and US5041584. Further, those obtained from trimethylaluminum and triisobutylaluminum and having R as an isobutyl group are commercially produced by Tosoh Finechem Co., Ltd. under the names MMAO and TMAO. Such MMAO is an aluminoxane having improved solubility in various solvents and storage stability. Specifically, the MMAO is insoluble in benzene such as the compounds represented by the above formulas [2] and [3]. Unlike poorly soluble aluminoxane, it dissolves in aliphatic and alicyclic hydrocarbons.

  Furthermore, as an organoaluminum oxy compound, an organoaluminum oxy compound containing boron represented by the following general formula [5] can be exemplified.

(In the above formula [5], R ^c represents a hydrocarbon group having 1 to 10 carbon atoms. R ^d may be the same as or different from each other, and may be a hydrogen atom, a halogen atom or a carbon atom having 1 to 10 carbon atoms. Indicates a hydrocarbon group.)
The organoaluminum oxy compound (II-1) as described above may be used alone or in combination of two or more.

Compound (II-2) which reacts with bridged metallocene compound (I) to form an ion pair
Compound (II-2) which forms an ion pair by reacting with bridged metallocene compound (I) used in the production of syndiotactic polypropylene (A) (in this specification, “ionic compound” or “component (II-2) Are also referred to as JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207703. Examples include Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-3-207704 and USP5321106. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

  The ionic compound preferably employed in the present invention is a compound represented by the following general formula [6].

In the above formula [6], examples of R ^{e +} include H ⁺ , a carbenium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, and a ferrocenium cation having a transition metal. R ^{f to} R ⁱ may be the same as or different from each other, and are an organic group, preferably an aryl group.

  Specific examples of the carbenium cation include trisubstituted carbenium cations such as triphenylcarbenium cation, tris (methylphenyl) carbenium cation, and tris (dimethylphenyl) carbenium cation.

  Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri (n-propyl) ammonium cation, triisopropylammonium cation, tri (n-butyl) ammonium cation, and triisobutylammonium cation. N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation, N, N-dialkylanilinium cation, diisopropylammonium cation, dicyclohexyl And dialkyl ammonium cations such as ammonium cations.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris (methylphenyl) phosphonium cation, and tris (dimethylphenyl) phosphonium cation.

Among the above, as R ^{e +} , a carbenium cation, an ammonium cation, and the like are preferable, and a triphenylcarbenium cation, an N, N-dimethylanilinium cation, and an N, N-diethylanilinium cation are particularly preferable.

  Specific examples of the carbenium salt include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (3,5-ditrifluoromethylphenyl) borate, tris (4-methyl And phenyl) carbenium tetrakis (pentafluorophenyl) borate and tris (3,5-dimethylphenyl) carbenium tetrakis (pentafluorophenyl) borate.

Examples of ammonium salts include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and the like.
Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetrakis (p-tolyl) borate, trimethylammonium tetrakis (o -Tolyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (2,4- Dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (4-trifluoro) (Romethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetraphenylborate, di Octadecylmethylammonium tetrakis (p-tolyl) borate, dioctadecylmethylammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, dioctadecylmethylammonium tetrakis (2,4-dimethylphenyl) borate, Dioctadecylmethylammonium tetrakis (3,5-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis (4-trifluoromethylphenyl) borate, dioctadecylmethylammonium Examples include mutetrakis (3,5-ditrifluoromethylphenyl) borate and dioctadecylmethylammonium.

  Specific examples of N, N-dialkylanilinium salts include N, N-dimethylanilinium tetraphenylborate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3 , 5-ditrifluoromethylphenyl) borate, N, N-diethylanilinium tetraphenylborate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (3,5-ditri Fluoromethylphenyl) borate, N, N-2,4,6-pentamethylanilinium tetraphenylborate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate and the like.

  Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.

In addition, ionic compounds described in Japanese Patent Application Laid-Open No. 2004-51676 by the present applicant can also be used without limitation.
The ionic compound (II-2) as described above may be used alone or in combination of two or more.

Organoaluminum compound (II-3)
The organoaluminum compound (II-3) used in the production of syndiotactic polypropylene (A) (also referred to herein as “component (II-3)”) is represented, for example, by the following general formula [7]. An organoaluminum compound, a complex alkylated product of a Group 1 metal represented by the following general formula [8] and aluminum, and the like can be exemplified.

R ^a _m Al (OR ^b ) _n H _p X _q ... [7]
(In the above formula [7], 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 X represents a halogen atom. M is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q <3, and m + n + p + q = 3.)

Specific examples of such compounds include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, trioctylaluminum;
Tri-branched alkyl aluminums such as triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum;
Tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum;
Triarylaluminum such as triphenylaluminum and tolylylaluminum;
Dialkylaluminum hydrides such as diisopropylaluminum hydride, diisobutylaluminum hydride;
Formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and z ≦ 2x.) Isoprenyl represented by like Alkenyl aluminum such as aluminum;
Alkylaluminum alkoxides such as isobutylaluminum methoxide and isobutylaluminum ethoxide;
Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, dibutylaluminum butoxide;
Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide;
Formula Ra _2.5 Al (ORb) partially alkylaluminum which is alkoxylated with an average composition represented by like _0.5;
Alkylaluminum aryloxides such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide);
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride;
Alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
Partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride;
Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride;
Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride, propylaluminum dihydride;
Examples include partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide.

M ² AlR ^a ₄ ... [8]
(In the above formula [8], 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.)

Examples of such a compound include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .
A compound similar to the compound represented by the general formula [8] can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded through a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

As the organoaluminum compound (II-3), trimethylaluminum and triisobutylaluminum are preferably used from the viewpoint of easy availability.
The organoaluminum compound (II-3) as described above may be used alone or in combination of two or more.
The above components (II-1) to (II-3) can also be used by being supported on a particulate carrier.

Carrier (III)
The carrier (III) (also referred to herein as “component (III)”) used as necessary is an inorganic or organic compound, and is a granular or particulate solid.
Among these, as the inorganic compound, a porous oxide, an inorganic halide, clay, clay mineral, or an ion-exchange layered compound is preferable.

Specific examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ or a composite or mixture containing these. For example, natural or synthetic zeolite, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , Si ₂ —V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , SiO ₂ —TiO ₂ —MgO, etc. Can be used. Of these, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferred.

The inorganic oxide includes a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ). ₂ , carbonates such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O, sulfates, nitrates or oxide components may be contained.

The properties of such a porous oxide vary depending on the type and production method, but the carrier preferably has a particle size of 3 to 300 μm, more preferably 10 to 300 μm, and even more preferably 20 to 200 μm, and a specific surface area. Preferably, it is in the range of 50 to 1000 m ² / g, more preferably in the range of 100 to 700 m ² / g, and the pore volume is preferably in the range of 0.3 to 3.0 cm ³ / g. Such a carrier is preferably used after being calcined at 100 to 1000 ° C., more preferably at 150 to 700 ° C., if necessary.

As the inorganic halide, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ or the like is used. The inorganic halide may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. Alternatively, the inorganic halide can be dissolved in a solvent such as alcohol and then precipitated into a fine particle with a precipitating agent.

  Clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak binding force, and the contained ions can be exchanged. Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used.

Examples of the clay, clay mineral, and ion-exchangeable layered compound include clay, clay mineral, hexagonal close packing type, ionic crystalline compound having a layered crystal structure such as antimony type, CdCl ₂ type, and CdI ₂ type. .

Such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite And ionizable layered compounds include α-Zr (HAsO ₄ ) ₂ · H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ · 3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ and crystalline acid salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.

Such clays, clay minerals and ion-exchangeable layered compounds preferably have a pore volume of 20 cc or more with a radius of 0.1 cc / g or more, and 0.3 to 5 cc / g as measured by mercury porosimetry. It is more preferable. Here, the pore volume is measured in the range of pore radius of 20 to 3 × 10 ⁴ Å by mercury porosimetry using a mercury porosimeter.

When a carrier having a pore volume with a radius of 20 mm or more and smaller than 0.1 cc / g is used as a carrier, high polymerization activity tends to be difficult to obtain.
It is also preferable to subject the clay and clay mineral to chemical treatment.

  As the chemical treatment, a surface treatment that removes impurities adhering to the surface, a treatment that affects the crystal structure of clay, and the like can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment. In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay. In the salt treatment and the organic matter treatment, an ion complex, a molecular complex, an organic derivative, and the like can be formed, and the surface area and interlayer distance can be changed.

The ion-exchangeable layered compound may be a layered compound in which the interlayer exchangeable ions are exchanged by exchanging the exchangeable ions between the layers with another large bulky ion. Such a bulky ion plays a role of a column supporting the layered structure and is usually called a pillar. Moreover, introducing another substance between the layers of the layered compound in this way is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) ₃ ( R is a hydrocarbon group), metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ Etc. These compounds may be used alone or in combination of two or more.

Further, when these compounds were intercalated, they were obtained by hydrolyzing metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.). Polymers and colloidal inorganic compounds such as SiO ₂ can coexist. Examples of the pillar include oxides generated by heat dehydration after intercalation of the metal hydroxide ions between layers. Among these, clay and clay mineral are preferable, and montmorillonite, vermiculite, pectolite, teniolite and synthetic mica are more preferable.

  Clay, clay mineral and ion-exchangeable layered compound may be used as they are, or may be used after a treatment such as ball milling or sieving. Further, it may be used after newly adsorbing and adsorbing water or by performing a heat dehydration treatment. Furthermore, you may use individually or in combination of 2 or more types.

  When using ion-exchange layered silicate, it is possible to reduce the amount of organoaluminum oxy-compounds such as alkylaluminoxane by utilizing its ion-exchange property and layer structure in addition to its function as a carrier. is there. The ion-exchange layered silicate is naturally produced mainly as a main component of clay minerals, but is not limited to natural products, and may be an artificial synthetic product. Specific examples of clay, clay mineral and ion-exchange layered silicate include kaolinite, montmorillonite, hectorite, bentonite, smectite, vermiculite, teniolite, synthetic mica, synthetic hectorite and the like.

  Examples of the organic compound include a granular or particulate solid having a particle size of preferably 3 to 300 μm, more preferably 10 to 300 μm. Specifically, a (co) polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene or vinylcyclohexane or styrene is used. (Co) polymers produced as the main component, or polymers having a polar functional group obtained by copolymerizing or graft-polymerizing polar monomers such as acrylic acid, acrylic acid ester and maleic anhydride to these polymers The body is mentioned.

These particulate carriers may be used alone or in combination of two or more.
In addition, the olefin polymerization catalyst used for the production of the syndiotactic polypropylene (A) may contain a specific organic compound component (IV) as described later together with the above components.

Organic compound component (IV)
The organic compound component (IV) (also referred to as “component (IV)” in the present specification) is used for the purpose of improving the polymerization performance and the physical properties of the produced polymer, if necessary. Examples of such organic compounds include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, and sulfonates.
The organic compound component (IV) may be used alone or in combination of two or more.

Production Method of Syndiotactic Polypropylene (A) In the polymerization, the use method and the order of addition of the above components are arbitrarily selected, and the following methods are exemplified.

(1) A method of adding component (I) alone to the polymerization vessel.
(2) A method in which component (I) and component (II) are added to the polymerization vessel in any order.
(3) A method in which the catalyst component having component (I) supported on carrier (III) and component (II) are added to the polymerization vessel in any order.
(4) A method in which the catalyst component having component (II) supported on carrier (III) and component (I) are added to the polymerization vessel in any order.
(5) A method in which a catalyst component in which component (I) and component (II) are supported on a carrier (III) is added to a polymerization vessel.

In the methods (2) to (5), at least two of the catalyst components may be contacted in advance.
In the methods (4) and (5) in which the component (II) is supported, the unsupported component (II) may be added in any order as necessary. In this case, the components (II) may be the same or different.

  In addition, the solid catalyst component in which component (I) is supported on component (III) and the solid catalyst component in which component (I) and component (II) are supported on component (III) are prepolymerized with olefin. Alternatively, a catalyst component may be further supported on the prepolymerized solid catalyst component.

  The syndiotactic polypropylene (A) is selected by homopolymerizing propylene in the presence of the olefin polymerization catalyst as described above, or from propylene and an α-olefin having 2 to 20 carbon atoms (excluding propylene). It is obtained by copolymerizing with one or more olefins.

  The polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. And alicyclic hydrocarbons such as benzene, toluene, xylene, and the like; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, or mixtures thereof. Moreover, olefin itself can also be used as a solvent.

In carrying out the polymerization using the olefin polymerization catalyst as described above, the component (I) is usually 10 ⁻⁹ to 10 ⁻¹ mol, preferably 10 ⁻⁸ to 10 ⁻² mol, per liter of reaction volume. Used in such amounts.

  Component (II-1) has a molar ratio [(II-1) / M] of component (II-1) and all transition metal atoms (M) in component (I) of usually 0.01 to 5000, Preferably it is used in such an amount that it is 0.05-2000. Component (II-2) has a molar ratio [(II-2) / M] of component (II-2) to transition metal atom (M) in component (I) of usually 1 to 10, preferably It is used in such an amount as to be 1-5. Component (II-3) has a molar ratio [(II-3) / M] of the aluminum atoms in component (II-3) to the total transition metals (M) in component (I) of usually 10 to 10. The amount used is 5000, preferably 20-2000.

  When component (II) is component (II-1), component (IV) has a molar ratio [(IV) / (II-1)] of usually 0.01 to 10, preferably 0.1 to 5. When the component (II) is the component (II-2), the molar ratio [(IV) / (II-2)] is usually 0.01 to 10, preferably 0.1 to 5. When the component (II) is the component (II-3), the molar ratio [(IV) / (II-3)] is usually 0.01 to 2, preferably 0.005 to It is used in such an amount that it becomes 1.

  Moreover, the polymerization temperature of the olefin using such an olefin polymerization catalyst is usually -50 to + 200 ° C, preferably 0 to 170 ° C. The polymerization pressure is usually from normal pressure to 10 MPa gauge pressure, preferably from normal pressure to 5 MPa gauge pressure, and 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 resulting olefin polymer can also be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature. Furthermore, it can also adjust with the quantity of the component (II) to be used. When hydrogen is added, the amount is suitably about 0.001 to 100 NL per kg of olefin.

  The olefin supplied to the polymerization reaction is only propylene, or one or more olefins selected from propylene and α-olefins having 2 to 20 carbon atoms (excluding propylene). As the α-olefin having 4 to 20 carbon atoms, a linear or branched α-olefin having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms, such as 1-butene, 2-butene, and 1-pentene. 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, -Octadecene, 1-eicosene, etc.

The resin (B) used in the present invention is selected from rosin resins, terpene resins, petroleum resins, and hydrogenated products thereof.
Examples of the rosin resin include modified rosin modified with natural rosin, polymerized rosin, maleic acid, fumaric acid or (meth) acrylic acid. A rosin derivative may be used, and examples of the rosin derivative include the above-mentioned natural rosin, polymerized rosin or esterified product of modified rosin, phenol-modified product and esterified product thereof.

  Examples of the terpene-based resin include resins made of α-pinene, β-pinene, limonene, dipentene, terpene phenol, terpene alcohol, and terpene aldehyde. In addition, aromatic-modified terpene resins obtained by polymerizing aromatic monomers such as styrene on α-pinene, β-pinene, limonene, dipentene, and the like can also be used.

  Examples of the petroleum resin include aliphatic petroleum resins whose main raw material is a C5 fraction of tar naphtha, aromatic petroleum resins whose main raw material is a C9 fraction, and copolymer petroleum resins thereof. That is, C5 petroleum resin (resin obtained by polymerizing C5 fraction of naphtha cracked oil), C9 petroleum resin (resin obtained by polymerizing C9 fraction of naphtha cracked oil), C5C9 copolymerized petroleum resin (C5 fraction of naphtha cracked oil) And a C9 fraction copolymerized resin). Further, styrenes, indenes, coumarone, other coumarone indene resins containing dicyclopentadiene, alkylphenol resins represented by condensates of p-tertiarybutylphenol and acetylene, ο Examples thereof include xylene-based resins obtained by reacting xylene, p-xylene, or m-xylene with formalin.

The rosin resin, terpene resin and petroleum resin described above may be hydrogenated products. In this case, since it is excellent in heat resistance, a weather resistance, and discoloration resistance, it is preferable.
Resin (B) has a softening point of usually 60 to 170 ° C, preferably 90 to 170 ° C.

  The softening point is measured as follows. In accordance with JIS K-2207, the ring-and-ball method is used. Fill the specified ring with the sample, support it horizontally in a water bath or glycerin bath, place the specified sphere in the center of the sample, raise the bath temperature at a rate of 5 ° C / min, and wrap the sample into the ring. Read the temperature when touching the base plate.

The resin (B) preferably has a number average molecular weight (Mn) measured by GPC in the range of 100 to 10,000.
Further, the resin (B) has a glass transition temperature obtained by differential scanning calorimeter (DSC) measurement of usually 30 to 100 ° C.

  The glass transition temperature is measured as follows. Using DSCPyris 1 or DSC7 manufactured by PerkinElmer, under a nitrogen atmosphere (20 ml / min), a sample of about 5 mg is heated to 200 ° C., held for 10 minutes, and then cooled to −80 ° C. at 10 ° C./min. After maintaining at −80 ° C. for 5 minutes, the glass transition temperature is measured from the DSC curve when the temperature is raised to 200 ° C. at 10 ° C./min.

Resin (B) may be used independently or may be used in combination of 2 or more type.
A commercially available product can be suitably used as the resin (B).
The resin composition used for preparation of the unstretched film is syndiotactic polypropylene (A) 51 to 99 parts by mass, preferably 70 to 99 parts by mass, and resin (B) 1 to 49 parts by mass, preferably 1 to 30. Part by mass. Here, the total amount of syndiotactic polypropylene (A) and resin (B) is 100 parts by mass. In addition, when using in combination of 2 or more types of syndiotactic polypropylene (A), the said quantity is a total amount of 2 or more types of syndiotactic polypropylene (A). Moreover, when using 2 or more types of resin (B) in combination, the said quantity is a total amount of 2 or more types of resin (B). The use of syndiotactic polypropylene (A) and resin (B) in the above amounts means that there is a structure in which vacancies exist in the interior and no vacancies exist on the surface, and the surface has a silver metallic luster. This is preferable from the viewpoint of producing a film. In particular, when syndiotactic polypropylene (A) is used in the above amounts, the surface roughness and surface glossiness of the obtained stretched film can be made within the preferred ranges. Moreover, when resin (B) is used in said quantity, the water vapor | steam barrier property of the obtained stretched film can also be made into a preferable range. Specifically, when the resin (B) is used in an amount larger than the above amount, the water vapor barrier property may be inferior.

  In addition, when the resin composition which contains a syndiotactic polypropylene (A) and resin (B) with the said quantity is used, also in the obtained film, syndiotactic polypropylene (A) and resin (B) are the above-mentioned normally. Included in quantity.

  Further, the resin composition does not contribute to the formation of pores in the stretched film, and may contain other additives as necessary within a range that does not impair the properties described later in addition to the silver metallic luster. Good. When the additive is detected in the pore or at the pore interface, it is considered that the additive contributes to the formation of the pore.

  Examples of the additives include known inorganic fillers, organic fillers, heat stabilizers, anti-aging agents, weathering stabilizers, antistatic agents, metal soaps, lubricants such as wax, crystal nucleating agents, flame retardants, and antiblocking agents. Etc.

  In the present invention, the syndiotactic polypropylene (A) and the resin (B) have a structure in which a large number of fine pores exist inside, and have the properties described later in addition to the silver metallic luster. Since a stretched film can be obtained, it is preferable not to use an inorganic filler and an organic filler.

Examples of the inorganic filler include a spherical filler, a plate-like filler, a fibrous filler, and an inorganic flame retardant.
Examples of the spherical filler include kaolin (aluminum silicate), silica, pearlite, shirasu balloon, sericite, diatomaceous earth, calcium sulfite, calcined alumina, and calcium silicate. Examples of the plate-like filler include talc and mica. Examples of the fibrous filler include wollastonite, magnesium oxysulfate (trade name: Moss Heidi, manufactured by Ube Industries), potassium titanate fiber, fibrous calcium carbonate, glass fiber, and the like. Examples of the inorganic flame retardant include aluminum hydroxide, hydrated gypsum, zinc borate, barium borate, borax, kaolin, clay, calcium carbonate, alum, magnesium carbonate, calcium hydroxide, magnesium hydroxide and the like.

  As the inorganic filler, an appropriate filler can be used depending on the application. For example, when providing flame retardancy, magnesium hydroxide and aluminum hydroxide are preferably used. In addition, calcium carbonate is preferably used when providing reflection performance, gloss, and porosity.

  The average particle size of the spherical filler and the plate-like filler is preferably 0.01 to 100 μm, and more preferably 0.1 to 80 μm. If the average particle size is less than 0.01 μm, it may be difficult to produce the film, and if it exceeds 100 μm, the impact resistance of the film may be reduced. The fiber length of the fibrous filler is preferably 10 μm to 10 mm, more preferably 20 μm to 3 mm. If the fiber length is less than 10 μm, the effect of reinforcement is reduced, and if it exceeds 10 mm, it may be difficult to produce a film. Moreover, 0.1-50 micrometers is preferable and, as for the diameter of a fibrous filler, 0.2-30 micrometers is more preferable. Moreover, 0.01-80 micrometers is preferable and, as for the average particle diameter of an inorganic type flame retardant, 0.1-20 micrometers is more preferable. If the average particle size exceeds 80 μm, impact resistance and tensile elongation may be reduced.

  Examples of the organic filler include wood particles such as wood powder and cotton powder, fir shell powder, crosslinked rubber powder, plastic powder, collagen powder, leather powder, protein powder, and silk powder. The particle size of the organic filler is preferably 10 to 325 mesh, more preferably 10 to 20 mesh. If the particle size exceeds 325 mesh, the impact resistance may be reduced.

An inorganic filler may be used independently or may be used in combination of 2 or more types. The organic fillers may be used alone or in combination of two or more.
When using an inorganic filler, it is desirable to use it in an amount of usually 50 to 200 parts by weight, preferably 100 to 200 parts by weight, based on 100 parts by weight of syndiotactic polypropylene (A). When an organic filler is used, it is desirable to use it in an amount of usually 10 to 100 parts by weight, preferably 30 to 100 parts by weight with respect to 100 parts by weight of syndiotactic polypropylene (A).

Examples of the heat resistance stabilizer, anti-aging agent, and weather resistance stabilizer include phenol-based, sulfite-based, phenylalkane-based, phosphite-based, and amine-based stabilizers.
As the crystal nucleating agent, talc, mica, silica, alumina, brominated biphenyl ether, aluminum hydroxydi-tert-butylbenzoate (TBBA), dibenzylidene sorbitol (DBS), substituted, which are commonly used for polyolefin resins DBS, lower alkyl dibenzylidene sorbitol (PDTS), organic phosphate, substituted triethylene glycol terephthalate, Terylene & Nylon fiber, etc., especially 2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphoric acid Sodium and PDTS are preferred. In some cases, the crystal nucleating agent can adjust the crystallization time and the crystallinity within an optimum range.

  When a crystal nucleating agent is used, it is desirable to use it in an amount of usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of syndiotactic polypropylene (A).

  In addition, when using additives other than an inorganic filler, an organic filler, and a crystal nucleating agent, it is 0.01-1 weight part normally with respect to 100 weight part of syndiotactic polypropylene (A), Preferably it is 0.1. It is desirable to use in an amount of ˜1 part by weight.

  The resin composition uses the above-mentioned syndiotactic polypropylene (A), resin (B) and, if necessary, the above additives in the above amounts, and is mixed with a Henschel mixer, a V-blender, a riboblender, a tumbler blender, or the like. Obtained. Or after the said mixing, it melt-kneads with a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer etc., Then, it granulates or grind | pulverizes.

<Unstretched film>
An unstretched film is produced from the said resin composition.
The unstretched film preferably has a thickness of 10 to 500 μm. The film thickness of an unstretched film is calculated | required by the method as described in the Example mentioned later. According to such an unstretched film, a structure in which pores exist inside and no pores exist on the surface can be more easily formed by stretching. That is, it is possible to more easily form a stretched film having the characteristics described later in addition to the silver metallic luster.

  The unstretched film is produced from the above resin composition by appropriately adjusting the extrusion conditions using an extruder such as a single screw extruder or a multi-screw extruder and a die such as a T die or a coat hanger die. The

  The resin composition may be prepared in advance before producing an unstretched film as described above, but the resin composition is used in an extruder used when producing an unstretched film. It may be prepared by kneading the syndiotactic polypropylene (A), the resin (B) and, if necessary, the above additives.

<Stretched film>
The stretched film is produced from the unstretched film.
The stretched film is composed of 51 to 99 parts by mass of syndiotactic polypropylene (A), 1 to 49 parts by mass of resin (B) selected from petroleum resin, terpene resin, rosin resin, and hydrogenated products thereof (syndiotactic) The total amount of polypropylene (A) and resin (B) is 100 parts by mass.) In addition, in the resin composition used for producing an unstretched film, if the amount of syndiotactic polypropylene (A) and the resin (B) is set in the above range, syndiotactic polypropylene (A ) And the amount of the resin (B) are usually in the above range.

  The stretched film has a total reflectance R1 measured on the surface of the film of 80% or more, that is, 80 to 100%, preferably 80 to 99%, and is measured on the surface of the film. The weight fraction φ (φ = R3 / R1 × 100) between the regular reflectance R3 obtained from the total reflectance R1 and the diffuse reflectance R2 by the following formula (1) and the total reflectance R1 is 5 to 20%. It is.

R3 = R1-R2 (1)
The total reflectance R1 and the diffuse reflectance R2 are obtained by the method described in the examples described later. The total reflectance R1 and the weight fraction φ being in the specific ranges mean that the stretched film has a silver metallic luster. Thus, the stretched film is excellent in cosmetics and reflection performance.

  The surface roughness of the stretched film is preferably 10 nm or less, that is, 0 to 10 nm, more preferably 0.1 to 10 nm. The surface glossiness of the stretched film is preferably 25% or more, that is, 25 to 100%, more preferably 25 to 99%. The surface roughness and surface glossiness are determined by the methods described in the examples described later. The surface roughness and surface glossiness in the specific ranges mean that the cosmetics, reflection performance and gloss are superior.

  As described above, the total reflectance R1, the weight fraction φ, the surface roughness, and the surface glossiness of the stretched film are in the specific ranges described above by stretching an unstretched film made of a specific resin composition. This is considered to be due to the structure of the stretched film to be formed, that is, a structure in which pores exist inside and no pores exist on the surface (see FIG. 1).

Further, the stretched film, stretched film is preferably the product of the thickness and the water vapor transmission rate ^{300μm · g / (m 2 ·} day) or less, more preferably ^{0.1~300μm · g / (m 2 ·} day ). The film thickness and water vapor transmission rate of the stretched film are determined by the methods described in the examples described later. The stretched film has excellent water vapor barrier properties when the product of the film thickness of the stretched film and the water vapor transmission rate is in the above range.

  By the way, in Patent Document 1, using a crystalline polymer such as isotactic polypropylene, polybutylene terephthalate or nylon, a stretched film having a structure in which pores are present and pores are not present on the surface is produced. Has been. Films obtained from isotactic polypropylene have a white gloss and cannot achieve a silver metallic luster. There is also room for improvement in terms of gloss. Further, a film obtained from polybutylene terephthalate or nylon also has a white gloss and cannot realize a silver metallic gloss. There is also room for improvement in terms of water vapor barrier properties.

  On the other hand, in the present invention, using a resin composition containing specific amounts of syndiotactic polypropylene (A) and resin (B), there are pores inside, and there are no pores on the surface. A film having a structure is produced. For this reason, the stretched film finally obtained satisfies the above-mentioned requirements concerning the total reflectance R1 and the weight fraction φ, and usually satisfies the above-mentioned requirements concerning the surface roughness and the surface glossiness. Furthermore, the above-mentioned requirements regarding the product of the film thickness of the stretched film and the water vapor transmission rate are usually satisfied. That is, the finally obtained stretched film has a silver metallic luster, is excellent in cosmetics, and is excellent in water vapor barrier properties. Thus, the stretched film according to the present invention is excellent in balance between cosmetic properties such as gloss and color and water vapor barrier properties.

  Moreover, in patent document 2, the stretched film containing a void | hole is produced using the propylene-type resin composition containing a propylene-type random block copolymer and an inorganic filler. This stretched film has room for improvement in terms of surface smoothness, heat resistance, and weight reduction by using many inorganic fillers to form pores.

  On the other hand, the stretched film according to the present invention uses a resin composition containing a specific amount of syndiotactic polypropylene (A) and resin (B), has pores inside, and has voids on the surface. A film having a structure in which no hole exists is produced. For this reason, the stretched film finally obtained satisfies the above-mentioned requirements concerning the total reflectance R1 and the weight fraction φ, and usually satisfies the above-mentioned requirements concerning the surface roughness and the surface glossiness. That is, the finally obtained stretched film is excellent in surface smoothness and reflection performance. In addition, a structure in which pores exist inside can be easily realized without using an inorganic filler, and it has excellent heat resistance and weight reduction.

  Furthermore, the stretched film according to the present invention is excellent in bleed-out properties by using a combination of syndiotactic polypropylene (A) and resin (B). On the other hand, when isotactic polypropylene and the resin (B) are used in combination, the bleed-out property is inferior. About this, since syndiotactic polypropylene has a higher degree of molecular entanglement than isotactic polypropylene, it is considered that the resin (B) can be held in the entanglement.

In addition, since the stretched film which concerns on this invention has a structure in which a void | hole exists inside, it is excellent also in heat insulation and cushioning properties.
The stretched film has a thickness of usually 5 to 300 μm.

  As described above, the stretched film is produced by stretching the unstretched film. Since syndiotactic polypropylene constituting an unstretched film has a non-uniform crystal state, it is considered that peeling causes separation at the interface between regions having different crystal states, and many fine pores are formed.

  As long as a specific stretching method can produce a stretched film having pores inside as described above and a silvery metallic luster, a tenter method (longitudinal and transverse stretching, transverse and longitudinal stretching), a simultaneous biaxial stretching method, Either a sequential biaxial stretching method or a uniaxial stretching method may be used. From the viewpoint of forming the above structure, a uniaxial stretching method is preferable. In the case of uniaxial stretching, the stretching may be performed in a single stage or in multiple stages of two or more stages. From the viewpoint of forming the above structure, it is preferable to stretch in one step.

In the case of uniaxial stretching, it is preferable that the take-up speed is usually 10 to 1000 mm / min from the viewpoint of realizing a structure in which pores exist inside.
In the method for producing a film according to the present invention (the stretched film), the unstretched film is not less than the glass transition temperature Tg (° C.) of the resin composition as measured by a differential scanning calorimeter (DSC), and the resin (B). It is preferable to include a step of producing a stretched film by stretching at a stretching temperature not higher than the softening temperature (° C.). Specifically, the stretching temperature is determined for the glass transition temperature Tg of the resin composition containing syndiotactic polypropylene (A) and the resin (B) actually used in the production of the unstretched film. The softening temperature of the resin (B) actually used in the production is obtained and selected from the glass transition temperature Tg to the softening temperature.

  The glass transition temperature (Tg) of the resin composition is determined by the method described in Examples described later. As described above, the glass transition temperature of the syndiotactic polypropylene (A) is usually −10 to 0 ° C., and the glass transition temperature of the resin (B) is usually 30 to 100 ° C. as described above. One glass transition temperature of the resin composition is observed between the glass transition temperature of the syndiotactic polypropylene (A) and the glass transition temperature of the resin (B), and is usually −10 to 100 ° C. Moreover, the softening temperature of resin (B) is 60-170 degreeC normally as above-mentioned. Here, since the softening temperature is always higher than the glass transition temperature in the same resin (B), when compared with the same resin (B), the softening temperature of the resin (B) is the glass transition temperature (Tg) of the resin composition. Always higher than.

By stretching at the stretching temperature, it is possible to more easily produce a stretched film having a structure in which pores are present inside and pores are not present on the surface and having a silvery metallic luster.
From the viewpoint of realizing a structure having pores in the interior, it is preferable to stretch the unstretched film 2 to 10 times.
In addition, preparation of an unstretched film and preparation of a stretched film may be performed independently or continuously.

<Application>
Since the film according to the present invention (stretched film obtained as described above) has the above-described characteristics, it remains as a single layer or as a laminate to be described later, food, medicine, electronic parts, electronic equipment, agricultural materials, The present invention can be applied to various fields such as daily necessities, building materials, decorative boards, sports equipment decorations, automobile materials, lighting members, and coating decoration members. Specifically, food packaging films, food / pharmaceuticals / cosmetics / daily necessities packaging, reflective films, light-shielding packaging films, light guide plates, automotive decorative films, crop growth promotion films, weed growth prevention films, glitter It can be suitably used for security members such as decorative labels and hologram reflectors.

  Examples of foods include sweets such as candy balls, granulated gums, cakes and cookies, fresh foods such as vegetables and meat, processed foods such as ham, cheese and paste, fermented dairy products such as yogurt, and jelly Examples include desserts, frozen preserved foods, retort foods, and cup noodles.

  Among these, the film according to the present invention has a silvery metallic luster and is excellent in water vapor barrier properties, and thus is particularly suitably used for food packaging films, foods, pharmaceuticals and the like. That is, the food packaging body according to the present invention is obtained from the above film (specifically, a stretched film).

  By the way, in packaging bodies for food packaging films, foods, pharmaceuticals, etc., resins (B) selected from petroleum resins, terpene resins, rosin resins and hydrogenated products thereof are not usually used because of fear of bleeding out. . On the other hand, in the film according to the present invention, since the resin (B) is combined with the syndiotactic polypropylene (A), the bleed-out property is suppressed. Therefore, even if the film according to the present invention contains the resin (B), it can be suitably used for packaging bodies for food packaging films, foods, pharmaceuticals and the like.

  Moreover, since the film which concerns on this invention has silver metallic luster and is excellent in reflective performance, it is used especially suitably also for a reflective film. That is, the reflective film according to the present invention is obtained from the above film (specifically, a stretched film).

  In addition, the film which concerns on this invention can exhibit the outstanding silver metallic luster, reflection performance, and water vapor | steam barrier property, without laminating | stacking a metal layer. That is, it can sufficiently function as a packaging film for food packaging, foods, pharmaceuticals and the like, and a reflective film. Therefore, a food packaging film or the like in which the metal layer is not laminated is preferable in terms of recyclability and productivity. Moreover, when the metal layer is not laminated in this way, it is preferable from the viewpoint of performing processing in a microwave oven and inspection for detecting foreign matter by X-rays.

<Laminated body>
The laminate according to the present invention includes the above-described film (stretched film obtained as described above). Specifically, for example, it is a laminate in which the above film is laminated with another film or a metal layer, and is a laminate having two layers or three or more layers. Moreover, the laminated body which laminated | stacked the said film 2 layers or 3 layers or more may be sufficient. Other films and metal layers may be appropriately selected according to the function desired to be imparted to the laminate, but films made of polyolefin resins other than the above films, metal vapor deposition layers such as aluminum, and the like are used.

  When the laminate according to the present invention is applied to a packaging for food packaging films, foods, pharmaceuticals, etc., in order to further improve the bleed out property and gas barrier property, other films to be laminated on the film are PET film, EVOH. It is preferable to use a film or a cyclic olefin resin film. In addition, you may laminate | stack these other films with the said film through the adhesive bond layer which consists of polyolefin which introduce | transduced the polar group. Moreover, you may use an aluminum vapor deposition layer. In this case, the aluminum vapor deposition layer may be formed directly on the film. Moreover, the film which formed the aluminum vapor deposition layer previously on the resin film may be produced, and the resin film and the said film may be adhere | attached and laminated | stacked, for example with an adhesive agent.

  When applying the laminated body which concerns on this invention to a reflective film, in order to improve reflective performance further, you may form a metal layer in the back surface side (namely, the opposite side to a reflective use surface) of the said film. The metal forming the metal layer is not particularly limited as long as it is a material having a high reflectance, but silver and aluminum are exemplified, and silver is more preferable. In this case, the metal layer may be formed by directly depositing on the film. Moreover, the film which formed the metal layer beforehand on the resin film is produced, and the resin film and the said film may be adhere | attached and laminated | stacked, for example with an adhesive agent.

  In addition, in the film which concerns on this invention, as above-mentioned, sufficient metal luster, water vapor | steam barrier property, and reflective performance can be exhibited, without laminating | stacking the said metal layer. That is, it can sufficiently function as a packaging film for food packaging, foods, pharmaceuticals and the like, and a reflective film. Therefore, it is preferable not to laminate a metal layer from the viewpoint of recyclability and productivity. Moreover, it is preferable not to laminate | stack a metal layer also from a viewpoint of performing the test | inspection for the process in a microwave oven, and the foreign material detection by X-ray | X_line.

<Other films>
When a pigment is further added to the resin composition used when producing the stretched film described above, a film having a metallic luster other than silver is obtained. For example, by adding a yellow pigment and a red pigment, films having a metallic luster of gold and copper can be obtained.

  In the resin composition, the pigment may be used in such a range that the pores are present inside and the pores are not present on the surface. However, the pigment is usually 0 per 100 parts by weight of the syndiotactic polypropylene (A). It is desirable to use it in an amount of 0.01 to 10 parts by weight, preferably 0.01 to 5 parts by weight.

Embodiments of the present invention relate to the following [1] to [8].
[1] 51 to 99 parts by mass of syndiotactic polypropylene (A), 1 to 49 parts by mass of a resin (B) selected from petroleum resins, terpene resins, rosin resins and hydrogenated products thereof (syndiotactic polypropylene) The total amount of (A) and the resin (B) is 100 parts by mass.), And the total reflectance R1 measured on the surface of the film is 80% or more, and the film The weight fraction φ (φ = R3 / R1 × 100) of the regular reflectance R3 obtained by the following formula (1) from the total reflectance R1 and diffuse reflectance R2 measured on the surface of the substrate and the total reflectance R1 ) Is 5 to 20%.
R3 = R1-R2 (1)
The film of [1] has a silver metallic luster.

[2] The film according to [1], wherein the film has a surface roughness of 10 nm or less and a surface glossiness of 25% or more.
The film of [2] is more excellent in gloss.

[3] The film according to [1], wherein the product of the film thickness and the water vapor transmission rate is 300 μm · g / (m ² · day) or less.
The film of [3] is excellent in water vapor barrier properties.

  [4] The film is composed of 51 to 99 parts by mass of syndiotactic polypropylene (A) and 1 to 49 parts by mass of resin (B) selected from petroleum resin, terpene resin, rosin resin and hydrogenated products thereof (Sinji An unstretched film made of a resin composition containing tactic polypropylene (A) and resin (B) in a total amount of 100 parts by mass) is obtained by measuring the resin composition glass by differential scanning calorimetry (DSC) measurement. The film according to the above [1] to [3], which is produced by stretching at a stretching temperature that is not lower than the transition temperature Tg (° C.) and not higher than the softening temperature (° C.) of the resin (B).

The film of [4] has a silvery metallic luster and excellent water vapor barrier properties.
[5] A laminate comprising the film according to the above [1] to [4].

[6] A food package obtained from the film according to [1] to [4] above.
[7] A reflective film obtained from the film according to the above [1] to [4].
Since the films [1] to [4] have the above characteristics, they can be applied to various fields as described in [5] to [7].

  [8] A resin composition comprising 51 to 99 parts by mass of syndiotactic polypropylene (A) and 1 to 49 parts by mass of a resin (B) selected from petroleum resins, terpene resins, rosin resins and hydrogenated products thereof. (The total amount of syndiotactic polypropylene (A) and resin (B) is 100 parts by mass), and the unstretched film is measured by a differential scanning calorimeter (DSC). A step of producing a stretched film by stretching at a stretching temperature not lower than the glass transition temperature Tg (° C.) of the resin composition and not higher than the softening temperature (° C.) of the resin (B). The total reflectance R1 measured on the surface of the stretched film is 80% or more, and the following formula is obtained from the total reflectance R1 and the diffuse reflectance R2 measured on the surface of the stretched film. A specular reflectance R3 obtained by 1) method for producing a film is the weight fraction φ (φ = R3 / R1 × 100) 5 to 20 percent of the total reflectivity R1.

By stretching at a specific temperature as in the above [8], a film having silver metallic luster and excellent in surface roughness, surface gloss and water vapor barrier properties can be obtained.
EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples.

[Example]
≪Component (A) ≫
The syndiotactic polypropylene (A-1) used for the Example and the comparative example was manufactured as follows.

[Synthesis Example 1] Bridged metallocene compound (I)
Dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride was produced by the method described in Synthesis Example 3 of Japanese Patent Application Laid-Open No. 2004-189666. That is, it was manufactured by the following method.

(I) Dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) methane [also known as: 2-cyclopentadienyl-2- [9- (3,6-ditert-butyl) Synthesis of fluorenyl)]-1,3-diphenylpropane] In a 100 ml Gildar flask, 1.06 g (3.81 mmol) of 3,6-ditert-butylfluorene and 40 ml of dehydrated THF were placed in a nitrogen atmosphere, and the ice bath was used. While cooling, 2.69 ml (4.22 mmol) of n-butyllithium / hexane solution (1.57M) was added dropwise with a dropping funnel. After dropping, the temperature was returned to room temperature and stirred overnight. The solution was cooled again in an ice-water bath and cooled, and a solution prepared by dissolving 1.09 g (4.22 mmol) of 6,6-dibenzylfulvene in 30 ml of dehydrated THF was added dropwise with a dropping funnel, and then returned to room temperature and stirred overnight. 1N Hydrochloric acid aqueous solution (50 ml) and ether (50 ml) were added, and the organic phase was separated with a separatory funnel. The organic phase was washed once with 50 ml of saturated saline and once with 50 ml of water, dried over magnesium sulfate, the solvent was distilled off, and the residue was purified using column chromatography (developing solvent hexane / toluene = 10/1). To obtain the target product as a pale yellow solid. The yield was 1.15 g, and the yield was 56%. The measured value of ¹ H NMR spectrum is shown below.
¹ H NMR (270 MHz, CDCL ₃ ) δ / ppm 6.9-7.5 (mx10, CH (Flu, Ph)), 5.9-6.8 (mx5, CH (Cp)), 4.5 (Sx2, CH (Flu)), 3.2 (sx2, CH2 (Et)), 3.0 (s, CH2 (Cp)), 2.8 (s, CH2 (Cp)), 1.4 (s , TBu)

(Ii) Synthesis of dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride [alias: 1,3-diphenylisopropylidene (cyclopentadienyl) (3,6- Synthesis of ditert-butylfluorenyl) zirconium dichloride] In a 100 ml Gildar flask dibenzylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) methane 0.60 g (1.12 mmol) Into a nitrogen atmosphere, 70 ml of dehydrated ether was added, and 1.46 ml (2.29 mmol) of n-butyllithium / hexane solution (1.57M) was added dropwise with a dropping funnel while cooling in an ice water bath. After dropwise addition, the mixture was returned to room temperature and stirred overnight. While cooling this solution to about −78 ° C. in a methanol / dry ice bath, 0.40 g (1.07 mmol) of zirconium tetrachloride tetrahydrofuran complex (1: 2) was added, and the mixture was taken overnight. And slowly returned to room temperature. The solvent was dried, dehydrated hexane was added, and hexane-soluble components were removed. Next, extraction was performed with dehydrated dichloromethane. After the solvent was distilled off, the residue was washed with dehydrated ether and subsequently with dehydrated hexane to obtain the desired product as a red solid. The yield was 0.41 g, and the yield was 53%. The measured values of ¹ H NMR spectrum and FD-MS spectrum are shown below.
¹ H NMR (270 MHz, CDCL ₃ ) δ / ppm 8.1 (d, 1.6 Hz, CH (Flu)), 7.7 (sx2, CH (Flu)), 7.4 (dx2, 1.9 Hz) , CH (Flu)), 7.0-7.2 (m> 6, CH (Ph)), 6.4 (t, 2.7 Hz, CH (Cp)), 5.9 (t, 2. 7 Hz, CH (Cp)), 4.0-4.2 (sx4, CH2 (Et)), 1.4 (s, tBu)
FD-MS: m / z = 696 (M ⁺ )
It should be noted that the above-mentioned compounds, 270 MHz ¹ H-NMR (JEOL GSH-270), was determined using FD- Mass spectrometry (JEOL SX-102A).

[Polymerization Example 1] Syndiotactic polypropylene (A-1)
To a glass autoclave having an internal volume of 500 ml sufficiently purged with nitrogen, 250 ml of toluene was charged, propylene was circulated in an amount of 150 L / hour, and kept at 25 ° C. for 20 minutes. On the other hand, a magnetic stirrer was placed in a 30 ml-branch flask with sufficient nitrogen substitution, and 5.00 mmol of a toluene solution of methylaluminoxane (Al = 1.53 mol / l), followed by dibenzylmethylene (cyclopentadienyl). ) 5.0 μmol of toluene solution of (3,6-di-tert-butylfluorenyl) zirconium dichloride was added and stirred for 20 minutes. This solution was added to toluene in a glass autoclave in which propylene had been circulated, and polymerization was started. Propylene gas was continuously supplied at a rate of 150 liters / hour, polymerization was carried out at 25 ° C. under normal pressure for 45 minutes, and then a small amount of methanol was added to stop the polymerization. The polymer solution was added to a large excess of methanol to precipitate the polymer and dried under reduced pressure at 80 ° C. for 12 hours. As a result, 2.38 g of polymer was obtained. The polymerization activity is 0.63 kg-PP / mmol-Zr · hr, and the polymer obtained [η] is 1.9 dl / g, Tm1 = 152 ° C., Tm2 = 158 ° C., and rrrr = 94%. Mw / Mn = 2.0. This operation was repeated to obtain the required amount of polymer and used in the examples.

  Table 1 shows the physical properties of the obtained syndiotactic polypropylene (A-1).

The measuring method of the physical property in Table 1 is as follows. In addition, since only propylene was used as a monomer, the C3 composition is 100 mol% and the C2 composition is 0 mol%.

<Melting point (Tm), heat of fusion (ΔH)>
Using DSCPyris 1 or DSC7 manufactured by PerkinElmer, under a nitrogen atmosphere (20 ml / min), a sample of about 5 mg was heated to 200 ° C., held for 10 minutes, and then cooled to 30 ° C. at 10 ° C./min. After maintaining at 30 ° C. for 5 minutes, the melting point was calculated from the peak of the crystal melting peak when the temperature was raised to 200 ° C. at 10 ° C./min, and the heat of fusion was calculated from the integrated value of the peak.

In addition, when two peaks are observed in the propylene polymer used in the examples, the low temperature side peak is Tm ₁ and the high temperature side peak is Tm ₂ . This Tm ₂ is defined as Tm defined in this specification. In the present specification, when three or more peaks are observed, the peak on the highest temperature side is defined as Tm.

<Amount of n-decane soluble part>
200 ml of n-decane was added to 5 g of a sample of syndiotactic polypropylene (A), and the polypropylene was dissolved by heating at 145 ° C. for 30 minutes. The resulting solution was allowed to cool to 20 ° C. over about 3 hours and left for 30 minutes. Thereafter, the precipitate (n-decane insoluble part) was filtered off. The filtrate was put in about 3 times the amount of acetone to precipitate the components dissolved in n-decane. The precipitate was filtered off from acetone and then dried. Even when the filtrate side was concentrated to dryness, no residue was observed. The amount of n-decane soluble part was determined by the following equation.
n-decane soluble part amount (wt%) = [precipitate weight / sample weight] × 100

<Stereoregularity rrrr>
Stereoregularity (rrrr) was calculated from ¹³ C-NMR spectrum measurement.

<MFR>
The MFR of the syndiotactic polypropylene (A) was measured at 230 ° C. and a load of 2.16 kg according to JIS K-6721.

<Intrinsic viscosity [η]>
It measured at 135 degreeC using the decalin solvent. That is, about 20 mg of resin mass is dissolved in 15 ml of decalin, and the specific viscosity ηsp is measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to the decalin solution for dilution, the specific viscosity ηsp is measured in the same manner. This dilution operation was further repeated twice, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity (see the following formula).
[Η] = lim (ηsp / C) (C → 0)

<density>
Density measurement was performed according to ASTM D1505.

<Glass transition temperature Tg>
Using DSCPyris 1 or DSC7 manufactured by PerkinElmer, under a nitrogen atmosphere (20 ml / min), a sample of about 5 mg is heated to 200 ° C., held for 10 minutes, and then cooled to −80 ° C. at 10 ° C./min. After maintaining at −80 ° C. for 5 minutes, the glass transition temperature was measured from the DSC curve when the temperature was raised to 200 ° C. at 10 ° C./min.

<Molecular weight distribution (Mw / Mn)>
The molecular weight distribution (Mw / Mn) was measured as follows using a gel permeation chromatograph Alliance GPC-2000 manufactured by Waters. The separation columns are two TSKgel GNH6-HT and two TSKgel GNH6-HTL, the column size is 7.5 mm in diameter and 300 mm in length, the column temperature is 140 ° C., and the mobile phase is o -Use dichlorobenzene (Wako Pure Chemical Industries) and 0.025% by weight of BHT (Takeda Pharmaceutical) as an antioxidant, move at 1.0 ml / min, set the sample concentration to 15 mg / 10 mL, and set the sample injection volume to 500 μL A differential refractometer was used as a detector. The standard polystyrene used was manufactured by Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and used by Pressure Chemical Co. for 1000 ≦ Mw ≦ 4 × 10 ⁶ .

Moreover, in the comparative example, the following component was used instead of the syndiotactic polypropylene (A).
Isotactic polypropylene (A-2); made by Aldorich, isotactic polypropylene (MI = 35g / 10min))
Random polypropylene (A-3); manufactured by Prime Polymer, F327 (MI = 7.0g / 10min)
Polybutylene terephthalate (A-4); manufactured by Mitsubishi Engineering Plastics Co., Ltd., Novaduran 5505S (MI = 27g / 10min))
Nylon (A-5); manufactured by Mitsubishi Gas Chemical Company, MXD6 S6007 (MI = 2.0g / 10min))

≪Ingredient (B) ≫
In the examples and comparative examples, the following resins were used as the resin (B).
Terpene resin (B-1); manufactured by Yasuhara Chemical Co., Ltd., Clearon P125 (softening temperature: 125 ° C)
Terpene resin (B-2): Clearon P150 (softening temperature: 150 ° C) manufactured by Yasuhara Chemical Co., Ltd.

Moreover, in the comparative example, the following component was used instead of resin (B).
PMMA (B-3); manufactured by Mitsubishi Rayon Co., Ltd., Acrypet MD001 (MI = 6.0g / 10min)
Barium sulfate (B-4); manufactured by Takehara Chemical Industry Co., Ltd., W-1 (average particle size: 1.5 μm)
In the examples, a terpene resin was used as the resin (B). However, when a petroleum resin or a rosin resin is used, it is considered that the same result as the terpene resin can be obtained.

≪Resin composition≫
The resin composition was prepared by mixing component (A) and component (B) in a molding machine as described later.

<Glass transition temperature Tg of resin composition>
Using DSCPyris 1 or DSC7 manufactured by PerkinElmer, under a nitrogen atmosphere (20 ml / min), a sample of about 5 mg is heated to 200 ° C., held for 10 minutes, and then cooled to −80 ° C. at 10 ° C./min. After maintaining at −80 ° C. for 5 minutes, the glass transition temperature was measured from the DSC curve when the temperature was raised to 200 ° C. at 10 ° C./min.

[Example 1]
A 25 mmφ T-die film molding machine with a stretching device (manufactured by Thermo Plastic Industry Co., Ltd.) was used in such an amount that 90% by weight of syndiotactic polypropylene (A-1) and 10% by weight of terpene resin (B-1). ) And then extruded from a T-die to obtain an unstretched film (film thickness 300 μm) (see Table 2). In addition, the film thickness of the unstretched film was measured similarly to the stretched film mentioned later.

Subsequently, uniaxial stretching with a roll was performed with a stretching apparatus at a stretching temperature of 30 ° C. and a take-up speed of 1 m / min to obtain a stretched film. The draw ratio was 6 times (roll rotation ratio).
FIG. 1 shows an SEM image of a cross section of the stretched film. In addition, the observation by SEM was performed by the magnification 600 times about the film cross section parallel to the extending | stretching direction. Thereby, it was confirmed that the stretched film had many fine pores inside and no pores on the surface. Moreover, the void | hole was elongate and was oriented along the extending | stretching direction.
The other evaluation results are shown in Table 2.

[Examples 2-3]
A stretched film was obtained in the same manner as in Example 1 except that the mixing ratio of syndiotactic polypropylene (A-1) and terpene resin (B-1) was changed as shown in Table 2. The evaluation results are shown in Table 2.

[Examples 4 to 5]
A stretched film was obtained in the same manner as in Example 1 except that the stretching temperature was changed as shown in Table 2. The evaluation results are shown in Table 2.

[Example 6]
A stretched film was obtained in the same manner as in Example 1 except that the terpene resin (B-2) was used as the component (B) as shown in Table 2. The evaluation results are shown in Table 2.

[Comparative Example 1]
A stretched film was produced in the same manner as in Example 1 except that only syndiotactic polypropylene (A-1) was used as shown in Table 3. However, the stretched film was not obtained because the film was broken during stretching.

[Comparative Example 2]
A stretched film was produced in the same manner as in Example 1 except that the mixing ratio of syndiotactic polypropylene (A-1) and terpene resin (B-1) was changed as shown in Table 3. However, the stretched film was not obtained because the film was broken during stretching.

[Comparative Example 3]
A stretched film was obtained in the same manner as in Example 1 except that the stretching temperature was changed as shown in Table 3. In this stretched film, no pores were formed inside.
The other evaluation results are shown in Table 3.

[Comparative Example 4]
A stretched film was obtained in the same manner as in Example 1 except that PMMA (B-3) was used as the component (B) as shown in Table 3. The evaluation results are shown in Table 3.

[Comparative Example 5]
Example 1 except that isotactic polypropylene (A-2) was used instead of syndiotactic polypropylene (A-1) as shown in Table 3, and the draw ratio was changed to 8 times (roll rotation ratio). In the same manner as above, a stretched film was obtained. The evaluation results are shown in Table 3.

[Comparative Example 6]
Same as Example 1 except that random polypropylene (A-3) was used instead of syndiotactic polypropylene (A-1) as shown in Table 3 and the draw ratio was changed to 10 times (roll rotation ratio). Thus, a stretched film was obtained. The evaluation results are shown in Table 3.

[Comparative Example 7]
A stretched film was prepared in the same manner as in Example 1 except that syndiotactic polypropylene (A-1) was used in amounts of 30 wt% and barium sulfate (B-4) was 70 wt% as shown in Table 3. Obtained. The evaluation results are shown in Table 3.

[Comparative Example 8]
A stretched film was obtained in the same manner as in Example 1 except that only isotactic polypropylene (A-2) was used as shown in Table 3 and the draw ratio was changed to 8 times (roll rotation ratio). The evaluation results are shown in Table 3.

[Comparative Example 9]
Using only polybutylene terephthalate (A-3), melted at 245 ° C. by a 25 mmφ T-die film molding machine with a stretching device (manufactured by Thermo Plastic Industry Co., Ltd.), and then extruded from a T-die, unstretched film (Film thickness 120 μm) was obtained (see Table 3). In addition, the film thickness of the unstretched film was measured similarly to the stretched film mentioned later.

  Subsequently, uniaxial stretching with a roll was performed with a stretching apparatus at a stretching temperature of 30 ° C. and a take-up speed of 1 m / min to obtain a stretched film. The draw ratio was 2 times (roll rotation ratio). The evaluation results are shown in Table 3.

[Comparative Example 10]
Using only nylon (A-4), it was melted at 260 ° C. by a 25 mmφ T-die film molding machine with a stretching device (manufactured by Thermo Plastic Industry Co., Ltd.), then extruded from a T-die, and an unstretched film (film) A thickness of 120 μm) was obtained (see Table 3). In addition, the film thickness of the unstretched film was measured similarly to the stretched film mentioned later.

  Subsequently, uniaxial stretching with a roll was performed with a stretching apparatus at a stretching temperature of 30 ° C. and a take-up speed of 1 m / min to obtain a stretched film. The draw ratio was 3 times (roll rotation ratio). The evaluation results are shown in Table 3.

The measuring method of the physical property in Tables 2-3 is as follows.

<Thickness of stretched film (total thickness of film (A))>
Measurement was performed using a micrometer.

<Surface roughness>
The surface roughness was measured using a non-contact 3D micro surface shape observation system NT-1100 manufactured by WYKO.
The film roughness was 0.9 mm × 0.12 mm, and the surface roughness was determined in the measurement mode PSI mode.

<Reflectance>
Using a spectrophotometer (manufactured by Hitachi, Ltd .: U-3310) equipped with an integrating sphere of φ150 mm, the total reflectance at a wavelength of 550 nm measured according to the method described in JIS-Z8722 Condition d was R1. Using a spectrophotometer (manufactured by Hitachi, Ltd .: U-3310) equipped with an integrating sphere of φ150 mm, the specular reflection component was cut using an optical trap according to the method described in JIS-Z8722 d, and measured. The reflectance at a wavelength of 550 nm was defined as diffuse reflectance R2.

Also, R1-R2 was designated as regular reflectance R3. Furthermore, the weight fraction φ was determined from the following equation.
φ = R3 / R1 × 100

<Surface gloss>
The surface glossiness was measured according to ASTM D 523 (incident angle 20 °).

<Water vapor transmission rate (B)>
The water vapor transmission rate was measured according to the cup method of JIS Z0208. The mass of water vapor that permeated in 30 minutes through a sample having a moisture permeable area of 25 cm ² or more was measured from an atmosphere at a temperature of 40 ° C. and a relative humidity of 90%, and was calculated per 1 m ^{2 of} sample for 24 hours. The atmosphere on the water vapor transmission side was dried with a hygroscopic agent.
Moreover, (A) × (B) value was determined from the total thickness (A) of the film and the water vapor transmission rate (B).

<Film color>
The color of the stretched film was confirmed by visual confirmation.

Claims (8)

51-99 parts by mass of syndiotactic polypropylene (A), 1-49 parts by mass of resin (B) selected from petroleum resin, terpene resin, rosin resin and hydrogenated products thereof (syndiotactic polypropylene (A) And the total amount of resin (B) is 100 parts by mass),
The total reflectance R1 measured on the surface of the film is 80% or more, and the positive reflectance determined by the following formula (1) from the total reflectance R1 and diffuse reflectance R2 measured on the surface of the film. A film having a weight fraction φ (φ = R3 / R1 × 100) of 5 to 20% between the reflectance R3 and the total reflectance R1.
R3 = R1-R2 (1)   The film according to claim 1, wherein the film has a surface roughness of 10 nm or less and a surface gloss of 25% or more. The film according to claim 1, wherein a product of the film thickness and the water vapor transmission rate is 300 μm · g / (m ² · day) or less.   The film is composed of 51 to 99 parts by mass of syndiotactic polypropylene (A), 1 to 49 parts by mass of a resin (B) selected from petroleum resins, terpene resins, rosin resins and hydrogenated products thereof (syndiotactic) (The total amount of polypropylene (A) and resin (B) is 100 parts by mass.)) An unstretched film comprising a resin composition containing glass transition temperature of the resin composition as measured by a differential scanning calorimeter (DSC) The film according to any one of claims 1 to 3, which is produced by stretching at a stretching temperature which is not lower than Tg (° C) and not higher than the softening temperature (° C) of the resin (B).   The laminated body containing the film in any one of Claims 1-4.   The food packaging body obtained from the film in any one of Claims 1-4.   The reflective film obtained from the film in any one of Claims 1-4. Unstretched from a resin composition comprising 51 to 99 parts by mass of syndiotactic polypropylene (A) and 1 to 49 parts by mass of a resin (B) selected from petroleum resins, terpene resins, rosin resins and hydrogenated products thereof A film is prepared (here, the total amount of syndiotactic polypropylene (A) and resin (B) is 100 parts by mass).
The unstretched film is stretched by stretching at a stretching temperature not lower than the glass transition temperature Tg (° C.) of the resin composition and not higher than the softening temperature (° C.) of the resin (B) as measured by a differential scanning calorimeter (DSC). Including the step of making a film,
The stretched film has a total reflectance R1 measured on the surface of the stretched film of 80% or more, and the total reflectance R1 and diffuse reflectance R2 measured on the surface of the stretched film are expressed by the following formula: A method for producing a film, wherein the weight fraction φ (φ = R3 / R1 × 100) between the regular reflectance R3 obtained by (1) and the total reflectance R1 is 5 to 20%.