JP2009084378A - Shrink label - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a shrink label excellent in shrinkage in high temperatures, dimensional stability at an ordinary temperature and impact resistance in low temperatures. <P>SOLUTION: The shrink label comprises a propylene-based random block copolymer (A) that has a melt flow rate in the range of 0.1-100 g/10 min and a melting point in the range of 100-155°C and is composed of 90-60 wt.% of a portion which is insoluble in n-decane (D<SB>insol</SB>) at room temperature and satisfies some specific requirements and 10-40 wt.% of a portion which is soluble in n-decane (D<SB>sol</SB>) at room temperature and satisfies some specific requirements. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a shrink label. More specifically, the present invention relates to a shrink label excellent in heat shrinkage characteristics and impact resistance.

  As materials widely used for shrink labels, polypropylene resins, polyvinyl chloride resins, polystyrene resins and the like are well known. Polypropylene resins have features such as light weight and good transparency, and polyvinyl chloride resins and polystyrene resins have features such as a high shrinkage rate and shrinkage rate.

  In recent years, environmental issues and recycling issues have become important, and attention has been paid to the development of shrink labels using polyolefins such as polypropylene without using polyvinyl chloride resins and polystyrene resins. Shrink labels using polyolefin often wrap containers of various shapes such as beverage bottle labels and cup noodle labels, so it has high shrinkage at high temperatures (high heat shrinkage) and dimensions at room temperature. Properties such as stability (high natural shrinkage) and impact resistance at low temperatures (low temperature brittleness) are required.

  The conventional shrink labels made of polyolefin resin have a higher thermal shrinkage rate, dimensional deformation during storage of the film at room temperature (so-called natural shrinkage rate), and impact resistance at low temperatures than those made of vinyl chloride resin. It was inferior.

For example, as a polyolefin-based shrink film, Patent Documents 1 and 2 describe a polypropylene-based shrink film made of a metallocene catalyst.
However, the above two shrink films are not necessarily sufficient in terms of heat shrinkage and natural shrinkage, and further, the impact resistance at low temperatures has not been improved at all. In a shrink film made of polyolefin, if a high heat shrinkage rate is to be achieved, the natural shrinkage rate at room temperature (25 to 40 ° C.) becomes large, which impedes film quality. For this reason, the shrink label excellent in the balance of a heat shrinkage rate and a natural shrinkage rate and the impact resistance at the time of low temperature is desired.
Japanese Patent No. 3787478 JP 2006-52313 A

  An object of the present invention is to provide a shrink label excellent in shrinkability at high temperature, dimensional stability at normal temperature, and impact resistance at low temperature.

  In order to solve the above problems, the present inventors have intensively studied a propylene random copolymer. As a result, the shrink film has a shrinkable property at a high temperature and a normal temperature by using a propylene random block copolymer. The present inventors have found that it has excellent dimensional stability and impact resistance at low temperatures, and has completed the present invention.

That is, this invention is specified by the matter described below.
The shrink label of the present invention has a melt flow rate in the range of 0.1 to 100 g / 10 min, a melting point in the range of 100 to 155 ° C., and a room temperature n− that satisfies the following (1) to (3): Propylene system composed of 90 to 60% by weight of a part insoluble in decane (D _insol ) and 10 to 40% by weight of a part soluble in room temperature n-decane (D _sol ) satisfying the following (4) to (6) It consists of a random block copolymer (A), It is characterized by the above-mentioned.

(1) The molecular weight distribution (Mw / Mn) determined from GPC of D _insol is 1.0 to 3.5.
(2) Content of skeleton derived from ethylene in D _insol is 0.5 to 13 mol%
(3) D sum of a 2,1-insertion bond amount and 1,3-insertion bond amount of propylene in _insol is 0.2 mole% (4) D molecular weight distribution determined by GPC of _sol (Mw / Mn ) Is 1.0 to 3.5
(5) The intrinsic viscosity [η] in 135 ° C. decalin of D _sol is 1.5 to 4 dl / g.
(6) The content of the skeleton derived from ethylene in D _sol is 15 to 35 mol%.

The copolymer (A) is preferably polymerized with a metallocene catalyst system.
The shrink label of the present invention has a layer made of the propylene random block copolymer (A) and a layer made of a mixture (B) of a cyclic olefin resin and an ethylene-α-olefin copolymer. Alternatively, the layer made of the mixture (B) is at least one surface layer.

Furthermore, the shrink label of the present invention preferably has a thickness of 30 to 100 μm.
Further, the shrink label of the present invention comprises a film having a layer made of the copolymer (A) and, if necessary, a layer made of the mixture (B) in a uniaxial direction or a biaxial direction with a surface magnification of 3 It can be stretched more than twice.

  The present invention can provide a shrink label excellent in shrinkability at high temperature, dimensional stability at normal temperature, and impact resistance at low temperature.

The shrink film of the present invention has a melt flow rate in the range of 0.1 to 100 g / 10 minutes, a melting point in the range of 100 to 155 ° C., and a room temperature n− satisfying the above (1) to (3). Propylene system comprising 90 to 60% by weight of decane insoluble part (D _insol ) and 10 to 40% by weight of part (D _sol ) soluble in room temperature n-decane satisfying the above (4) to (6) It consists of a random block copolymer (A), It is characterized by the above-mentioned.

<Propylene Random Block Copolymer (A)>
The propylene random block copolymer (A) used in the present invention is preferably a propylene block copolymer obtained by copolymerizing propylene and ethylene in the first polymerization step in the presence of a metallocene catalyst system. A certain propylene / ethylene random copolymer is produced, and then a propylene-ethylene random copolymer rubber is produced in the second polymerization step. The copolymer (A) has a melt flow rate of 0.1 to 100 g / 10 minutes and a melting point of 100 to 155 ° C., and is mainly a propylene-ethylene random copolymer produced in the first polymerization step. Soluble in room temperature n-decane mainly composed of propylene-ethylene random copolymer rubber produced in the second polymerization step and 90 to 60% by weight of the component insoluble in room temperature n-decane (D _insol ) (D _sol ) 10 to 40% by weight. Here, the melt flow rate, the melting point, the weight fraction of the portion insoluble in room temperature n-decane (D _insol ), the portion soluble in room temperature n-decane (D _sol ) in the propylene random block copolymer (A) The weight fraction of can be suitably changed according to various molded object uses.

Here, the propylene-based block copolymer is desirably obtained by polymerizing with a metallocene catalyst system.
In the propylene random block copolymer (A), the D _insol satisfies the requirements (1) to (3), and the D _sol satisfies the requirements (4) to (6).

(1) The molecular weight distribution (Mw / Mn) determined from GPC of D _insol is 1.0 to 3.5.
(2) Content of skeleton derived from ethylene in D _insol is 0.5 to 13 mol%
(3) D sum of a 2,1-insertion bond amount and 1,3-insertion bond amount of propylene in _insol is 0.2 mole% (4) D molecular weight distribution determined by GPC of _sol (Mw / Mn ) Is 1.0 to 3.5
(5) The intrinsic viscosity [η] in 135 ° C. decalin of D _sol is 1.5 to 4 dl / g.
(6) The content of the skeleton derived from ethylene in D _sol is 15 to 35 mol%.

Hereinafter, the requirements (1) to (6) included in the propylene random block copolymer (A) will be described in detail.
[Requirement (1)]
The molecular weight distribution (Mw / Mn) obtained from GPC (gel permeation chromatography) of a portion (D _insol ) insoluble in room temperature n-decane of the propylene random block copolymer (A) used in the present invention is 1. It is 0 to 3.5, preferably 1.5 to 3.2, and more preferably 2.0 to 3.0. Thus, about the part ( _Dinsol ) insoluble in room temperature n-decane contained in this copolymer (A), molecular weight distribution (Mw / Mn) _{calculated |} required from GPC
) Can be narrowed as described above because a metallocene catalyst system is used as the catalyst. And when Mw / Mn is larger than 3.5, since low molecular weight components increase, the bleed out of the film occurs, and the transparency after the heat treatment may decrease.

[Requirement (2)]
The content of the skeleton derived from ethylene in the portion (D _insol ) insoluble in room temperature n-decane of the propylene random block copolymer (A) used in the present invention is 0.5 to 13 mol%, preferably 0. 0.7 to 10 mol%, more preferably 1.0 to 8 mol%. When the content of the skeleton derived from ethylene in D _insol is less than 0.5 mol%, the copolymer (A)
The melting point (Tm) of the resin becomes high, the transparency is lowered, and the low temperature heat sealability is deteriorated. Moreover, when there is more content of the frame _| skeleton derived from ethylene in _Dinsol than 13 mol%, melting | fusing point of a propylene random block copolymer (A) will become low, film forming property fall, and various molded objects. In some cases, such as a decrease in rigidity at high temperatures.

[Requirement (3)]
Sum of 2,1-insertion bond amount and 1,3-insertion bond amount of propylene in a portion (D _insol ) insoluble in room temperature n-decane of the propylene random block copolymer (A) used in the present invention Is 0.2 mol% or less, preferably 0.1 mol% or less. When the sum of the 2,1-insertion bond amount and 1,3-insertion bond amount of propylene in D _insol is more than 0.2 mol%, the random copolymerizability of propylene and ethylene decreases, and as a result In addition, since the composition distribution of the propylene-ethylene copolymer rubber in the portion soluble in n-decane at room temperature (D _sol ) is widened, the impact resistance is lowered, and further, the transparency is lowered after the heat treatment. May occur.

[Requirement (4)]
The molecular weight distribution (Mw / Mn) obtained from GPC of the portion soluble in room temperature n-decane (D _sol ) of the propylene random block copolymer (A) used in the present invention is 1.0 to 3.
. 5, Preferably it is 1.2-3.0, More preferably, it is 1.5-2.5. As described above, the molecular weight distribution (Mw / Mn) obtained from GPC for the part (D _sol ) soluble in room temperature n-decane of the copolymer (A) can be narrowed as described above. This is because a catalyst system is used. And when Mw / Mn is larger than 3.5, since low molecular weight propylene-ethylene random copolymer rubber increases in D _sol , impact resistance is lowered, transparency is deteriorated after heat treatment, and moldings are stored. Problems such as blocking may occur.

[Requirement (5)]
The intrinsic viscosity [η] in 135 ° C. decalin of the portion (D _sol ) soluble in room temperature n-decane of the propylene random block copolymer (A) used in the present invention is 1.5-4.
dl / g, preferably more than 1.5 dl / g and not more than 3.5 dl / g, more preferably 1.8 to 3.5 dl / g, most preferably 2.0 to 3.0 dl / g. In the production of such a random block copolymer, when a catalyst other than the metallocene catalyst system used in the present invention is used, a propylene random block copolymer (A) having an intrinsic viscosity [η] exceeding 1.5 dl / g (A It is extremely difficult to produce a propylene random block copolymer (A) having an intrinsic viscosity [η] of 1.8 dl / g or more. In addition, the intrinsic viscosity of the intrinsic viscosity D _sol in 135 ° C. decalin [
When η] is higher than 4 dl / g, a very small amount of ultra-high molecular weight or high ethylene content propylene-ethylene random copolymer rubber is by-produced when producing the propylene-ethylene random copolymer rubber in the second polymerization step. To do. The propylene-ethylene random copolymer rubber produced as a by-product in a small amount is unevenly present in the propylene-based random block copolymer (A), so that appearance such as reduced impact resistance, fish eyes, etc. is generated. Failure may occur.

[Requirement (6)]
The content of the skeleton derived from ethylene in the portion soluble in room temperature n-decane (D _sol ) of the propylene-based random block copolymer (A) used in the present invention is 15 to 35 mol%,
Preferably it is 18-30 mol%, More preferably, it is 20-25 mol%. When the content of the skeleton derived from ethylene in D _sol is lower than 15 mol%, the impact resistance of the propylene random block copolymer is lowered. The content of skeletons derived from ethylene is high, transparency lower than 35 mol% in the D _sol.

The content of normally 17 to 28 mole% of the backbone derived from the room temperature n- decane ethylene in the portion soluble (D _sol), preferably by in the range of 20 to 25 mol%, The transparency of the injection-molded product is less likely to be lowered, and the impact resistance of the injection-molded product is less likely to be reduced.

  The propylene random block copolymer (A) used in the present invention is preferably a propylene random block copolymer comprising propylene and a small amount of ethylene in the first polymerization step ([Step 1]) in the presence of a metallocene catalyst. Propylene random block copolymer obtained by producing propylene-ethylene copolymer rubber by copolymerizing propylene and a larger amount of ethylene than the first step in the second polymerization step ([Step 2]) after the production of the polymerization. It is a polymer.

  The metallocene catalyst used in the present invention includes a metallocene compound and at least one compound selected from compounds capable of reacting with an organometallic compound, an organoaluminum oxy compound and a metallocene compound to form an ion pair, A metallocene catalyst comprising a particulate carrier as required, preferably a metallocene catalyst capable of performing stereoregular polymerization such as isotactic or syndiotactic structure. Among the metallocene compounds, the following crosslinkable metallocene compounds exemplified in the international application (WO01 / 27124 pamphlet) by the applicant of the present application are used.

In the general formula [I], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ ,
R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are selected from a hydrogen atom, a hydrocarbon group, and a silicon-containing group, and may be the same or different. Such hydrocarbon groups include methyl, ethyl, n-propyl, allyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n -Linear hydrocarbon group such as nyl group and n-decanyl group; isopropyl group, tert-butyl group, amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group Branched hydrocarbons such as 1-methyl-1-propylbutyl, 1,1-propylbutyl, 1,1-dimethyl-2-methylpropyl, 1-methyl-1-isopropyl-2-methylpropyl Groups: cyclic saturated hydrocarbon groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, adamantyl; phenyl, tolyl, naphthyl, biphenyl Cyclic unsaturated hydrocarbon groups such as enyl, phenanthryl and anthracenyl groups; saturated hydrocarbon groups substituted with cyclic unsaturated hydrocarbon groups such as benzyl, cumyl, 1,1-diphenylethyl and triphenylmethyl A hetero atom-containing hydrocarbon group such as methoxy group, ethoxy group, phenoxy group, furyl group, N-methylamino group, N, N-dimethylamino group, N-phenylamino group, pyryl group, thienyl group, etc. Can do. Examples of the silicon-containing group include a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylsilyl group, and a triphenylsilyl group.

In the general formula [I], the substituents R ^{5 to} R ¹² may be bonded to adjacent substituents to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, octamethyloctahydrodibenzofluorenyl group, octamethyltetrahydrodicyclopentafluorenyl group, etc. Can be mentioned.

In the general formula [I], R ¹ , R ² , R ³ , and R ⁴ substituted on the cyclopentadienyl ring are preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 1 to 1 carbon atom
Examples of the hydrocarbon group 20 include the above-described hydrocarbon groups. More preferably, R ³ is a hydrocarbon group having 1 to 20 carbon atoms.

In the above general formula [I], R ^{5 to} R ¹² substituted on the fluorene ring have 1 to 20 carbon atoms.
The hydrocarbon group is preferably. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the hydrocarbon groups listed above. Substituents R ⁵ to R ¹² are substituents adjacent may form a ring bonded to each other.

In the general formula [I], Y that bridges the cyclopentadienyl ring and the fluorenyl ring is preferably a group 14 element of the periodic table, more preferably carbon, silicon, or germanium, and still more preferably a carbon atom. It is. R ¹³ and R ¹⁴ substituted on Y are preferably a hydrocarbon group having 1 to 20 carbon atoms. These may be the same as or different from each other, and may be bonded to each other to form a ring. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the hydrocarbon groups listed above. More preferably, R ¹⁴ is an aryl group having 6 to 20 carbon atoms. Examples of the aryl group include the above-mentioned cyclic unsaturated hydrocarbon group, a saturated hydrocarbon group substituted with a cyclic unsaturated hydrocarbon group, and a heteroatom-containing cyclic unsaturated hydrocarbon group. R ¹³ and R ¹⁴ may be the same or different, and may be bonded to each other to form a ring. As such a substituent, a fluorenylidene group, a 10-hydroanthracenylidene group, a dibenzocycloheptadienylidene group, and the like are preferable.

In the metallocene compound represented by the above general formula [I], the substituent selected from R ¹ , R ⁴ , R ⁵ or R ¹² and R ¹³ or R ^{14 at the} bridging part are bonded to each other to form a ring. May be.
In the above general formula [I], M is preferably a Group 4 transition metal of the periodic table, more preferably Ti, Zr, or Hf. Q is selected from the same or different combinations from a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair. j is an integer of 1 to 4, and when j is 2 or more, Qs may be the same or different from each other. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and specific examples of the hydrocarbon group include the same as those described above. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxy. And ethers such as ethane. It is preferable that at least one Q is a halogen atom or an alkyl group.

Such bridged metallocene compounds include diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl). ) (2,
7-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butyl-5-methyl-cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (methyl) (Phenyl) methylene (3-tert-butyl-5-methyl-cyclopentadienyl) (octamethyloctahydrobenzofluorenyl) zirconium dichloride, [3- (1′1 ′, 4 ′, 4 ′, 7 ′ , 7 ′, 10 ′, 10′-octamethyloctahydrodibenzo [b, h] fluorenyl) (1,1,3-trimethyl-5-tert-butyl-1,2,3,3a-tetrahydropentalene)] Zirconium dichloride (see the following formula [II]) and the like are preferred.

  In the metallocene catalyst used in the present invention, an ion pair reacts with an organometallic compound, an organoaluminum oxy compound, and a transition metal compound used together with the Group 4 transition metal compound represented by the general formula [I]. At least one compound selected from the compounds that form, and a particulate carrier that is used as necessary. These are disclosed in the above-mentioned publication (WO01 / 27124 pamphlet) or JP-A-11-315109. The compounds disclosed in the publication can be used without limitation.

  The propylene random block copolymer (A) in the present invention uses a polymerization apparatus in which two or more reaction apparatuses are connected in series, and continuously performs the following two steps ([Step 1] and [Step 2]). It is obtained by carrying out.

[Step 1] copolymerizes propylene and ethylene at a polymerization temperature of 0 to 100 ° C. and a polymerization pressure of normal pressure to 5 MPa gauge pressure. In [Step 1], the propylene-based random copolymer produced in [Step 1] is made the main component of D _{insol by reducing} the amount of ethylene fed relative to propylene.

In [Step 2], propylene and ethylene are copolymerized at a polymerization temperature of 0 to 100 ° C. and a polymerization pressure of normal pressure to 5 MPa gauge pressure. In [Step 2], the propylene-ethylene copolymer rubber produced in [Step 2] becomes the main component of D _sol by increasing the amount of ethylene fed to propylene than in [Step 1]. To do.

By doing in this way, requirements (1)-(3) concerning D _insol are adjusted by adjusting polymerization conditions in [Step 1], and requirements (4)-(6) concerning D _sol are [Step 2]. It can be satisfied by adjusting the polymerization conditions.

Further, the physical properties that the propylene random block copolymer (A) used in the present invention should satisfy are often determined by the chemical structure of the metallocene catalyst used. Specifically, requirement (1) molecular weight distribution (Mw / Mn) obtained from GPC of D _insol , requirement (3) 2,1-insertion bond amount and 1,3-insertion bond amount of propylene in D _insol , Requirement (4) molecular weight distribution (Mw / Mn) obtained from GPC of D _sol , and melting point of propylene-based random block copolymer (A) mainly in [Step 1] and [Step 2] By appropriate selection of the metallocene catalyst used, it can be adjusted to meet the requirements of the present invention. The metallocene catalyst preferably used in the present invention is as described above.

Further, the content of the skeleton derived from ethylene in the requirement (2) D _insol can be adjusted by the amount of ethylene feed in [Step 1]. Requirement (5) The intrinsic viscosity [η] of D _sol in 135 ° C. decalin can be adjusted by the feed amount of a molecular weight regulator such as hydrogen in [Step 2]. Requirement (6) The content of the skeleton derived from ethylene in D _sol can be adjusted by the amount of ethylene feed in [Step 2]. Furthermore, by adjusting the amount ratio of the polymer produced in [Step 1] and [Step 2], the composition ratio of D _insol and D _sol and the melt flow of the propylene random block copolymer (A) It is possible to adjust the rate appropriately.

  In addition, the propylene random block copolymer (A) used in the present invention is produced by the propylene-ethylene random copolymer produced in [Step 1] of the above method and [Step 2] of the above method. Propylene-ethylene random copolymer rubbers may be produced separately in the presence of a metallocene compound-containing catalyst and then blended using these physical means.

<Elastomer (B)>
To the propylene random block copolymer (A) used in the present invention, an elastomer (B) is added for the purpose of imparting properties such as impact resistance, heat sealability, transparency, dimensional stability and flexibility. can do.

  As the elastomer (B), an ethylene-α-olefin random copolymer (Ba), an ethylene-α-olefin / non-conjugated polyene random copolymer (Bb), a hydrogenated block copolymer (Bc) ), Propylene-α-olefin copolymer (Bd), other elastic polymers, and mixtures thereof.

  The content of the elastomer (B) in the propylene resin composition containing the propylene random block copolymer (A) and the elastomer (B) varies depending on the properties to be imparted, but is usually 1 to 50% by weight, preferably Is 3 to 30% by weight, more preferably 5 to 25% by weight.

  The ethylene-α-olefin random copolymer rubber (Ba) is a random copolymer rubber of ethylene and an α-olefin having 3 to 20 carbon atoms. In the ethylene-α-olefin random copolymer rubber (Ba), the molar ratio between the structural unit derived from ethylene and the structural unit derived from α-olefin (structural unit derived from ethylene / α- The structural unit derived from olefin) is usually 95/5 to 15/85, preferably 80/20 to 25/75. Moreover, MFR measured by 230 degreeC and the load 2.16kg about this ethylene-alpha-olefin random copolymer (Ba) is 0.1 g / 10min or more normally, Preferably it is 0.5-30 g / 10 Within minutes.

The ethylene-α-olefin-nonconjugated polyene random copolymer (Bb) is a random copolymer rubber of ethylene, an α-olefin having 3 to 20 carbon atoms, and a nonconjugated polyene. Examples of the α-olefin having 3 to 20 carbon atoms include those described above. As non-conjugated polyethylene, 5-ethylidene-2-norbornene, 5-propylidene-5-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene Acyclic dienes such as norbornadiene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 5-methyl-1,5-heptadiene, 6-methyl-1, Examples include chain non-conjugated dienes such as 5-heptadiene, 6-methyl-1,7-octadiene, and 7-methyl-1,6-octadiene; and trienes such as 2,3-diisopropylidene-5-norbornene. . Among these, 1,4-hexadiene, dicyclopentadiene, and 5-ethylidene-2-norbornene are preferably used. In the ethylene-α-olefin-nonconjugated polyene random copolymer (Bb), the constitutional unit derived from ethylene is usually 94.9 to 0.1 mol%, preferably 89.5 to 40 mol%. Yes, the structural unit derived from α-olefin is usually 5 to 45 mol%, preferably 10 to 40 mol%, the structural unit derived from non-conjugated polyene is usually 0.1 to 25 mol%, Preferably it is 0.5-20 mol%. However, in the present invention, the total of the structural unit derived from ethylene, the structural unit derived from α-olefin, and the structural unit derived from non-conjugated polyene is 100 mol%. The MFR measured at 230 ° C. under a load of 2.16 kg for the ethylene-α-olefin-nonconjugated polyene random copolymer (Bb) is usually 0.05 g / 10 min or more, preferably 0.1-30 g / 10. Within minutes. Specific examples of the ethylene-α-olefin-nonconjugated polyene random copolymer (Bb) include an ethylene-propylene-diene terpolymer (EPDM).

  The hydrogenated block copolymer (Bc) is a hydrogenated block copolymer represented by the following formula (a) or (b), and the hydrogenation rate is usually 90 mol%. More preferably, the hydrogenated block copolymer is 95 mol% or more.

Examples of the monovinyl-substituted aromatic hydrocarbon constituting the polymerization block represented by X in the above formula (a) or formula (b) include styrene, α-methylstyrene, p-methylstyrene, chlorostyrene, and lower alkyl-substituted styrene. And styrene such as vinyl naphthalene or derivatives thereof. These can be used alone or in a combination of two or more. Examples of the conjugated diene constituting the polymer block represented by Y in the formula (a) or (b) include butadiene, isoprene, chloroprene and the like. These can be used alone or in a combination of two or more. n is usually an integer of 1 to 5, preferably 1 or 2. Specific examples of the hydrogenated block copolymer (Bc) include styrene-ethylene-butene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), and styrene. -Styrenic block copolymers such as ethylene-propylene block copolymer (SEP). The block copolymer before hydrogenation can be produced, for example, by a method in which block copolymerization is performed in an inert solvent in the presence of a lithium catalyst or a Ziegler catalyst. A detailed manufacturing method is described in, for example, Japanese Patent Publication No. 40-23798. The hydrogenation treatment can be performed in an inert solvent in the presence of a known hydrogenation catalyst. Detailed methods are described in, for example, Japanese Patent Publication Nos. 42-8704, 43-6636, and 46-20814. When butadiene is used as the conjugated diene monomer, the ratio of the 1,2-bond amount in the polybutadiene block is usually 20 to 80% by weight, preferably 30 to 60% by weight. A commercial item can also be used as a hydrogenated block copolymer (Bc). Specific examples include Clayton G1657 (registered trademark) (manufactured by Shell Chemical Co., Ltd.), Septon 2004 (registered trademark) (manufactured by Kuraray Co., Ltd.), Tuftec H1052 (registered trademark) (manufactured by Asahi Kasei Co., Ltd.), and the like. Is mentioned.

  The propylene-α-olefin copolymer rubber (Bd) is a random copolymer rubber of propylene and an α-olefin having 4 to 20 carbon atoms. In the propylene-α-olefin random copolymer (Bd), the molar ratio between the structural unit derived from propylene and the structural unit derived from α-olefin (the structural unit derived from propylene / α-olefin). The structural unit derived from is usually 95/5 to 5/95, preferably 80/15 to 20/80. In the propylene-α-olefin random copolymer rubber (Bd), two or more α-olefins may be used, one of which may be ethylene. MFR measured at 230 ° C. and a load of 2.16 kg for the propylene-α-olefin random copolymer rubber (Bd) is usually 0.1 g / 10 min or more, preferably in the range of 0.5 to 30 g / 10 min. Is in.

An elastomer (B) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
In the present invention, the elastomer (B) is usually used in an amount in the range of 0 to 50 parts by weight, preferably 1 to 50 parts by weight with respect to 100 parts by weight of the propylene-based block random copolymer (A). To do.

<Polyethylene resin (C)>
For the purpose of imparting functions such as impact resistance, heat sealability, transparency, dimensional stability, and high-speed extrusion sheet formability to the propylene random block copolymer (A) of the present invention, the elastomer (B) In addition, a polyethylene resin (C) may be added instead of the elastomer (B).

For example, when imparting impact resistance while suppressing a decrease in transparency, a density of 0.900 to 0.930 kg / manufactured by copolymerizing ethylene and a C4 or higher α-olefin in the presence of a metallocene catalyst. It is preferred to add m ³ linear low density polyethylene.

As another example, when improving high-speed extrusion moldability, it is desirable to add high-pressure polyethylene. Here, the high-pressure polyethylene is a polyethylene having a long chain branch obtained by radical polymerization of ethylene in the presence of peroxide at a pressure of 100 kg / cm ² or more. The preferred melt flow rate (measured at ASTM D1238, 190 ° C., load 2.16 kg) of the high pressure polyethylene is usually in the range of 0.01 to 100 g / 10 min, preferably 0.1 to 10 g / 10 min. The density (ASTM D1505) is usually 0.900 to 0.940 g / cm ³ , preferably 0.910 to 0.9.
It is in the range of 30 g / cm ³ .

  The content of the polyethylene resin (C) in the propylene resin composition containing the propylene random block copolymer (A) and the polyethylene resin (C) varies depending on the properties to be imparted, but is usually 0 to 50% by weight. , Preferably 1 to 50 parts by weight, particularly preferably 3 to 30% by weight, more preferably 5 to 25% by weight. Polyethylene resin (C) can also be used individually by 1 type, and can also be used in combination of 2 or more type. However, in the propylene resin composition of the present invention, the above-mentioned elastomer (B) and the polyethylene resin (C) do not simultaneously become 0 parts by weight.

In the case of a propylene-based resin composition comprising a propylene-based random block copolymer (A), an elastomer (B), and a polyethylene resin (C), the amount of the propylene-based random block copolymer (A) is given. Depending on the characteristics, it is usually in the range of 50 to 99% by weight, preferably 70 to 97% by weight, more preferably 75 to 95% by weight. The total amount of the elastomer (B) and the polyethylene resin (C) is usually 1 to 50% by weight, preferably 3 to 30% by weight, further based on 100 parts by weight of the propylene block random copolymer (A). Preferably it is 5-25% of polymerization. In addition, the ratio of an elastomer and polyethylene can be arbitrarily adjusted according to the objective.

<Crystal nucleating agent (D)>
A crystal nucleating agent (D) may be added to the propylene random block copolymer (A) of the present invention as necessary for improving transparency, heat resistance, moldability and the like.

  Examples of the crystal nucleating agent (D) used in the present invention include sorbitol compounds such as dibenzylidene sorbitol, organophosphate compounds, rosinate compounds, aliphatic dicarboxylic acids having 4 to 12 carbon atoms, and their Examples thereof include inorganic substances such as metal salts and talc. Moreover, the polymer nucleating agent by pre-polymerization of 3 methyl-butene 1 etc. can also be mentioned.

<Petroleum resin E>
A petroleum resin (E) may be added to the propylene-based random block copolymer (A) of the present invention as necessary for improving the thermal shrinkage rate and natural shrinkage rate. The petroleum resin (E) used in the present invention is an aliphatic hydrocarbon resin, an aromatic hydrocarbon resin, an alicyclic hydrocarbon, or a hydrogenated product thereof generally called a petroleum resin, or It refers to rosin, rosin ester, terpene resin and the like, and these hydrogenated products are particularly preferred.

If necessary, the propylene resin (P) may be added to the propylene random block copolymer (A) of the present invention or the propylene resin composition containing the polymer. The propylene resin (P) used here is a propylene homopolymer, propylene / ethylene copolymer, propylene / α-olefin copolymer different from the propylene random block copolymer (A) of the present invention. Polymer, propylene / ethylene block copolymer, propylene / α-olefin block copolymer, syndiotactic propylene polymer, atactic propylene polymer and the like. Here, as the α-olefin, an α-olefin having 4 to 20 carbon atoms can be used.

  The propylene-based random block copolymer (A) of the present invention or the propylene-based resin composition containing the copolymer is within the range not impairing the object of the present invention. It may contain additives such as stabilizers, weathering stabilizers, slip agents, antiblocking agents, petroleum resins, mineral oils and the like.

  After blending each of the above components and, if necessary, various additives using a mixer such as a Henschel mixer, a Banbury mixer, or a tumbler mixer, the pellets are obtained using a single or twin screw extruder, and then obtained. Using the obtained pellets and the like, a molded body can be obtained by various methods such as extrusion molding, injection molding and injection stretch molding.

<Shrink label>
In the shrink label of the present invention, by using the propylene random block copolymer (A) having a relatively low ethylene content compared to the propylene random copolymer, the same degree of thermal shrinkage can be achieved. Can do. This is because the propylene random block copolymer (A) can have a high melting point by keeping the ethylene content relatively low. Therefore, it is possible to suppress spontaneous shrinkage at room temperature and improve label rigidity. Moreover, since the said propylene-type random block copolymer (A) contains the propylene-ethylene block, the improvement of impact resistance at the time of low temperature and the improvement of piercing strength are also recognized.

  In particular, when the propylene random block copolymer (A) used in the present invention is compared with, for example, a propylene random copolymer having a melting point of 115 ° C., the copolymer (A) has a heat shrink property (at room temperature). Dimensional stability and high shrinkage at high temperature) and label rigidity, and excellent impact resistance at low temperatures.

<Mixture of cyclic olefin resin and ethylene-α-olefin copolymer (F)>
The shrink label of the present invention has a layer made of the propylene random block copolymer (A) and a layer made of a mixture (F) of a cyclic olefin resin and an ethylene-α-olefin copolymer. Alternatively, the layer made of (F) is at least one surface layer.

  The shrink label of the present invention is a laminate having one or more layers, and most preferably has a structure of three or more layers, and is a label formed by laminating a cyclic olefin resin on the outermost layer. Such a structure is preferable in the case of solvent bonding during label processing, because the cyclic olefin resin is present on the front and back surfaces of the label, and thus has self-adhesive properties due to the solvent.

As the cyclic olefin-based resin, a resin having a glass transition temperature (Tg) of 50 ° C. to 90 ° C. and a number average molecular weight (Mn) measured by the GPC method exceeding 1000 is suitable. In such a cyclic olefin-based resin, if a product having a number average molecular weight of 1000 or less is used, moldability may be difficult when laminating.

  The ethylene-α-olefin copolymer is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. Examples of α-olefins include propylene, butene-1, pentene-1, hexene-1, 4-methyl-pentene-1, heptene-1, octene-1, decene-1, and the like. A polymer in which one or more of these α-olefins are copolymerized with ethylene may be used. Specific examples include an ethylene-propylene copolymer, an ethylene-butene-1 copolymer, an ethylene-hexene-1 copolymer, and an ethylene-octene-1 copolymer.

  The mixture (E) of the olefin resin and the ethylene-α-olefin copolymer is obtained by drying the olefin resin and the ethylene-α-olefin copolymer at a weight ratio of 60:40 to 90:10. Before kneading (melting) with a blend, a Henschel mixer or a tumbler mixer, etc., the components are appropriately dispersed, then mixed (melting) with a uniaxial or biaxial kneader and pelletized.

  Moreover, although the shrink label of this invention changes with specific uses, it has a thickness of 30-100 micrometers before the shrinkage | contraction, Preferably it is 30-80 micrometers, More preferably, it has a thickness of 30-60 micrometers. In the case of a multilayer, the ratio of the mixture (E) of the propylene random block copolymer (A), the cyclic olefin resin and the ethylene-α-olefin copolymer has a relationship of 6: 4 to 9: 1. As a whole, it is preferable to have a thickness of 30 to 80 μm.

  Furthermore, the shrink label of the present invention comprises a layer made of the copolymer (A) and, if necessary, a layer made of a mixture (E) of the following cyclic olefin resin and ethylene-α-olefin copolymer. The film can be stretched in a uniaxial direction or a biaxial direction at a surface magnification of 3 times or more, preferably 5 times or more. Such a magnification is preferable in that the stretch spots are reduced and the shrinkage ratio is improved.

〔Example〕
EXAMPLES Next, although this invention is demonstrated in detail based on an Example, this invention is not limited to the Example which concerns. In addition, the measuring method of the physical property in an Example and a comparative example is as follows.

(M1) MFR (melt flow rate)
MFR was measured according to ASTM D1238 (230 ° C., load 2.16 kg).
(M2) Melting point (Tm)
The measurement was performed using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer). The endothermic peak at the third step measured here was defined as the melting point (Tm).

(Measurement condition)
First step: The temperature is raised to 240 ° C. at 10 ° C./min and held for 10 minutes.
Second step: The temperature is lowered to 60 ° C. at 10 ° C./min.

Third step: The temperature is raised to 240 ° C. at 10 ° C./min.
(M3) Amount of room temperature n-decane soluble part (D _sol ) 200 ml of n-decane was added to 5 g of the final product (ie, propylene random block polymer of the present invention) and heated and dissolved at 145 ° C. for 30 minutes. . It was cooled to 20 ° C. over about 3 hours and left for 30 minutes. Thereafter, the precipitate (hereinafter, n-decane insoluble part: D _insol ) was filtered off. The filtrate was put in about 3 times the amount of acetone to precipitate the components dissolved in n-decane (precipitate (A)). The precipitate (A) and acetone were separated by filtration, and the precipitate was 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 formula.
n-decane soluble part amount (wt%) = [precipitate (A) weight / sample weight] × 100
(M4) Mw / Mn measurement [weight average molecular weight (Mw), number average molecular weight (Mn)]
It measured as follows using GPC-150C Plus by Waters. The separation columns are TSKgel GMH6-HT and TSKgel GMH6-HTL, the column size is 7.5 mm in inner diameter and 600 mm in length, respectively, and the column temperature is 140 ° C.
The mobile phase was o-dichlorobenzene (Wako Pure Chemical Industries, Ltd.) and BHT (Wako Pure Chemical Industries, Ltd.) 0.025% by weight as an antioxidant, which was moved at 1.0 ml / min. The sample concentration was 0.1% by weight, the sample injection amount was 500 microliters, and a differential refractometer was used as a detector. Standard polystyrene has molecular weights of Mw <1000 and Mw> 4 × 10 ⁶
Tosoh Co., Ltd. was used, and for 1000 ≦ Mw ≦ 4 × 10 ⁶ , manufactured by Pressure Chemical Co., Ltd. was used.

(m5) Content of skeleton derived from ethylene In order to measure the skeleton concentration derived from ethylene in D _insol and D _sol , 20 to 30 mg of sample was subjected to 1,2,4-trichlorobenzene / heavy benzene (2: 1 ) After dissolving in 0.6 ml of the solution, carbon nuclear magnetic resonance analysis ( ¹³ C-NMR) was performed. Propylene, ethylene and α-olefin were quantitatively determined from the dyad chain distribution. For example, in the case of propylene-ethylene copolymer,

Was obtained by the following calculation formulas (Eq-1) and (Eq-2).

(M6) Intrinsic viscosity [η]
It measured at 135 degreeC using the decalin solvent. About 20 mg of the sample was dissolved in 15 ml of decalin, and the specific viscosity η _sp was measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to the decalin solution for dilution, the specific viscosity η _sp was measured in the same manner. This dilution operation was further repeated twice, and the value of η _sp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity.

[Η] = lim (η _sp / C) (C → 0)
(m7) Measurement of 2,1-insertion bond amount and 1,3-insertion bond amount
^{Using 13} C-NMR, the 2,1-insertion bond amount and 1,3-insertion bond amount of propylene were measured according to the method described in JP-A-7-145212.

(M8) Young's modulus of the film The Young's modulus of the stretched film was measured according to JIS K6781. The tensile speed is 200 mm / min, and the distance between chucks is 80 mm.

(M9) Impact test of film The film was sampled to 5 cm × 5 cm, and the surface impact strength was measured with an impact tester (a method of pushing a hammer from the bottom to the top) at a predetermined temperature (hammer condition: 1 inch tip, 3.0J).

(M10) Haze of film (HAZE)
Measured according to ASTM D-1003.
Moreover, the haze measurement was similarly performed about the film after heat-processing for 4 days at 80 degreeC.

(M11) Thermal Shrinkage Ratio of Film A film is cut into 140 mm × 25 mm from the stretched film in the machine direction (MD) and the transverse direction (TD), and a 100 mm mark is attached to the central surface of the film, and an arbitrary temperature (100 ° C. ) Was set for 15 minutes in an air oven, the distance between the marked lines was measured, and the value obtained by dividing the decrease in the distance between the marked lines by the distance between the marked lines (100 mm) was displayed as a percentage.

(M12) Natural shrinkage ratio of the film A film was cut into a length of 140 mm × 25 mm in the machine direction (MD) and the transverse direction (TD) from the stretched film, a 100 mm mark was attached to the central surface of the film, and the film was set to 40 ° C. It was left in an air oven for 7 days, the distance between the marked lines was measured, and the value obtained by dividing the decrease in the distance between the marked lines by the distance between the marked lines (100 mm) was displayed as a percentage.

[Production Example 1]
(1) Production of solid catalyst carrier 300 g of SiO ₂ was sampled in a 1-liter branch flask and 800 m of toluene.
l was added to make a slurry.

Next, the slurry was transferred to a 4-liter flask having a volume of 5 liters, and 260 ml of toluene was added.
2830 ml of methylaluminoxane (hereinafter MAO) -toluene solution (Albemarle 10 wt% solution) was introduced into the solution, and the mixture was stirred at room temperature for 30 minutes. The temperature was raised to 110 ° C. over 1 hour, and the reaction was carried out for 4 hours. After completion of the reaction, it was cooled to room temperature. After cooling, the supernatant toluene was extracted and replaced with fresh toluene until the replacement rate reached 95%.

(2) Production of solid catalyst component (support of metal catalyst component on carrier)
In a glove box, a four-necked flask with a capacity of 5 liters
2.0 g of diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride (M1) synthesized according to the description in No. 5 It was. The flask was taken out of the glove box, 0.46 liters of toluene and 1.4 liters of MAO / SiO ₂ / toluene slurry prepared in the above (1) were added under nitrogen, and the mixture was stirred for 30 minutes to carry.

The obtained diphenylmethylene (3-tert-butyl-5-methylcyclopentadienyl) (
The 2,7-t-butylfluorenyl) zirconium dichloride / MAO / SiO ₂ / toluene slurry was 99% substituted with n-heptane to a final slurry volume of 4.5 liters. This operation was performed at room temperature.

(3) Production of prepolymerized catalyst 202 g of the solid catalyst component prepared in (2) above, 109 ml of triethylaluminum, and 100 liters of heptane were introduced into an autoclave with a stirrer having an internal volume of 200 liters, and the internal temperature was maintained at 15 to 20 ° C. 2020 g of ethylene was introduced and reacted with stirring for 180 minutes.

  After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice. The resulting prepolymerized catalyst was resuspended in purified heptane and adjusted with heptane so that the solid catalyst component concentration was 2 g / liter. This prepolymerized catalyst contained 10 g of polyethylene per 1 g of the solid catalyst component.

(4) Main polymerization In a tubular polymerization vessel having an internal volume of 58 liters, propylene is 40 kg / hour, hydrogen is 5 N liters / hour, the catalyst slurry produced in the above (3) is used as a solid catalyst component, 3.6 g / hour, triethylaluminum 2 .2 g / hour was continuously fed, and polymerization was performed in a full liquid state in which no gas phase was present in the tubular polymerizer. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G. The catalyst in this reaction is an M1 catalyst.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 liters, and further polymerized. To the polymerization vessel, propylene was supplied at 45 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 1.5 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.2 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization apparatus, propylene was supplied at 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.5 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.2 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization apparatus, propylene was supplied at 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.5 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.2 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters for copolymerization. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.11 mol%. Polymerization was performed by supplying ethylene so as to maintain a polymerization temperature of 61 ° C. and a pressure of 2.9 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene random block copolymer (A-1). The resulting propylene random block copolymer (A-1) was vacuum dried at 80 ° C. The properties of the resulting propylene random block copolymer (A-1) are shown in Table 1.

[Production Example 2]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization In a tubular polymerization vessel having an internal volume of 58 liters, propylene is 40 kg / hour, hydrogen is 5 N liters / hour, and the catalyst slurry produced in (3) of Production Example 1 is 3.6 g / hour as a solid catalyst component. Triethylaluminum (2.2 g / hour) was continuously supplied, and polymerization was performed in a full liquid state without a gas phase in the tubular polymerization reactor. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G. The catalyst in this reaction is an M1 catalyst.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 liters, and further polymerized. To the polymerization vessel, propylene was supplied at 45 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 1.5 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.2 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization apparatus, propylene was supplied at 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.5 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.2 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization apparatus, propylene was supplied at 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.5 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.2 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters for copolymerization. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.1 mol%. Polymerization was performed by supplying ethylene so as to maintain a polymerization temperature of 54 ° C. and a pressure of 2.9 MPa / G.

  After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene random block copolymer (A-2). The resulting propylene random block copolymer (A-2) was vacuum dried at 80 ° C. The properties of the resulting propylene random block copolymer (A-2) are shown in Table 1.

[Production Example 3]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization In a tubular polymerization vessel having an internal volume of 58 liters, propylene is 40 kg / hour, hydrogen is 5 N liters / hour, and the catalyst slurry produced in (3) of Production Example 1 is 3.6 g / hour as a solid catalyst component. Triethylaluminum was continuously supplied at 2.2 g / hour, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G. The catalyst in this reaction is an M1 catalyst.

The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 liters, and further polymerized. To the polymerization vessel, propylene was supplied at 45 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 1.5 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.2 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization apparatus, propylene was supplied at 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.5 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.2 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization apparatus, propylene was supplied at 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.5 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.2 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters for copolymerization. Propylene was supplied to the polymerization vessel at a rate of 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.1 mol%. Polymerization was performed by supplying ethylene so as to maintain a polymerization temperature of 51 ° C. and a pressure of 2.9 MPa / G.

  After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene random block copolymer (A-3). The resulting propylene random block copolymer (A-3) was vacuum dried at 80 ° C. The properties of the resulting propylene random block copolymer (A-3) are shown in Table 1.

[Production Example 4]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization In a tubular polymerization vessel having an internal volume of 58 liters, propylene is 40 kg / hour, hydrogen is 5 N liters / hour, and the catalyst slurry produced in (3) of Production Example 1 is 3.6 g / hour as a solid catalyst component. Triethylaluminum (2.2 g / hour) was continuously supplied, and polymerization was performed in a full liquid state without a gas phase in the tubular polymerization reactor. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G. The catalyst in this reaction is an M1 catalyst.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 liters, and further polymerized. To the polymerization vessel, propylene was supplied at 45 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.6 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.2 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization apparatus, propylene was supplied at 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.6 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.2 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization apparatus, propylene was supplied at 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.6 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.2 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters for copolymerization. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.11 mol%. Polymerization was performed by supplying ethylene so as to maintain a polymerization temperature of 63 ° C. and a pressure of 2.9 MPa / G.

  After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene random block copolymer (A-4). The resulting propylene random block copolymer (A-4) was vacuum dried at 80 ° C. The properties of the resulting propylene random block copolymer (A-4) are shown in Table 1.

[Production Example 5]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization In a tubular polymerization vessel having an internal volume of 58 liters, propylene is 40 kg / hour, hydrogen is 5 N liters / hour, and the catalyst slurry produced in (3) of Production Example 1 is 2.6 g / hour as a solid catalyst component. 1.6 g / hour of triethylaluminum was continuously supplied, and polymerization was performed in a full liquid state without a gas phase in the tubular polymerizer. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G. The catalyst in this reaction is an M1 catalyst.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 liters, and further polymerized. To the polymerization reactor, propylene was supplied at 45 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase portion was 3.7 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase portion was 0.3 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization reactor, propylene was supplied at 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase portion was 3.7 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase portion was 0.3 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization reactor, propylene was supplied at 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase portion was 3.7 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase portion was 0.3 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters for copolymerization. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.11 mol%. Polymerization was performed by supplying ethylene so as to maintain a polymerization temperature of 61 ° C. and a pressure of 2.9 MPa / G.

  After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene random block copolymer (A-5). The resulting propylene random block copolymer (A-5) was vacuum dried at 80 ° C. The properties of the resulting propylene random block copolymer (A-5) are shown in Table 1.

[Production Example 6]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization In a tubular polymerization vessel having an internal volume of 58 liters, propylene is 40 kg / hour, hydrogen is 5 N liters / hour, and the catalyst slurry produced in (3) of Production Example 1 is 3.6 g / hour as a solid catalyst component. Triethylaluminum (2.2 g / hour) was continuously supplied, and polymerization was performed in a full liquid state without a gas phase in the tubular polymerization reactor. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G. The catalyst in this reaction is an M1 catalyst.

The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 liters, and further polymerized. To the polymerization vessel, propylene was supplied at 45 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.5 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.2 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization apparatus, propylene was supplied at 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.5 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.2 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization apparatus, propylene was supplied at 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.5 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.2 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters for copolymerization. To the polymerization vessel, propylene was supplied at 10 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 0.1 mol%. Polymerization was performed by supplying ethylene so as to maintain a polymerization temperature of 48 ° C. and a pressure of 2.9 MPa / G.

  After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene random block copolymer (A-6). The resulting propylene random block copolymer (A-6) was vacuum dried at 80 ° C. Table 1 shows the properties of the resulting propylene random block copolymer (A-6).

[Production Example 7]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization In a tubular polymerization vessel having an internal volume of 58 liters, propylene is 40 kg / hour, hydrogen is 5 N liters / hour, and the catalyst slurry produced in (3) of Production Example 1 is 2.7 g / hour as a solid catalyst component. 1.6 g / hour of triethylaluminum was continuously supplied, and polymerization was performed in a full liquid state without a gas phase in the tubular polymerizer. The temperature of the tubular reactor was 30 ° C., and the pressure was 3.2 MPa / G. The catalyst in this reaction is an M1 catalyst.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 liters, and further polymerized. To the polymerization vessel, propylene was supplied at 45 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.6 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.4 mol%. Polymerization was performed at a polymerization temperature of 72 ° C. and a pressure of 3.1 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization vessel, propylene was supplied at 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.6 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.4 mol%. Polymerization was performed at a polymerization temperature of 71 ° C. and a pressure of 3.0 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization vessel, propylene was supplied at 10 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase part was 1.6 mol%, and hydrogen was supplied so that the hydrogen concentration in the gas phase part was 0.4 mol%. Polymerization was performed at a polymerization temperature of 70 ° C. and a pressure of 3.0 MPa / G.

The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters for copolymerization. To the polymerization vessel, propylene is 10 kg / hour, hydrogen is in the gas phase with a hydrogen concentration of 0.2.
It supplied so that it might become mol%. Polymerization was performed by supplying ethylene so as to maintain a polymerization temperature of 61 ° C. and a pressure of 2.9 MPa / G.

  After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene random block copolymer (A-7). The resulting propylene random block copolymer (A-7) was vacuum dried at 80 ° C. Table 1 shows the properties of the resulting propylene random block copolymer (A-7).

[Production Example 8]
(1) Preparation of Solid Titanium Catalyst Component 952 g of anhydrous magnesium chloride, 4420 ml of decane and 3906 g of 2-ethylhexyl alcohol were heated at 130 ° C. for 2 hours to obtain a homogeneous solution. To this solution, 213 g of phthalic anhydride was added, and further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride.

  After cooling the homogeneous solution thus obtained to 23 ° C., 750 ml of this homogeneous solution was dropped into 2000 ml of titanium tetrachloride maintained at −20 ° C. over 1 hour. After the dropwise addition, the temperature of the resulting mixture was raised to 110 ° C. over 4 hours. When the temperature reached 110 ° C., 52.2 g of diisobutyl phthalate (DIBP) was added, and the mixture was stirred at the same temperature for 2 hours. Held on. Subsequently, the solid part was collected by hot filtration, and the solid part was resuspended in 2750 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours.

After the heating, the solid part was again collected by hot filtration, and washed with decane and hexane at 110 ° C. until no titanium compound was detected in the washing solution.
The solid titanium catalyst component prepared as described above was stored as a hexane slurry, and a part of the catalyst was dried to examine the catalyst composition. The solid titanium catalyst component contained 2% by weight of titanium, 57% by weight of chlorine, 21% by weight of magnesium and 20% by weight of DIBP.

(2) Preparation of prepolymerization catalyst 56 g of transition metal catalyst component, 8.0 g of triethylaluminum, and 80 liters of heptane were introduced into an autoclave with a stirrer having an internal volume of 200 liters, and the internal temperature was kept at 5 ° C. and 560 g of propylene was inserted for 60 minutes. The reaction was carried out with stirring. After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice. The obtained prepolymerized catalyst was resuspended in purified heptane and prepared by adding heptane so that the transition metal catalyst component concentration was 0.7 g / liter. This prepolymerized catalyst contained 10 g of polypropylene per 1 g of the transition metal catalyst component.

(3) Main polymerization A tubular polymerizer having an internal volume of 58 liters was supplied with 30 kg / hour of propylene, 0.4 kg / hour of ethylene, 300 Nliter / hour of hydrogen, 0.4 g / hour of catalyst slurry as a solid catalyst component, triethylaluminum 2 0.7 g / hour and 1.8 g / hour of dicyclopentyldimethoxysilane were continuously fed, and polymerization was performed in a full liquid state without a gas phase in the tubular polymerizer. The temperature of the annular reactor was 65 ° C., and the pressure was 3.6 MPa / G. The catalyst in this reaction is a ZN catalyst.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 100 liters, and further polymerized. To the polymerization vessel, propylene was supplied at 15 kg / hour, ethylene at 0.3 kg / hour, and hydrogen was supplied so that the hydrogen concentration in the gas phase was 15.0 mol%. Polymerization was performed at a polymerization temperature of 63 ° C. and a pressure of 3.4 MPa / G.

  The obtained slurry was transferred to a sandwiching tube having an internal volume of 2.4 liters, and the slurry was gasified and subjected to gas-solid separation. After that, a polypropylene homopolymer powder was sent to a 480 liter gas phase polymerization vessel, and ethylene / Propylene block copolymerization was performed. Propylene, ethylene, hydrogen so that the gas composition in the gas phase polymerizer is ethylene / (ethylene + propylene) = 0.30 (molar ratio), hydrogen / (ethylene + propylene) = 0.068 (molar ratio). Was fed continuously. Polymerization was conducted at a polymerization temperature of 70 ° C. and a pressure of 1.2 MPa / G to obtain a propylene random block copolymer (A-8).

The resulting propylene random block copolymer (A-8) was vacuum dried at 80 ° C. Table 1 shows the properties of the resulting propylene random block copolymer (A-8).
[Production Example 9]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.

(1) Main polymerization In a tubular polymerization vessel having an internal volume of 58 liters, propylene is 57 kg / hour, hydrogen is 2.5 Nliters / hour, and the catalyst slurry produced in (3) of Production Example 1 is used as a solid catalyst component at 5.0 g / For 2.3 hours, 2.3 g / hour of triethylaluminum was continuously supplied, and polymerization was performed in a full liquid state without a gas phase. The temperature of the tubular reactor was 30 ° C., and the pressure was 2.6 MPa / G. The catalyst in this reaction is an M1 catalyst.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 liters, and further polymerized. To the polymerization reactor, propylene was supplied at 50 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 1.4 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.2 mol%. Polymerization was performed at a polymerization temperature of 60 ° C. and a pressure of 2.5 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization reactor, propylene was supplied at 11 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 1.4 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.2 mol%. Polymerization was performed at a polymerization temperature of 59 ° C. and a pressure of 2.4 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene-ethylene random copolymer (R-1). Obtained propylene-ethylene random copolymer (R-1) at 80 ° C.
And dried in vacuum. The properties of the resulting propylene-ethylene random copolymer (R-1) are shown in Table 1.

[Production Example 10]
The polymerization was carried out in the same manner as in Production Example 1 except that the polymerization method was changed as follows.
(1) Main polymerization In a tubular polymerizer having an internal volume of 58 liters, propylene is 57 kg / hour, hydrogen is 2.5 Nliters / hour, and the catalyst slurry produced in (3) of Production Example 1 is used as a solid catalyst component. For 2.3 hours, 2.3 g / hour of triethylaluminum was continuously supplied, and polymerization was performed in a full liquid state without a gas phase in the tubular polymerizer. The temperature of the tubular reactor was 30 ° C., and the pressure was 2.7 MPa / G. The catalyst in this reaction is an M1 catalyst.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 1000 liters, and further polymerized. To the polymerization reactor, propylene was supplied at 50 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 3.9 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.28 mol%. Polymerization was performed at a polymerization temperature of 60 ° C. and a pressure of 2.6 MPa / G.

  The obtained slurry was sent to a vessel polymerization vessel equipped with a stirrer having an internal volume of 500 liters, and further polymerized. To the polymerization reactor, propylene was supplied at 11 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 3.9 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.28 mol%. Polymerization was performed at a polymerization temperature of 59 ° C. and a pressure of 2.5 MPa / G.

After vaporizing the resulting slurry, gas-solid separation was performed to obtain a propylene-ethylene random copolymer (R-2). Obtained propylene-ethylene random copolymer (R-2) at 80 ° C.
And dried in vacuum. The properties of the resulting propylene-ethylene random copolymer (R-2) are shown in Table 1.

[Production Example 11]
(1) Preparation of Solid Titanium Catalyst Component 952 g of anhydrous magnesium chloride, 4420 ml of n-decane and 3906 g of 2-ethylhexyl alcohol were heated at 130 ° C. for 2 hours to obtain a homogeneous solution. To this solution, 213 g of phthalic anhydride was added, heated to 130 ° C. and stirred for 1 hour to dissolve phthalic anhydride.

  The homogeneous solution thus obtained was cooled to 23 ° C., and then 750 ml of this uniform solvent was dropped into 2000 ml of titanium tetrachloride maintained at −20 ° C. over 1 hour. After the dropwise addition, the temperature of the resulting mixture was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 52.2 g of diisobutyl phthalate (DIBP) was added, and this temperature was maintained and stirred for 2 hours. Continued.

Next, the solid part was collected by hot filtration, and the solid part was resuspended in 2750 ml of titanium tetrachloride, and then heated again at a temperature of 110 ° C. for 2 hours.
After the heating, the solid part was again collected by hot filtration and washed with decane and hexane at 110 ° C. until no titanium compound was detected in the washing solution.

The solid titanium catalyst component prepared as described above was stored as a hexane slurry. A part of the catalyst was dried to examine the catalyst composition.
The solid titanium catalyst component contained 2% by weight of titanium, 57% by weight of chlorine, 21% by weight of magnesium and 20% by weight of DIBP.

(2) Preparation of prepolymerization catalyst 56 g of transition metal catalyst component, 8.0 g of triethylaluminum, and 80 liters of heptane were introduced into an autoclave with a stirrer having an internal volume of 200 liters, and 560 g of propylene was introduced at an internal temperature of 5 ° C. for 60 minutes. The reaction was carried out with stirring. After completion of the polymerization, the solid component was precipitated, and the supernatant was removed and washed with heptane twice.

  The obtained prepolymerization catalyst was resuspended in purified heptane and adjusted by adding heptane so that the transition metal catalyst component concentration was 0.7 g / liter. This polymerization catalyst contained 10 g of polypropylene per 1 g of the transition metal catalyst component.

(3) Main polymerization In a vessel polymerization vessel with an internal volume of 100 liters, 1.1 g / hour of catalyst slurry as a solid catalyst component, 4.5 g / hour of triethylaluminum, and 12.5 g / hour of cyclohexylmethyldimethoxysilane were continuously used. Then, propylene was supplied at 110 kg / hour, ethylene was supplied so that the ethylene concentration in the gas phase was 0.8 mol%, and hydrogen was supplied in the gas phase so that the hydrogen concentration was 0.65 mol%. Polymerization was performed at a polymerization temperature of 65 ° C. and a pressure of 2.7 MPa / G. The catalyst in this reaction is a ZN catalyst.

  The obtained slurry was sent to a vessel polymerizer with a stirrer having an internal volume of 1000 liters, and further polymerization was performed. To the polymerization apparatus, propylene is 18 kg / hour, ethylene is in the gas phase with an ethylene concentration of 3.4 mol%, 1-butene is in the gas phase with 1-butene in a concentration of 2.7 mol%, and hydrogen is in the gas phase. Was supplied so that the hydrogen concentration was 1.8 mol%. Polymerization was performed at a polymerization temperature of 65 ° C. and a pressure of 2.5 MPa / G.

  After vaporizing the obtained slurry, gas-solid separation was performed to obtain a propylene random copolymer (r-1). The resulting propylene random copolymer (r-1) was vacuum dried at 80 ° C. The properties of the resulting propylene random copolymer (r-1) are shown in Table 1.

[Examples 1 to 5]
Irgnox 3114 [Ciba Geigy Co., Ltd.] as a phenol-based antioxidant for a mixture of 70 parts by weight of a propylene random block copolymer of A-1 to A-5 and 30 parts by weight of Alcon P140 [Arakawa Chemical] as petroleum juice. ] 0.1 part by weight, Irgfos 168 [Ciba Geigy Co., Ltd.] 0.06 part by weight as a phosphorus-based antioxidant, 0.06 part by weight calcium stearate as a hydrochloric acid absorbent, and 0.1 part by weight alkanoic acid amide as a slip agent Part, 0.15 part by weight of Silysia 530 [Fujishiri Silysia] as an antiblocking agent was added, and it was melt-kneaded with a 30 mmφ twin screw extruder to obtain pellets. This pellet is melted by an extruder at 230 ° C., and a mixture of a cyclic olefin resin (Appel 8008T Mitsui Chemicals) and an ethylene-α-olefin copolymer (MFR = 4.1, density = 0.920) becomes the surface layer. Extruded in three layers from a T-die, a sheet with a take-off thickness of 0.5 mm was created at a chill roll temperature of 30 ° C. and a take-up speed of 1.0 m / min, and the sheet was cut into a square with a side of 80 mm. Thereafter, uniaxial stretching of MD = 5 was performed using a biaxial stretching machine at a melting temperature of −10 ° C. to obtain a stretched laminated label having a thickness of 18 μm. At this time, the composition ratio of the intermediate layer made of propylene random copolymer or the like and the surface layer made of cyclic olefin resin or the like was 7: 3.

Table 2 shows physical property values of the stretched laminated labels of Examples 1 to 5.
[Comparative Examples 1-4]
A stretched laminated film was obtained by the same method as in Examples 1 to 5, except that A-6, A-8, R-1, and R-2 were used.

Table 2 shows the physical property values of the stretched laminated labels of Comparative Examples 1 to 4.
[Comparative Example 5]
A stretched laminated film was obtained in the same manner as in Examples 1 to 5 except that F232DC [Prime Polymer Co., Ltd., propylene-random copolymer MFR = 2.3 g / 10 min, Tm = 138 ° C.] was used. Table 2 shows each physical property value of such a film.

The shrink label of the present invention is suitably used for beverage bottle labels, cup noodle labels and the like.

Claims (5)

The melt flow rate is in the range of 0.1-100 g / 10 min;
The melting point is in the range of 100-155 ° C,
The portion insoluble in room temperature n-decane satisfying the following (1) to (3) (D _insol ) 90 to 60% by weight and the portion soluble in room temperature n-decane satisfying the following (4) to (6) (D _sol ) 10-40% by weight
A shrink label comprising a propylene random block copolymer (A) composed of:
(1) The molecular weight distribution (Mw / Mn) determined from GPC of D _insol is 1.0 to 3.5.
(2) Content of skeleton derived from ethylene in D _insol is 0.5 to 13 mol%
(3) Sum of propylene 2,1-insertion bond amount and 1,3-insertion bond amount in D _insol is 0.2 mol% or less (4) Molecular weight distribution (Mw / Mn) determined from GPC of D _sol ) Is 1.0 to 3.5
(5) The intrinsic viscosity [η] in 135 ° C. decalin of D _sol is 1.5 to 4 dl / g.
(6) The content of the skeleton derived from ethylene in D _sol is 15 to 35 mol%.   The shrink label according to claim 1, wherein the propylene random block copolymer (A) is polymerized with a metallocene catalyst system. A layer comprising the propylene random block copolymer (A);
A layer made of a mixture (B) of a cyclic olefin-based resin and an ethylene-α-olefin copolymer, wherein the layer made of (B) is at least one surface layer. 2. The shrink label according to 2.   The shrink label according to claim 1, which has a thickness of 30 to 100 μm. A layer comprising the propylene random block copolymer (A);
As needed, the film which has a layer which consists of a mixture (B) of the said cyclic olefin resin and an ethylene-alpha-olefin copolymer is extended | stretched by 3 times or more of surface magnification in a uniaxial direction or a biaxial direction. The shrink label according to claim 1, wherein: