JP2002060566A - Resin composition for heat-shrinkable polypropylene label and film using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition for a heat-shrinkable polypropylene label having improved thermal shrinkability, especially low-temperature shrinkability and a film using the same. SOLUTION: This resin composition for a shrink label comprises 50-95 wt.% of a crystalline propylene-α-olefin random copolymer having specific physical properties and 5-50 wt.% of a specific alicyclic hydrocarbon resin. This film is obtained by using the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for heat-shrinkable polypropylene shrink label and a film using the same, and more particularly, to a heat-shrinkable polypropylene shrink having improved heat shrinkage, especially low-temperature shrinkage. The present invention relates to a label resin composition and a film using the same.

[0002]

2. Description of the Related Art In recent years, the purpose of packaging articles is to improve the appearance, to prevent the contents from being directly impacted, to tightly package them, to protect glass bottles or plastic bottles, and to label products that combine the display of goods. Shrink labels are widely used. As plastic materials used for these purposes, polyvinyl chloride, polystyrene, polyethylene terephthalate, polypropylene and the like are known. However, although the polyvinyl chloride label has excellent shrink properties, it has a problem of environmental pollution such as generation of chlorine gas at the time of incineration. Further, polystyrene and polyethylene terephthalate labels have good heat shrinkage but have a small difference in specific gravity from polyethylene terephthalate bottles, so that they are difficult to float and separate, and hinder the recycling of polyethylene terephthalate bottles. Furthermore, in order to obtain sufficient heat shrinkage, a resin having poor heat resistance is used, and there is a problem that when retort sterilization is performed, a printing ink flow is caused by a molten resin. Polypropylene has a large difference in specific gravity from a polyethylene terephthalate bottle, is easy to float and separate, and is excellent in heat resistance, but insufficient in low-temperature shrinkage. In order to improve low-temperature shrinkability, a method of adding a propylene-butene-1 copolymer to polypropylene and a method of adding a petroleum resin or a terpene resin (Japanese Patent Application Laid-Open No.
No. 62846) is known, but the effect is still insufficient, and further improvement in shrinkage performance of a polypropylene resin as a base is desired.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polypropylene resin composition having improved heat shrinkage, especially low temperature shrinkage under such circumstances, and a heat shrinkable shrink label film using the same. To provide.

[0004]

The present inventors have conducted various studies to solve the above-mentioned problems, and as a result, have found that a specific crystalline propylene-α-olefin random copolymer and a specific alicyclic carbon By using a resin composition containing a hydrogen resin in a specific ratio, it has been found that a heat-shrinkable polypropylene shrink label film having improved low-temperature shrinkability can be obtained, and the present invention has been completed. .

That is, according to the first aspect of the present invention,
50 to 95% by weight of a crystalline propylene-α-olefin random copolymer mainly composed of propylene satisfying the following characteristics to characteristics, and 5 to 50% by weight of an alicyclic hydrocarbon resin having a softening point of 110 ° C. or more. % Heat-shrinkable polypropylene-based shrink label resin composition. Characteristics: melt flow rate (230 ° C, 2.16 kg
Load) is 0.5 to 10 g / 10 min. Characteristics: Main melting peak temperature (Tp) determined by a differential scanning calorimeter (DSC) is in the range of 100 to 140 ° C. Characteristics: T ₅₀ ≦ 125 ° C. (where T ₅₀ is the temperature at which the total heat of fusion of the polypropylene resin composition determined by DSC is ΔHm and the heat of fusion calculated from the low temperature side is 50% of ΔHm) (° C).)

According to a second aspect of the present invention, the resin composition for a heat-shrinkable polypropylene shrink label as described above, wherein the crystalline propylene-α-olefin random copolymer is a propylene-ethylene random copolymer. Things are provided.

According to a third aspect of the present invention, there is provided a resin for a heat-shrinkable polypropylene shrink label as described above, which is a copolymer obtained by polymerizing a crystalline propylene-α-olefin random copolymer with a metallocene catalyst. A composition is provided.

Further, according to a fourth aspect of the present invention, the above resin composition is used to form at least two axes in at least one axial direction.
A heat-shrinkable polypropylene-based shrink label film stretched at least twice is provided.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition for heat-shrinkable polypropylene shrink label of the present invention and a film using the same will be described in detail below.

[I] Resin composition Crystalline propylene-α-olefin random copolymer (1) Characteristics: melt flow rate (hereinafter abbreviated as MFR) The MFR of the crystalline propylene-α-olefin random copolymer used in the present invention (230 ° C, 2. 16kg load)
Is 0.5 to 10 g / 10 min, preferably 1.0 to 10 g
g / 10 minutes. If the MFR is less than 0.5 g / 10 minutes, the extrusion characteristics may be deteriorated and the productivity may be reduced. On the other hand, if the MFR is more than 10 g / 10 minutes, the shrinkage characteristics may be deteriorated or the thickness may be uneven.

(2) Characteristics: Main melting peak temperature (Tp) determined by DSC The main melting peak temperature (Tp) determined by DSC of the crystalline propylene-α-olefin random copolymer used in the present invention is 100 to 100%. 140 ° C, preferably 100-1
The temperature is 30 ° C, more preferably 100 to 125 ° C. When the melting peak temperature (Tp) is less than 100 ° C., the unstretched sheet is difficult to be solidified by cooling, and film forming becomes difficult. On the other hand, when it exceeds 140 ° C., the shrinkage properties become insufficient.

(3) Characteristics: Relation between heat of fusion and temperature The crystalline propylene-α-olefin random copolymer used in the present invention needs to satisfy the following formula. T ₅₀ ≦ 125 ° C. (where T ₅₀ is the temperature (° C.) when the total heat of fusion of the polypropylene resin composition determined by DSC is ΔHm, and the heat of fusion calculated from the low temperature side is 50% of ΔHm. ).)

The T ₅₀ is 125 ° C. or less, preferably 12 ° C.
The temperature is 0 ° C or lower, more preferably 115 ° C or lower. T
_{If 50} exceeds 125 ° C., the shrinkage properties deteriorate.

(4) Constituent components of the crystalline propylene-α-olefin random copolymer The α-olefin which is randomly copolymerized with propylene of the crystalline propylene-α-olefin random copolymer used in the present invention.
Examples of the olefin include ethylene or an α-olefin having 4 to 20 carbon atoms, and it is preferable to use ethylene, butene-1, hexene-1, octene-1, and the like,
The crystalline propylene-α of the present invention is particularly preferably ethylene.
-Olefin random copolymer is not limited as long as it satisfies the above-mentioned properties-properties, usually α- olefin content in the random copolymer is 2.0 to 30
% By weight, and particularly when the α-olefin is ethylene, about 2.0 to 10% by weight, preferably 2.0% by weight.
It is about 6.0% by weight. Moreover, as long as it is a crystalline propylene-α-olefin random copolymer satisfying the above characteristics to characteristics, two or more kinds may be used in combination.

(5) Method for producing crystalline propylene-α-olefin random copolymer The crystalline propylene-α-olefin random copolymer used in the present invention is preferably polymerized using a metallocene catalyst. The following catalyst component (A), component (B),
And optionally propylene and ethylene or 4-2 carbon atoms in the presence of a metallocene catalyst comprising component (C).
Those produced by random copolymerization with 0 α-olefin are preferred.

[0016] (a) a metallocene catalyst component ^{_{(A) Q (C 5 H}} 4-a R 1 a) (C 5 H 4-b R 2 b) Me
XY ^{_{(where, C 5 H 4-a R}} 1 a and _C 5 _{H 4-b} ^{R 2}
_b represents a conjugated five-membered ring ligand, and Q represents a binding group bridging two conjugated five-membered ring ligands, and has 1 carbon atom.
A divalent hydrocarbon group having a hydrocarbon group of 1 to 20; a silylene group having a hydrocarbon group having 1 to 20 carbon atoms; or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms; Me represents zirconium or hafnium; Y is independently hydrogen, halogen, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylamide group having 1 to 20 carbon atoms, a trifluoromethanesulfonic acid group, And represents a phosphorus-containing hydrocarbon group having from 20 to 20 or a silicon-containing hydrocarbon group having from 1 to 20 carbon atoms. R ¹ and R ² are substituents on the conjugated five-membered ring ligand, and each is independently
It represents a hydrocarbon group having 1 to 20 carbon atoms, a halogen, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group. Two adjacent R ¹ or two R ² may be bonded to each other to form a ring. a and b are 0 ≦ a ≦ 4, 0
It is an integer satisfying ≦ b ≦ 4. Where R ¹ and R
^{The two} five-membered ligands with 2 are asymmetric with respect to the plane containing Me in terms of their relative position via the group Q. )

Q is, as described above, two conjugated five-membered rings.
Ligand C₅H_4-aR¹ _aAnd C ₅H_4-bR² _bTo
A crosslinkable bonding group, specifically, for example, (a)
Divalent hydrocarbon having 1 to 20, preferably 1 to 6 carbon atoms
Group, specifically, for example, an alkylene group, cycloalkylene
Groups, arylene, etc., (b) having 1 to 20 carbon atoms, preferably
Is a silylene group having 1 to 12 hydrocarbon groups;
Having a hydrocarbon group having a prime number of 1 to 20, preferably 1 to 12
There are germylene groups. Both bonds of the divalent Q group
Q is a chain regardless of the number of carbon atoms.
In the case of the shape, it is about 4 atoms or less, especially 3 atoms or less.
When Q has a cyclic group,
Group + about 2 atoms or less, especially the cyclic group only
Are each preferred. Therefore, in the case of alkylene
Is ethylene and isopropylidene (the distance between the bonds is
2 and 1 atom) are cycloalkylene groups
Cyclohexylene (the distance between bonds is cyclohexylene
Group only) is alkylsilylene, dimethylsilylene
Len (each atom is 1 atom) is preferred
No.

Me is zirconium or hafnium.

X and Y may be each independently, that is, they may be the same or different; (a) hydrogen, (b) halogen (fluorine, chlorine, bromine or iodine, preferably chlorine), (c) carbon number 1 A hydrocarbon group having 1 to 20 carbon atoms, (d) an alkoxy group having 1 to 20 carbon atoms, (e) an alkylamide group having 1 to 20 carbon atoms, (f) a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, (g) It represents a silicon-containing hydrocarbon group having 1 to 20 carbon atoms or a (thi) trifluoromethanesulfonic acid group.

R¹And R²Is on the conjugated five-membered ligand
Substituents, each independently having 1 to 20 carbon atoms
Hydrocarbon group, halogen, alkoxy having 1 to 20 carbon atoms
Group, silicon-containing hydrocarbon group having 3 to 20 carbon atoms, 2 carbon atoms
To 20 phosphorus-containing hydrocarbon groups and 2 to 20 carbon atoms containing nitrogen.
A hydrocarbon group or a boron-containing hydrocarbon having 2 to 20 carbon atoms
Represents an elementary group. In addition, two adjacent R¹Two or two
R²Are bonded to each other at the ω-
A ring may be formed together with a part of the enyl group. That's it
A typical example of such a case is that on the cyclopentadienyl group
Two adjacent R ¹(Or R²) Is the cyclopen
Form a fused six-membered ring by sharing the double bond of the tadienyl group
(Ie, indenyl and fluorenyl)
Group) and those forming a fused seven-membered ring (ie,
Zurenyl group).

A and b are integers satisfying 0 ≦ a ≦ 4 and 0 ≦ b ≦ 4.

Non-limiting examples of the above metallocene compounds include the following. In addition, these compounds are indicated by only chemical names, but needless to say, the three-dimensional structure has the asymmetry referred to in the present invention.

(A1) a transition metal compound having two silylene-bridged five-membered ring ligands, for example, (1) dimethylsilylenebis (1-indenyl) zirconium dichloride;
(2) dimethylsilylenebis {1- (4,5,6,7-
Tetrahydroindenyl) zirconium dichloride,
(3) dimethylsilylenebis {1- (2,4-dimethylindenyl)} zirconium dichloride, (4) dimethylsilylenebis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, (5) dimethyl Silylene bis {1- (2-methyl-4-phenyl-4H-)
Azulenyl) {zirconium dichloride, (6) dimethylsilylenebis} 1- (2-methyl-4-phenyl-4)
H-5,6,7,8-tetrahydroazulenyl) {zirconium dichloride, (7) dimethylsilylenebis} 1
-(2-methyl-4- (4-chlorophenyl) -4H-
Azulenyl) {zirconium dichloride, (8) dimethylsilylenebis {1- (2-methyl-4- (4-chlorophenyl) -4H-5,6,7,8-tetrahydroazulenyl)} zirconium dichloride, (9) dimethyl Silylenebis {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride, (10) dimethylsilylenebis [1- {2-methyl-4- (1-naphthyl)]
Indenyl}] zirconium dichloride, (11) dimethylsilylene bis [1- {2-methyl-4- (1-naphthyl) -4H-azulenyl}] zirconium dichloride, (12) dimethylsilylenebis [1- {2-methyl- 4- (1-naphthyl) -4H-5,6,7,8-tetrahydroazulenyl}] zirconium dichloride, (1
3) methylphenylsilylenebis (1-indenyl) zirconium dichloride, (14) methylphenylsilylenebis {1- (4,5,6,7-tetrahydroindenyl)} zirconium dichloride, (15) methylphenylsilylenebis} 1 -(2,4-dimethylindenyl) zirconium dichloride, (16) methylphenylsilylene bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, (17) methylphenylsilylene bis} 1- ( 2-methyl-4-phenyl-4H-azulenyl) zirconium dichloride, (1
8) Methylphenylsilylenebis {1- (2-methyl-)
4-phenyl-4H-5,6,7,8, -tetrahydroazulenyl) {zirconium dichloride, (19) methylphenylsilylenebis} 1- (2-methyl-4,5-
Benzoindenyl) zirconium dichloride, (2
0) methylphenylsilylenebis [1- {2-methyl-
4- (1-naphthyl) indenyl}] zirconium dichloride, (21) methylphenylsilylenebis [1-
{2-Methyl-4- (1-naphthyl) -4H-azulenyl}] zirconium dichloride, (22) methylphenylsilylenebis [1- {2-methyl-4- (1-naphthyl) -4H-5,6, 7,8-tetrahydroazulenyl}] zirconium dichloride, (23) dimethylsilylenebis {1- (2-methyl-4,5-benzoindenyl)} zirconiumdimethyl, (24) dimethylsilylenebis {1- (2- Methyl-4,5-benzoindenyl) zirconium methyl chloride, (25) dimethylsilylene bis {1- (2-methyl-4-phenylindenyl)} zirconium dimethyl, (26) dimethylsilylene bis} 1- (2 -Methyl-4-phenyl-4H-azulenyl) {zirconium dimethyl, (27) dimethylsilylenebis} 1- ( - methyl-4-phenyl indenyl)} zirconium chloro dimethylamide, (28)
Dimethylsilylenebis {1- (2-ethyl-4,5-benzoindenyl)} zirconium dichloride, (29)
(30) Dimethylsilylenebis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, (30) Dimethylsilylenebis {1- (2-ethyl-4-phenyl-4H-azulenyl)} zirconium dichloride, (3
1) dimethylsilylenebis {1- (2-ethyl-4-phenyl-4H-5,6,7,8-tetrahydroazulenyl)} zirconium dichloride, (32) dimethylsilylenebis {1- (2-ethyl-4) -(Chlorophenyl)
-4H-azulenyl) zirconium dichloride, (3
3) dimethylsilylenebis {1- (2-ethyl-4-)
(4-chlorophenyl) -4H-5,6,7,8-tetrahydroazulenyl) zirconium dichloride, (3
4) Dimethylsilylene {1- (2-ethyl-4-phenylindenyl)} 1- (2,3,5-trimethylcyclopentadienyl)} zirconium dichloride, (3
5) Dimethylsilylene {1- (2-ethyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)}
{1- (2,3,5-trimethylcyclopentadienyl)} zirconium dichloride, (36) dimethylsilylenebis} 1- (2-methyl-4,4-dimethyl-sila-4,5,6,7- Tetrahydroindenyl) {zirconium dichloride, (37) dimethylsilylenebis} 1
-(2-ethyl-4-phenylindenyl) zirconium bis (trifluoromethanesulfonic acid), (38)
Dimethylsilylenebis {1- (2-ethyl-4-phenylazulenyl)} zirconiumbis (trifluoromethanesulfonic acid), (39) dimethylsilylenebis {1-
(2-ethyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl) {zirconium bis (trifluoromethanesulfonic acid), (40) dimethylsilylenebis} 1- (2-ethyl-4- (Pentafluorophenyl) indenyl) zirconium dichloride, (41)
Dimethylsilylenebis {1- (2-ethyl-4-phenyl-7-fluoroindenyl)} zirconium dichloride, (42) dimethylsilylenebis {1- (2-ethyl-4-indolylindenyl)} zirconium dichloride, (43) Dimethylsilylene bis {1- (2-dimethylborano-4-indolylindenyl)} zirconium dichloride.

(A2) Transition metal compounds having two 5-membered ring ligands bridged by an alkylene group, for example, (1) ethylene-1,2-bis (1-indenyl) zirconium dichloride, (2) ethylene-1 , 2-bis @ 1- (4,
(5,6,7-tetrahydroindenyl)} zirconium dichloride, (3) ethylene-1,2-bis {1-
(2,4-dimethylindenyl) {zirconium dichloride, (4) ethylene-1,2-bis} 1- (2,4-
Dimethyl-4H-azulenyl) {zirconium dichloride, (5) ethylene-1,2-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, (6) ethylene-1,2-bis} 1 -(2-methyl-4-phenyl-4H-azulenyl) {zirconium dichloride, (7) ethylene-1,2-bis} 1- (2-
Methyl-8,5-benzoindenyl) zirconium dichloride, (8) ethylene-1,2-bis [1- {2-
Methyl-4- (1-naphthyl) indenyl}] zirconium dichloride, (9) ethylene-1,2-bis [1-
{2-methyl-4- (1-naphthyl) -4H-azulenyl}] zirconium dichloride, (10) ethylene-
1,2-bis [1- {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium dichloride and the like.

(A3) A transition metal compound having a five-membered ring ligand bridged by a hydrocarbon residue containing germanium, aluminum, boron, phosphorus or nitrogen, such as (1) dimethylgermylenebis (1-indenyl) zirconium Dichloride, (2) dimethylgermylene bis {1- (2
-Methyl-4-phenylindenyl) {zirconium dichloride, (3) dimethylgermylene bis} 1- (2-
Methyl-4-phenyl-4H-azulenyl) {zirconium dichloride, (4) dimethylgermylene bis} 1-
(2-methyl-4- (4-chlorophenyl) -4H-azulenyl)｝ zirconium dichloride, (5) dimethylgermylene bis ｛1- (2-methyl-4,5-benzoindenyl)｝ zirconium dichloride, (6 ) Methylaluminum bis (1-indenyl) zirconium dichloride, (7) phenylphosphinobis (1-indenyl) zirconium dichloride, (8) ethylholanobis (1-indenyl) zirconium dichloride, (9) phenylaminobis (1-indenyl) Zirconium dichloride and the like can be mentioned.

Among these complexes, particularly preferred are complexes having an azulene skeleton.

Component (B) As the component (B), an ion-exchange layered silicate is used. The ion-exchange layered silicate is a silicate compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak bonding force to each other, and include those that can be ion-exchanged. Most ion-exchanged phyllosilicates occur naturally mainly as a main component of clay minerals, but these ion-exchanged phyllosilicates are not limited to those of natural origin but are artificially synthesized. You may. Specific examples of the ion-exchangeable layered silicate include known layered silicates described in, for example, "Clay Mineralogy" written by Haruo Shimizu, Asakura Shoten (1995), and include dickite, nacrite, kaolinite, and the like. Kaolins such as anoxite, metahaloysite, halloysite, serpentine such as chrysotile, lizardite, antigolite, montmorillonite, zauconite, beidellite, nontronite,
Smectites such as saponite, hectorite, and stevensite, vermiculites such as vermiculite, mica, illite, sericite, mica such as chlorite,
Attapulgite, sepiolite, palygorskite,
Bentonite, pyrophyllite, talc, and chlorites. These may form a mixed layer.

Among these, montmorillonite, zauconite, beidellite, nontronite, saponite,
Smectites such as hectorite, stevensite, bentonite and teniolite, vermiculites and mica are preferred. When a compound having a radius of 20 angstroms or more measured by a mercury intrusion method and having a pore volume of less than 0.1 cc / g is used as the component (B), a high polymerization activity tends to be hardly obtained. 0.1 cc / g or more, particularly preferably 0.3 to 5 cc / g. Further, the component (B) can be used without any particular treatment, but it is also preferable to subject the component (B) to a chemical treatment. Here, the chemical treatment can be any of a surface treatment for removing impurities adhering to the surface and a treatment that affects the structure of the clay.

Specific examples include acid treatment, alkali treatment, salt treatment, and organic substance treatment. The acid treatment increases the surface area by removing impurities on the surface and 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 salt treatment and organic matter treatment,
An ion complex, a molecular complex, an organic derivative, or the like can be formed to change a surface area or an interlayer distance. By utilizing the ion exchange property and replacing the exchangeable ions between the layers with another large bulky ion, it is also possible to obtain a layered material in which the layers are expanded. That is, the bulky ions play a pillar-like role to support the layered structure, and are called pillars. Introducing another substance between layered substance layers is called intercalation.

Examples of the guest compound to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , Ti (OR) ₄ , Zr (OR) ₄ and PO (OR).
₃ , metal alcoholates such as B (OR) ₃ (R is alkyl, aryl, etc.), [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ ,
[Zr ₄ (OH) ₁₄ ] ²⁺ , [Fe ₃ O (OCOCH
₃ ) ₆ ] ^{+ and the} like. These compounds may be used alone or in combination of two or more. When intercalating these compounds, Si (OR) ₄ , Al (OR) ₃ , G
A polymer obtained by hydrolyzing a metal alcoholate such as e (OR) _4, a colloidal inorganic compound such as SiO _{2, and the} like can also coexist. Examples of pillars include oxides formed by intercalating the hydroxide ions between layers and then heating and dehydrating. Component (B) may be used as it is, or may be used after heat dehydration treatment. Further, even when used alone, the solid 2
Mixtures of more than one species may be used.

The ion-exchangeable phyllosilicate used in the present invention is preferably at least 40% of the exchangeable Group 1 metal cation contained in the ion-exchange phyllosilicate before being treated with salts, preferably Preferably, 60% or more is ion-exchanged with a cation dissociated from the following salts. The salt used in the salt treatment for the purpose of ion exchange is a compound containing a cation containing at least one atom selected from the group consisting of Group 2 to 14 atoms, preferably 2 to 14 A cation containing at least one atom selected from the group consisting of group atoms, a halogen atom, a compound consisting of at least one anion selected from the group consisting of inorganic acids and organic acids, more preferably, A cation containing at least one atom selected from the group consisting of Group 2 to 14 atoms, Cl, Br,
I, F, PO ₄ , SO ₄ , NO ₃ , CO ₃ , C ₂ O ₄ ,
OCOCH ₃ , CH ₃ COCHCOCH ₃ , OCl ₃ ,
O (NO ₃ ) ₂ , O (ClO ₄ ) ₂ , O (SO ₄ ), O
H, O ₂ Cl ₂ , OCl ₃ , OCOH, OCOCH ₂ C
It is a compound comprising at least one anion selected from the group consisting of H ₃ , C ₂ H ₄ O ₄ and C ₆ H ₅ O ₇ .

Specifically, CaCl₂, CaSO₄, C
aC₂O₄, Ca (NO₃)₂, Ca₃(C₆H
₅O₇)₂, MgCl₂, MgBr₂, MgSO₄, M
g (PO₄)₂, Mg (ClO₄)₂, MgC₂O₄,
Mg (NO₃)₂, Mg (OCOCH₃)₂, MgC₄
H₄O₄, Sc (OCOCH₃)₂, Sc₂(CO₃)
₃, Sc₂(C₂O₄)₃, Sc (NO₃)₃, Sc₂
(SO₄)₃, ScF₃, ScCl₃, ScBr₃, S
cI₃, Y (OCOCH₃)₃, Y (CH₃COCHC
OCH₃)₃, Y₂(CO₃)₃, Y₂(C
₂O₄)₃, Y (NO₃)₃, Y (ClO₄)₃, YP
O₄, Y₂(SO₄)₃, YF₃, YCl₃, La (O
OCH₃)₃, La (CH₃COCHCOCH₃)₃,
La₂(CO₃)₃, La (NO₃)₃, La (ClO
₄)₃, La₂(C₂O₄)₃, LaPO₄, La
₂(SO₄)₃, LaF₃, LaCl₃, LaBr
₃ , LaI₃, Sm (OCOCH₃)₃, Sm (CH
₃COCHCOCH₃)₃, Sm₂(CO₃)₃, Sm
(NO₃)₃, Sm (ClCO₄)₃, Sm₂(C₂O
₄)₃, SmPO₄, Sm₂(SO₄)₃, SmF₃,
SmCl₃, SmBr₃, SmI₃, Yb (OCOCH
₃)₃, Yb (NO₃)₃, Yb (ClO₄)₃, Yb
(C₂O₄)₃, Yb (SO₄)₃, YbF₃, YbC
l₃, Ti (OCOCH₃)₄, Ti (CO₃)₂, T
i (NO₃)₄, Ti (SO₄)₂, TiF₄, TiC
l₄, TiBr₄, TiI₄, Zr (OCOC
H₃)₄, Zr (CO₃)₂, Zr (NO ₃)₄, Zr
(SO₄)₂, ZrF₄, ZrCl₄, ZrBr₄, Z
rI₄, ZrOCl₂, ZrO (NO₃)₂, ZrO
(ClO₄)₂, ZrO (SO₄), Hf (OCOCH
₃)₄, Hf (CO₃)₂, Hf (NO₃)₄, Hf
(SO₄)₂, HfOCl₂, HfF₄, HfCl₄,
HfBr₄, HfI₄, V (CH ₃COCHCOC
H₃)₃, VOSO₄, VOCl₃, VCl₃, VCl
₄, VBr₃, Nb (CH₃COCHCOCH₃)₅,
Nb₂(CO₃)₅, Nb (NO₃)₅, Nb₂(SO
₄)₅, ZrF₅, ZrCl₅, NbBr₅, Nb
l₅, Ta (OCOCH₃)₅, Ta₂(CO3)₅,
Ta (NO)₅, Ta₂(SO₄)₅, TaF₅, Ta
Cl₅, TaBr₅, TaI₅, Cr (OOCH₃) ₂
OH, Cr (CH₃COCHCOCH₃)₃, Cr (N
O₃)₃, Cr (ClO₄)₃, CrPO₄, Cr
₂(SO₄)₃, CrO₂Cl₂, CrF₃, CrCl
₃, CrBr₃, CrI₃, MoOCl₄, MoC
l₃, MoCl₄, MoCl₅, MoF₆, MoI₂,
WCl₄, WCl₆, WF₆, WBr₅, Mn (OOC
H₃)₂, Mn (CH₃COCHCOCH₃)₂, Mn
CO₃, Mn (NO₃)₂, MnO, Mn (ClO₄)
₂, MnF₂, MnCl₂, MnBr₂, MnI₂, F
e (OCOCH₃)₂, Fe (CH₃COCHCOCH
₃)₃, FeCO₃, Fe (NO₃)₃, Fe (ClO
₄)₃, FePO₄, FeSO₄, Fe₂(S
O₄)₃, FeF₃, FeCl₃, FeBr₃, FeI
₂, FeC₆H₅O₇, Co (OCOCH₃)₂, Co
(CH₃COCHCOCH₃)₃, CoCO₃, Co
(NO₃)₂, CoC₂O₄, Co (ClO₄)₂, C
o₃(PO₄)₂, CoSO₄, CoF₂, CoC
l₂, CoBr₂, CoI₂, NiCO₃, Ni (NO
₃)₂, NiC₂O₄, Ni (ClO₄)₂, NiSO
₄, NiCl₂, NiBr₂, Pb (OCOC
H₃)₄, Pb (OOCH₃)₂, PbCO₃, Pb
(NO₃)₂, PbSO₄, PbHPO₄, Pb (Cl
O₄)₂, PbF₂, PbCl₂, PbBr₂, PbI
₂, CuI₂, CuBr₂, Cu (NO₃)₂, CuC
₂O₄, Cu (ClO₄)₂, CuSO₄, Cu (OC
OCH₃)₂, Zn (OOCH₃)₂, Zn (CH₃C
OCHCOCH₃)₂, ZnCO₃, Zn (N
O₃)₂, Zn (ClO₄)₂, Zn₃(PO₄)₂,
ZnSO₄, ZnF₂, ZnCl₂, ZnBr₂, Zn
I₂, Cd (OCOCH₃)₂, Cd (CH₃COCH
COCH₃)₂, Cd (OCOCH₂CH₃)₂, Cd
(NO₃)₂, Cd (ClO₄)₂, CdSO₄, Cd
F₂, CdCl₂, CdBr₂, CdI₂, AlF₃,
AlCl₃, AlBr₃, AlI₃, Al₂(SO₄)
₃, Al₂(C₂O₄)₃, Al (CH₃COCHCO
CH₃)₃, Al (NO₃)₃, AlPO₄, GeCl
₄, GeBr₄, GeI₄, Sn (OCOCH₃)₄,
Sn (SO₄)₂, SnF₄, SnCl₄, SnB
r₄, SnI₄And the like. Acid treatment is a surface impurity
Cations such as Al, Fe, Mg etc.
Can be partially or entirely eluted.

The acid used in the acid treatment is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, phosphoric acid and acetic acid. The salt and the acid used for the treatment may be two or more. When the salt treatment and the acid treatment are combined, there are a method of performing the salt treatment and then performing the acid treatment, a method of performing the acid treatment and then performing the salt treatment, and a method of simultaneously performing the salt treatment and the acid treatment.

The treatment conditions with salts and acids are not particularly limited, but usually, the concentration of salts and acids is 0.1 to 3
0% by weight, treatment temperature from room temperature to boiling point, treatment time from 5 minutes to
It is preferable to select the condition for 24 hours and to elute at least a part of at least one compound contained in the ion-exchange layered silicate. Further, salts and acids are generally used in an aqueous solution.

In the present invention, the above-mentioned salt treatment and / or acid treatment is preferably performed, but shape control may be performed by pulverization or granulation before, during, or after the treatment. Further, a chemical treatment such as an alkali treatment or an organic substance treatment may be used in combination.
These ion-exchange layered silicates usually contain adsorbed water and interlayer water. In the present invention, it is preferable to remove these adsorbed water and interlayer water to use as component (B).

Here, the adsorbed water is water adsorbed on the surface of the ion-exchanged layered silicate compound particles or the crystal fracture surface, and the interlayer water is water existing between the crystal layers. In the present invention, these adsorbed water and / or interlayer water can be removed by heat treatment before use. The method for heat treatment of the adsorbed water and interlayer water of the ion-exchanged layered silicate is not particularly limited, and methods such as heat dehydration, heat dehydration under gas flow, heat dehydration under reduced pressure, and azeotropic dehydration with an organic solvent are used. Can be The temperature at the time of heating cannot be specified unconditionally because it depends on the types of ion-exchanged layered silicate and interlayer ions. However, the temperature is 100 ° C. or higher, preferably 150 ° C. or higher, so that interlayer water does not remain. Temperature conditions (for example, 800 ° C. or more, depending on the heating time)
Not preferred. Further, a heat dehydration method for forming a crosslinked structure such as heating under air flow is not preferable because the polymerization activity of the catalyst is reduced. The heating time is at least 0.5 hour, preferably at least 1 hour. At this time, the water content of the component (B) after the removal was 200 ° C. at a pressure of 1 mmHg.
0% by weight when dehydrated for 2 hours
It is preferably 3% by weight or less, more preferably 1% by weight or less.

As described above, in the present invention, particularly preferred as the component (B) is a salt treatment and / or
Or, the water content obtained by performing the acid treatment is 1% by weight.
The following are ion-exchangeable layered silicates. As the component (B), it is preferable to use spherical particles having an average particle diameter of 5 μm or more. More preferably, spherical particles having an average particle size of 10 μm or more are used. More preferably, the average particle size is 10
Spherical particles having a size of not less than μm and not more than 100 μm are used. The average particle size referred to here is an optical microscope photograph of the particles (100 times magnification).
Is represented by a number average particle diameter calculated by image processing. As the component (B), a natural product or a commercially available product may be used as it is as long as the shape of the particle is spherical, or a component in which the shape and particle size of the particle are controlled by particle size, size distribution, fractionation, or the like may be used. You may.

The granulation method used here includes, for example, stirring granulation, spray granulation, tumbling granulation, briquetting, compacting, extrusion granulation, fluidized bed granulation, and emulsion granulation. And an in-liquid granulation method and a compression molding granulation method, but are not particularly limited as long as the method can granulate the component (B). The granulation method is preferably a stirring granulation method, a spray granulation method, a tumbling granulation method, or a fluidized bed granulation method, and particularly preferably a stirring granulation method or a spray granulation method. When the spray granulation is performed, water or an organic solvent such as methanol, ethanol, chloroform, methylene chloride, pentane, hexane, heptane, toluene, and xylene is used as a dispersion medium of the raw material slurry. Preferably, water is used as the dispersion medium. The concentration of the raw material slurry liquid component (B) in the spray granulation for obtaining spherical particles is 0.1 to 70%, preferably 1 to 70%.
-50%, particularly preferably 5-30%. The inlet temperature of the hot air in the spray granulation for obtaining spherical particles varies depending on the dispersion medium, but is 80 to 260 ° C, preferably 100 to 220 ° C in the case of water.

At the time of granulation, an organic substance, an inorganic solvent, an inorganic salt and various binders may be used. Examples of the binder used include sugar, dextrose, corn syrup, gelatin, glue, carboxymethylcellulose, polyvinyl alcohol, water glass, magnesium chloride, aluminum sulfate, aluminum chloride, magnesium sulfate, alcohols, glycol, starch, casein,
Latex, polyethylene glycol, polyethylene oxide, tar, pitch, alumina sol, silica gel,
Gum arabic, sodium alginate and the like can be mentioned.

The spherical particles obtained as described above preferably have a compressive breaking strength of 0.2 MPa or more in order to suppress crushing and fine powder in the polymerization step. In the case of such a particle strength, the effect of improving the particle properties is effectively exhibited, particularly when prepolymerization is performed.

Component (C) Component (C) is an organoaluminum compound. Organic aluminum compounds used as component (C) in the present invention, the compound represented by formula ^{_{(AlR 4 n X 3-n}} ) m is appropriate. In the present invention, it goes without saying that the compounds represented by this formula can be used alone, in combination of two or more kinds or in combination. This use is possible not only at the time of catalyst preparation but also at the time of prepolymerization or polymerization. In this formula, R ⁴ represents a hydrocarbon group having 1 to 20 carbon atoms, and X represents a halogen, hydrogen, an alkoxy group, or an amino group. n is an integer of 1-3 and m is an integer of 1-2. R ⁴ is preferably an alkyl group, and X is chlorine when it is halogen, and has 1 carbon atom when it is an alkoxy group.
When the alkoxy group of 8 to 8 is an amino group, it has 1 to 1 carbon atoms.
Eight amino groups are preferred. Accordingly, specific examples of preferred compounds include trimethylaluminum, triethylaluminum, trinormal propyl aluminum, trinormal butyl aluminum, triisobutyl aluminum, trinormal hexyl aluminum, trinormal octyl aluminum, trinormal decyl aluminum, diethyl aluminum chloride, diethyl aluminum chloride, and diethyl aluminum. Aluminum sesquichloride, diethylaluminum hydride, diethylaluminum ethoxide, diethylaluminum dimethylamide, diisobutylaluminum hydride, diisobutylaluminum chloride and the like can be mentioned. Of these, preferred compounds are m
= 1 and n = 3 are trialkylaluminum and dialkylaluminum hydrides. A more preferred compound is a trialkylaluminum in which R ⁴ has 1 to 8 carbon atoms.

Formation of Catalyst The catalyst used for producing the crystalline propylene-α-olefin random copolymer of the present invention includes the components (A) and (B) described above, and the components used if necessary. It can be prepared by contacting the catalyst comprising (C) in a polymerization vessel or outside the polymerization vessel in the presence or absence of a monomer to be polymerized. Also,
The catalyst may be one obtained by performing prepolymerization in the presence of an olefin. As the olefin used for the prepolymerization, propylene, ethylene, 1-butene, 3-methylbutene-1, styrene, divinylbenzene and the like are used, but a mixture of these with other olefins may be used. Component (A) used in the preparation of the catalyst,
The amounts of component (B) and component (C) can be used in any ratio.

(B) Polymerization The polymerization of the crystalline propylene-α-olefin random copolymer used in the present invention is carried out by using a catalyst comprising component (A), component (B) and, if necessary, component (C). It is carried out by mixing and contacting propylene with ethylene or an α-olefin having 4 to 20 carbon atoms. The amount ratio of each monomer in the reaction system does not need to be constant over time, and it is convenient to supply each monomer at a constant mixing ratio, and to change the mixing ratio of the supplied monomers over time. Is also possible. Further, any of the monomers can be dividedly added in consideration of the copolymerization reaction ratio.

As the polymerization method, any method can be adopted as long as the catalyst component and each monomer are efficiently contacted. Specifically, a slurry method using an inert solvent, a bulk method using propylene as a solvent without substantially using an inert solvent, a solution method, or substantially converting each monomer into a substantially gaseous state without using a substantially liquid solvent A keeping gas phase method can be employed. Either continuous polymerization or batch polymerization may be used. In the case of slurry polymerization, a single or a mixture of saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene can be used as a polymerization solvent.

The polymerization conditions are as follows.
The temperature is 60 ° C., preferably 0 ° C. to 150 ° C. At that time, hydrogen can be used as a molecular weight regulator in an auxiliary manner. The polymerization pressure is 0 to 90 kg / cm ² · G, preferably 0 to 60 kg / cm ² · G, particularly preferably 1 to 90 kg / cm ² · G.
It is 50 kg / cm ² · G.

2. Alicyclic hydrocarbon resin Examples of the alicyclic hydrocarbon resin used in the present invention include:
Examples include petroleum resins, terpene resins, rosin-based resins, coumarone-indene resins, and hydrogenated derivatives thereof. Among these, those having no polar group or resins having a hydrogenation ratio of 95% or more by adding hydrogen are preferable. More preferred resins are petroleum resins or hydrogenated derivatives of petroleum resins, and examples of the petroleum resins include commercially available products such as Alcon manufactured by Arakawa Chemical Industry Co., Ltd. and Escolets manufactured by Tonex Corporation.

The softening point of the alicyclic hydrocarbon resin is 110
C. or higher, preferably 115 ° C.
The temperature is more preferably 125 ° C. or more. When the softening point of the alicyclic hydrocarbon resin is lower than 110 ° C., the film becomes sticky or becomes cloudy due to a change with time.

3. Compounding ratio of resin composition Crystalline propylene-α- in the resin composition used in the present invention
The mixing ratio of the olefin random copolymer and the alicyclic hydrocarbon resin is such that the crystalline propylene-α-olefin random copolymer is 50 to 95% by weight, preferably 60 to 90% by weight, and the alicyclic hydrocarbon resin is It is 5 to 50% by weight, preferably 10 to 40% by weight. When the content of the crystalline propylene-α-olefin random copolymer in the resin composition exceeds 95% by weight (when the content of the alicyclic hydrocarbon resin is less than 5% by weight), the shrinkage property deteriorates. On the other hand, when the amount of the crystalline propylene-α-olefin random copolymer is less than 50% by weight (when the amount of the alicyclic hydrocarbon resin exceeds 50% by weight), the moldability of the film is deteriorated and the obtained label is used. The film is sticky.

4. Other Components An antioxidant, an antistatic agent, a neutralizing agent, a nucleating agent, an antiblocking agent, a slip agent and the like can be added as long as the effects of the present invention are not impaired. In order not to impair the effects of the present invention, propylene-butene-1 copolymer and polybutene-
1. Known shrinkage property improving components such as linear low density polyethylene may be added.

[II] Method of Forming Shrink Label Film The heat-shrinkable polypropylene shrink label film of the present invention is prepared by subjecting the above-mentioned polypropylene resin composition to a known forming method such as an inflation method or a flat stretching method. Although it can be molded using, in the present invention,
It is preferable to use a flat stretching method, particularly a tenter type uniaxial stretching method.

After being melt-extruded by the above-mentioned molding method, the film is stretched at least twice in at least one axial direction by a known method to produce the shrink label film of the present invention.
The stretching direction may be uniaxial or more, but it is preferable to uniaxially stretch only in a direction perpendicular to the flow direction of the label. On the other hand, if the stretching ratio is less than 2, sufficient shrinkage cannot be obtained. Further, for the purpose of improving the shrinkage, it is preferable to perform stretching at a temperature as low as possible. In particular, when there is a step of applying preheating to the unstretched sheet, the preheating temperature is set as low as possible within a moldable range. This is preferable from the viewpoint of improving the shrinkage.

The thickness of the shrink label film of the present invention is not particularly limited, but is 100 μm or less, preferably 30 to 80 μm. Further, the film for shrink labels of the present invention can be used as a film for a single-layer label or as a film for a multilayer label having two or more layers. In the case of a multilayer label film, the label film from the resin composition of the present invention may have at least one layer. Examples of the lamination method include a multilayer coextrusion method and a dry lamination method.

[III] Use of heat-shrinkable film The heat-shrinkable polypropylene shrink label film of the present invention has a greatly improved heat shrinkage, and is therefore a material for a PET bottle display label and a bottle container display label. It has practical characteristics as a material for use. Further, since the low-temperature shrinkage rate is improved, the high-speed label packaging property is excellent, and particularly, it can be suitably used for label packaging in PET bottles and bottle containers preliminarily filled at low temperature.

[0054]

EXAMPLES The present invention will be specifically described with reference to examples below, but the present invention is not limited to these examples. In addition, the evaluation method used in the Examples and Comparative Examples,
The method for forming the label film is as follows.

(1) MFR: Measured according to JIS K-6758 (condition 230 ° C., load 2.16 kg). (2) Tp and T ₅₀ : Using a differential scanning calorimeter (DSC) manufactured by Seiko, a sample (crystalline propylene-α-
(Olefin random copolymer) 5.0 mg, 20
After holding at 0 ° C. for 5 minutes, the mixture was cooled to 40 ° C. at a rate of temperature decrease of 10 ° C./min, and further melted at a rate of temperature rise of 10 ° C./min to obtain a heat of fusion curve. And _T50 were determined. (3) Softening point temperature: Measured according to JIS K-2207. (4) Heat shrinkage: Stretched film at 40 ° C. for 24
After aging for a time, it was cut out into a 10 cm × 10 cm square shape so that one side was parallel to the film flow direction, and this was immersed in a water bath heated to a predetermined temperature for 10 seconds. Immediately after the elapse of 10 seconds, the film was immersed in a separately prepared water bath at 23 ° C. for 20 seconds, and then the length of each of the film in the flow direction and the orthogonal direction was measured to determine the heat shrinkage. The average value in the film flow direction and the orthogonal direction was defined as the heat shrinkage ratio. (5) Stickiness of film: stretched film at 10c
20 pieces cut into squares of mx 10 cm are stacked,
After sandwiching it between two 10 cm × 10 cm glass plates, placing a 2 kg weight on it and leaving it under an atmosphere of 23 ° C. and 50% humidity for 24 hours to remove the weight, one 20 film film Each was evaluated by peeling. Those that peeled off easily were not sticky, and those that were difficult to peel off were sticky.

(6) Method for Forming Label Film (i) Method for Forming Unstretched Sheet The resin composition is melt-extruded at 200 ° C. by a T-die method, cooled and solidified with a cooling roll at 30 ° C. 300
A μm unstretched sheet was obtained. (Ii) Forming method of stretched film The unstretched sheet obtained above is introduced into a tenter furnace, and preheating is performed for 30 seconds at a temperature at which molding is possible and at a minimum, and a temperature equivalent to the preheating temperature is applied. The film was stretched 6.5 times in the width direction over 30 seconds. Subsequently, the film was annealed at 85 ° C. for 30 seconds while being relaxed in the width direction by 7.5% in the same tenter furnace to obtain a heat-shrinkable shrink label film having a draw ratio of 6 and a thickness of 50 μm.

Example 1 (1) Production of a crystalline propylene-α-olefin random copolymer (i) Dimethylsilylenebis [1- {2-methyl-4-
(4-Chlorophenyl) -4H-azulenyl}] Synthesis of Racemic Form of Zirconium Dichloride (a) Synthesis of Racemic / Meso Mixture 1.84 g of 1-bromo-4-chlorobenzene (9.6 m
mol) of n-hexane (10 ml) and diethyl ether (10 ml) at -78 ° C in 11.7 ml of a pentane solution of t-butyllithium (1.64 M) (19.
2 mmol) was added dropwise. The resulting solution was treated at -5 ° C with 1.
After stirring for 5 hours, 1.2 g of 2-methylazulene was added to the solution.
(8.6 mmol) was added to carry out the reaction. The reaction solution was stirred for 1.5 hours while gradually returning to room temperature.
Thereafter, the reaction solution was cooled to 0 ° C., and 15 μl (0.19 mmol) of 1-methylimidazole was added.
0.52 ml of dichlorodimethylsilane (4.3 mmo
l) was added. After stirring the reaction solution at room temperature for 1.5 hours,
The reaction was stopped by adding dilute hydrochloric acid, the separated organic phase was concentrated under reduced pressure, dichloromethane was added, and the mixture was dried over magnesium sulfate. After evaporating the solvent under reduced pressure, the residue was purified by silica gel column chromatography to obtain 2.1 g of an amorphous solid.

Next, 1.27 g of the above reaction product was dissolved in 15 ml of diethyl ether.
1. n-hexane solution of butyllithium (1.66 M)
8 ml (4.5 mmol) were added dropwise. After completion of the dropwise addition, the reaction solution was stirred for 12 hours while gradually returning to room temperature.
After distilling off the solvent under reduced pressure, 5 ml of a mixed solvent of toluene and diethyl ether (40: 1) was added, and the mixture was cooled to -78 ° C, and 0.53 g of zirconium tetrachloride (2.3 g) was added thereto.
mmol) was added. Then, immediately return to room temperature,
The reaction was performed with stirring at room temperature for 4 hours. The obtained reaction solution was filtered over celite, and the solid separated by filtration was mixed with 3 ml of toluene.
And washed. The collected solid was extracted with dichloromethane, the solvent was distilled off from the extract, and dimethylsilylenebis [1- {2-methyl-4- (4-chlorophenyl)-
906 mg (56% yield) of a racemic / meso mixture of [4H-azulenyl}] zirconium dichloride was obtained.

(B) Purification of racemic body Further, 900 mg of the above-mentioned racemic / meso mixture was dissolved in 20 ml of dichloromethane, and a 100 W high-pressure mercury lamp was used.
The ratio of the racemate was increased by irradiating for 0 minutes, then the insoluble matter was separated by filtration, and the collected filtrate was concentrated to dryness. Then, the obtained solid component was stirred with 22 ml of toluene, and after standing, the supernatant was removed.
This was repeated twice, and the remaining solid component was dried to obtain 275 mg of a racemic dimethylsilylenebis [1- {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium dichloride.

(Ii) Chemical treatment of clay mineral 218.1 g of sulfuric acid (96%) and magnesium sulfate 13
A commercially available montmorillonite (Kunimine F, Kunipia F) 20 was added to an aqueous solution in which 0.4 g was mixed with 909 ml of demineralized water.
0.03 g was dispersed and stirred at 100 ° C. for 2 hours. This aqueous slurry of montmorillonite was solidified at a solid concentration of 12%.
And subjected to spray granulation with a spray drier to obtain particles. Thereafter, the particles were dried under reduced pressure at 200 ° C. for 2 hours.

(Iii) Preparation of catalyst component 230 ml of dehydrated and deoxygenated heptane after sufficiently replacing the inside of a 1-liter stirred autoclave with propylene.
Was introduced, and the temperature in the system was maintained at 40 ° C. Here, 10 g of chemically treated clay slurried with toluene was added. Further, in a separate container, 0.15 mmol of racemic dimethylsilylenebis [1- {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] zirconium dichloride and 1.5 mmol of triisobutylaluminum mixed under toluene were mixed. Was added. Where propylene is 1
Introduced at a rate of 0 g / h for 120 minutes, and then polymerization was continued for 120 minutes. Further, the solvent was removed and dried under nitrogen to obtain a solid catalyst component. This solid catalyst component is 1 g of a solid component.
Per 1.9 g of polypropylene.

(Iv) Polymerization After sufficiently replacing propylene in the stirred autoclave having an internal volume of 200 l, liquefied propylene
5 kg were introduced. To this were added 500 ml (0.12 mol) of a triisobutylaluminum / n-heptane solution, 2.0 kg of ethylene, and 3.5 l of hydrogen (as a standard state volume), and the internal temperature was maintained at 30 ° C. Then, 1.45 g of the above solid catalyst component was injected with argon to start polymerization, the temperature was raised to 70 ° C. over 30 minutes, and the temperature was maintained for 1 hour. Here, 100 ml of ethanol was added to stop the reaction. The residual gas is purged and propylene-ethylene random copolymer (PP) 13.7 as shown below
kg. MFR: 2.58 g / 10 minutes, ethylene content: 3.42
% By weight, Tp: 122.7 ° C., T ₅₀ : 113 ° C.

(V) Production of Resin Composition and Film Molding 80% by weight of the PP powder obtained above, Alcon P125 manufactured by Arakawa Chemical Industry Co., Ltd. (softening point temperature: 125 ° C.) 2
0.05 part by weight of calcium stearate, 0.1 part by weight of Irganox 1010, and 0.1 part by weight of Irgafos 168 0.1 with respect to 100 parts by weight of the resin composition comprising 0% by weight.
Parts by weight and 0.1 parts by weight of synthetic silica having an average particle size of 2.5 μm as an antiblocking agent were mixed with a Henschel mixer, and then granulated with a 50 mm single screw extruder to obtain resin composition pellets. Using the pellets, a shrink label film was formed by the method described above. The minimum preheatable temperature at which the film was formed was 60 ° C.
Table 1 shows the evaluation results of the obtained films.

Example 2 A shrink label film was prepared in the same manner as in Example 1, except that Alcon P140 (softening point temperature: 140 ° C.) manufactured by Arakawa Chemical Industries, Ltd. was used as the alicyclic hydrocarbon resin. Molded. The minimum preheatable temperature at which the label film was formed was 60 ° C. Table 1 shows the evaluation results of the obtained films.

Example 3 A film for a shrink label was formed in the same manner as in Example 1 except that Escolets 228F (softening point temperature: 137 ° C.) manufactured by Tonex Corporation was used as the alicyclic hydrocarbon resin. . The minimum preheatable temperature at which the label film was formed was 60 ° C. Table 1 shows the evaluation results of the obtained films.

Example 4 0.05 parts by weight of calcium stearate was added to 100 parts by weight of a resin composition consisting of 75% by weight of PP powder and 25% by weight of Escolets 5320HC (softening point temperature: 125 ° C.) manufactured by Tonex Corporation. Irganox 10
10 0.1 part by weight, 0.1 part by weight of Irgafos 168 and an average particle diameter of 2.5 as an anti-blocking agent.
After mixing 0.1 part by weight of synthetic silica having a particle size of 0.1 μm with a Henschel mixer, the mixture was granulated with a 50 mm single screw extruder to obtain resin composition pellets. Using the pellets, a shrink label film was formed by the method described above. The minimum preheatable temperature at which the film was formed was 60 ° C. Table 1 shows the evaluation results of the obtained films.

Example 5 0.05% by weight of calcium stearate based on 100% by weight of a resin composition comprising 70% by weight of PP powder and 30% by weight of Alcon P140 (softening point temperature: 140 ° C.) manufactured by Arakawa Chemical Industries, Ltd. Department, Irganox 1010
0.1 part by weight, 0.1 part by weight of Irgafos 168 and 0.1 part by weight of synthetic silica having an average particle size of 2.5 μm as an antiblocking agent were mixed with a Henschel mixer, and then granulated with a 50 mm single screw extruder. Thus, a resin composition pellet was obtained. Using the pellets, a shrink label film was formed by the method described above. The minimum preheatable temperature at which the film was formed was 60 ° C. Table 1 shows the evaluation results of the obtained films.

COMPARATIVE EXAMPLE 1 Propylene was prepared using an ordinary Ziegler-Natta catalyst.
An ethylene random copolymer (PP) was produced. The obtained propylene-ethylene random copolymer had the following physical properties. MFR: 2.30 g / 10 minutes, ethylene content: 3.60
_{Wt%, Tp: 138.3 ℃, T} 50: 130 ℃. 80% by weight of the above PP powder, Arakawa Chemical Industry Co., Ltd.
0.05 parts by weight of calcium stearate and Irganox 101 per 100 parts by weight of a resin composition composed of Alcon P140 (softening point temperature: 140 ° C.) 20% by weight
0 0.1 part by weight, 0.1 part by weight of Irgafos 168 and 2.5 μm
After mixing 0.1 part by weight of synthetic silica with a Henschel mixer, the mixture was granulated with a 50 mm single screw extruder to obtain resin composition pellets. Using the pellets, a shrink label film was formed by the method described above. The minimum preheatable temperature at which the film was formed was 80 ° C. Table 1 shows the evaluation results of the obtained films. Crystalline propylene-
Because T ₅₀ ethylene random copolymer is high, heat shrinkage is significantly reduced.

Comparative Example 2 A shrink label film was formed in the same manner as in Example 1 except that Escolez 5300HC (softening point temperature: 105 ° C.) manufactured by Tonex Corporation was used as the alicyclic hydrocarbon resin. . The minimum preheatable temperature at which the label film was formed was 60 ° C. Table 1 shows the evaluation results of the obtained films. Since the softening point temperature of the alicyclic hydrocarbon resin was low, stickiness was observed in the film.

[0070]

[Table 1]

[0071]

The heat shrinkable polypropylene resin composition for shrink labels of the present invention and the film using the same have significantly improved heat shrinkage and low temperature shrinkage as compared with other conventional films. Because it is improved, it is suitable for use as a shrink label.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) // C08F 4/642 C08F 4/642 (C08L 23/14 (C08L 23/14 45:00) 45:00) B29K 23 : 00 B29K 23:00 45:00 45:00 B29L 7:00 B29L 7:00 (72) Inventor Tadashi Sezume 1 Tohocho, Yokkaichi-shi, Mie Japan F-term in Material Development Center, Polychem Corporation (Reference) 3E086 AB03 AD16 BA15 BB67 CA11 4F071 AA14 AA14X AA20 AA20X AA21 AA39 AA69 AA83 AA84 AA88 AB26 AC09 AF61 AH04 AH19 BA01 BB07 BB09 BC12 4F210 AA11H AA12 AE01 AG01 RA03 RC02 RG021 002 002

Claims (4)

[Claims] An alicyclic hydrocarbon having a crystalline propylene-α-olefin random copolymer containing 50 to 95% by weight and a softening point of 110 ° C. or higher, which satisfies the following characteristics. 5-50% by weight of resin
A heat shrinkable polypropylene resin composition for shrink labels comprising: Characteristics: melt flow rate (230 ° C, 2.16 kg
Load) is 0.5 to 10 g / 10 min. Characteristics: Main melting peak temperature (Tp) determined by a differential scanning calorimeter (DSC) is in the range of 100 to 140 ° C. Characteristics: T ₅₀ ≦ 125 ° C. (where T ₅₀ is the temperature at which the total heat of fusion of the polypropylene resin composition determined by DSC is ΔHm and the heat of fusion calculated from the low temperature side is 50% of ΔHm) (° C).) 2. The resin composition for a heat-shrinkable polypropylene shrink label according to claim 1, wherein the crystalline propylene-α-olefin random copolymer is a propylene-ethylene random copolymer. 3. The resin composition for a heat-shrinkable polypropylene shrink label according to claim 1, wherein the crystalline propylene-α-olefin random copolymer is a copolymer obtained by polymerization with a metallocene catalyst. 4. A heat-shrinkable polypropylene shrink label film obtained by stretching the resin composition according to claim 1 at least twice in at least one axial direction.