JP2003313316A - Polypropylene-olefin copolymer film and sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a propylene-olefin copolymer film or sheet having balanced properties, e.g. rubber elasticity and processing stability, and excellent environmental compatibility and economical efficiency. <P>SOLUTION: The film and sheet are composed of a resin composition comprising 99.50-99.95 pts.wt. of a propylene-olefin copolymer consisting of 85-99.99 mol% of propylene units, in terms of the mol number of monomer units constituting the copolymer, and 0.01-15 mol% of olefin units other that propylene, and 0.05-0.50 pts.wt. of a slipping agent and have a permanent set of 50% or lower. The copolymer meets the conditions: (a) the melting point is 110-150°C; (b) the melt flow rate (MFR) is 0.3-30 g/10 min; (c) the distribution of molecular weights (Mw/Mn) is 2.5-5.5; and (d) the isotactic pentad fraction (mmmm) is 0.20-0.55, and the triad chain fraction, or mm, rr and mr, is specified as mm> rr>mr. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a propylene-olefin copolymer film or sheet having rubber elasticity. Specifically, it has an excellent balance of various properties such as rubber elasticity and processing stability, as well as excellent environmental suitability and economy.
The present invention relates to a propylene-olefin copolymer film or sheet suitable for applications such as medical bandages, medical films, care films, and diapers.

[0002]

2. Description of the Related Art Polyurethane elastomers and polyvinyl chloride resins are mainly used as resins for rubber elastic films or sheets used in adhesive plasters and patch materials, but polyurethane elastomers are very expensive. However, there is a problem that harmful gas is generated during combustion.

Further, as has been pointed out in the past, polyvinyl chloride resin has a problem of environmental hormones caused by a plasticizer and generation of toxic gas during combustion. The use of an ethylene copolymer produced by a metallocene catalyst or a polyolefin thermoplastic elastomer produced only by polymerization has been proposed as a means for improving them, but the resulting film or sheet has a problem that the rubber elasticity is extremely low. there were.

On the other hand, in order to impart rubber elasticity to the film, polystyrene elastomer or dynamically crosslinked polyolefin thermoplastic elastomer is used as a rubber elastic material, or unsaturated elastomer such as ethylene-propylene-diene copolymer is crosslinked. There is also a method. However, polystyrene elastomers and dynamically crosslinked polyolefin thermoplastic elastomers are expensive and have problems such as stickiness or reduced heat resistance of products, and unsaturated elastomers are not suitable for recycling due to crosslinking, etc. It wasn't enough.

Further, as an elastomeric polypropylene having rubber elasticity which is considered to be suitable for solving the above problems, Japanese Patent No. 2912483 discloses a substantially amorphous elastic high molecular weight propylene homopolymer having a melting point of 145. C.-165.degree. C., the melt viscosity at 190.degree. C. is 200,000 cps (200 Pa.s) or more, and the heat of fusion is 4 cal. / Gm. -10 cal. / G
m. (16.7-41.9 J / g), and the polymer is 3
Disclosed is a propylene homopolymer characterized by comprising a diethyl ether-soluble fraction having an intrinsic viscosity of 1.0 dl / g or less and having substantially no isotactic crystallinity of 5% to 55%. . In this case, although it is considered that the above problems have been improved to some extent, the polypropylene of the present invention contains an ether-soluble component having a low molecular weight of 1.0 dl / g or less, which makes the product sticky (particularly stickiness). It has poor impact resistance when used at low temperature, because the film or sheet obtained by using the polymer is inferior in stickiness at high temperature) and heat resistance and the glass transition temperature is around 0 ° C. I was not satisfied.

Further, when the polymer is processed into a film or a sheet, stickiness is likely to occur in a usual processing machine due to stickiness, rewinding property after winding and film-forming stability in a thin film are remarkably poor, and yield and production are increased. A special processing machine was required because the properties deteriorated significantly.

Further, as means for improving rewinding property and slipping property after winding, there is a method of applying or directly spraying silicone oil or starch powder (Nikkarico (trade name) etc.) on the surface of the film or sheet. But,
Since it is necessary to introduce a coating device or a spraying device, the economical efficiency is reduced, the processing machine is limited, the secondary processing suitability such as printing and adhesion is deteriorated, and further, there are problems such as hygiene.

[0008]

SUMMARY OF THE INVENTION The present invention is directed to rubber elasticity,
An object of the present invention is to provide a propylene-olefin copolymer film or sheet which is excellent in balance of various properties such as processing stability and is also excellent in environmental suitability and economy.

[0009]

Means for Solving the Problems As a result of earnest studies, the present inventors have found that propylene units are 85 to 99.99 mol% based on the number of moles of monomer units constituting a copolymer, and olefin units excluding propylene are 0.01 to 15 mol%, melting point 110 to 150 ° C., melt flow rate (M
FR) 0.3 to 30 g / 10 minutes, molecular weight distribution (Mw /
Mn) is 2.5 to 5.5, the isotactic pentad fraction (mmmm) is 0.20 to 0.55, and the triad chain fractions mm, rr, and mr are in the relationship of mm>rr> mr. A certain propylene-olefin copolymer was added to 99.50.
˜99.95 parts by weight, and 0.05 to 0.
It consists of a resin composition containing 50 parts by weight and has a permanent set of 5
The present invention has been completed based on the finding that the above problems can be solved by a film or sheet having a content of 0% or less.

The present invention has the following configuration. (1) The propylene unit is 85 to 99.99 mol% and the olefin unit excluding propylene is 0.01 to 15 mol% based on the number of moles of the monomer unit constituting the copolymer,
The resin composition contains 99.50 to 99.95 parts by weight of a propylene-olefin copolymer satisfying the following (a) to (d) and 0.05 to 0.50 parts by weight of a slip agent, and is a permanent composition. A film or sheet having an elongation of 50% or less. (A) Melting point is 110 to 150 ° C. (B) Melt flow rate (MFR) is 0.3 to 30 g
/ 10 minutes. (C) The molecular weight distribution (Mw / Mn) is 2.5 to 5.5. (D) Isotactic pentad fraction (mmmm) is 0.20 to 0.55, triad chain fraction mm,
rr and mr have a relation of mm>rr> mr.

(2) The film or sheet according to item (1), wherein the slip agent is at least one selected from higher fatty acid amides.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. In the following, films and sheets are generically called films.

The propylene-olefin copolymer film of the present invention has a permanent elongation (measured according to JIS K6301) of 50% or less. Since the permanent elongation is 50% or less, it exhibits suitable elongation recovery when the film is elongated, and fits well to a treated body or the like, and thus can be suitably used for applications such as medical adhesive plasters.

The propylene-olefin copolymer used in the present invention has 85 to 99.9 propylene units based on the number of moles of the monomer units constituting the copolymer.
9 mol%, 0.01 olefin units excluding propylene
Propylene-olefin copolymer containing 0.1 to 15 mol%, a melting point of 110 to 150 ° C., a melt flow rate (MFR) of 0.3 to 30 g / 10 minutes, and an isotactic pentad fraction (mmmm) of 0. .20 to 0.55, and triad chain fractions mm, rr, and mr are mm>
It is characterized in that there is a relationship of rr> mr.

In the present invention, olefins other than propylene include ethylene, 1-butene, 1-hexene, 1
-At least one olefin selected from octene and 4-methyl-pentene-1 can be used. Among them, ethylene, 1-butene, or a mixture of ethylene and 1-butene is preferable, and ethylene is particularly preferable.

The propylene-olefin copolymer used in the present invention has 85 to 99.9 propylene units based on the number of moles of the monomer units constituting the copolymer.
9 mol%, preferably 89 to 98 mol%, more preferably 89 to 95 mol%, particularly preferably 89 to 93 mol%
Contains 0.01 to 0.01 olefin units excluding propylene
15 mol%, preferably 2 to 11 mol%, more preferably 5 to 11 mol%, and particularly preferably 7 to 11 mol%.

Olefin unit excluding propylene is 0.0
If it is less than 1 mol%, the transparency of the film may be lowered, and if the olefin unit exceeds 15 mol%,
The heat resistance may decrease and it may become sticky.

The melting point (Tm) of the propylene-olefin copolymer used in the present invention is 110 to 150 ° C,
Preferably 120 to 140 ° C., particularly preferably 125 to 125 ° C.
It is in the range of 135 ° C. When the melting point is less than 110 ° C,
The heat resistance of the film may decrease, and the melting point is 150.
If the temperature exceeds ℃, the flexibility of the film may be deteriorated and the transparency may be lowered. The melting point (Tm) is measured using "DSC7 type differential scanning calorimeter" manufactured by Perkin-Elmer. First, the polymer, which is a test body, is heated from room temperature to 30 ° C /
The temperature is raised to 230 ° C. at a rate of minutes, the temperature is held at the same temperature for 10 minutes, the temperature is lowered to −20 ° C. at a rate of −20 ° C./minute, and the temperature is held for 10 minutes. After that, 20 ℃ again
The temperature at which the peak of melting occurs when the temperature was raised at a rate of / minute was taken as the melting point.

The heat of fusion of the propylene-olefin copolymer used in the present invention is preferably 10 to 60 J.
/ G, more preferably 10 to 40 J / g, further preferably 10 to 30 J / g, particularly preferably 15 to 25 J / g.
Is the range. When the heat of fusion is in the range of 10 to 60 J / g, the film has a good balance between heat resistance and flexibility.
The heat of fusion is a value indicating the amount of heat required for melting, which is obtained when measuring the melting point.

Melt flow rate (MFR; JI) of the propylene-olefin copolymer used in the present invention.
SK7210 condition 1 of Table 1, 230 ° C., load 21.
18N) is 0.3 to 30 g / 10 minutes, preferably 1 to
It is in the range of 15 g / 10 minutes. MFR is 0.3g / 10
If it is less than minutes, there is a possibility that molding by a conventionally known molding machine becomes difficult. On the other hand, if the MFR exceeds 30 g / 10 minutes, the molded product may become significantly sticky and the workability may deteriorate.

The propylene-olefin copolymer used in the present invention has an isotactic pentad fraction (mmmm) of 0.20 to 0.55 and a triad chain fraction mm, rr, mr of mm>. It is characterized in that there is a relationship of rr> mr.

"Isotactic pentad fraction (mm
mm) ”and the triad chain fraction mm, rr, mr are
"Macromolecules 6, such as A. Zambelli 6,
925 (1973) ”, which is an index showing the stereoregularity of the polymer, which is determined by measurement by the ¹³ C nuclear magnetic resonance spectrum. A method for determining the attribution of peaks in the measurement of the present ¹³ C nuclear magnetic resonance spectrum is described by A. Zamberg (A. Za
mbelli) and other "Macro Molecules (Macr
, 687 (1975) ”.

The ¹³ C nuclear magnetic resonance spectrum is measured, for example, as follows. That is, a test body (polymer) is dissolved in a mixed solution of o-dichlorobenzene / benzene bromide = 8/2 (weight ratio) so that the concentration in the mixed solution is 20% by weight. For this test solution, the measurement frequency was 67.20 MHz and the measurement temperature was 130.
At ¹³ ° C., ¹³ C nuclear magnetic resonance spectrum is measured. Examples of the measuring device include "JEOL-GX" manufactured by JEOL Ltd.
270 NMR (trade name) ”can be used.

Isotactic pentad fraction (mmm
m) represents the ratio of five consecutive propylene units forming meso bonds to the total number of propylene units constituting polypropylene, and the triad fraction mm,
rr and mr are the case where three consecutive meso bonds are formed with respect to the total number of propylene units in polypropylene (m
m) When three consecutive racemic bonds (rr),
The 1st and 2nd of 3 consecutive propylenes are meso bonds, the 2nd and 3rd are racemic bonds, or the 1st and 2nd are racemic bonds, and the 2nd and 3rd When the second part is meso-bonded (mr), it represents the ratio of each propylene unit.

Also in the case of the propylene-olefin copolymer used in the present invention, the attribution of each peak is determined according to the case of the above polypropylene, and the isotactic pentad fraction (mmmm) and the triad fraction are determined. mm, rr, and mr are calculated.

The isotactic pentad fraction (mmmm) of the propylene-olefin copolymer used in the present invention is 0.20 to 0.55, preferably 0.3.
It is 0 to 0.50, more preferably 0.30 to 0.40, and particularly preferably 0.30 to 0.35. If the isotactic pentad fraction (mmmm) exceeds 0.55, the flexibility of the film may deteriorate and the transparency may decrease, and if it is less than 0.20, the film may become sticky and the heat resistance may deteriorate. is there.

The propylene-olefin copolymer used in the present invention has a triad chain fraction mm, rr,
The relationship of mm>rr> mr is established between mr. If this relational expression is not satisfied, the heat resistance and tackiness of the film obtained using the propylene-olefin copolymer may deteriorate. The numerical values of mm, rr, and mr are not particularly limited as long as the above relational expressions are satisfied, but mm is preferably 0.25 to 0.65, more preferably 0.40 to 0.60. , Particularly preferably 0.
It is 40 to 0.50. Further, rr is preferably 0.
20 to 0.35, more preferably 0.25 to 0.29, mr is preferably 0.10 to 0.30, more preferably 0.15 to 0.30, and particularly preferably 0.15.
Is about 0.27. Specifically, mm is 0.40 to 0.
60, rr is 0.22 to 0.31, mr is 0.18 to
0.29 is preferable, and mm is 0.40
~ 0.50, rr 0.26 to 0.32, mr 0.2
It is preferably 4 to 0.28.

The propylene-olefin copolymer of the present invention has a molecular weight distribution, that is, a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn),
It is 2.5 to 5.5, preferably 3.0 to 4.0, and more preferably 3.5 to 4.0. Molecular weight distribution (Mw / M
When n) is less than 2.5, the resulting film is inferior in processability, so that the appearance tends to be poor, and when it exceeds 5.5, the film may be sticky.

Further, regarding the molecular weight distribution, a propylene-olefin copolymer is dissolved in orthodichlorobenzene to obtain a solution having a concentration of 0.75 mg / ml, and a GPC apparatus (W
ATER 150C type, used column; TSK GEL
It is a value calculated from the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured at 135 ° C. using GMH6-HT).

The propylene-olefin copolymer used in the present invention reflects the above characteristics, and has a glass transition temperature (Tg) of preferably -6 ° C or lower, more preferably -8 ° C or lower, and particularly preferably- It is 12 ° C or lower, and most preferably -16 ° C or lower. When the glass transition temperature (Tg) is -6 ° C or lower, the resulting film has good impact resistance at low temperatures.

In the present invention, the glass transition temperature (Tg)
Is measured using a "DSC7 type differential scanning calorimeter" manufactured by Perkin Elmer. First, the test sample polymer was heated from room temperature to 230 ° C. at a rate of 10 ° C./min, held at the same temperature for 10 minutes, and then cooled to −80 ° C. at a rate of −10 ° C./min. Hold at the same temperature for 10 minutes.
Then, it was determined from the thermogram when the temperature was raised again at a rate of 10 ° C./min.

The propylene-olefin copolymer used in the present invention preferably has an intrinsic viscosity [η] of 1.0 dl / of 20 to 70 wt% based on the weight of the copolymer.
Includes boiling diethyl ether solubles with greater than g and substantially no isotactic crystallinity. The intrinsic viscosity [η] is, for example, an intrinsic viscosity measured using an automatic viscosity measuring device (model AVS2, manufactured by Mitsui Toatsu Chemicals, Inc.) and using tetralin as a solvent under a temperature condition of 135 ° C.

The boiling diethyl ether-soluble component of the propylene-olefin copolymer used in the present invention has an intrinsic viscosity [η] of preferably more than 1 dl / g, more preferably more than 1 dl / g and less than 5 dl / g. , Particularly preferably more than 1 dl / g and less than 2 dl / g, most preferably more than 1 dl / g and less than 1.5 dl / g. Intrinsic viscosity of soluble components of boiling diethyl ether [η]
Is more than 1 dl / g, the heat resistance of the film is good and there is no stickiness.

The boiling diethyl ether-soluble component contained in the propylene-olefin copolymer used in the present invention does not have substantially isotactic crystallinity, but the boiling diethyl ether-soluble component is It means that no melting point is shown, or even if the melting point is shown, the heat of fusion shows only a small value of 10 J / g or less, more preferably 5 J / g or less. When the boiling diethyl ether-soluble component exhibits isotactic crystallinity, the flexibility of the film may be deteriorated.

The propylene-olefin copolymer used in the present invention is preferably 20 to 70 wt%, more preferably 35 to 70 wt%, and particularly preferably 50 to 70 wt%.
It has 70 wt%, most preferably 60-70 wt% boiling diethyl ether solubles. When the boiling diethyl ether-soluble content is in the range of 20 to 70 wt%, the flexibility of the film is good and the heat resistance is not deteriorated.

The propylene-olefin copolymer used in the present invention has a type A durometer hardness HDA measured in accordance with JIS K7215,
It is preferably less than 90, more preferably 40 or more and less than 90, and particularly preferably 60 or more and less than 90. The durometer hardness indicates that the smaller the value, the better the flexibility. The propylene-olefin copolymer of the present invention is very excellent in flexibility.

As the catalyst used for producing the propylene-olefin copolymer used in the present invention, any catalyst may be used as long as it can produce a propylene-olefin copolymer satisfying the above characteristics. However, it is preferable to use the titanium-based solid catalyst produced as described below, because it has a high catalytic activity, is economically advantageous, and is easy to produce a high-molecular-weight propylene-olefin copolymer.

The titanium-based solid catalyst preferably used for producing the propylene-olefin copolymer used in the present invention is obtained by reacting the following compounds of the groups (I) to (III) as described below. A catalyst comprising a combination of a solid product (described in detail below) and an organoaluminum compound of group (IV).

(I) Group (A) Trivalent metal halide (B) Divalent metal hydroxide, oxide, carbonate, double salt containing them or divalent metal hydrate (II ) Group (C) Polysiloxane (III) Group (D) Liquid titanium compound (IV) Group (E) Organoaluminum compound

The method for preparing the titanium-based solid catalyst preferably used for the production of the propylene-olefin copolymer of the present invention will be described in detail below. A ball mill comprising (A) a trivalent metal halide of group (I) and (B) a divalent metal hydroxide, oxide, or carbonate, a double salt containing them, or a divalent metal hydrate. Use a vibrating mill etc. to reach room temperature to 5
The solid product (1) obtained by mixing and pulverizing at 00 ° C. and reacting both components (A) and (B) is reacted with the (C) polysiloxane of the group (II) to produce a solid product (2 ) Get. The solid product (2) was reacted with the liquid titanium compound (D) of the group (III), filtered, and washed with a solvent such as normal hexane until no free titanium compound was detected. Thereafter, the solid product (3) thus obtained is dried, and the catalyst is obtained by combining the obtained solid product (3) with the (E) organoaluminum compound of the (IV) group.

Halogen of trivalent metal (A) of group (I)
As chlorides, aluminum trichloride (anhydrous), trichloride
There is iron (anhydrous). As a compound of the divalent metal (B)
Is, for example, Mg (OH)_Two, Ca (OH)_Two, Zn
(OH)_Two, Mn (OH)_TwoHydroxide like, Mg
Oxides such as O, CaO, ZnO, MnO, MgAl
_TwoO _Four, Mg_TwoSiO_FourCompounds containing divalent metals such as
Oxide, MgCO_Three, MnCO_Three, MgCO_Three・ CaC
O_ThreeOxides such as SnCl_Two・ 2H_TwoO, MgC
l_Two・ 6H_TwoO, NiCl_Two・ 6H_TwoO, MnCl_Two・
4H_TwoO, KMgCl _Three・ 6H_TwoHalogenation like O
Hydrate, 8MgO / MgCl_Two・ 15H_TwoLike O
Double salt hydrate containing oxide and halide, 3MgO
2SiO / 2H _TwoCompounds containing oxides of divalent metals such as O
Hydrate of salt, 3MgCO_Three・ Mg (OH)_Two・ 3H_TwoO
Hydrates of double salts of carbonates and hydroxides, such as
To be

The reaction of the group (I) by mixing the halide of the trivalent metal of (A) and the compound of the divalent metal of (B) is carried out in a ball mill for 5 to 50 hours, and in the vibration mill to 1 to 1
It is desirable to carry out mixing and pulverization for 0 hours to obtain a sufficiently mixed state. In the group (I), the mixing ratio of the trivalent metal halide of (A) and the divalent metal compound of (B) is
With respect to 1 mol of the trivalent metal halide of (A),
The amount of the divalent metal compound (B) is usually 0.1 to 20 mol, and preferably 1 to 10 mol. The reaction temperature is generally room temperature to 500 ° C, preferably 50 to 300 ° C. Reaction time is 30 minutes to 5
When 0 hours is suitable and the reaction temperature is low, the reaction is carried out for a long time and the reaction is sufficiently carried out so that unreacted trivalent metal does not remain, and the obtained solid product is referred to as the solid product (1). To do.

The solid product (1) obtained by the reaction of the trivalent metal halide of (A) and the divalent metal compound of (B) of group (I) is then (II) React with the group (C) polysiloxane. In the present invention, the polysiloxane used as the group (II) (C) is a compound represented by the general formula Is a chain or cyclic siloxane compound represented by
Each R may be the same or different,
Represents a substituent that can be bonded to silicon, specifically, hydrogen,
A hydrocarbon group such as an alkyl group and an aryl group, a halogen, an alkoxy group or an aryloxy group, a fatty acid group and the like.

The polysiloxane usually used is one in which each R in the above formula is a hydrocarbon group, and examples thereof include an alkylsiloxane polymer, an arylsiloxane polymer and an alkylarylsiloxane polymer.

Examples of the alkyl siloxane polymer include octamethyltrisiloxane CH ₃ [Si (C
H _{3) 2} O] _{2 Si (CH 3) 2 OCH} 3, octaethyl cyclotetrasiloxane _{[Si (C 2 H 5) 2} O ]
Lower polymer such as ₄ and dimethyl polysiloxane
Polymers of [Si (CH ₃ ) ₂ O] _n , ethyl polycyclosiloxane [SiH (C ₂ H ₅ ) O] _n , methylethyl polysiloxane [Si (CH ₃ ) (C ₂ H ₅ ) O] _{n, and the} like. Is mentioned.

The aryl siloxane polymer is, for example, hexaphenylcyclotrisiloxane.
_{[Si (C 6 H 5) 2} O ] _3, diphenyl polysiloxane _{[Si (C 6 H 5) 2} O ] _n, and examples of the alkyl aryl siloxane polymer, for example, diphenyl hexamethyl tetrasiloxane (CH ₃ ) ₂ SiO
[Si (CH ₃ ) (C ₆ H ₅ ) O] ₂ Si (C
H ₃ ) ₂ , methylphenylpolysiloxane [Si (C
H ₃ ) (C ₆ H ₅ ) O] _{n and the} like.

These various polysiloxanes can also be used as a mixture. The polysiloxane used is
It is desirable to be liquid, and the kinematic viscosity is 0.1 to 100.
cm ² / s is suitable, and preferably 0.1 to 10 cm ² /
The range is s.

The reaction between the solid product (1) and polysiloxane is usually from room temperature to 300 ° C, preferably 60 ° C to
Reaction at 200 ° C. for 10 minutes to 5 hours is sufficient. The amount ratio of the solid product (1) to the polysiloxane is such that the polysiloxane is 10 to 1.00 with respect to 100 g of the solid product (1).
It is preferred to add 0 g. Also, a solid product (1)
The reaction between polysiloxane and polysiloxane can be carried out in the presence of a solvent, and the presence of the solvent does not impair the effects of the present invention.

Examples of the solvent used include aliphatic hydrocarbons such as normal heptane, normal octane, normal nonane, and normal decane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, and the like.
Examples thereof include halogenated aromatic hydrocarbons such as chlorobenzene and orthodichlorobenzene, and halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloroethane, trichloroethylene, tetrachloroethylene and carbon tetrabromide.

It is also possible to simultaneously add and react these solvents and polysiloxane, and the mixing ratio thereof is 0 to 1,000 m of the solvent with respect to 100 g of the solid product (1).
1 and 10 to 1,000 g of polysiloxane are preferable. Further, after reacting the solid product (1) with the polysiloxane, the solvent may be added, and conversely, after adding the solvent to the solid product (1), the polysiloxane may be added and reacted.

The solid product (2) is obtained by the reaction of the solid product (1) and polysiloxane. After the reaction of the solid product (1) with the polysiloxane, it may be used as it is in the slurry state for the reaction with the liquid titanium compound of the following (III) group (D). ) And polysiloxane are reacted and then filtered to remove unreacted polysiloxane and washed with a solvent such as normal hexane to obtain a solid product (2), which is obtained by the following (III) group (D). It may be used for the reaction with the liquid titanium compound of (1).

Examples of the liquid titanium compound of the group (III) (D) include titanium halides, oxyhalides, alcoholates, alkoxy halides, acetooxyhalides and the like, and examples thereof include titanium tetrachloride and titanium tetrabromide. Examples thereof include tetraethoxy titanium, tetrabutoxy titanium, monochlorotributoxy titanium, dichlorodibutoxy titanium and trichloromonoethoxy titanium.

The mixing ratio of the solid product (2) and the liquid titanium compound of the group (III) (D) is such that the solid product (2) 1
It is preferably in the range of 1 g to 1,000 g with respect to 00 g, and more preferably in the range of 10 g to 500 g.

The reaction conditions of the solid product (2) and the liquid titanium compound are usually 50 to 300 ° C., preferably 80.
At ˜200 ° C., a reaction time of 10 minutes to 5 hours is sufficient. This reaction depends on the mixture of the solid product (2) and the liquid titanium compound, but during the reaction, aliphatic or aromatic carbonization such as normal hexane, normal heptane, normal nonane, benzene, toluene, xylene, ethylbenzene, cumene Solvents such as hydrogen, chlorobenzene, orthodichlorobenzene, chloroform, halogenated hydrocarbons such as carbon tetrachloride, dichloroethane, trichloroethylene, tetrachloroethylene and the like can be added to facilitate mixing for the reaction. The amount of the solvent added is preferably in the range of 0 to 1,000 ml with respect to 100 g of the solid product (2).

After completion of the reaction between the solid product (2) and the liquid titanium compound, the unreacted titanium compound or the same compound and the solvent are separated by filtration, and washing with a solvent such as normal hexane is repeated to release a trace amount of the free compound. The titanium compound is removed and the obtained solid is designated as a solid product (3).

The titanium-based solid catalyst preferably used in the production of the propylene-olefin copolymer of the present invention includes the solid product (3) obtained as described above and the organic group (IV) group (E). It is a catalyst in combination with an aluminum compound.

Examples of the organoaluminum compound include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum and trihexylaluminum, dialkylaluminum monochloride such as diethylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichloride. In addition, alkoxyalkylaluminum such as monoethoxydiethylaluminum and diethoxymonoethylaluminum can be used.

The titanium-based solid catalyst obtained as described above can be used for producing the propylene-olefin copolymer of the present invention without substantially adding a donor.

As the process for producing the propylene-olefin copolymer of the present invention, a known olefin polymerization process can be used. Aliphatic hydrocarbons such as butane, pentane, hexane, heptane and isooctane, cyclopentane and cyclohexane. A slurry polymerization method is used to polymerize olefins in an alicyclic hydrocarbon such as methylcyclohexane, aromatic hydrocarbon such as toluene, xylene and ethylbenzene, and an inert solvent such as gasoline fraction and hydrogenated diesel oil fraction. can do. Further, a bulk polymerization method using olefins themselves as a solvent, or a gas phase polymerization method in which olefins are polymerized in a gas phase can be adopted. A polymerization process combining two or more of these processes can also be adopted.

The propylene-olefin copolymer of the present invention is produced at a polymerization temperature of -50 to 150 ° C, preferably 2
The polymerization is carried out under the conditions of 0 to 120 ° C., more preferably 40 to 100 ° C., and a polymerization pressure of atmospheric pressure to 9.9 MPa (gauge pressure), preferably 0.4 to 5.0 MPa (gauge pressure). . Moreover, you may adjust the molecular weight of the propylene-olefin copolymer obtained by introduce | transducing a chain transfer agent like hydrogen as needed. After the completion of the polymerization reaction, the unreacted monomer and hydrogen are separated from the polymerization system, and the catalyst deactivation treatment and the like can be performed to obtain the propylene-olefin copolymer of the present invention.

Examples of the slip agent used in the present invention include higher fatty acid amides, lower fatty acid amides, substituted amides such as N-stearyl stearic acid amide, methylol amides such as methylol stearic acid amide, and methylenebissteric acid amide. Examples thereof include bisamides, glycerin esters such as stearic acid monoglyceride, ethylene oxide adducts such as polyoxyethylene nonylphenyl ether, and the like, but higher fatty acid amides are preferable in terms of slip properties and anti-adhesion properties. The higher fatty acid amide preferably has 12 to 22 carbon atoms, and unsaturated higher fatty acid amide represented by oleic acid amide and erucic acid amide is more preferable.

The blending amount of the slip agent in the present invention is such that the propylene-olefin copolymer is 99.95 to 99.50.
It is 0.05 to 0.5 parts by weight, preferably 0.1 to 0.3 parts by weight, based on parts by weight. When the compounding amount of the slip agent is less than 0.05 parts by weight, no great effect is observed on the roll releasability and the rewinding property after winding, and when the compounding amount exceeds 0.5 part by weight, a large amount of the slip agent is present on the surface of the film. There is a risk of depositing and impairing the appearance.

The method for obtaining the resin composition containing the propylene-olefin copolymer of the present invention and the slip agent is not particularly limited, and various known methods can be used. For example, Henschel mixer (trade name)
Masterbatch blended with pellets or powder of propylene-olefin copolymer, powder or liquid of slip agent or various plastics by using a conventional mixer such as a mixer with a high-speed stirrer, ribbon blender, and tumbler mixer. An example of the method is to mix each of them in a predetermined amount. Furthermore, a method of pelletizing the mixed product using a normal single-screw extruder, a twin-screw extruder, or the like can be exemplified.

In the resin composition, known antioxidants, neutralizing agents, metal deactivators, light stabilizers, ordinarily used for polyolefins may be added, if necessary, within a range not impairing the object of the present invention. UV absorber, antistatic agent, nucleating agent, flame retardant,
Various additives such as an anti-blocking agent, a colorant, an inorganic or organic filler, and various synthetic resins can be blended.

Examples of the antioxidant include phenolic antioxidants, phosphite type antioxidants and thio type antioxidants, and examples of the neutralizing agent include higher fatty acid salts such as calcium stearate and zinc stearate. , As a light stabilizer and an ultraviolet absorber, hindered amines,
Examples include nickel complex compounds, benzotriazoles, benzophenones, and the like, and examples of metal deactivators include triazines, phosphones, epoxies, triazoles, hydrazides, oxamides, and the like.

The method for producing the propylene-olefin copolymer film of the present invention is not particularly limited, and various known and publicly known film forming methods, that is, an extrusion molding method, a calendering method, a compression molding method, using the above resin composition. Examples of the manufacturing method include a method, a cast molding method, and the like.

Among the known and publicly known film forming methods, the calendering method and the extrusion molding method are preferable from the viewpoint of good productivity. In the case of the calender method, a method using a calender molding machine including a Banbury mixer, a mixing roll, a warming roll, an extruder, a calender roll, a cooling roll, a trimming cutter, masking, a constant length cutting cutter, and a winding machine is used. It can be illustrated. In the case of extrusion molding method, extruder, T-die, cooling roll, guide roll, take-up roll, trimming cutter, standard length cutting cutter,
A method using an apparatus (T die sheet molding machine) equipped with a winding machine and the like can be exemplified. Of these, the extrusion molding method using a T die is preferable.

In the propylene-olefin copolymer film of the present invention, a resin composition comprising a propylene-olefin copolymer and a slip agent is used as a core layer, and polyethylene, polypropylene, and polypropylene are provided on at least one surface of the core layer. It may be a multilayer film in which a skin layer made of at least one selected from a copolymer of them and an α-olefin is laminated. The method for producing a multilayer film is not particularly limited, and various publicly known and publicly-used overlaying methods,
That is, it is possible to exemplify a method of manufacturing by a coextrusion method having two or more extruders, an extrusion laminating method, a dry laminating method, etc. Particularly, the coextrusion method does not require a secondary step as compared with other methods and is economical. Also advantageous and preferable.

The thickness of each skin layer of the multilayer film is 3 μm
The above is preferable, more preferably 3 to 500 μm, and particularly preferably 3 to 100 μm. If the skin layer is too thin, defective appearance such as film cracking occurs. The composition ratio of the core layer and the skin layer (core layer thickness / total skin layer thickness) is 20.
The following is preferable, and 0.5 to 20 is more preferable.
If the composition ratio is too large, it is economically disadvantageous.

In the various raw materials used for the skin layer, known antioxidants, neutralizing agents, light stabilizers, ultraviolet absorbers, and electrification agents which are usually used for thermoplastic resins can be used within the range not impairing the object of the present invention. Inhibitor, metal deactivator, plasticizer, filler,
Additives such as colorants can be added.

The thickness of the propylene-olefin copolymer film of the present invention is not particularly limited and the optimum thickness can be selected according to various uses, but it is usually 10 to 1,000 μm,
Most are in the range of 30 to 300 μm.

The propylene-olefin copolymer film of the present invention has a corona discharge treatment, a flame treatment, and a plasma treatment, which are usually employed industrially, for the purpose of imparting printability, paintability, metal vapor deposition, and the like. Surface treatment such as treatment is possible. Further, it is also possible to make a composite by laminating it with a cloth, non-woven fabric, paper or the like made of synthetic fibers or natural fibers or a film made of a polymer material. 2
When the propylene-olefin copolymer film composed of layers is compounded, it is advisable to laminate the film to the core layer so that the skin layer becomes the surface layer.

[0073]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited thereto.

The evaluation methods and measurement conditions used in the examples and comparative examples are described below. (1) Isotactic pentad fraction (mmmm):
^It was measured by the method described above using ¹³ C-NMR. (2) Triad chain fraction mm, rr, mr: ¹³ C-N
It was measured by the above-mentioned method using MR.

(3) Melting point (Tm), heat of fusion, glass transition temperature (Tg): Determined by the above-mentioned method using "DSC7 type differential scanning calorimeter" manufactured by Perkin-Elmer. (4) Boiling diethyl ether soluble content: Using a heating press, a film having a size of 100 × 100 × 1 mm was prepared in a non-pressurized state, and the obtained film was then cooled with a cooling press set at 20 ° C. Cooling. Then, the obtained film is finely cut into a size of 20 × 20 × 1 mm, and pulverized to a pass of 500 μm (32 mesh) using a pulverizer. (During this crushing operation, the sample is cooled beforehand with dry ice.) Using a Soxhlet extractor,
2 g of the obtained 500 μm-pass sample is extracted with boiling diethyl ether for 3 hours. 8 samples after extraction
It is vacuum dried at 0 ° C. and weighed. From the sample before extraction, the weight reduction rate of the sample after extraction is calculated to obtain the boiling diethyl ether soluble content. (Unit: wt%)

(5) Molecular weight distribution (weight average molecular weight (M
ratio of w) to number average molecular weight (Mn) (Mw / M
n)): Determined by the above-mentioned method using a GPC device (150C type manufactured by WATER, column used; TSK GEL GMH6-HT). (6) Melt flow rate (MFR): JIS K 7
210, in accordance with condition 14 of Table 1 (230 ° C, load 2
It was measured at 1.18 N). (Unit: g / 10 minutes) (7) Permanent elongation: J in accordance with JIS K 6301
The IS No. 1 dumbbell was stretched 100%, held for 10 minutes, the sample was taken out, and the length after 10 minutes was measured and determined. Those having a small permanent elongation have excellent rubber elasticity. (Unit:%) (8) Durometer hardness: Type A durometer hardness (HDA) measured according to JIS K7215.
I asked. (9) Flexural modulus: In accordance with JIS K7203,
It was measured at 23 ° C. (Unit: MPa)

(10) Haze: Measured according to ASTM D1003 using a test piece having a thickness of 1 mm. (Unit:%) (11) Gloss: 23 according to ASTM D523
It was determined by measuring at ° C and an angle of 60 °. (Unit:%) (12) Heat distortion temperature: Measured according to JIS K 7207. (Unit: ° C) (13) Izod impact strength: Measured according to JIS K 7110 with a notch. (Unit: kJ / m ² ) (14) Specific gravity: Measured according to JIS K7112. (15) Intrinsic viscosity [η]: Automatic viscosity measuring device (AVS2
Type, manufactured by Mitsui Toatsu Chemicals, Inc., was used, and tetralin was used as a solvent at a temperature of 135 ° C. for measurement. (Unit: dl / g)

(16) Bleed: The film was left in an atmosphere of 40 ° C. for 7 days, and the leaching condition of the slip agent on the film surface was visually confirmed. ◯: The slip agent hardly exudes, and the film maintains transparency. B: There is a problem in use because the slip agent exudes and the film becomes cloudy. X: Unusable because slip agent leaching and film turbidity were remarkable.

(17) Roll releasability: The presence or absence of adhesion to a chill roll or pinch roll during film processing was observed. ○: Continuous production is possible without sticking to the roll. Δ: Adhesion to the roll and peeling, but there is a problem in continuous production. X: The film cannot be processed because it adheres to the roll.

Next, the catalyst, propylene-olefin copolymer, film production method and the like used in Examples and Comparative Examples will be described below. [Production of Titanium-based Solid Catalyst] 80 g of aluminum trichloride (anhydrous) and 58 g of magnesium hydroxide were mixed with a vibration mill for 5 times.
When the mixture was mixed, pulverized, and heated at 130 ° C. for 10 hours, the reaction took place with dehydrochlorination reaction. After completion of heating, the mixture was cooled under a nitrogen stream and finely pulverized to obtain a solid product (1). To a 500 ml round bottom flask, 100 g of the solid product (1), 100 g of chain dimethylpolysiloxane (kinematic viscosity 1 cm ² / s) and 100 ml of toluene were added, and the mixture was reacted at 120 ° C. for 2 hours to give the solid product (2). Obtained. After the reaction was completed, the supernatant was removed and normal hexane 2 was added.
The procedure of adding 00 ml and removing the supernatant was repeated 4 times, 200 ml of titanium tetrachloride was added, and the mixture was heated at 110 ° C. for 1 hour for reaction. After completion of the reaction, the product was separated by filtration in a nitrogen-substituted dry box and then repeatedly washed with normal hexane until titanium was not detected in the filtrate, followed by drying under reduced pressure for 1 hour to obtain a solid product (3 ) Got. The content of titanium atoms in the solid product (3) is 7.
It was 7 mg (titanium atom) / g (solid product (3)).

[Propylene Using Titanium Solid Catalyst]
Production of Olefin Copolymer] 50 mmol of triethylaluminum and 20 ml of liquid propylene monomer were placed in an autoclave having an internal volume of 50 liters, which was sufficiently replaced with nitrogen.
After introducing kg, the temperature was raised to 60 ° C. with stirring. Then, ethylene monomer was supplied, and the gas composition in the autoclave was [ethylene / (propylene + ethylene)].
Of 250 mg of the above solid product (3) as a hexane slurry.
The polymerization reaction was initiated by pressurizing with nitrogen gas, and the polymerization reaction was carried out at 60 ° C. for 2 hours while keeping the gas composition in the autoclave at the above constant gas composition. The termination of the polymerization reaction was performed by pressing in 1 liter of methanol, and unreacted propylene and ethylene monomer were purged to recover 7 kg of a propylene-ethylene copolymer.

[Analysis of Propylene-Olefin Copolymer] When the propylene-ethylene copolymer obtained above was analyzed, the content of ethylene units was 9.1 mol%, the melting point was 133.3 ° C., and the melting point was 133.3 ° C. Heat is 17.1 J / g, Tg is -17.6 ° C, MFR is 3.9 g / 1.
0 minutes, Mw / Mn is 3.9, mmmm is 0.33, mm
Is 0.47, rr is 0.28, mr is 0.24,
Therefore, it was found that the relationship of mm>rr> mr holds. In addition, the boiling diethyl ether soluble content is 63.4.
%, and the intrinsic viscosity [η] of the boiling diethyl ether-soluble component was 1.7 dl / g.

[Measurement of Physical Properties of Propylene-Olefin Copolymer] The above-mentioned propylene-ethylene copolymer 99.
To 8 parts by weight of tetrakis [methylene (3,5-di-t-butyl-4-hydroxyl hydrocinnamate)] methane 0.05 part by weight, tris (2,4-di-
t-butylphenyl) phosphite was added at a ratio of 0.1 parts by weight and oleic acid amide at a ratio of 0.2 parts by weight, and a single screw extrusion granulator having a screw diameter of 40 mm and an extrusion temperature set at 200 ° C. was used. Then, a resin composition pellet containing a propylene-ethylene copolymer and a slip agent was obtained. Prepare a predetermined test piece using the obtained pellets,
The physical properties were measured. As a result, the permanent elongation was 19%, the durometer hardness of type A was HDA86, the haze was 19%, the heat deformation temperature was 72 ° C, and the flexural modulus was 30MP.
a, specific gravity was 0.87, and gloss was 106%. -20
An attempt was made to measure the Izod impact strength at 0 ° C, but the test piece did not undergo impact failure.

[Propylene Using Titanium Solid Catalyst]
Production of Olefin Copolymer] Except that 3 L of hydrogen was introduced, in the same manner as the propylene-olefin copolymer,
Copolymerization of propylene and ethylene was performed to recover 7.2 kg of a propylene-ethylene copolymer.

[Analysis of Propylene-Olefin Copolymer] When the propylene-ethylene copolymer obtained above was analyzed, the content of ethylene units was 9.5 mol%, the melting point was 134 ° C., and the heat of fusion was 23.3 J / g,
Tg is -19.0 ° C and MFR is 11.1 g / 10
Min, Mw / Mn is 3.6, mmmm is 0.34, mm is 0.49, rr is 0.27, and mr is 0.24. Therefore, it is understood that the relation of mm>rr> mr is established. It was In addition, the boiling diethyl ether soluble content was 60.
It was 9 wt%, and the intrinsic viscosity [η] of the boiling diethyl ether-soluble component was 1.3 dl / g.

[Measurement of Physical Properties of Propylene-Olefin Copolymer] The above-mentioned propylene-ethylene copolymer 99.
To 8 parts by weight of tetrakis [methylene (3,5-di-t-butyl-4-hydroxyl hydrocinnamate)] methane 0.05 part by weight, tris (2,4-di-
0.1 parts by weight of t-butylphenyl) phosphite,
And oleic acid amide as a slip agent were added at a ratio of 0.2 parts by weight, and the extrusion temperature was set to 200 ° C.
A resin composition pellet containing a propylene-ethylene copolymer and a slip agent was prepared using a 0 mmφ single-screw extruder. Predetermined test pieces were prepared using the obtained pellets, and physical properties were measured. As a result, the permanent elongation was 17% and the durometer hardness of type A was HDA.
83, the haze was 20%, the heat deformation temperature was 70 ° C., the flexural modulus was 37 MPa, the specific gravity was 0.87, and the gloss was 79%. The Izod impact strength at −20 ° C. was measured, but the test piece did not undergo impact failure.

[Evaluation of Single Layer Film]

Examples 1 and 2 Using an extruder equipped with a T-die (Labo Plastomill manufactured by Toyo Seiki Seisaku-sho, Ltd.), 200 resin compositions containing the above-mentioned propylene-ethylene copolymer or a slip agent were used. It is extruded while being melted at ℃, and is cooled and solidified by a cooling roll having a surface temperature of 30 ℃ to obtain a film having a thickness of 50 μm at a film forming processing speed of 4 m / min.
A film sample was obtained by winding 00 m around a paper tube with a constant tension using a winder. The obtained winding film was evaluated, and the results are shown in Table 1 below.

[Evaluation of Multilayer Film]

[Example 3] Multi-layer extruder equipped with a T-die (core layer extruder diameter 65 mm, φ1 unit, skin layer extruder diameter 40 mm
φ2 units), and the same resin composition pellets as in Example 1 except that the propylene-ethylene copolymer was changed to 99.95 parts by weight and the slip agent was changed to 0.05 parts by weight in the core layer. LDPE (PETROSEN 190 manufactured by Tosoh Corp .; trade name) was used as the skin layer laminated on both sides at 200 ° C. from each extruder so that the multilayer composition ratio shown in Table 1 was obtained.
Extruded while being melted at 50 ° C., cooled and solidified with a cooling roll having a surface temperature of 30 ° C., and a film-forming speed of 4 m / min and a thickness of 50 μm.
A film having a winding length of 100 m was wound around a paper tube with a constant tension using a winder to obtain a multilayer film sample.
Evaluate the obtained winding film as a multilayer film,
The results are shown in Table 1.

[0089]

Comparative Example 1 Example 1 except that the propylene-ethylene copolymer was 100 parts by weight and no slip agent was added.
The film was evaluated in the same manner as in Example 1, and the results are shown in Table 2 below.
It was shown to.

[0090]

Comparative Example 2 Example 1 except that the propylene-ethylene copolymer was changed to 99 parts by weight and the slip agent was changed to 1 part by weight.
The film was evaluated in the same manner as in Example 1, and the results are shown in Table 2 below.
It was shown to.

[0091]

[Table 1]

[0092]

[Table 2]

As is clear from the above table, the propylene-ethylene copolymer films of the examples of the present invention are superior to the comparative examples in bleeding property and are not sticky, so that they are also excellent in roll releasability and have good rubber elasticity. It has both flexibility and heat resistance, and balances workability and physical properties.

[0094]

According to the present invention, a propylene-olefin copolymer film having an excellent balance of various properties such as rubber elasticity and processing stability, as well as excellent environmental suitability and economy can be obtained. The propylene-olefin copolymer film of the present invention is suitable for applications such as medical bandages, medical films, care films, diapers, stretch films, wrap films, automobile supplies, interior materials for homes, protect films, and decorative paper. Can be used.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hitoshi Sato             1 Chisso at 5 Goi Coast, Ichihara City, Chiba Prefecture             Petrochemical Co., Ltd. Processed Product Development Laboratory F-term (reference) 4F071 AA15X AA20X AA21X AA80                       AA81 AA84 AA88 AC12 AE11                       AF21Y AH19 BB06 BC01                 4J002 BB141 BB151 EH046 EP016                       FD176 GB01

Claims (2)

[Claims] 1. A propylene unit is 85 to 99.99 mol% and an olefin unit excluding propylene is 0.01 to 15 mol% based on the number of moles of monomer units constituting the copolymer, and the following (a) to A resin composition containing 99.50 to 99.95 parts by weight of a propylene-olefin copolymer satisfying (d) and 0.05 to 0.50 parts by weight of a slip agent, and having a permanent elongation of 50% or less. A film or sheet characterized by: (A) Melting point is 110 to 150 ° C. (B) Melt flow rate (MFR) is 0.3 to 30 g
/ 10 minutes. (C) The molecular weight distribution (Mw / Mn) is 2.5 to 5.5. (D) Isotactic pentad fraction (mmmm) is 0.20 to 0.55, triad chain fraction mm,
rr and mr have a relation of mm>rr> mr. 2. The film or sheet according to claim 1, wherein the slip agent is at least one selected from higher fatty acid amides.