JP2002142947A - Table cloth - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a table cloth by using a film or a sheet which can be easily recycled, can be discarded or incinerated with a low risk of generating poisonous gases, is good for the global environment, is non-sticky and exhibits high softness and transparency. SOLUTION: The table cloth a film or a sheet having at least one layer of propylene polymer [I] (1) whose meso-pentad fraction (mmmm) is 0.2-0.6 and (2) whose racemic pentad fraction (rrrr) and (1-mmmm) satisfies the condition [rrrr/(1-mmmm)]<=0.1. The table cloth also uses a film or a sheet having at least one layer of resin composition which contains 1-99% by mass of propylene polymer [I] and 99-1% by mass of olefinic polymer [II].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention has excellent moldability, is easy to recycle, is less likely to generate toxic gases such as hydrogen chloride gas and chlorine gas at the time of disposal and incineration, and is friendly to the global environment. The present invention relates to a table cloth using a film or sheet having low stickiness, having the same flexibility as polyvinyl chloride, and having excellent transparency and gloss.

[0002]

2. Description of the Related Art Conventionally, as a table cloth, a soft polyvinyl chloride resin (PV) having excellent flexibility and transparency has been used.
Table cloths made of soft polyvinyl chloride resin are laminated on a base cloth such as cotton cloth. However, since polyvinyl chloride resin generates hydrogen chloride gas, chlorine gas, and the like at the time of incineration, it is said that it causes acid rain and the like, and a problem on environmental hygiene has been pointed out. In addition, it has been pointed out that the bleed-out of the plasticizer used for plasticization causes the tablecloth to become sticky and that the plasticizer adversely affects the human body as an environmental hormone. Furthermore, there is a problem that the printing ink is transferred to the surface of the table cloth from a printed matter placed on the table cloth mainly due to the plasticizer, and the table cloth turns yellow when used for a long time.

[0003]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems in tablecloths, is environmentally friendly, has little tackiness, has the same flexibility as a polyvinyl chloride resin, and is transparent. It is an object of the present invention to provide a table cloth using a film or a sheet having high performance.

[0004]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that at least one layer made of a specific propylene polymer or a specific propylene polymer and an olefin-based The present inventors have found that a table cloth using a film or a sheet having at least one layer made of a resin composition containing a polymer can achieve the object, and have completed the present invention. That is, the present invention provides: (1) the following (1) and (2) (1) the mesopentad fraction (mmmm) is 0.2 to 0.6; (2) the racemic pentad fraction (rrrr) 1-mm
mm) is [rrrr / (1-mmmm)] ≦ 0.1 Provided is a table cloth characterized by using a film or sheet having at least one layer of a propylene polymer [I] satisfying the following condition. And (2) the following (1) and (2) (1) the mesopentad fraction (mmmm) is 0.2 to 0.6 (2) the racemic pentad fraction (rrrr) and ( 1-mm
mm) and [rrrr / (1-mmmm)] ≦ 0.1 A resin composition comprising 1 to 99% by mass of a propylene polymer [I] and 99 to 1% by mass of an olefin polymer [II]. A table cloth characterized by using a film or sheet having at least one layer consisting of

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The table cloth of the present invention is a table cloth (a) using a film or a sheet having at least one layer composed of a specific propylene polymer [I], or a specific propylene polymer [I]. A table cloth (b) using a film or sheet having at least one layer made of a resin composition containing olefin and a olefin polymer [II]. Specific propylene polymer [I]
Is a propylene polymer satisfying the following (1) and (2). (1) The mesopentad fraction (mmmm) is 0.2 to 0.6. (2) The racemic pentad fraction (rrrr) and (1-mm)
mm) and [rrrr / (1-mmmm)] ≦ 0.1 In the propylene polymer [I], the mesopentad fraction (mmmm) is preferably from 0.3 to 0.6, and more preferably from 0.4 to 0.4. 5 is more preferred. The relationship between the racemic pentad fraction (rrrr) and (1-mmmm) is [rrrr / (1-mmmm)
mm)] ≦ 0.08, [rrrr /
(1-mmmm)] ≦ 0.06 is more preferable, and it is particularly preferable that [rrrr / (1-mmmm)] ≦ 0.05. When the propylene polymer [I] satisfies the above relationship, the obtained tablecloth has an excellent balance between the amount of the sticky component, the low elastic modulus and the transparency. That is, the elastic modulus is low, the flexibility (also referred to as softness) is excellent, the sticky component is small, and the surface characteristics (for example, the transfer of the sticky component to bleed or other products is small) are excellent, and There is an advantage that transparency is also excellent. Mesopentad fraction of propylene polymer [I] (m
mmm) is less than 0.2, causing stickiness and
If it exceeds, the elastic modulus is undesirably high. [Rrrr / (1-mmmm)] of the propylene polymer [I] is 0.1.
Exceeding the range may cause stickiness. Note that the mesopendad fraction (mmmm fraction) used in the present invention is defined as “Mac” by A. Zambelli and the like.
It is a meso fraction in a pentad unit in a polypropylene molecular chain measured by a signal of a methyl group in a ¹³ C-NMR spectrum in accordance with a method proposed in Romolecules, 6, 925 (1973). When this is increased, it means that stereoregularity is increased. Similarly, the racemic pentad fraction (rrrr fraction) is a racemic fraction in pentad units in a polypropylene molecular chain. [Rrrr / (1-mmmm)] is an index obtained from the above fraction of the pentad unit and is an index indicating the uniformity of the stereoregularity distribution of the propylene polymer. When this value is increased, the stereoregularity distribution broadens, and high stereoregularity PP (polypropylene) and atactic PP (APP) as in conventional polypropylene produced using an existing catalyst system.
, Which means that the tackiness increases and the transparency decreases. The measurement of the ¹³ C-NMR spectrum was carried out by A. Zambelli et al. In “Macromolecules, 8, 687 (197).
5) According to the assignment of the peaks proposed in "), the measurement is performed using the following apparatus and conditions.

Apparatus: JNM-EX40 manufactured by JEOL Ltd.
Type 0 ¹³ C-NMR apparatus Method: Proton complete decoupling method Concentration: 220 mg / ml Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C. Pulse width: 45 ° Pulse repetition time: 4 seconds Integration: 10000 times As the propylene polymer [I], in addition to the requirements (1) and (2),

(3) It is preferable that the intrinsic viscosity [η] measured in tetralin at 135 ° C. is 1.0 to 3.0 deciliter / g. Among them, more preferably, it is 1.0 to 2.5 deciliter / g, and particularly preferably, it is 1.2 to 2.2 deciliter / g. If the intrinsic viscosity [η] is less than 1.0 deciliter / g, stickiness may occur. On the other hand, if it exceeds 3.0 deciliters / g, the flowability may be reduced and the moldability may be poor. Further, the above (1) and (2)
In addition to the requirements of (3) and (4), it is preferable that the component amount (W25) eluted at 25 ° C. or lower in the temperature rising chromatography is 20 to 100% by mass, more preferably 30 to 100% by mass,
Particularly preferred is 50 to 100% by mass, most preferably 60 to 100% by mass. W25 refers to the amount (mass) of a component that is eluted without being adsorbed by the packing material at a TREF column temperature of 25 ° C. in an elution curve determined by temperature-raising chromatography under the operating method, apparatus configuration, and measurement conditions described in Examples. %). W25 is an index indicating whether or not the propylene polymer is soft. When this value is increased, it means that the component having a low elastic modulus is increased and / or the non-uniformity of the stereoregularity distribution is widened. In the present invention, if W25 is less than 20%, flexibility may be lost, which is not preferable.

The propylene polymer [I] preferably further satisfies any of the following requirements. The molecular weight distribution (Mw / Mn) measured by the gel permeation (GPC) method is 4 or less, more preferably 3.
It is 5 or less, particularly preferably 3 or less. Molecular weight distribution (M
If (w / Mn) exceeds 4, stickiness may occur. Note that the above Mw / Mn is determined by a gel permeation chromatography (GPC) method described in Examples. When the melting endothermic amount ΔH by DSC measurement is 30 J / g or less, flexibility is excellent and preferable. ΔH is an index indicating whether the material is soft or not, and as this value increases, the elastic modulus increases,
It means that the softness is reduced. A melting point (Tm) and a crystallization temperature (Tc) may or may not be present, but it is preferable not to have softness or to have a low value, particularly, Tm of 100 ° C. or less. Note that ΔH, Tm, and Tc are determined by DSC measurement described in Examples.

The propylene polymer [I] may be any as long as it satisfies the above (1) and (2), and a comonomer other than propylene is copolymerized in an amount of 2% by mass or less as long as the object of the present invention is not impaired. May be used.
Examples of the comonomer include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, and 1-hexene.
Examples thereof include octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. In the present invention, one or more of these can be used. The method for producing the propylene polymer [I] used in the present invention includes:
A method of polymerizing or copolymerizing propylene using a metallocene catalyst obtained by combining (A) a transition metal compound forming a crosslinked structure via two crosslinking groups and (B) a cocatalyst is preferable. Specifically, the general formula (I)

[0010]

Embedded image

[Wherein M is a group 3 to 10 of the periodic table or La
E represents a tanthanoid metal element ¹And E^TwoIs it
Substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, heterocyclopentadienyl group,
Telocyclopentadienyl group, amide group, phosphide
Ligand selected from the group consisting of a group, a hydrocarbon group and a silicon-containing group
And A¹And A^TwoTo form a crosslinked structure via
And they may be the same or different
X represents a σ-binding ligand, and when there are a plurality of Xs,
A plurality of X may be the same or different, and other X,
E¹, E^TwoAlternatively, it may be crosslinked with Y. Y is Lewis salt
A plurality of Y are the same or different
Other Y, E¹, E^TwoOr cross-linked with X
May be, A¹And A^TwoIs the two that binds the two ligands
A divalent crosslinking group, a hydrocarbon group having 1 to 20 carbon atoms,
A halogen-containing hydrocarbon group having a prime number of 1 to 20, a silicon-containing group,
Germanium-containing groups, tin-containing groups, -O-, -CO-,
-S-, -SO_Two-, -Se-, -NR¹-, -PR¹
-, -P (O) R¹-, -BR¹-Or-AlR¹-
And R¹Is a hydrogen atom, a halogen atom, a carbon number of 1 to 20
A hydrocarbon group or a halogen-containing hydrocarbon having 1 to 20 carbon atoms
Denote radicals, which may be the same or different
Good. q is an integer of 1 to 5 and represents ((valence of M) -2).
And r represents an integer of 0 to 3. Transition metallization represented by
Compound (A), and the transition metal compound or the component (A).
Capable of forming an ionic complex by reacting with derivatives of
Selected from (B-1) and aluminoxane (B-2)
In the presence of a polymerization catalyst containing the co-catalyst component (B),
A method of polymerizing or copolymerizing pyrene is exemplified.

A specific example of the transition metal compound represented by the general formula (I) is (1,2′-dimethylsilylene)
(2,1′-dimethylsilylene) bis (3-n-butylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium Dichloride, (1,2′-dimethylsilylene) (2,
1′-dimethylsilylene) bis (3-phenylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4,5
-Benzoindenyl) zirconium dichloride, (1,
2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4-isopropylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2
1′-dimethylsilylene) bis (5,6-dimethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4,7-di-i-propylindenyl) ) Zirconium dichloride, (1,2′-dimethylsilylene) (2,
1'-dimethylsilylene) bis (4-phenylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-methyl-4-i-propylindenyl) zirconium Dichloride, (1,2'-dimethylsilylene) (2,1'-
Dimethylsilylene) bis (5,6-benzoindenyl)
Zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis ( 3-
Methylindenyl) zirconium dichloride, (1,
2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-i-propylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2
1'-isopropylidene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride , Etc. and those obtained by substituting zirconium in these compounds with titanium or hafnium.

Next, the component (B-1) of the component (B) includes triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, Examples thereof include methyl tetraphenylborate (tri-n-butyl) ammonium and benzyltetraphenylborate (tri-n-butyl) ammonium. (B-1) may be used alone, or two or more kinds may be used in combination. On the other hand, as the aluminoxane of the component (B-2),
Methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane and the like are mentioned. These aluminoxanes may be used alone or in a combination of two or more. As the polymerization catalyst, an organoaluminum compound can be used as the component (C) in addition to the components (A) and (B).

As the organoaluminum compound of the component (C), trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutyl Aluminum hydride,
Examples thereof include diethyl aluminum hydride and ethyl aluminum sesquichloride. These organoaluminum compounds may be used alone or in combination of two or more. Here, in the polymerization of propylene, at least one of the catalyst components can be used by being supported on a suitable carrier.

The polymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, and a suspension polymerization method may be used. Legitization is particularly preferred. The polymerization temperature is usually -100 to 2
At 50 ° C., the usage ratio of the catalyst to the reaction raw material is such that the raw material monomer / the component (A) (molar ratio) is preferably 1 to 10%.
^8, it is preferable that the particular 100 to 10 ^5. Further, the polymerization time is usually 5 minutes to 10 hours, and the reaction pressure is usually
Normal pressure to 20 MPa (gauge).

The olefin polymer [II] contained in the resin composition forming the table cloth (b) of the present invention includes polypropylene, propylene-ethylene copolymer, propylene-ethylene other than propylene polymer [I]. −
Examples include diene copolymers, polyethylene, ethylene / α-olefin copolymers, ethylene-vinyl acetate copolymers, and the like. These may be used alone or in combination of two or more. This resin composition is
It is composed of 1 to 99% by mass of the propylene polymer [I] and 99 to 1% by mass of the olefin polymer [II]. Preferably, it is composed of 10 to 80% by mass of the propylene polymer [I] and 90 to 20% by mass of the olefin polymer [II]. More preferably, it is composed of 25 to 75% by mass of the propylene polymer [I] and 75 to 25% by mass of the olefin polymer [II]. Particularly preferably, the propylene polymer [I] is 40 to 75% by mass.
And 60 to 25% by mass of the olefin polymer [II].

The resin composition for forming the table cloth (b) of the present invention comprises 1 to 99% by mass of the propylene polymer [I].
And 99 to 1% by mass of the olefin polymer [II] and various additives used as desired are dry-blended using a Henschel mixer or the like, and melted using a single-screw or twin-screw extruder, a Banbury mixer, or the like. It is kneaded.
Various additives used as desired include ultraviolet absorbers, HALS (hindered amine light stabilizers), lubricants, antioxidants, antiblocking agents, nucleating agents, petroleum resins, antibacterial agents, antistatic agents, coloring agents , Heat stabilizer, release material,
Examples include anti-fogging agents, inorganic fillers such as talc and calcium carbonate, reinforcing agents such as glass fibers and carbon fibers, flame retardants, and silicone. These additives can also be added to a tablecloth (a) using a film or sheet having at least one layer made of a propylene polymer [I].

The tablecloth of the present invention comprises a single layer having only one layer comprising a propylene polymer [I] or a layer comprising a resin composition containing a propylene polymer [I] and an olefin polymer [II]. It may be a film or sheet having a layer structure, or a film or sheet having a multilayer structure having at least one of these layers. The multi-layer table cloth has two or more layers, and the number of layers is preferably 3 to 10, and more preferably 3 to 5. When the table cloth of the present invention has a three-layer structure, the center layer is a layer made of a propylene polymer [I], or a propylene polymer [I] and an olefin polymer [I
It is preferable to form a layer made of a resin composition containing the composition [I], and the thickness of the central layer is preferably 0.5 to 20 times the thickness of the other layers. The tablecloth of the present invention also includes a tablecloth obtained by laminating a film or sheet having the single-layer structure or the multilayer structure on a base cloth.

Layers other than the layer composed of the propylene polymer [I] or layers other than the layer composed of the resin composition containing the propylene polymer [I] and the olefin-based polymer [II] are formed by adding propylene to these layers. It can be formed by blending a polypropylene resin other than the polymer [I], a polyethylene resin, or a thermoplastic elastomer, or by using such a polypropylene resin or a polyethylene resin. Also in this case, the various additives described above can be added. Examples of the polypropylene resin other than the propylene polymer [I] include homopropylene and propylene-
Examples include an ethylene random copolymer, a propylene-ethylene-butene terpolymer, and SPP (syndiotactic polypropylene). Examples of the polyethylene resin include LDPE (low density polyethylene), LLDPE (linear low density polyethylene) having 4, 6 or 8 carbon atoms, metallocene LLDPE, EVA (ethylene-vinyl acetate copolymer), and EMMA (ethylene・ Methyl methacrylate copolymer), EEA (ethylene-ethyl acrylate copolymer), EMA (ethyl methacrylate),
EMAA (ethylene / methyl acrylate copolymer) and ethylene ionomer. As thermoplastic elastomers, EPR (ethylene / propylene rubber elastomer), HSBR (hydrogenated-styrene / butadiene rubber elastomer), SBS (styrene / butadiene / styrene elastomer), SEBS (styrene /
(Ethylene / butylene / styrene elastomer), SEP
S (styrene / ethylene / propylene / styrene elastomer), SIS (styrene / isoprene / styrene elastomer) and the like.

The film or sheet used for the table cloth of the present invention can be produced by a known sheet forming method (calender forming method, T-die extrusion forming method, inflation forming method). The thickness of the film or sheet used for the table cloth of the present invention is preferably 0.02 to 2 mm. When only the film or sheet is used as the tablecloth, the thickness of the film or sheet is 0.
The thickness is preferably 3 to 2 mm. When a table cloth is produced by laminating a film or sheet on a base fabric, the thickness of the film or sheet is preferably 0.02 to 1 mm. The tensile modulus of the film or sheet is preferably from 20 to 500 MPa, and from 50 to 500 MPa.
300 MPa is more preferable, and 50 to 200 MPa is particularly preferable. The total haze measured according to JIS K 7105 is preferably 3% or less. The glossiness of the film or sheet (measured in accordance with JIS K 7105-1982) is preferably 100% or more,
More preferably 110% or more, particularly preferably 120%
That is all. The total light transmittance measured according to JIS K 7105-1982 is preferably 80% or more.

When a table cloth is produced by laminating the above-mentioned film or sheet of the present invention on a base cloth, a woven fabric using fibers such as cotton, rayon, polyester, polyacrylonitrile, polyethylene and polypropylene is used as the base cloth. , Nonwoven fabric or knitted fabric can be used. Further, these may be made flame-retardant, designed into a patterned fabric, or printed. In the present invention, a cotton fabric, a 100% polyester fabric, a polyester / cotton blend fabric, and a polyester / rayon blend fabric are preferred. Examples of a method for laminating the above-described film or sheet on these base fabrics include a heat lamination method and a dry lamination method using an adhesive. The lamination may be performed on one side of the base fabric, or may be performed on both sides of the base fabric. One surface of the film or sheet is a layer composed of a propylene polymer [I] or a layer composed of a resin composition containing a propylene polymer [I] and an olefin polymer [II], and the other surface of the film or sheet is When it is a layer composed of another resin, the layer that adheres to the base fabric is a layer composed of a propylene polymer [I] or a layer composed of a resin composition containing a propylene polymer [I] and an olefin-based polymer [II]. It is preferable that

[0022]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. Production Example 1 Production of Propylene Polymer (P1) (1) Synthesis of Complex (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride Synthesis (1,2'-dimethylsilylene) (2,
3.0 g (6.97 mmol) of lithium salt of 1'-dimethylsilylene) -bis (indene) was dissolved in 50 ml of THF and cooled to -78 ° C. 2.1 ml (14.2 mmol) of iodomethyltrimethylsilane is slowly added dropwise and stirred at room temperature for 12 hours. The solvent is distilled off, 50 ml of ether is added, and the mixture is washed with a saturated ammonium chloride solution. After liquid separation, the organic phase was dried, and the solvent was removed. 3.04 g (5.88 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) was removed. I got (Yield 8
Next, 3.04 g of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) obtained above was placed in a Schlenk bottle under a nitrogen stream. 5.88 mmol) and 50 ml of ether. Cool to -78 ° C and n-BuLi
(Hexane solution 1.54M) in 7.6 ml (11.7
(mmol), and stirred at room temperature for 12 hours. The solvent was distilled off, and the obtained solid was washed with 40 ml of hexane to convert the lithium salt into an ether adduct.
06 g (5.07 mmol) was obtained (yield 73%). ¹ H
_{-NMR (90MHz, THF-d 8} ) results of measurement by the,: δ 0.04 (s, 18H , trimethylsilyl), 0.48 (s, 12H, dimethylsilylene), 1.1
0 (t, 6H, methyl), 2.59 (s, 4H, methylene), 3.38 (q, 4H, methylene), 6.2-7.7
(M, 8H, Ar-H). The lithium salt obtained above was dissolved in 50 ml of toluene under a nitrogen stream. After cooling to −78 ° C., a toluene (20 ml) suspension of zirconium tetrachloride (1.2 g, 5.1 mmol) previously cooled to −78 ° C. was added dropwise. After the addition, the mixture was stirred at room temperature for 6 hours. The solvent of the reaction solution was distilled off.
The obtained residue was recrystallized from dichloromethane to give 0.9 g of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride (1. 3
3 mmol) (26% yield). ¹ H-NMR (9
0 MHz, CDCl ₃ ) gives: δ
0.0 (s, 18H, trimethylsilyl), 1.02, 1.1
2 (s, 12H, dimethylsilylene), 2.51 (dd,
4H, methylene), 7.1-7.6 (m, 8H, Ar-H)
Met.

(2) Polymerization of Propylene In a stainless steel autoclave having a stirrer and having an internal volume of 10 liters, 4 liters of n-heptane, 2 mmoles of triisobutylaluminum, and 2 mmoles of methylaluminoxane (manufactured by Albemarle) were obtained as described above. (1,
2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl)
2 micromoles of zirconium dichloride were charged sequentially. Then, after introducing 0.06 MPa (gauge) of hydrogen, the temperature was raised to 60 ° C., and the total pressure was 0.8.
Propylene gas was introduced up to MPa (gauge).
During the polymerization, propylene was supplied by a pressure regulator so that the total pressure became 0.8 MPa (gauge). Polymerization temperature 60 ° C
After conducting polymerization for 30 minutes, the content is taken out and dried under reduced pressure to obtain a propylene polymer (P1).
I got Table 1 shows the results obtained by the “method for evaluating resin properties of propylene polymer” shown below.

<Method for Evaluating Resin Properties of Propylene Polymer> (1) Measurement of [η] The measurement was performed at 135 ° C. in a tetralin solvent using a VMR-053 automatic viscometer manufactured by Rigo Co., Ltd. (2) Measurement of Pentad Fraction It was measured by the method described in the text of the specification. (3) Measurement of melt flow rate (MFR) 230 ° C., load 21.1 according to JIS K7210
Measured at 8N. (4) Measurement of molecular weight distribution (Mw / Mn) Mw / Mn was measured by an apparatus described below.

GPC measuring device Column: TOSO GMHHR-H (S) HT Detector: RI detector for liquid chromatogram WATERS 150C Measurement conditions Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C. Flow rate: 1.0 Milliliter / min Sample concentration: 2.2 mg / ml Injection volume: 160 microliter Calibration curve: Universal Calibration Analysis program: HT-GPC (Ver. 1.0)

(5) DSC measurement Differential scanning calorimeter (manufactured by Perkin-Elmer, DSC-
7) Using a 10 mg sample at 220 ° C. in a nitrogen atmosphere for 3
After melting for 1 minute, the peak top of the maximum peak of the crystallization exothermic curve obtained when the temperature was lowered to -40 ° C at 1 ° C / minute was defined as crystallization temperature: Tc. Furthermore, after holding at −40 ° C. for 3 minutes, the melting endotherm obtained by increasing the temperature at 10 ° C./min was defined as ΔH. In addition, the peak top of the maximum peak of the melting endothermic curve obtained at this time is defined as melting point:
Tm. (6) Elevated Temperature Separation Chromatograph The amount W25 (% by mass) of the component eluted without being adsorbed by the filler at the TREF column temperature of 25 ° C. in the elution curve was determined as follows. (A) Operation method A sample solution is introduced into a TREF column adjusted to a temperature of 135 ° C., and then gradually cooled to 0 ° C. at a rate of 5 ° C./hour, held for 30 minutes, and the sample is adsorbed on a filler. Thereafter, the column was heated to 135 ° C. at a heating rate of 40 ° C./hour.
The temperature was raised to ℃ to obtain an elution curve. (B) Apparatus configuration TREF column: Silica gel column (4.6φ x 150mm) manufactured by GL Sciences Flow cell: 1mm optical path length KBr cell manufactured by GL Sciences Pump: SSC-3100 pump manufactured by Senshu Kagaku Valve oven: GL Sciences Model 554 oven (high temperature type) TREF oven: GL Science's two-line temperature controller: Rigaku Corporation REX-C100 temperature controller Detector: Infrared detector for liquid chromatography FOXBORO's MIRAN 1A CVF 10-way valve : Barco electric valve loop: Barco 500 microliter loop (c) Measurement conditions Solvent: o-dichlorobenzene Sample concentration: 7.5 g / liter Injection volume: 500 microliter Pump flow rate: 2.0 ml / min Detection Wave number: 3. 1μm column filler: Chromosorb P (30 to 60 mesh) Column temperature distribution: within ± 0.2 ° C.

Production Example 2 [Production of Propylene Polymer (P2)] (1) Preparation of Magnesium Compound A glass reactor equipped with a stirrer having an internal volume of about 6 liters was sufficiently replaced with nitrogen gas, and then ethanol was added to the reactor.
30 g, 16 g of iodine and 160 g of metallic magnesium were charged, heated with stirring, and reacted under reflux conditions until hydrogen gas was not generated from the inside of the system to obtain a solid reaction product. The reaction solution containing the solid product was dried under reduced pressure to obtain a magnesium compound. (2) Preparation of solid catalyst component (A) 160 g of the magnesium compound (not pulverized) obtained in the above (1) and purified heptane 80 were placed in a glass reactor having an internal volume of 5 liters which had been sufficiently purged with nitrogen gas. Milliliter, 24 milliliters of silicon tetrachloride and 23 milliliters of diethyl phthalate were charged, the system was maintained at 80 ° C, 770 milliliters of titanium tetrachloride was added with stirring, and the mixture was reacted at 110 ° C for 2 hours. Washed with purified heptane at 90 ° C. Further, after adding 1220 ml of titanium tetrachloride and reacting at 110 ° C. for 2 hours, it was sufficiently washed with purified heptane to obtain a solid catalyst component (A).

(3) Gas phase polymerization of propylene In a polymerization tank having an internal volume of 200 liters, 6.0 g / h of the solid catalyst component obtained in the above (2), 0.2 mol / h of triisobutylaluminum (TIBA), 1-allyl-3,4
-Dimethoxybenzene (ADMB) 0.012 mol / h, cyclohexylmethyldimethoxysilane (CHMD)
(MS) 0.012 mol / h, propylene 37 kg / h, and polymerization was performed at 70 ° C. and 2.8 MPa (gauge) to produce a propylene polymer. The obtained propylene powder was added to 2,5-dimethyl-2,5-di- (t
-Butyl peroxy) -hexane, and the following additive formulation was performed, and a single screw extruder (manufactured by Tsukada Juki Seisakusho, Ltd.):
TLC (Model 35-20) for extrusion granulation to produce pellets. Table 1 shows the results obtained for the obtained pellets (P2) by the above-mentioned "Method for evaluating resin properties of propylene polymer".

(Additive formulation) Phenolic antioxidant: Ciba Specialty Chemicals, Irganox 1010; 1,000 pp
m Phosphorus antioxidant: P-EPQ, manufactured by Clariant Co .;
500 ppm-Neutralizing agent: calcium stearate; 500 ppm-Neutralizing agent: DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd .; 500p
pm

Production Example 3 [Production of propylene polymer (P3)] 400 ml of heptane and triisobutylaluminum were placed in a stainless steel autoclave having an internal volume of 1 liter.
0.5 mmol, dimethylanilinium (pentafluorophenyl) borate (2 μmol), and (tertiary butylamido) dimethyl (tetramethyl-η) produced in the same manner as in Example 1 of JP-A-3-16388.
A catalyst component obtained by preliminarily contacting 1 micromol of ⁵ -cyclopentadienyl) silanetitanium dichloride in toluene for 5 minutes was added. Here, 0.03 MPa of hydrogen (gaug
After introducing e), propylene gas was introduced to a total pressure of 0.8 MPa (gauge), and propylene was supplied by a pressure regulator so that the pressure during polymerization was constant. Polymerization temperature 70 ° C
After polymerization for 1 hour, the content was taken out and dried under reduced pressure to obtain a propylene polymer (P3). "Method for evaluating resin properties of propylene polymer" was performed, and the obtained results are shown in Table 1.

[0031]

[Table 1]

Example 1 The following additives were formulated into the propylene polymer (P1) obtained above, and a single screw extruder (TLC 35, manufactured by Tsukada Juki Seisakusho) was used.
-20) and extruded to produce P1 pellets. (Additive formulation)-Phenolic antioxidant: Ciba Specialty Chemicals, Irganox 1010; 500 ppm-Phosphorus antioxidant: Ciba Specialty Chemicals, Irgafos 168; 1,000 ppm

The obtained P1 pellets are 65 mm in diameter.
And extruded from a T-die of an extruder (PO-65, manufactured by Placo Co., Ltd.), and formed at a forming temperature of 230 ° C. and a drawing speed of 2 m / min to produce a raw sheet. A polyurethane adhesive is applied to one or both sides of a 100% polyester plain fabric, and the obtained sheet is laminated on one or both sides of the plain fabric,
After drying at room temperature for 24 hours, a table cloth having sheets laminated on both sides of a base cloth or a table cloth having sheets laminated on one side of a base cloth was produced. Table 2 shows the evaluation results obtained by the following “Method for evaluating characteristics of table cloth”.

<Evaluation Method of Characteristics of Table Cloth> (1) Tensile Modulus Tensile modulus was measured by a tensile test according to JIS K7113. Cross head speed: 50 mm / min Load cell: 100 kg Measurement direction: machine direction (MD direction) (2) Flexibility The table cloth was touched by hand, and the touch was evaluated. ：: Soft and good feel, ×: Hard and unsuitable as a tablecloth. (3) Feeling of stickiness The mat was touched by hand and evaluated by its feeling. ：: non-sticky, ×: sticky, dust and ink adhered, unsuitable as a tablecloth.

Example 2 70% by mass of the pellets of P1 obtained above were mixed with 30 parts of polypropylene E-304GP (propylene homopolymer, melt index = 3) (denoted as 304 in Table 2) manufactured by Idemitsu Petrochemical Co., Ltd. % By mass and extruded and granulated with a single screw extruder (TLC35-20, manufactured by Tsukada Juki Seisakusho) to produce pellets as a resin composition for extrusion molding. Using the pellets, a table cloth was prepared in the same manner as in Example 1, and the same evaluation was performed. Table 2 shows the evaluation results. Example 3 Three extruders similar to those used in Example 1 were used, and polypropylene F-744NP manufactured by Idemitsu Petrochemical Co., Ltd. (propylene random copolymer, melt index = 7) was obtained from the T die of each extruder. (In Table 2, 7
44), a layer consisting of the pellets of P1 obtained above and a layer consisting of polypropylene F-744NP were extruded, and these layers were sequentially laminated at a thickness ratio of 1/6/1. Example 1 was prepared by preparing a raw sheet having
In the same manner as in the above, a table cloth was produced. Table 2 shows the evaluation results of this table cloth.

Example 4 In Example 3, the layer made of P1 pellets was replaced with P1
Example 3 except that the pellets of Example 3 were changed to a layer composed of pellets (same pellets as in Example 2) obtained by blending 70% by mass of polypropylene pellets and 30% by mass of polypropylene E-304GP manufactured by Idemitsu Petrochemical Co., Ltd. A table cloth was produced in the same manner. Table 2 shows the evaluation results of this table cloth. Comparative Example 1 A table cloth was prepared in the same manner as in Example 1, except that the P2 pellet obtained above was used instead of the P1 pellet. Table 2 shows the evaluation results of this table cloth. Comparative Example 2 A table cloth was produced in the same manner as in Example 1, except that the P3 pellet obtained above was used instead of the P1 pellet. Table 2 shows the evaluation results of this table cloth.

[0037]

[Table 2]

[0038]

According to the present invention, there is provided a film or film which is easy to recycle, has little risk of generating toxic gas at the time of disposal or incineration, is friendly to the global environment, has low stickiness, and is excellent in flexibility and transparency. A table cloth using the sheet can be obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 3B102 CB01 4F071 AA20 AF26 AF30 AF32 AH03 BA01 BB06 BC01 4J100 AA02Q AA03P AA04Q AA07Q AA16Q AA17Q AA19Q AA21Q DA09 DA50 DA62 EA05 FA10 FA18 FA19 JA57

Claims (9)

[Claims] 1. The following (1) and (2) (1) a mesopentad fraction (mmmm) is 0.2 to 0.6 (2) a racemic pentad fraction (rrrr) and (1-mm)
mm) and [rrrr / (1-mmmm)] ≦ 0.1. A table cloth characterized by using a film or sheet having at least one layer of a propylene polymer [I] satisfying the following. 2. The propylene polymer [I] further satisfies the following (3) (3): intrinsic viscosity [η] measured in tetralin at 135 ° C. is 1.0 to 3.0 deciliter / g. The table cloth according to claim 1, which is a propylene polymer. 3. A propylene polymer which satisfies the following (4) and (4) the amount of a component (W25) eluted at 25 ° C. or lower in temperature rising chromatography at 20 ° C. to 100% by mass. The table cloth according to claim 1 or 2, which is a united product. 4. The propylene polymer [I] is polymerized using a metallocene catalyst comprising a transition metal compound having a crosslinked structure via two crosslinking groups and a cocatalyst. 3. The table cloth according to any one of 3. 5. The following (1) and (2) (1) a mesopentad fraction (mmmm) is 0.2 to 0.6 (2) a racemic pentad fraction (rrrr) and (1-mm)
mm) and [rrrr / (1-mmmm)] ≦ 0.1 A resin composition comprising 1 to 99% by mass of a propylene polymer [I] and 99 to 1% by mass of an olefin polymer [II]. Characterized by using a film or sheet having at least one layer consisting of: 6. The propylene polymer [I] further satisfies the following (3) (3): intrinsic viscosity [η] measured in tetralin at 135 ° C. is 1.0 to 3.0 deciliter / g. The table cloth according to claim 5, which is a propylene polymer. 7. The propylene polymer which further satisfies the following (4) (4) the amount of a component (W25) eluted at 25 ° C. or lower in temperature rising chromatography (W25) is 20 to 100% by mass. The table cloth according to claim 5 or 6, which is united. 8. The propylene polymer [I] is polymerized using a metallocene catalyst comprising a transition metal compound having a crosslinked structure via two crosslinking groups and a cocatalyst. 7. The table cloth according to any one of 7. 9. A table cloth comprising the film or sheet according to claim 1 laminated on a base fabric.