JP2002137595A - Polyolefin desk mat - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyolefin desk mat having suitable flexibility, good non-transferability, excellent transparency, rewinding properties and writability. SOLUTION: The polyolefin desk mat comprises a layer containing a copolymer obtained by copolymerizing (a) an α-olefin, (b) a cyclic olefin and/or (c) an aromatic vinyl compound and having a glass transition temperature of -30 to 30 deg.C, a tensile elastic modulus of 1,000 MPa or less and an elastic recovery rate of 20% or more.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin-based desk mat, and more particularly, to a polyolefin-based desk mat which has appropriate flexibility and good non-transfer properties and is excellent in transparency, rewinding property and writing quality. It is.

[0002]

2. Description of the Related Art Conventionally, a transparent sheet made of a soft vinyl chloride resin or a polyolefin resin has been often used as a desk mat to be laid on an office desk or a study desk.
However, in the case of a sheet made of a soft vinyl chloride resin,
(1) Since hydrogen chloride is generated during incineration, an incinerator with abatement equipment is required. (2) When used for a long time, the plasticizer may come out on the surface and become sticky.
(3) There is an inconvenience that ink transfer (a phenomenon in which ink such as printed matter is transferred to or transferred to a mat surface), which is mainly caused by the plasticizer contained in the sheet, easily occurs. On the other hand, those made of a polyolefin-based resin which is considered to be excellent in non-transferability without using a plasticizer are inferior in transparency and rewinding (the desk mat is a sheet-like molded product having a thickness of usually about 2 mm). Therefore, when the scroll is unwrapped and laid on an office desk or the like, it may not be possible to lay the sheet horizontally in close contact with the surface. In addition, since there is no appropriate flexibility, there is a problem that writing quality on writing on a desk mat is inferior and the like, and the desk mat cannot always be said to be sufficiently satisfactory.

[0003]

SUMMARY OF THE INVENTION The present invention provides a polyolefin-based desk mat which has appropriate flexibility and good non-transferability, and is excellent in transparency, rewinding property and writability under such circumstances. It is intended to provide.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to develop a polyolefin-based desk mat having the above-mentioned preferable properties, and as a result, have found that α-olefins and cyclic olefins and aromatic vinyl compounds can be used together. It has been found that a mat having a layer containing a copolymer having specific properties obtained by polymerization can be suitable for the purpose. The present invention
It has been completed based on such knowledge. That is,
The present invention is obtained by copolymerizing (a) an α-olefin with (b) a cyclic olefin and / or (c) an aromatic vinyl compound, and has a glass transition temperature of -30 ° C to 30 ° C and a tensile elasticity. Rate is less than 1000MPa and elastic recovery rate is 20%
An object of the present invention is to provide a polyolefin-based desk mat having a layer containing the above copolymer.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The copolymer used for the polyolefin-based desk mat of the present invention (hereinafter sometimes simply referred to as the desk mat of the present invention) comprises (1) (a) an α-olefin and (b) ) Copolymers with cyclic olefins, (2)
(A) a copolymer of α-olefin and (c) aromatic vinyl compound or (3) a copolymer of (a) α-olefin, (b) cyclic olefin and (c) aromatic vinyl compound is there. Among them, the copolymer (1) is particularly preferable. Examples of the α-olefin of the component (a) include α-monoolefins having 2 to 22 carbon atoms and halogen-substituted α-olefins.
At least one selected from olefins and chain diolefins can be mentioned. Specifically, ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-phenyl-1-butene, 1-pentene, 3-
Methyl-1-pentene, 4-methyl-1-pentene,
3,3-dimethyl-1-pentene, 3,4-dimethyl-
1-pentene, 4,4-dimethyl-1-pentene, 1-
Hexene, 4-methyl-1-hexene, 5-methyl-1
-Hexene, 6-phenyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1
-Hexadecene, 1-octadecene, 1-eicosene,
Α-monoolefins such as vinylcyclohexane, hexafluoropropene, tetrafluoroethylene, 2-fluoropropene, fluoroethylene, 1,1-difluoroethylene, 3-fluoropropene, trifluoroethylene, 3,4-dichloro-1- Halogen-substituted α-olefins such as butene, butadiene, isoprene, 1,4-
Examples thereof include chain diolefins such as pentadiene and 1,5-hexadiene. One of these α-olefins may be used alone, or two or more thereof may be used in combination. The cyclic olefin of the component (b) is not particularly limited, but may be represented by the general formula (I):

[0006]

Embedded image

(Where k is 0 or 1, m is 0 or 1, and n is 0 or a natural number. R ^{1 to} R ²⁰
Is each independently a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group or an amino group). Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. As the hydrocarbon group, those having 1 to 20 carbon atoms are preferable, and specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, amyl group, hexyl group, Octyl, decyl, dodecyl, octadecyl, cyclohexyl, phenyl,
Examples include a naphthyl group, a tolyl group, a benzyl group, a phenylethyl group, a naphthyl group, and an anthracenyl group.

[0008] The alkoxy group may have 1 to 20 carbon atoms.
Are preferred, specifically, methoxy group, ethoxy
Group, propoxy group, isopropoxy group, butoxy group,
Sobutoxy group, t-butoxy group, phenoxy group, 2,6
-Dimethylphenoxy group, trimethylsiloxy group, etc.
No. Amino groups having 1 to 20 carbon atoms
Are preferred, specifically, dimethylamino group, diethyl
Amino group, diisopropylamino group, diphenylamino
Group, pyrrolidinyl group, bis (trimethylsilyl) amino
And the like. R¹⁷~ R²⁰Are simply connected to each other
May form a ring or polycycle, and the monocycle or
The polycyclic ring may have a double bond;¹⁷And R¹⁸When
Or R ¹⁹And R²⁰Form an alkylidene group with
May be.

The cyclic olefin represented by the above general formula (I)
For example, bicyclo [2.2.1] hep
To-2-ene (norbornene), 5-methylbicyclo
[2.2.1] Hept-2-ene, 5,6-dimethylbi
Cyclo [2.2.1] hept-2-ene, 1-methylbi
Cyclo [2.2.1] hept-2-ene, 5-ethylbi
Cyclo [2.2.1] hept-2-ene, 5-n-buty
Rubicyclo [2.2.1] hept-2-ene, 5-iso
Butylbicyclo [2.2.1] hept-2-ene, 7-
Methylbicyclo [2.2.1] hept-2-ene, ethi
Bicyclo [2.2.1] hept such as lidennorbornene
To-2-ene derivative, tricyclo [4.3.0.
1^2,5] -3-decene, 2-methyltricyclo [4.
3.0.1.^2,5] -3-decene, 5-methyltricyclo
[4.3.0.1^2,5] -3-decene and other tricyclo
[4.3.0.1^2,5] -3-decene derivatives, trisic
B [4.4.0.1^2,5] -3-undecene, 10-meth
Tiltricyclo [4.4.0.1^2,5] -3-Undesse
Tricyclo [4.4.0.1^2,5] -3-un
Decene derivative, tetracyclo [4.4.0.1^2,5. 1
^7,10] -3-dodecene, 8-methyltetracyclo [4.
4.0.1.^2,5. 1^7,10] -3-dodecene, 8-ethyl
Tetracyclo [4.4.0.1^2,5. 1^7,10] -3-do
Decene, 5,10-dimethyltetracyclo [4.4.
0.1^2,5. 1^7,10] -3-dodecene, 2,10-dimene
Tyltetracyclo [4.4.0.1^2,5. 1^7,10] -3
-Dodecene, 8,9-dimethyltetracyclo [4.4.
0.1^2,5. 1^7,10] -3-dodecene, tetracyclo
[4.4.0.1^2,5. 1^7,10] -3-Dodecene induction
Pentacyclo [6.5.1.1]^3,6. 0^2,7. 0
^9,13] -4-pentadecene derivative, pentacyclo [7.
4.0.1.^2,5. 1^9,12. 0^8,13] -3-pentadecene
Derivative, pentacyclopentadecadiene compound, penta
Cyclo [8.4.0.1^{2, Five}. 1^9,12. 0^8,13] -3-
Pentacyclo [8.4.0.
1 ^2,5. 1^9,12. 0^8,13] -3-hexadecene derivative,
Pentacyclo [6.6.1.1^3,6. 0^2,7. 0^9,14]
-4-hexadecene derivative, hexacyclo [6.6.
1.1^3,6. 1^10,13. 0^2,7. 0^9,14] -4-hepta
Decene derivatives, heptacyclo-5-eicosene derivatives,
5-phenylbicyclo [2.2.1] hept-2-e
, 5-methyl-5-phenylbicyclo [2.2.1]
Hept-2-ene, 1,4-methano-1,4,4a, 9
a-tetrahydrofluorene, 1,4-methano-1,
4,4a, 5,10,10a-Hexahydroanthrace
And the like. A compound represented by the general formula (I)
Cyclic olefins other than
Monocyclic olefins such as 1-cyclooctene,
1,3-cyclohexadiene, 1,5-octadiene,
Examples include cyclic dienes such as 2,5-norbornadiene.
I can do it.

These cyclic olefins represented by the general formula (I) and the above cyclic olefins may be used alone or in combination of two or more. Further, as the aromatic vinyl compound as the component (c), styrene, p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-isopropylstyrene, p-butylstyrene, p-tert-butylstyrene, o-methyl Styrene, o-ethylstyrene, o-propylstyrene, o-isopropylstyrene, m-methylstyrene,
m-ethylstyrene, m-isopropylstyrene, m-
Alkyl styrenes such as butyl styrene, mesityl styrene, 2,4-dimethyl styrene, 2,5-dimethyl styrene and 3,5-dimethyl styrene, and alkoxy such as p-methoxy styrene, o-methoxy styrene and m-methoxy styrene Styrenes, p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o- Examples include halogenated styrenes such as methyl-p-fluorostyrene, and further, p-phenylstyrene, p-trimethylsilylstyrene, vinyl benzoate, divinylbenzene, and the like. These aromatic vinyl compounds may be used alone or in a combination of two or more.

In the copolymer used in the desk mat of the present invention, the content of the α-olefin unit is 70 to 9
9.9 mol%, the content of the cyclic olefin unit is 0 to 30 mol%, the content of the aromatic vinyl compound unit is 0 to 30 mol%, and the total content of the cyclic olefin unit and the aromatic vinyl compound unit Preferably the amount is between 30 and 0.1 mol%. When the content of the α-olefin unit is less than 70 mol%, the glass transition temperature (Tg) becomes high, and flexibility at normal temperature may be lost. When it exceeds 99.9 mol%, the crystallinity becomes high, and The rate is increased, the flexibility is lost, and the transparency may be reduced. Therefore, the more preferable content of each unit is that the α-olefin unit is 80 to 98 mol% and the cyclic olefin unit is 0 to 20 mol%.
Mole% and the aromatic vinyl compound unit is 0 to 20 mole%
And the total content of the cyclic olefin unit and the aromatic vinyl compound unit is 20 to 2 mol%, and more preferably, the α-olefin unit is 80 to 96 mol%, and the cyclic olefin unit is 4 to 20 mol%. And the aromatic vinyl compound unit is 0 to 16 mol%.

In the present invention, the copolymer needs to have a glass transition temperature (Tg) in the range of -30 to 30 ° C. When this Tg is lower than -30 ° C, the balance of physical properties is deteriorated, and particularly, transparency and flexibility are reduced,
Elastic recovery may decrease, while above 30 ° C., flexibility at room temperature is lost. Therefore, the preferred T
g is in the range of −20 to 25 ° C., particularly −10 to 25 ° C.
Is preferable. In addition, the glass transition temperature (Tg) of the copolymer is as follows.
Test specimens (width 4mm, length 40m) by hot press molding
m, thickness 0.1 mm), and measured at a temperature rising rate of 3 ° C./min and a frequency of 3.5 Hz using a vibron 11-EA type manufactured by Toyo Bolding Co., Ltd. as a measuring device. It is determined from the peak of (E "). The copolymer must have a tensile modulus of 1000 MPa or less.
If the value exceeds a, the flexibility is reduced, and when writing a character, the character becomes too slippery to write. On the other hand, if it is too low, the paper will be dented by the pen pressure, and the writing taste will be poor. Therefore, the preferred tensile modulus is in the range of 5 to 500 MPa, and especially 10 to 200 MPa.
The range of MPa is suitable. The tensile modulus is
It is obtained by performing a tensile test using an autograph according to JIS K7127 using a No. 2 type test piece having a thickness of 1 mm at a test speed of 10 mm / min.

On the other hand, the copolymer needs to have an elastic recovery of 20% or more. If the elastic recovery is less than 20%, the rewinding property tends to be poor. The preferred elastic recovery is 50% or more, and particularly preferably 70% or more.
The elastic recovery was measured by using an autograph at a pulling speed of 62 mm / min, a width of 6 mm, and a distance between clamps of 50 mm.
After stretching the side bottom piece of (L ₀ ) by 150% and pulling it, keeping it as it is for 5 minutes, it suddenly shrinks without rebounding and after 1 minute, measure the sheet length (L ₁ ) between the clamps. , wherein elastic recovery (%) = [1 - _{[(L 1 -L 0) / L} 0 ]]
× 100 This is a value obtained from:

In the present invention, the copolymer preferably has a crystallinity of 20% or less. When the crystallinity exceeds 20%, transparency and flexibility tend to decrease,
On the other hand, if it is too low, the surface hardness is reduced, and the surface is apt to be scratched or sticky during molding. Therefore, the crystallinity is more preferably not more than 15%, especially 0.1.
A range from 10% to 10% is preferred. In addition, this crystallinity is
This is a value determined by X-ray diffraction analysis. In addition, the copolymer preferably has a surface hardness (Shore D) of 30 or more. If the surface hardness (Shore D) is less than 30, the surface of the molded product is easily damaged, which causes a decrease in transparency and gloss. If the surface hardness is too high, flexibility may be impaired. Therefore, a more preferable surface hardness (Shore D) is in the range of 30 to 90, and especially 30
The range of ~ 60 is preferred. The surface hardness is J
Based on IS K7215, this is a value obtained by determining the Shore hardness D of a film having a thickness of 3 mm with a durometer. Next, the melt index (M
I) is usually 0.01 to 50 g / 10 min, preferably 0.0.
5 to 20 g / 10 min, more preferably 0.1 to 10 g / 1
The range is 0 minutes. This MI is based on JIS K72
Measurement temperature 190 ° C, measurement load 21.18N
Is a value measured under the condition of The copolymer used in the present invention has a formula (MPa) ≦ tensile modulus ≦ 200 (MP
a) Surface hardness [Shore-D (%)] ≧ (tensile modulus / 10)
Those satisfying +30 elastic recovery rate (%) ≧ 140−50 × log tensile elastic modulus are preferable.

The method for producing the copolymer having the above properties and used in the present invention is not particularly limited as long as it is a method capable of obtaining the copolymer having the above properties. It can be manufactured efficiently.
In this method, (A) the following general formulas (II) to (V)
And at least one selected from transition metal compounds belonging to Groups 4 to 6 of the periodic table and transition metal compounds belonging to Groups 8 to 10 of the periodic table, and (B) an ionizing agent, that is, (B-1).
Selected from oxygen-containing organometallic compounds, (B-2) an ionic compound capable of forming an ionic complex by reacting with the transition metal compound, and (B-3) a clay, a clay mineral or an ion-exchange layered compound. A desired copolymer can be obtained by copolymerizing an α-olefin with a cyclic olefin and / or an aromatic vinyl compound in the presence of at least one olefin polymerization catalyst.

The transition metal compound of the component (A) is as follows:
General formulas (II), (III), (IV) and (V)¹ _a(C_FiveH_5-abR^{twenty one} _b) (C_FiveH_5-acR^{twenty two} _c) M¹X¹Y¹ ... (II) Q^Two _a(C_FiveH_5-adR^{twenty three} _d) Z¹M¹X¹Y¹ ... (III) (C_FiveH_5-eR^{twenty four} _e) M¹X¹Y¹W¹ ... (IV) L¹L^TwoM^TwoX¹Y¹ ... (V) [wherein, Q¹Represents two conjugated five-membered ring ligands (C_FiveH_5-ab
R^{twenty one} _b) And (C_FiveH_{Five- ac}R^{twenty two} _c) Crosslinkability
Represents a group, Q^TwoIs a conjugated five-membered ring ligand (C_FiveH_{5-a- d}R^{twenty three}
_d) And Z¹Shows a binding group that crosslinks the group. R^{twenty one}, R^{twenty two},
R^{twenty three}And R^{twenty four}Represents a hydrocarbon group, a halogen atom,
Alkoxy groups, silicon-containing hydrocarbon groups, phosphorus-containing hydrocarbons
Group, nitrogen-containing hydrocarbon group or boron-containing hydrocarbon group
And when there is more than one, they may be the same or different from each other,
It may combine with each other to form a ring structure. a is 0, 1 or
Is 2. b, c and d are respectively when a = 0
An integer of 0 to 5, an integer of 0 to 4 when a = 1,
When a = 2, each represents an integer of 0 to 3. e is 0
Indicates an integer of 5. M¹Is the periodic table 4-6 group and the periodic rule
The transition metals of Tables 8 to 10 are represented by M^TwoMeans Periodic Table 8-10
Represents a transition metal. Also, L¹, L^TwoAre shared
Are ligands that are compatible or coordinated
May be combined. Also, X¹, Y¹, Z¹, W¹Each
X represents a covalent or ionic ligand;¹,
Y¹And W¹May be bonded to each other. ]
At least one selected from the compounds represented by
You.

In the formulas (II) and (III), Q ¹ and Q ^{2 each} represent a bonding group. Specific examples thereof include (a) a methylene group, an ethylene group, an isopropylene group, and methylphenylmethylene. Group, diphenylmethylene group, alkylene group having 1 to 4 carbon atoms such as cyclohexylene group, cycloalkylene group or lower alkyl or phenyl substituted side chain thereof, (a) silylene group, dimethylsilylene group, methylphenylsilylene group, diphenyl A silylene group such as a silylene group, a disilylene group, or a tetramethyldisilylene group, an oligosilylene group or a lower alkyl or phenyl-substituted side chain thereof, (u) a hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum [lower alkyl Group, phenyl group, hydrocarbyloxy group (preferably lower alkoxy group), etc.] Thereof include (CH _{3) 2} Ge group,
(C ₆ H ₅ ) ₂ Ge group, (CH ₃ ) P group, (C ₆ H ₅ )
P group, (C ₄ H ₉ ) N group, (C ₆ H ₅ ) N group, (C
H ₃ ) B group, (C ₄ H ₉ ) B group, (C ₆ H ₅ ) B group,
(C ₆ H ₅ ) Al group, (CH ₃ O) Al group and the like. Of these, Q ¹ and Q ² are preferably an alkylene group and a silylene group.

Also, (C ₅ H _5-ab R ²¹ _b ), (C ₅ H
_5-ac R ²² _c) and _{(C 5 H 5-ad R} 23 d) is a conjugated five-membered cyclic ligands, R ^21, R ²² and R ²³ are each a hydrocarbon group, a halogen atom, an alkoxy group Represents a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group, and a is 0, 1 or 2.
b, c and d each represent an integer of 0 to 5 when a = 0, an integer of 0 to 4 when a = 1, and an integer of 0 to 3 when a = 2. Here, the hydrocarbon group preferably has 1 to 20 carbon atoms, and particularly preferably has 1 to 12 carbon atoms. This hydrocarbon group may be bonded as a monovalent group to a cyclopentadienyl group which is a conjugated five-membered ring group, and when there are a plurality of these, two of them are bonded to each other to form a cyclopentadienyl group. A ring structure may be formed together with a part of the pentadienyl group. That is, typical examples of the conjugated five-membered ring ligand include a substituted or unsubstituted cyclopentadienyl group, an indenyl group, and a fluorenyl group.

As the halogen atom, chlorine, bromine, iodine
And fluorine atoms, and as the alkoxy group,
Those having 1 to 12 carbon atoms are preferred. Silicon content
Examples of the hydrocarbon group include -Si (R^{twenty five}) (R²⁶)
(R²⁷) (R^{twenty five}, R²⁶And R²⁷Is carbonization having 1 to 24 carbon atoms
A hydrogen-containing hydrocarbon group, and a nitrogen-containing hydrocarbon group.
As the hydrocarbon group and the boron-containing hydrocarbon group,
Re-P (R²⁸) (R²⁹), -N (R²⁸) (R²⁹) And-
B (R²⁸) (R²⁹) (R²⁸And R ²⁹Has 1 to 18 carbon atoms
Hydrocarbon group) and the like. R^{twenty one}, R^{twenty two}And R^{twenty three}But
When there are a plurality of each, a plurality of R^{twenty one}, Multiple R^{twenty two}Passing
And multiple R^{twenty three}Are the same but different
It may be. In general formula (II),
Ring ligand (C_FiveH_5-abR^{twenty one} _b) And (C_FiveH_5-acR
^{twenty two} _c) May be the same or different. On the other hand, M
¹Is the transition gold of group 4 to 6 of the periodic table and group 8 to 10 of the periodic table
Genus elements, such as titanium and zirconium
, Hafnium, vanadium, niobium, molybdenum,
Ngustene, iron, cobalt, nickel, palladium, white
Gold, etc.
, Zirconium, hafnium, iron, nickel and para
Pb is preferred.

Z¹Is a covalent ligand, specific
Has oxygen (-O-), sulfur (-S-), carbon number 1-2.
0, preferably 1 to 10 alkoxy groups, 1 to 2 carbon atoms
0, preferably 1 to 12 thioalkoxy group, 1 carbon atom
To 40, preferably 1 to 18, nitrogen-containing hydrocarbon groups, charcoal
Phosphorus-containing hydrocarbon having a prime number of 1 to 40, preferably 1 to 18
Represents a group. X¹And Y¹Are covalent or
On-bonding ligand, specifically, hydrogen atom, halo
Gen atom, carbonization of 1 to 20, preferably 1 to 10 carbon atoms
Hydrogen group, alcohol having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms
Xy group, amino group, C1-20, preferably 1-1
2 phosphorus-containing hydrocarbon groups (for example, diphenylphosphine
Group) or C 1-20, preferably C 1-12
Silicon-containing hydrocarbon groups (for example, trimethylsilyl group
), A hydrocarbon having 1 to 20, preferably 1 to 12 carbon atoms
Group or a halogen-containing boron compound (for example, B (C₆
H_Five)_Four, BF _Four). Among these halogen sources
Peptides, hydrocarbon groups and alkoxy groups are preferred. X¹as well as
Y¹May be the same or different
No.

Next, in the above general formula (IV), M ¹ is a transition metal of Group 4 to 6 of the Periodic Table and Group 8 to 10 of the Periodic Table as described above, and W ¹ is a covalent bond. Or an ionic bonding ligand, specifically, a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, or an alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. Groups, amino groups, amidinate groups, phosphorus-containing hydrocarbon groups having 1 to 20, preferably 1 to 12 carbon atoms (such as diphenylphosphine groups) or silicon-containing hydrocarbons having 1 to 20, preferably 1 to 12 carbon atoms Group (for example, a trimethylsilyl group), having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms.
Hydrocarbon compounds or halogen-containing boron compounds (for example, B (C ₆ H ₅ ) ₄ , BF ₄ ). Among these, a halogen atom, a hydrocarbon group and an alkoxy group are preferred.
Specific examples of the compounds represented by the general formulas (II) and (III) include the following compounds.

(1) bis (cyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) titanium dichloride, bis (pentamethylcyclopentadienyl) titanium dichloride, bis (n-butylcyclopentadienyl) titanium It has a crosslinking group such as dichloride, bis (indenyl) titanium dichloride, bis (cyclopentadienyl) titanium chlorohydride, bis (cyclopentadienyl) dimethyltitanium, (cyclopentadienyl) (fluorenyl) titanium dichloride, etc. Transition metal compound having two conjugated five-membered ring ligands,

(2) rac-methylenebis (indenyl) titanium dichloride, rac-ethylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride, ethylene (2,4-dimethylcyclopentadienyl) (3 '5,5'-dimethylcyclopentadienyl) titanium dichloride, rac-isopropylidenebis (4,5-benzoindenyl) titanium dichloride, crosslinked with an alkylene group such as isopropylidene (cyclopentadienyl) (fluorenyl) titanium dichloride A transition metal compound having two conjugated five-membered ring ligands,

(3) rac-dimethylsilylenebis (indenyl) titanium dichloride, dimethylsilylenebis (2,4-dimethylcyclopentadienyl) (3 ′,
A transition metal compound having two silylene group-bridged conjugated five-membered ring ligands such as 5′-dimethylcyclopentadienyl) titanium dichloride and rac-phenylmethylsilylenebis (indenyl) titanium dichloride;

(4) rac-Dimethylgermylene Transition metal having two conjugated five-membered ring ligands bridged by a hydrocarbon group containing germanium such as bis (indenyl) titanium dichloride, aluminum, boron, phosphorus or nitrogen Compound,

(5) (pentamethylcyclopentadienyl) [bis (phenyl) amino] titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (tert-butylamino) titanium dichloride, dimethylsilylene (2-indenyl) (Tert-
Conjugated 5-membered ring ligands such as butylamino) titanium dichloride, dimethylsilylene (2-indenyl) (isopropylamino) titanium dichloride, pentamethylcyclopentadienyltitanium trimethoxide, and pentamethylcyclopentadienyltitanium trichloride. A transition metal compound having one,

(6) (1,1'-dimethylsilylene)
(2,2′-isopropylidene) bis (cyclopentadienyl) titanium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (indenyl) titanium dichloride, (1,1′- Dimethylsilylene) (2,2'-ethylene) bis (indenyl)
Titanium dichloride, (1,2′-ethylene) (2,
A transition metal compound having two conjugated five-membered ring ligands in which ligands are double-bridged, such as 1′-ethylene) bis (3-methylindenyl) titanium dichloride,

(7) Further, the compounds according to the above (1) to (6), wherein the chlorine atom of these compounds is replaced by a bromine atom, an iodine atom, a hydrogen atom, a methyl group, a phenyl group, etc. Examples of the transition metal compound in which titanium as a central metal is replaced with zirconium, hafnium, vanadium, niobium, molybdenum, tungsten, or the like can also be given. Specific examples of the transition metal compound represented by the general formula (IV) include, for example, cyclopentadienyl titanium trichloride, methylcyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride, and In these compounds, the chlorine atom of these compounds is replaced by a bromine atom, an iodine atom, a hydrogen atom, a methyl group, a phenyl group, or the like.In addition, zirconium, hafnium, vanadium, niobium, or titanium, which is the central metal of the above transition metal compound,
Molybdenum or tungsten can be used.

On the other hand, in the transition metal compound represented by the general formula (V), L ¹ and L ² each represent a covalent or coordinating ligand, and X ¹ and Y ¹ each represent a covalent ligand. It represents a binding or ionic binding ligand.
Here, X ¹ and Y ¹ are, as described above, specifically a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and 1 to 20 carbon atoms, preferably 1 carbon atom. 10 to 10 alkoxy groups, amino groups, 1 to 2 carbon atoms
0, preferably 1 to 12 phosphorus-containing hydrocarbon groups (such as diphenylphosphine groups) or 1 to 2 carbon atoms
0, preferably 1 to 12 silicon-containing hydrocarbon groups (eg, trimethylsilyl group, etc.), 1 to 20, preferably 1 to 12 carbon atoms, or halogen-containing boron compounds (eg, B (C ₆ H ₅ ) ₄ and BF ₄ ). Of these, a halogen atom and a hydrocarbon group are preferred. X ¹ and Y ¹ may be the same or different. Further, specific examples of L ¹ and L ² include a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms,
-30, preferably 1-20 alkoxy, amino, amidinate, 1-20 carbon atoms, preferably 1-20
12 phosphorus-containing hydrocarbon groups (such as diphenylphosphine groups) or silicon-containing hydrocarbon groups having 1 to 20, preferably 1 to 12 carbon atoms (such as trimethylsilyl groups), triphenylphosphine, acetonitrile, benzonitrile, 1 , 2-bisdiphenylphosphinoethane, 1,3-bisdiphenylphosphinopropane,
Examples thereof include 1'-bisdiphenylphosphinoferrocene, cyclooctadiene, pyridine, bistrimethylsilylaminobistrimethylsilyliminophosphorane, and the like. The above L ¹ and L ² , X ¹ and Y
¹ may each be connected to each other.

Specific examples of the transition metal compound represented by the general formula (V) include bis [bis (trimethylsilyl)
Benzamidinate] zirconium dichloride, bis (dimethylbenzamidinate) zirconium dichloride, bis (dicyclohexylacetamidinate) zirconium dichloride, dipromobistriphenylphosphine nickel, and the like. Further, a compound having a diimine compound as a ligand is preferable, and examples of such a compound include a compound represented by the general formula (VI):

[0031]

Embedded image

Wherein R ³⁰ and R ³³ are each independently an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a total of 7 to
An aromatic group having a hydrocarbon group on the ring 20; R ³¹ and R ³² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R ³¹ and R ³² are bonded to each other to form a ring; X ² and Y ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and M ² represents a transition metal belonging to Groups 8 to 10 of the periodic table. )). In the general formula (VI), among R ³⁰ and R ³³ , as the aliphatic hydrocarbon group having 1 to 20 carbon atoms, a linear or branched alkyl group having 1 to 20 carbon atoms or 3 to 20 carbon atoms is preferable. Examples thereof include 20 cycloalkyl groups, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, and a cyclohexyl group. An appropriate substituent such as a lower alkyl group may be introduced on the ring of the cycloalkyl group. As the aromatic group having a hydrocarbon group on a ring having a total of 7 to 20 carbon atoms, for example, on an aromatic ring such as a phenyl group or a naphthyl group, a linear, branched or Examples include groups into which one or more cyclic alkyl groups have been introduced. As R ³⁰ and R ³³ ,
An aromatic group having a hydrocarbon group on the ring is preferable, and a 2,6-diisopropylphenyl group is particularly preferable. R ³⁰
And R ³³ may be the same or different.

Further, among R ³¹ and R ³² , one having 1 to carbon atoms
Examples of the hydrocarbon group having 20 carbon atoms include a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a carbon atom having 7 carbon atoms.
To 20 aralkyl groups. Here, as the linear or branched alkyl group having 1 to 20 carbon atoms and the cycloalkyl group having 3 to 20 carbon atoms, among the above R ³⁰ and R ³³ , an aliphatic hydrocarbon group having 1 to 20 carbon atoms The same ones as exemplified in the description can be given. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a methylnaphthyl group. Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenethyl group. And the like. R ³¹ and R ³² may be the same or different. Further, they may combine with each other to form a ring.

On the other hand, X^TwoAnd Y^TwoAmong which carbon number 1
As the hydrocarbon group of No. 20, the above R ³¹And R³²Smell
As described above.
It is. This X^TwoAnd Y^TwoIs especially a methyl group
Is preferred. Also, X^TwoAnd Y ^TwoAre identical
Or may be different. M^TwoNo 8th periodic table
The transition metals of Group 10 include, for example, nickel, para
Such as indium, platinum, iron, cobalt, rhodium and ruthenium
And nickel and palladium are preferred. Departure
In the description, the transition metal compound of the component (A)
Species may be used alone or in combination of two or more
You may. Olefin polymerization catalyst used in the present invention
(B-1) of the ionizing agent of the component (B) in the medium
As the oxygen organometallic compound, general formula (VII) or general formula
(VIII)

[0035]

Embedded image

[In the formula, R ^{34 to} R ⁴⁰ each independently represent an alkyl group having 1 to 8 carbon atoms, and A ^{1 to} A ⁵ each independently represent a Group 13 metal element of the periodic table. H, i, j and u
Is a number from 0 to 50, and both (h + i) and (j + u) are 1 or more. ] The compound represented by this is mentioned. In the general formulas (VII) and (VIII), R ³⁴ to
Examples of the alkyl group having 1 to 8 carbon atoms represented by R ⁴⁰ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, and various octyl groups. Examples of the metal element belonging to Group 13 of the periodic table represented by A ^{1 to} A ⁵ include boron, aluminum, gallium, indium, and thallium. Among these metal elements, boron and aluminum are particularly preferably used. The values of h, i, j and u are
Those having a range of 1 to 20, especially 1 to 5 are preferred.

The oxygen-containing organometallic compounds represented by the general formulas (VII) and (VIII) include, for example, tetramethyl dialumoxane, tetraisobutyl dialumoxane, methylalumoxane, ethylalumoxane, butylalumoxane And alumoxanes such as isobutylalumoxane, and boroxanes such as trimethylboroxine and methylboroxane. Of these, alumoxanes are preferred, and methylalumoxane and isobutylalumoxane are particularly preferably used. These alumoxanes may be modified with alcohols. Specific examples of alcohols used for denaturation include methanol, ethanol, propanol, butanol, triphenylmethanol, 2,6-dimethylphenol, 1,4-butanediol, catechol, trimethylsilanol, triphenylsilanol and the like. Can be

The ionic compound (B-2) of the component (B) which can react with the transition metal compound to form an ionic complex includes an anion having a plurality of groups bonded to a metal and a cation. Or a Lewis acid. As the coordination complex compound comprising an anion and a cation in which a plurality of groups are bonded to a metal, a general formula (I
X) or (X) ([L ³ -H] ^{g +} ) _f ([M ³ D ¹ D ² ... D ^p ] ^(pq)- ) _t (IX) ([L ⁴ ] ^{g +} ) _f ([M ⁴ D ¹ D ² ... D ^p ] ^(pq)- ) _t (X) [wherein L ³ is a Lewis base, and L ⁴ is M ⁵ or R ⁴¹ described below.
R ⁴² M ⁶ or R ⁴³ ₃ C, wherein M ³ and M ⁴ are each a metal selected from Groups 5 to 15 of the periodic table, M ⁵
Is a metal selected from Groups 1 and 8 to 12 of the periodic table; M ⁶ is a metal selected from Groups 8 to 10 of the periodic table; D ^{1 to} D ^p are each a hydrogen atom; dialkylamino Group, alkoxy group, aryloxy group, carbon number 1-2
0 alkyl group, aryl group having 6 to 20 carbon atoms, alkylaryl group, arylalkyl group, substituted alkyl group,
Indicates an organic metalloid group or a halogen atom. R ⁴¹ and R ⁴² each represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, or a fluorenyl group, and R ⁴³ represents an alkyl group. q is M ³ , M ⁴
Is an integer of 1 to 7, p is an integer of 2 to 8, g is [L
³ -H], [L ^4] ion valence of 1-7 integer, f is an integer of 1 or more, t is a value calculated by the equation [f × g / (p- q)] . ] Is preferably used.

The metals represented by M ³ and M ⁴ in the general formulas (IX) and (X) include boron, aluminum,
Silicon, phosphorus, arsenic, antimony is preferable, as the metal represented by M ⁵ include silver, copper, sodium, lithium is preferred as the metal represented by M ^6, iron, cobalt, and nickel are preferable. Further, as specific examples of D ^{1 to} D ^p in the general formulas (IX) and (X), for example, a dimethylamino group, a diethylamino group or the like is preferable as the dialkylamino group, and a methoxy group or ethoxy group is preferable as the alkoxy group. Group, n-butoxy group and the like, and as the aryloxy group, a phenoxy group, a 2,6-dimethylphenoxy group, a naphthyloxy group and the like are preferable.

Next, as the alkyl group having 1 to 20 carbon atoms, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-octyl group, a 2-ethylhexyl group and the like are preferable. An aryl group of the formulas 6 to 20,
Examples of the alkylaryl group or the arylalkyl group include a phenyl group, a p-tolyl group, a benzyl group, a pentafluorophenyl group, and 3,5-di (trifluoromethyl)
Phenyl group, 4-tert-butylphenyl group, 2,6
-Dimethylphenyl group, 3,5-dimethylphenyl group,
A 2,4-dimethylphenyl group and a 2,3-dimethylphenyl group are preferred. Further, as the halogen, fluorine, chlorine, bromine and iodine are preferable, and as the organic metalloid group, a pentamethylantimony group, a trimethylsilyl group, a trimethylgermyl group, a diphenylarsine group, a dicyclohexylantimony group and a diphenylboron group are preferable. Further, as the substituted cyclopentadienyl group represented by R ⁴¹ and R ⁴² , a methylcyclopentadienyl group, a butylcyclopentadienyl group, a pentamethylcyclopentadienyl group and the like are preferable.

In the present invention, a plurality of groups are bonded to a metal.
Specific examples of the anion include B (C₆F_Five)_Four ^-,
B (C₆HF_Four)_Four ^-, B (C₆H_TwoF_Three)_Four ^-, B
(C ₆H_ThreeF_Two)_Four ^-, B (C₆H_FourF)_Four ^-, B [C
₆(CF_Three) F_Four]_Four ^-, B (C₆H_Five)_Four ^-, FB
(C₆F_Five)_Three ^-, FB (C_TenF₇)_Three ^-, PF₆ ^-,
P (C₆F_Five)₆ ^-, Al (C₆F_Five)_Four ^-, Al (C
₆HF_Four)_Four ^-, FAl (C₆F_Five)_Three ^-, FAl (C
_TenF₇)_Three ^-And the like. Ma
The metal cation is Cp_TwoFe⁺, (MeC
p)_TwoFe⁺, (TBuCp)_TwoFe⁺, (Me_TwoC
p)_TwoFe⁺, (Me_ThreeCp)_TwoFe⁺, (Me _FourC
p)_TwoFe⁺, (Me_FiveCp)_TwoFe⁺, Ag⁺, Na
⁺, Li⁺And the like.

Other cations include pyridinium, 2,4-dinitro-N, N-diethylanilinium, diphenylammonium, p-nitroanilinium, 2,5-dichloroanilinium, p-nitro-N ,
Nitrogen-containing compounds such as N-dimethylanilinium, quinolinium, N, N-dimethylanilinium, N, N-diethylanilinium, triphenylcarbenium, tri (4-methylphenyl) carbenium, tri (4-methoxyphenyl) Carbenium compounds such as carbenium, alkylphosphonium ions such as CH ₃ PH ₃ ⁺ ,
And arylphosphonium ions such as C ₆ H ₅ PH ₃ ⁺ .

Next, a compound represented by the general formula (IX)
Are, for example, triethyl alcohol tetraphenylborate
Ammonium, tetrakis (pentafluorophenyl) pho
Triethylammonium borate, tetrakis (pentaflu
O-phenyl) borate N, N-dimethylanilinium
Are preferably used. Also, represented by the general formula (X)
As the compound, for example, ferrocetyl tetraphenylborate
, Tetrakis (pentafluorophenyl) borate
Ferrocenium, tetrakis (pentafluorophenyl
B) Silver borate, tetrakis (pentafluorophenyl)
Trityl borate, silver tetrafluoroborate, etc. are preferred.
Used. Further, as a Lewis acid, for example, B (C
₆F_Five)_Three, B (C₆HF_Four)_Three, B (C₆H_TwoF_Three)
_Three, B (C₆H_ThreeF_Two)_Three, B (C₆H_FourF)_Three, B
(C₆H_Five)_Three, BF_Three, B [C₆(CF_Three)
F_Four]_Three, B (C_TenF₇)_Three, FB (C ₆F_Five)_Two, P
F_Five, P (C₆F_Five)_Five, Al (C₆F_Five)_Three, Al
(C₆HF _Four)_Three, Al (C_TenF₇)_ThreeAlso use
Can be.

On the other hand, as the (B-3) clay, clay mineral or ion-exchangeable layered compound of the component (B), the following can be mentioned. (1) Clay or clay mineral Clay is an aggregate of fine hydrated silicate minerals,
A substance that produces plasticity when mixed with an appropriate amount of water, exhibits rigidity when dried, and sinters when baked at high temperatures. The clay mineral refers to a hydrated silicate that is a main component of clay. These are not limited to natural products, and may be artificially synthesized. (2) Ion-exchangeable layered compound The ion-exchanged layered compound is a compound having a crystal structure in which surfaces constituted by ionic bonds and the like are stacked in parallel with a weak bonding force, and contained ions are exchangeable. A thing.

In the present invention, when the component (B-3) is brought into contact with the component (A), the other component (B-1) or the component (B-2) or the component (C) described below, It is also preferable to carry out a chemical treatment from the viewpoint of removing impurities from the clay mineral and the ion-exchangeable layered compound or changing the structure and function. In addition, the component (B-3) may be used as it is, may be newly added and adsorbed water, or may be subjected to heat dehydration treatment. Alternatively, a material further treated with an organic aluminum compound and / or an organic silane compound may be used. As the component (B-3), preferred are clay or clay mineral, and most preferred are phyllosilicates, among which smectite is good and montmorillonite is more preferred. In the present invention, as the component (B),
The component (B-1) may be used alone or in combination of two or more. The component (B-2) may be used alone or in combination of two or more. ) The components may be used alone or in combination of two or more. Alternatively, the component (B-1), the component (B-2), and the component (B-3) may be appropriately used in combination.

Further, in the olefin polymerization catalyst, if necessary, a component represented by the general formula (XI):
(XII) and _{^{(XIII) R 44 r Al (}} OR 45) S E 3-rs ··· (XI) R 44 2 Mg ··· (XII) R 44 2 Zn ··· (XIII) [ in the formula R ⁴⁴ and R ⁴⁵ each independently have 1 to 8 carbon atoms.
And E represents a hydrogen atom or a halogen atom. r is 0 <r ≦ 3, and s is 0 ≦ s <3. ] Are preferably used. What the alkyl group represented by R ⁴⁴ or R ⁴⁵ in the general formulas (XI) ~ (XIII), having a carbon number 1 to 8, preferably carbon atoms 1 to 4 such as methyl group, ethyl Groups, propyl groups, isopropyl groups, various butyl groups and the like are preferred. Also, r in the equation
Is preferably 2 or 3, and most preferably 3. Further, s is preferably 0 or 1.

The organometallic compounds represented by the general formulas (XI) to (XIII) include, for example, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, Trialkylaluminums such as isobutylaluminum and tri-tert-butylaluminum, dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-tert-butyl Dialkylaluminum halides such as aluminum chloride, dimethylaluminum methoxide, diethylaluminum methoxide, diethylaluminum Dialkylaluminum alkoxides such as ammonium ethoxide and diisobutylaluminum methoxide; organic aluminum compounds such as dialkylaluminum hydrides such as dimethylaluminum hydride and diisobutylaluminum hydride; dialkylmagnesium such as dimethylmagnesium and diethylmagnesium; and dialkylzinc such as diethylzinc. No. Among these organometallic compounds, organoaluminum compounds, particularly trialkylaluminum, are preferred.
In the present invention, as the component (C), one kind of the organometallic compound may be used, or two or more kinds thereof may be used in combination.

Next, when preparing an olefin polymerization catalyst using each of the above catalyst components, it is desirable to carry out the reaction in an atmosphere of an inert gas such as nitrogen gas. The catalyst may be prepared in advance in a catalyst preparation tank,
It may be prepared in a polymerization reactor for copolymerizing an α-olefin or an aromatic vinyl compound. When preparing a catalyst in this polymerization reactor,
It is desirable to carry out at a temperature lower than the polymerization temperature, for example, -30 to
It is good to carry out at a temperature of 00 ° C, preferably in the range of 0 to 80 ° C.
The mixing ratio of these components is such that the molar ratio of the component (B-1) to the transition metal compound of the component (A) is 1: 0.1 to 1: 100,000, preferably 1: 0.
It is good to be 5 to 1: 10000. Further, an ionic compound capable of forming an ionic complex by reacting with the transition metal compound as the component (B-2) is used in a molar ratio of 1: 0.1 to 1:
1000, preferably 1: 1 to 1: 100. The mixing ratio of the clay, the clay mineral or the ion-exchange layered compound of the component (B-3) is defined as the amount of the component (A) added to the unit weight (g) of the component (B-3).
0.1-1000 micromol, preferably 1-200
Micromolar. Further, the compounding ratio of the organometallic compound of the component (C) is 1: 1 to 1: 100000, preferably 1:10 to 1: 10000 in terms of molar ratio with respect to the transition metal compound of the component (A).

In the polymerization catalyst used in the present invention, at least one of the components (A), (B-1), (B-2) and (C) is supported on a fine particle carrier. It may be a solid catalyst comprising: Further, the polymerization catalyst comprises a particulate carrier, a component (A), a component (B-1) (or a component (B-2)), and a polymer or copolymer produced by prepolymerization, and if necessary, (C) It may be a prepolymerization catalyst comprising the components. The particulate carrier used for the solid catalyst and the prepolymerization catalyst is an inorganic or organic compound, and has a particle size of 10 to 300 μm,
Preferably, it is a solid of 20 to 200 μm in the form of granules or fine particles. Among them, SiO ₂ and Al ₂ O ₃
Those having at least one component selected from the above as a main component are preferable. The copolymer in the present invention, using the olefin polymerization catalyst prepared in this manner, α- olefin and cyclic olefin and / or aromatic vinyl compound, butane, hexane, toluene, hydrocarbon compounds such as cyclohexane, It can be produced by copolymerizing in the presence of a solvent such as a liquefied α-olefin or in the absence of a solvent. The polymerization temperature is not particularly limited,
It is preferably in the range of -50 ° C to 250 ° C, and particularly preferably in the range of 0 ° C to 200 ° C. The pressure is not particularly limited, but is preferably in the range of normal pressure to 20 MPa, particularly preferably normal pressure to 10 MPa.

The desk mat of the present invention may use only the copolymer obtained as described above as a resin component, or the copolymer may be used as long as the object of the present invention is not impaired. A mixed soft resin obtained by blending another resin with a polymer may be used. In this case, the copolymer and the other resin are usually in a weight ratio of 50:50 to 99.9.
Blend at a rate of ~ 0.1. Examples of the other resin include crystalline polyolefin resins such as high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE) and polypropylene, and polyvinyl acetate and ethylene-vinyl acetate. Other resins such as polymers, polyvinyl alcohol, polar vinyl resins such as ethylene-vinyl alcohol copolymer, fluororesin, silicone resin, ABS resin, acrylonitrile-styrene copolymer resin, methacrylic resin, epoxy resin, and polyisoprene rubber , Polybutadiene rubber, styrene-butadiene copolymer, butyl rubber, halogenated butyl rubber, chloroprene rubber, acrylic rubber,
EPR, EPDM, acrylonitrile-butadiene copolymer, fluoro rubber, silicone rubber, styrene-butadiene block copolymer, hydrogenated styrene / butadiene / styrene block copolymer rubber, acrylonitrile
Synthetic rubbers such as EPDM-styrene terpolymer, styrene-methyl methacrylate copolymer, and other natural rubbers and thermoplastic elastomers are included.

These may be used alone or in a combination of two or more, but a crystalline polyolefin resin is particularly preferred. The desk mat of the present invention is
It may be a single layer consisting of only the layer containing the mixed soft resin obtained by blending the copolymer or another resin with the above-mentioned copolymer, or the above-mentioned layer, and a multilayer body consisting of a layer containing the crystalline polyolefin resin. There may be. In order to produce the desk mat of the present invention, first, a molding material containing the copolymer is prepared. The molding material may be any of various known additives such as a heat stabilizer, if desired, as long as the object of the present invention is not impaired with respect to the soft resin component composed of the copolymer and the other resin used in some cases. , Antioxidants, UV absorbers,
It can be prepared by blending a light stabilizer, an anti-blocking agent, a slip agent, a crystal nucleating agent, a pigment, a dye, an organic or inorganic filler, and the like.

The above-mentioned inorganic or organic fillers can be blended within a range that does not impair the transparency, or can be blended for the purpose of positively coloring. Examples of the fillers include carbon black, silica and silica. Alumina, diatomaceous earth, alumina, calcium carbonate, titanium oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, barium carbonate, barium sulfate, talc, clay, mica, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite , Graphite, powder such as aluminum powder, fibers, beads, flame retardants and the like. Among these fillers, carbon black, calcium carbonate, titanium oxide, alumina, silica, silica alumina, talc, and barium carbonate are preferably used. These fillers may be used alone or in a combination of two or more. The molding material is prepared by mixing the copolymer according to the present invention and each component used as required with a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, or the like, or after mixing. It can be performed by melt-kneading with an extruder, a multi-screw extruder, a kneader, a Banbury mixer or the like. The desk mat of the present invention can be manufactured by molding the molding material thus prepared into a sheet by a conventionally known molding method, for example, a T-die extrusion method, a calendar method, or the like. The thickness of this sheet is
Usually, it is in the range of 0.5 to 5 mm, preferably 1 to 3 mm.

The desk mat of the present invention thus obtained can be crosslinked as required for the purpose of improving its heat resistance, chemical resistance and the like. In this case, heat,
A method of crosslinking in advance by a method such as ultraviolet ray, electron beam or γ-ray crosslinking, or a method of crosslinking after preparing a desk mat can be adopted. The desk mat of the present invention is formed by applying and curing an ultraviolet curable paint having excellent chemical resistance, weather resistance, flexibility and the like on the upper surface of the mat body and curing it.
A film having a thickness of about 30 μm may be provided. As the paint, a urethane acrylate paint is preferable. Further, for the purpose of improving printability and the like, one or both surfaces can be subjected to a surface treatment by an oxidation method, a roughening method, or the like, if desired. Examples of the oxidation method include a corona discharge treatment, a chromic acid treatment (wet method), a flame treatment, a hot air treatment, an ozone / ultraviolet irradiation treatment, and the like.
For example, a sand blast method, a solvent treatment method and the like can be mentioned. As these surface treatment methods, generally, a corona discharge treatment method is preferably used from the viewpoint of effects and operability.

Further, the desk mat of the present invention is usually wound and stored after the sheet is manufactured. In order to prevent the sheets from sticking to each other during storage, the above-mentioned inorganic filler is added to the extent that the transparency is not impaired. For example, 0.01 to 10% by weight,
Preferably, 0.1 to 5% by weight is blended or the surface is embossed. The surface may be mirror-finished on both sides, or embossed on one or both sides to give a matte finish or the like. When both surfaces are mirror surfaces, the haze is 5% or less, and a desk mat having extremely good transparency can be obtained.

[0055]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The melt index (MI), tensile modulus, glass transition temperature (Tg), elastic recovery, crystallinity, and surface hardness (Shore-D) of the polymer in each example were measured according to the methods described in the specification. did. In addition, the composition of the comonomer was determined according to the following method, and the desk mat was evaluated. (1) Composition of Comonomer The content of comonomer units was determined by isotope carbon nuclear magnetic resonance spectroscopy ( ¹³ C-NMR). (2) Performance Evaluation of Desk Mat A sheet having a size of 450 mm × 600 mm and a thickness of 1.5 mm was prepared using a 30 mmφ extruder, and the performance was evaluated by the following method.

1. The sheet is rolled up in the length direction so that the diameter of the roll is about 6 cm, the end is fixed with an adhesive tape, and left at room temperature for 24 hours. This was rewound, laid on a desk and left for 2 hours, and the adhesion to the desk surface was visually evaluated according to the following criteria. ：: Adhered to the surface without any problem △: Floating in some places ×: Hardly adhered Writing taste Paper was placed on a desk mat laid on a desk, and based on the situation when characters were written on the paper with a ballpoint pen, evaluation was made according to the following criteria. ○: Letters can be written smoothly ×: Paper dents or ballpoint pen slips

Preparation Example Preparation of (tert-butylamide) (2-indenyl) dimethylsilanetitanium dichloride (1) Synthesis of 2-bromoindene 100 g (0.47 mol) of indene bromohydrin was added to 1
Dissolved in 1 liter of toluene. To this, 3.5 ml of concentrated sulfuric acid was added and refluxed for 1 hour. After allowing to cool to room temperature, water was added and washed with water. After separating the organic layer, the solvent was distilled off under reduced pressure. The residue was distilled under reduced pressure to obtain the desired product as a yellow oil in a yield of 8.46 g and a yield of 9.42%. _{^{(1 H-NMR (COC1 3}} ): 3.52 (s, 2
H), 6.88 (s, H), 6.97 to 7.70 (m, 4
H))

(2) Synthesis of 2- (dimethylchlorosilyl) indene 2 g of magnesium was added to 50 ml of tetrahydrofuran under a nitrogen stream. To this, 0.1 ml of 1,2-dipromoethane was added and heated with a drier to activate magnesium. The solvent is distilled off under reduced pressure,
50 ml of tetrahydrofuran was newly added.
To this, 5.90 g of 2-bromoindene (25.63 mmol)
1) 300 ml of tetrahydrofuran solution in 2
It was dropped over time. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. The reaction mixture was cooled to -78 ° C, and a solution of 5.0 ml (41 mmol) of dichlorodimethylsilane in 200 ml of tetrahydrofuran was added dropwise over 1 hour. After completion of the dropwise addition, the temperature was raised to room temperature, and the mixture was stirred at room temperature for 12 hours, and then the solvent was distilled off under reduced pressure. After the residue was extracted with hexane, the solvent was distilled off under reduced pressure to obtain the desired product as an orange oil in a yield of 5.00 g and a yield of 93.2%.
_{^{(1 H-NMR (CDCl 3}} ): 0.62 (s, 6H),
3.56 (2H), 6.9 to 7.65 (5H))

(3) Synthesis of (2-indenyl) -tert-butylaminodimethylsilane 3.00 g of 2- (dimethylchlorosilyl) indene (14.
37 mmol) was dissolved in 100 ml of hexane and cooled with ice. To this, tert-butylamine 7.55
Milliliter (71.9 mmol) was added dropwise in 10 minutes.
After the dropwise addition, the temperature was raised to room temperature, and the mixture was stirred for 12 hours. The supernatant was filtered off, and the solvent was distilled off under reduced pressure to obtain 3.08 g of the desired product.
Obtained in a yield of 87.3%. _{^{(1 H-NMR (CDCl 3}} ):
0.29 (s, 6H), 1.12 (s, 9H), 3.48 (2
H), 7.0-7.6 (m, 5H))

(4) (tert-butylamide) (2-
Synthesis of indenyl) dimethylsilanetitanium dichloride (2-indenyl) -tert-butylaminodimethylsilane 3.05 g (12.4 mmol) was added to ether 100
Dissolved in milliliters and cooled on ice. 17.6 ml of n-butyllithium (1.64 mol / l, 2
8.8 mmol), and the mixture was heated to room temperature and stirred for 12 hours. The resulting precipitate of the lithium salt was separated by filtration, washed three times with 50 ml of hexane, and then dried under reduced pressure. The resulting lithium salt weighed 1.65 g. This was dissolved in 100 ml of tetrahydrofuran and cooled to -78 ° C. 2.08 g of TiCl ₃ (THF) ₃ (5.6
50 mmol of a 1 mmol) solution in tetrahydrofuran was added. The temperature was raised to room temperature, and the mixture was stirred for 12 hours. Thereafter, 2.5 g of AgCl (17.4 m
mol), and the mixture was stirred for 24 hours. The supernatant was filtered off, and the solvent was distilled off under reduced pressure. Crystallize from toluene / hexane and wash with hexane to give the desired product in a yield of 0.
Obtained in 3 g. _{^{(1 H-NMR (CDCl 3}} ): 0.78
(S, 6H), 1.41 (s, 9H), 6.78 (s, 2
H), 7.2 to 7.5 (m, 2H), 7.6 to 7.8 (m,
H))

Example 1 Toluene 3 was placed in a 100-liter circular autoclave.
7.5 liters, 115 mmol of triisobutylaluminum, 80 mol of norbornene as a comonomer component,
After charging 100 micromol of dimethylanilinium tetrakis (pentafluorophenyl) borate and 100 micromol of bis (cyclopentadienyl) dichlorozirconium, ethylene partial pressure is 0.75 MPa, polymerization temperature is 9
Polymerization was carried out at 0 ° C. for 150 minutes to obtain 9.1 kg of an ethylene-norbornene copolymer. Of the resulting polymer
^The norbornene unit content by ¹³ C-NMR analysis was 1
It was 4.6 mol%. In addition, temperature 190 ° C, load 2
1. Melt index (M
I) was 4.3 g / 10 min. The results are shown in Table 1.

Example 2 An ethylene-norbornene copolymer was obtained in the same manner as in Example 1, except that the amount of norbornene used was changed to 45 mol and polymerization was carried out at a temperature of 90 ° C. The norbornene unit content of this polymer was 8.9 mol%, and the melt index (MI) was 3.2 g / 10 minutes. The results are shown in Table 1. Example 3 An ethylene-norbornene copolymer was obtained in the same manner as in Example 2, except that the amount of norbornene used was changed to 30 mol. The norbornene unit content of this polymer was 5.0 mol%. The results are shown in Table 1. Comparative Example 1 For comparison, a commercially available ethylene-octene-1 copolymer (LLDPE) [“MORETECH 039 manufactured by Idemitsu Petrochemical Co., Ltd.”
Table 1 shows the properties and the evaluation results of the desk mat for "8CN"].

Example 4 An autoclave having a catalyst charging tube having an internal volume of 10 liters was charged with 2 liters of toluene, 30 ml of styrene,
90 ml of norbornene and 3 ml of a toluene solution of triisobutylaluminum at a concentration of 1.0 mol / liter were sequentially added thereto, and the temperature was raised to 45 ° C. Next, ethylene was added to the autoclave at a pressure of 0.3 MPa.
・ Introduced to be G. And from the catalyst input pipe,
30 micromolar of (tert-butylamide) (2-
Indenyl) dimethylsilanetitanium dichloride, 3
A solution in which 0 mmol of methylalumoxane was dissolved in 250 ml of toluene was charged. With the progress of copolymerization of ethylene, styrene and norbornene, the internal pressure of the autoclave decreases.
While continuously introducing so that Pa · G can be maintained,
The copolymerization reaction was performed for one hour. Thereafter, the copolymerization was stopped by adding methanol. A large amount of methanol was further added to the reaction product, followed by filtration, and the resulting solid was dried at 60 ° C. under reduced pressure for 4 hours. As a result, 94 g of an ethylene / styrene / norbornene copolymer was obtained. The glass transition temperature was 7 ° C, the MI was 5.0, the styrene unit content measured by ¹³ C-NMR was 5.0 mol%, and the norbornene unit content was 9.0 mol. The tensile modulus was 25 MPa and the elastic recovery was 78%. Temperature 190 ° C, pressure 10M
200mm x 200mm by hot press molding at Pa,
A sheet having a thickness of 1.5 mm was prepared, and the performance of the desk mat was evaluated. The results are shown in Table 1.

[0064]

[Table 1]

[0065]

Industrial Applicability The polyolefin-based desk mat of the present invention has moderate flexibility and good non-transfer property, and is excellent in transparency, rewinding property and writing taste, and can be applied to office desks and study desks. It can also be used as a mat for protecting furniture, dining tables, etc., and for preventing objects placed thereon from falling.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4F071 AA15 AA21 AA86 AA88 AA89 AF20 AF20Y AF25 AF25Y AH16 BB03 BB04 BC01 BC03 4J100 AA02P AA03P AA04P AA07P AA15P AA17P AA18P AA19P ABABACB ABB ACB ABAC ACB AG08R AR09Q AR11Q AS01P AS02P AS03P BA05R BC43P BC43R CA04 CA05 DA25 DA41 DA48 DA49 JA57

Claims (4)

[Claims] 1. A copolymer obtained by copolymerizing (a) an α-olefin with (b) a cyclic olefin and / or (c) an aromatic vinyl compound, and having a glass transition temperature of -30 ° C to 30 ° C.
A polyolefin-based desk mat having a layer containing a copolymer having a tensile elastic modulus of 1000 MPa or less and an elastic recovery rate of 20% or more. 2. The polyolefin-based desk mat according to claim 1, wherein the copolymer has a crystallinity of 20% or less and a surface hardness (Shore-D) of 30 or more. 3. The polyolefin-based desk mat according to claim 1, wherein the copolymer is a copolymer of an α-olefin and a cyclic olefin. 4. The copolymer has a formula: 10 (MPa) ≦ tensile modulus ≦ 200 (MPa) Surface hardness [Shore-D (%)] ≧ (tensile modulus / 10)
The polyolefin-based desk mat according to claim 1, 2, or 3, which satisfies +30 elastic recovery (%) ≧ 140-50 × log tensile modulus.