JP3307457B2 - Tarpaulin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a waterproof sheet which is excellent in various performances and workability, and is preferably used as a waterproof material for civil engineering, construction and industrial use.

[0002]

2. Description of the Related Art Conventionally, as a waterproof material stretched on a waste disposal site, a building roof, or the like, sheets such as ethylene propylene rubber (EPDM), butyl rubber (IIR), and flexible polyvinyl chloride resin (PVC) are used. 2. Description of the Related Art A waterproof type material and a coated type waterproof material such as asphalt and mortar are known. However, none of these waterproof materials sufficiently satisfied both the durability and the water resistance. That is, in the case of a conventional waterproof sheet made of ethylene-propylene rubber (EPDM) and butyl rubber (IIR), the water resistance is good, but when joining using an adhesive, the bonding strength can be increased by immersing in hot water for a long time. And the durability is poor. In the case of a waterproof sheet made of a conventional soft polyvinyl chloride resin, a long-term immersion in hot water causes a reversible agent,
And a stabilizer was eluted, whereby the flexibility of the waterproof sheet was impaired and the mechanical strength was lowered. Also, due to water absorption swelling, wrinkles and sagging occur in the sheet,
There is a problem that stress is locally generated in the sheet, and if the stress is prolonged, the sheet is cracked and the waterproof performance is impaired. On the other hand, a soft polyvinyl chloride resin-based waterproof sheet having improved hot water resistance and durability has been disclosed (JP-A-57-3845 and JP-A-4-238).
No. 37). On the other hand, an ethylene-α-olefin-non-conjugated diene copolymer rubber-based sheet has ideal properties as a waterproof sheet, but has low adhesiveness and requires labor and skill when bonding with an adhesive. As a recent technology, ethylene-α-olefin-non-conjugated diene rubber (EPDM)
(Japanese Patent Laid-Open No. 4-31450) discloses a method of solving difficulties during construction by adding a tackifier to the composition.

[0003]

However, the former waterproof sheet cannot completely prevent the dissolution of the plasticizer and the stabilizer and cannot be said to be necessarily sufficient because of adverse effects on the environment. In addition, the latter tarpaulin is
At the time of construction, it is necessary to heat and press at a temperature of 180 ° C. or more, and there is a problem that the flexibility as a sheet is significantly deteriorated depending on the treatment method. The present invention has been made in view of the above-described problems, and has excellent waterproofness and durability, and has no adverse effect on the environment because there is no elution of a plasticizer and a stabilizer. It is an object of the present invention to provide a waterproof sheet which has good flexibility and excellent workability at the time of bonding and the like.

[0004]

According to the present invention,Below
Catalysts containing compounds (A) and (B) as main components or
Use catalysts containing compounds (A), (B) and (C) as main components
ManufacturingFrom α-olefins and cyclic olefins
Having a derived repeating unit and having a glass transition temperature
(Tg) cyclic olefin copolymer having a temperature of 70 ° C. or lower
Is a waterproof sheet characterized by containing
Provided.(A) containing a transition metal selected from Group IVB of the periodic table
Transition metal compounds (B) a transition metal compound (A) or a derivative thereof
Complex Compounds (C) Organoaluminum compound

Further, a waterproof sheet containing the following components (a), (b) and (c) is provided. (A) 99 to 10 parts by weight of the cyclic olefin-based copolymer (b) 1 to 90 parts by weight of the thermoplastic resin (c) 0.1 to 400 parts by weight of the filler ((a) the cyclic olefin-based copolymer, And when the total of the thermoplastic resins of (b) is 100 parts by weight)

Hereinafter, the present invention will be described specifically. 1. Cyclic olefin copolymer (a) Cyclic olefin copolymer (a) used in the present invention
Has a repeating unit derived from an α-olefin and a cyclic olefin. Here, there is no particular limitation on the α-olefin, but for example, the following general formula [X]

Embedded image (In the formula [X], Ra represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)

In the α-olefin repeating unit represented by the general formula [X], Ra represents ^a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms as described above.
Here, specific examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an isopropyl group, an isobutyl group, an n-butyl group, an n-hexyl group, an octyl group, and an octadecyl group. be able to. Specific examples of the α-olefin that gives the α-olefin repeating unit represented by the general formula [X] include, for example, ethylene, propylene, 1-butene, 3-methyl-1-butene, and 4-methyl-1 -Pentene, 1-hexene, 1-octene, decene, eicosene and the like.

The cyclic olefin is not particularly limited, but may be, for example, a compound represented by the following general formula [Y]:

Embedded image (In the formula [Y], R ^{b to} R ^m each represent a hydrogen atom and a carbon atom of 1;
Represents a hydrocarbon group or a substituent containing a halogen atom, an oxygen atom or a nitrogen atom, and n represents an integer of 0 or more. R ^j or R ^k and R ^l or R ^m may form a ring with each other. R ^{b to} R ^m may be the same or different from each other. )).

Here, as the hydrocarbon group having 1 to 20 carbon atoms, specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, An alkyl group having 1 to 20 carbon atoms such as a hexyl group, an aryl group having 6 to 20 carbon atoms such as a phenyl group, a tolyl group, a benzyl group, an alkylaryl group or an arylalkyl group, a methylidene group, an ethylidene group, a propylidene group; An alkylidene group having 1 to 20 carbon atoms,
Examples thereof include an alkenyl group having 2 to 20 carbon atoms such as a vinyl group and an allyl group. Where R ^b , R ^c , R ^f , and R ^g
Excludes an alkylidene group. When any of R ^d , R ^e , and R ^{h to} R ^m is an alkylidene group, the carbon atom to which it is bonded has no other substituent.

Specific examples of the substituent containing a halogen atom include halogen substituents having 1 to 20 carbon atoms such as a halogen group such as fluorine, chlorine, bromine and iodine, and chloromethyl, bromomethyl and chloroethyl groups. Examples include an alkyl group. Specific examples of the substituent containing an oxygen atom include, for example, an alkoxy group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a phenoxy group, and a carbon atom having 1 to 20 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group. And the like. Specific examples of the substituent containing a nitrogen atom include an alkylamino group having 1 to 20 carbon atoms such as a dimethylamino group and a diethylamino group, and a cyano group.

Specific examples of the repeating unit of the cyclic olefin represented by the general formula [Y] include, for example, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, Methyl norbornene, 7-methyl norbornene, 5,5,6-trimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-
Ethylidene norbornene, 5-vinyl norbornene,
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-methyl-
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-ethyl-
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2,3,4
4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,3,4
4a, 5,8,8a-octahydronaphthalene, 1,5
-Dimethyl-1,4,5,8-dimethano-1,2,3
4,4a, 5,8,8a-octahydronaphthalene, 2
-Cyclohexyl-1,4,5,8-dimetano-1,
2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- Octahydronaphthalene, 1,2-dihydrodicyclopentadiene,
5-chloronorbornene, 5,5-dichloronorbornene, 5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5-methoxynorbornene,
5,6-dicarboxyl norbornene anhydrate, 5-dimethylamino norbornene, 5-cyano norbornene and the like can be mentioned.

The cyclic olefin-based copolymer (a) is basically composed of the α-olefin component and the cyclic olefin component as described above, but these are not detracted from the object of the present invention. In addition to the essential two components, other copolymerizable unsaturated monomer components may be contained as necessary. As such an unsaturated monomer which may be optionally copolymerized, specifically, among the above-mentioned α-olefin components, those not previously used, among the above-mentioned cyclic olefin components, Those not used,
Examples thereof include cyclic dienes such as dicyclopentadiene and norbornadiene, chain dienes such as butadiene, isoprene and 1,5-hexadiene, and monocyclic olefins such as cyclopentene and cycloheptene.

The cyclic olefin-based copolymer (a) is α-
Regarding the content [x] of the olefin unit and the content [y] of the cyclic olefin unit, [x] is 80 to 99.9 mol%.
[Y] is 20 to 0.1 mol%, and especially [x] is 82 mol%.
[Y] is 18 to 0.5 mol% with respect to ９９99.5 mol%,
Among them, [x] is 85 to 98 mol% and [y] is 15 to
More preferably, it is 2 mol%. When the content [x] of the α-olefin unit is less than 80 mol%, the glass transition temperature (Tg) and the tensile modulus of the copolymer become high, and the obtained copolymer composition and The elastic recovery, impact resistance, and elasticity of the sheet contained as a component may be insufficient. On the other hand, when the content of the cyclic olefin unit [y] is less than 0.1 mol%, the crystallinity of the copolymer increases, and the effect of introducing the cyclic olefin component such as elastic recovery becomes insufficient. The cyclic olefin-based copolymer (a) is a substantially linear copolymer in which α-olefin units and cyclic olefin units are linearly arranged and does not have a gel-like crosslinked structure. preferable. Not having a gel-like cross-linked structure means that the copolymer
It can be confirmed by complete dissolution in decalin at 5 ° C. If necessary, it may have an appropriate crosslinked structure.

The glass transition temperature (Tg) of the cyclic olefin copolymer (a) must be 70 ° C. or less. By using such a copolymer, a waterproof sheet that can be suitably used at a low temperature can be obtained. A preferred glass transition temperature (Tg) is -30 to 60C,
In particular, it is more preferably −30 to 40 ° C. In this case, the cyclic olefin-based copolymer (a) has a glass transition temperature (Tg) by changing the type and composition of the monomer.
Can be arbitrarily controlled, and the glass transition temperature (Tg) can be arbitrarily changed according to the intended field of use, the temperature used, and the like.

The cyclic olefin-based copolymer (a) contains 13
The intrinsic viscosity [η] measured in decalin at 5 ° C. is 0.01
It is preferably ２０20 dl / g. Intrinsic viscosity [η]
If it is less than 0.01 dl / g, the strength may be significantly reduced, and if it exceeds 20 dl / g, the moldability may be significantly deteriorated. More preferable intrinsic viscosity [η] is 0.1.
05 to 10 dl / g.

The molecular weight and molecular weight distribution of the cyclic olefin copolymer (a) are not particularly limited, but the weight average molecular weight Mw measured by gel permeation chromatography (GPC) (in terms of polyethylene) is 1, 2,000 to 2,000,000, especially 5,000 to
1,000,000, number average molecular weight Mn is 500 to 1,
And the molecular weight distribution (Mw / Mn) is 1.3-3, especially 1.
It is preferably from 4 to 2.5.

The cyclic olefin copolymer (a) preferably has a crystallinity of 0 to 40% as measured by an X-ray diffraction method. When the crystallinity exceeds 40%, elastic recovery and transparency may be reduced. A more preferred crystallinity is 0 to 30%, particularly 0 to 25%.

The cyclic olefin copolymer (a) preferably has a tensile modulus of less than 3,000 kg / cm ² . When the tensile elastic modulus is 3,000 Kg / cm ² or more, for example, when a waterproof sheet is formed with the copolymer (a) or the composition used in the present invention, a large amount of energy is required at the time of enforcement. Poor flexibility at low temperatures causes problems in cold resistance. In addition, the impact resistance and the substrate compatibility become insufficient. Tensile modulus is 50-2,000
More preferably, it is Kg / cm ² .

The cyclic olefin copolymer (a) has a DS
It is preferable that a broad melting peak by C (measurement of temperature rise) is below 90 ° C. A copolymer having a sharp melting peak at 90 ° C. or higher by DSC (temperature rise measurement) has a wide composition distribution of the copolymer of cyclic olefin and α-olefin, and the elastic recovery of the molded product is insufficient. It may be. In addition, it is more preferable that the broad melting peak by DSC (temperature rise measurement) is in the range of 10 to 85 ° C. In DSC (temperature rise measurement), the melting point (melting peak) of the olefin-based copolymer cannot be seen sharply. No peak appears. By having such characteristics of thermal properties,
The waterproof sheet having excellent physical properties as described above can be obtained, and the waterproof sheet can be formed stably, for example, the molding temperature range is widened.

The cyclic olefin-based copolymer (a) may be a copolymer consisting of only those having the physical properties in the above-mentioned range, and some copolymers having physical properties outside the above-mentioned range are included. May be used. In the latter case, it is sufficient that the entire physical property value is included in the above range.

The method for producing the cyclic olefin copolymer (a) is not particularly limited, but the following compounds (A) and (B)
Is efficiently produced by copolymerizing an α-olefin and a cyclic olefin using a catalyst mainly composed of, or a catalyst mainly composed of the following compounds (A), (B) and (C). be able to. (A) a transition metal compound containing a transition metal selected from Group IVB of the periodic table (B) a compound capable of forming an ionic complex from the transition metal compound (A) or a derivative thereof (C) an organoaluminum compound

In this case, the compound (A) may be any compound containing a transition metal selected from Group IVB of the periodic table, ie, titanium (Ti), zirconium (Zr) or hafnium (Hf). Although it is also possible to use a compound represented by the following general formula (I), (II) or (III), a cyclopentadienyl compound or a derivative thereof, or a compound represented by the following general formula (IV) or a derivative thereof is particularly preferable. It is.

CpM ¹ R ¹ _a R ² _b R ³ _c (I) Cp ₂ M ¹ R ¹ _d R ² _e (II) (Cp-A _f -Cp) M ¹ R ¹ _d R ² _e ( III) M ¹ R ¹ _g R ² _h R ³ _i R ⁴ _j (IV) [In the formulas (I) to (IV), M ¹ represents a Ti, Zr or Hf atom, and Cp represents a cyclopentadienyl group. , Substituted cyclopentadienyl group, indenyl group, substituted indenyl group, tetrahydroindenyl group, substituted tetrahydroindenyl group, fluorenyl group or substituted fluorenyl group. R
¹ , R ² , R ³ and R ⁴ are each a hydrogen atom, an oxygen atom,
Halogen atom, alkyl group having 1 to 20 carbon atoms, 1 carbon atom
An alkoxy group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms,
Alkylaryl group or arylalkyl group, acyloxy group having 1 to 20 carbon atoms, allyl group, substituted allyl group, acetylacetonate group, substituted acetylacetonate group, substituent containing silicon atom, or carbonyl, oxygen molecule, nitrogen A ligand such as a molecule, a Lewis base, a chain unsaturated hydrocarbon or a cyclic unsaturated hydrocarbon is shown, and A represents a crosslink by a covalent bond. a, b and c each represent an integer of 0-3, d and e each represent an integer of 0-2, f represents an integer of 06, and g, h, i and j each represent an integer of 0-4.
Two or more of R ¹ , R ² , R ³ and R ⁴ may combine with each other to form a ring. When Cp has a substituent, the substituent is preferably an alkyl group having 1 to 20 carbon atoms. In the formulas (II) and (III), two Cp
May be the same or different from each other. ]

The substituted cyclopentadienyl group in the above formulas (I) to (III) includes, for example, methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, 1,2-dimethyl Cyclopentadienyl group, tetramethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,
2,3-trimethylcyclopentadienyl group, 1,2,2
Examples thereof include a 4-trimethylcyclopentadienyl group, a pentamethylcyclopentadienyl group, and a trimethylsilylcyclopentadienyl group. Specific examples of R ^{1 to} R ⁴ include, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom as a halogen atom;
Methyl, ethyl, n-propyl, iso-propyl, n-butyl, octyl,
2-ethylhexyl group; methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group as C1-C20 alkoxy group; phenyl group, tolyl as C6-C20 aryl group, alkylaryl group or arylalkyl group Group, xylyl group, benzyl group;
A heptadecylcarbonyloxy group as an acyloxy group of 20; a trimethylsilyl group, a (trimethylsilyl) methyl group as a substituent containing a silicon atom: dimethyl ether, diethyl ether, ethers such as tetrahydrofuran as Lewis bases, thioethers such as tetrahydrothiophene, ethyl Esters such as benzoate, nitriles such as acetonitrile and benzonitrile, trimethylamine, triethylamine, tributylamine,
Amines such as N, N-dimethylaniline, pyridine, 2,2′-bipyridine and phenanthroline; phosphines such as triethylphosphine and triphenylphosphine;
As chain unsaturated hydrocarbons, ethylene, butadiene, 1-
Pentene, isoprene, pentadiene, 1-hexene and derivatives thereof; cyclic unsaturated hydrocarbons such as benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and derivatives thereof; Can be. Examples of the crosslink by the covalent bond of A include a methylene crosslink, a dimethylmethylene crosslink, an ethylene crosslink, a dimethylsilylene crosslink, a dimethylgermylene crosslink, and a dimethylstannylene crosslink.

Examples of such compounds include the following compounds and compounds obtained by substituting zirconium of these compounds with titanium or hafnium. Compounds of formula (I) (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl) tribenzylzirconium, (pentamethylcyclopentadienyl) trichloro Zirconium, (pentamethylcyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) triphenylzirconium, (cyclopentadienyl) tribenzylzirconium, (cyclopentadienyl) trichloro Zirconium, (cyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) dimethyl (methoxy) zirconium, (methylcyclopentadienyl) trimethyldi Ruconium, (methylcyclopentadienyl) triphenylzirconium, (methylcyclopentadienyl) tribenzylzirconium, (methylcyclopentadienyl) trichlorozirconium, (methylcyclopentadienyl) dimethyl (methoxy) zirconium,
(Dimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trichlorozirconium, (trimethylsilylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trichlorozirconium,

A compound of formula (II) bis (cyclopentadienyl) dimethylzirconium,
Bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) diethyl zirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium , Bis (cyclopentadienyl) dihydridozirconium, bis (cyclopentadienyl) monochloromonohydridozirconium, bis (methylcyclopentadienyl) dimethylzirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclo Pentadienyl) dibenzyl zirconium, bis (pentamethylcyclopentadienyl) dimethyl zirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, Scan (pentamethylcyclopentadienyl) dibenzyl zirconium, bis (pentamethylcyclopentadienyl) chloromethyl zirconium,
Bis (pentamethylcyclopentadienyl) hydridomethylzirconium, (cyclopentadienyl) (pentamethylcyclopentadienyl) dichlorozirconium,

Compound of Formula (III) Ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) dichloro zirconium, ethylene bis (tetrahydroindenyl) dimethyl zirconium, ethylene bis (tetrahydroindenyl) dichloro zirconium, dimethylsilylene bis (cyclo Pentadienyl) dimethyl zirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropyl (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, isopropyl (cyclopentadienyl) (9-fluorenyl) dichlorozirconium, [ Phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethylzirconium,
Diphenylmethylene (cyclopentadienyl) (9-fluorenyl) dimethyl zirconium, ethylidene (9-
Fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclohexyl (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclopentyl (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclobutyl (9-fluorenyl) (cyclopentane Dienyl) dimethyl zirconium,
Dimethylsilylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3
5-trimethylcyclopentadienyl) dimethyl zirconium,

Examples of compounds other than the cyclopentadienyl compounds represented by the above general formulas (I), (II) and (III) include the compounds of the above formula (IV). Alternatively, a zirconium compound having one or more of an alkyl group, an alkoxy group, and a halogen atom such as a compound in which zirconium is replaced with hafnium or titanium, a hafnium compound, or a titanium compound can be given. Tetramethyl zirconium, tetrabenzyl zirconium, tetramethoxy zirconium, tetraethoxy zirconium, tetrabutoxy zirconium, tetraphenoxy zirconium, tetrakis (2-ethylhexyloxy) zirconium, tetrachloro zirconium, tetrabromo zirconium, butoxy trichloro zirconium, dibutoxy dichloro zirconium Bis (2,6-di-t-butylphenoxy) dimethyl zirconium, bis (2,6-di-t-butylphenoxy) dichlorozirconium, zirconium tetrakis (acetylacetonate)

The compound (B) is not limited, but may be an ionic compound (B-B) capable of forming an ionic complex from the transition metal compound (A) or a derivative thereof.
1) Specifically, compounds represented by the following formula (V) or (VI) can be suitably used. ^{([L 1 -R 7] k} +) p ([M 3 Z 1 Z 2 ... Z n] (nm) -) q ... (V) ([L 2] k +) p ([M 4 Z 1 Z 2 ... ^{Z n] (nm) -)} q ... (VI) ( where, L ² is ^{M 5, R 8 R 9 M} 6, R 10 is ₃ C or ^{R 11 M 6) [(V} ), (VI) formula Where L ¹ is a Lewis base, M ³ and M ⁴
Are VB, VIB, VIIB, and VIII of the periodic table, respectively.
Group, IB, IIB, Group IIIA, elements selected from Group IVA, and group VA, of M ⁵ and M ^6, respectively Periodic Table IIIB
Group, IVB group, VB group, VIB group, VIIB group, VIII group, IA
Group, IB group, IIA group, an element selected from Group IIB and VIIA group, Z ¹ to Z ⁿ are each a hydrogen atom, a dialkylamino group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an organic metalloid It represents a group or a halogen atom, Z ¹ to Z ⁿ may form a ring of two or more thereof with each other. R ⁷ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group having 6 to 20 carbon atoms, and R ⁸ and R ⁹ each represent a cyclopentadienyl group or a substituted cyclopentane. dienyl group, an indenyl group or a fluorenyl group, R ¹⁰ represents an alkyl group, an aryl group, alkylaryl group or arylalkyl group having 1 to 20 carbon atoms. R ¹¹ represents a macrocyclic ligand such as tetraphenylporphyrin and phthalocyanine. m is a valence of M ³ or M ⁴ and is an integer of 1 to 7, n is an integer of 2 to 8, and k is [L ¹ −
R ⁷ ] and [L ² ] are ionic valences and are integers of 1 to 7, and p is 1
The above integer, q = (p × k) / (nm). ]

Specific examples of the above Lewis base include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as trimethylamine, triethylamine, tri-n-butylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine, p- bromo- N, N-dimethylaniline, p-nitro-N, N-dimethylaniline; Phosphines such as fin, triphenylphosphine and diphenylphosphine;
Dimethyl ether, diethyl ether, tetrahydrofuran, and dioxane, diethyl thioether, thioethers such as tetrahydrothiophene, ethyl
Esters such as Rubenzoeto, and the like can be given. Specific examples of M ³ and M ⁴ include B, Al, Si,
P, As, Sb, etc., Li Specific examples of ^{M 5,} Na,
Ag, Cu, Br, I, I 3 , etc., specific examples of ^{M 6} may be mentioned Mn, Fe, Co, Ni, and Zn, and the like. Specific examples of Z ^l to Z ^n, for example, dimethylamino group as a dialkylamino group, a diethylamino group;
A methoxy group, an ethoxy group, an n-butoxy group as an alkoxy group having 1 to 20 carbon atoms; a phenoxy group, a 2,6-dimethylphenoxy group, a naphthyloxy group as an aryloxy group having 6 to 20 carbon atoms; Methyl, ethyl, n-propyl, iso-
A propyl group, an n-butyl group, an n-octyl group, a 2-ethylhexyl group; a phenyl group as an aryl group, an alkylaryl group or an arylalkyl group having 6 to 20 carbon atoms;
p-tolyl group, benzyl group, 4-tert-butylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4-dimethylphenyl group, 2,3
-Dimethylphenyl group; p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group,
4,5-trifluorophenyl group, pentafluorophenyl group, 3,5- bis (trifluoromethyl) phenyl group; F, Cl, Br, I as a halogen atom; pentamethylantimony group, trimethylsilyl group as an organic metalloid group; Trimethylgermyl group, diphenylarsine group,
Examples thereof include a dicyclohexylantimony group and a diphenylboron group. Specific examples of R ⁷ and R ¹⁰ are the same as those described above. Specific examples of the substituted cyclopentadienyl group of R ⁸ and R ⁹ include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. be able to.
Here, the alkyl group usually has 1 to 6 carbon atoms, and the number of substituted alkyl groups can be selected as an integer of 1 to 4.

Among the compounds of the formulas (V) and (VI),
Those in which M ³ and M ⁴ are boron are preferred. (V), (V
Among the compounds of the formula (I), the following compounds can be particularly preferably used. Compound of formula (V): Triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyltri (n-butyl) ammonium tetraphenylborate, benzyltriphenyltetraphenylborate (N-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methylphenylphenylborate (2-cyanopyridinium ), Trimethylsulfonium tetraphenylborate, benzyldimethyltetraphenylborate Honiumu, tetrakis (pentafluorophenyl) borate triethylammonium tetrakis (pentafluorophenyl) borate tri (n-
Butyl) ammonium tetrakis (pentafluorophenyl) borate triphenyl ammonium, tetrakis (pentafluorophenyl) borate, tetrabutylammonium tetrakis (pentafluorophenyl) borate (tetraethylammonium) tetrakis (pentafluorophenyl) borate (methyltri (n- butyl) ammonium), tetrakis (pentafluorophenyl) borate (benzyltri (n- butyl) ammonium), tetrakis (pentafluorophenyl) borate methyldiphenyl ammonium tetrakis (pentafluorophenyl) borate methyltriphenylphosphonium ammonium tetrakis (pentafluorophenyl ) borate dimethyl diphenyl ammonium tetrakis (pentafluorophenyl) borate anilinium, Tetoraki (Pentafluorophenyl) borate-methyl anilinium, tetrakis (pentafluorophenyl) borate dimethylanilinium tetrakis (pentafluorophenyl) borate trimethyl anilinium tetrakis (pentafluorophenyl) borate dimethyl (m-nitro anilinium), tetrakis ( pentafluorophenyl) borate dimethyl (p- bromo anilinium), tetrakis (pentafluorophenyl) borate pyridinium tetrakis (pentafluorophenyl) borate (p- cyanopyridinium) tetrakis (pentafluorophenyl) borate (N- methylpyridinium) , tetrakis (pentafluorophenyl) borate (N- benzyl pyridinium), tetrakis (pentafluorophenyl) borate (O-cyano -N- methylpyridinium , Tetrakis (pentafluorophenyl) borate (p- cyano -N- methylpyridinium) tetrakis (pentafluorophenyl) borate (p- cyano -N- benzyl pyridinium), tetrakis (pentafluorophenyl) borate trimethylsulfonium tetrakis (penta Benzyldimethylsulfonium fluorophenyl) borate, tetraphenylphosphonium tetrakis (pentafluorophenyl) borate, tetrakis [3,5-bis (trifluoromethyl) phenate
Nyl] dimethylanilinium borate, triethylammonium hexafluoroarsenate,

[0033]Compound of formula (VI) Ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylborate (tetraphenylporphyrin man
gun),Tetrakis (Pentafluorophenyl) borate ferroseni
Umm,Tetrakis (Pentafluorophenyl) decamethyl borate
Ferrocenium,Tetrakis (Pentafluorophenyl) acetyl borate
Erosenium,Tetrakis (Pentafluorophenyl) formylph borate
Erosenium,Tetrakis (Pentafluorophenyl) cyanofe borate
Rosenium,Tetrakis (Pentafluorophenyl) silver borate,Tetrakis (Pentafluorophenyl) trityl borate,Tetrakis Lithium (pentafluorophenyl) borate,Tetrakis Sodium (pentafluorophenyl) borate
,Tetrakis (Pentafluorophenyl) boric acid (tetraf
Enylporphyrin manganese),Tetrakis (Pentafluorophenyl) boric acid (tetraf
Enylporphyrin iron chloride),Tetrakis (Pentafluorophenyl) boric acid (tetraf
Zinc porphyrin), silver tetrafluoroborate, silver hexafluoroarsenate, silver hexafluoroantimonate, and compounds other than formulas (V) and (VI), for example,Tris
(Pentafluorophenyl) boron,Tris [3,5-bi
[(Trifluoromethyl) phenyl]Boron, Trifeni
Leboron or the like can also be used. Further, as compound (B)
Is methylaluminoxane, ethylaluminoxane, i
Sobutylaluminoxane, chloro-containing alkylalumino
Organoaluminum oxy compounds such as xane (B-2)
Can also be used. Degree of polymerization of this aluminoxane
Is 3 to 50, preferably 5 to 30.

Examples of the organoaluminum compound as the component (C) include those represented by the following general formula (VII). R ¹² _r AlQ _3-r (VII) (R ¹² is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to ¹² carbon atoms such as an alkyl group, an alkenyl group, an aryl group and an arylalkyl group; Q is a hydrogen atom; Represents a halogen atom or an alkoxy group having 1 to 20 carbon atoms, and r is in the range of 1 ≦ r ≦ 3.) More specifically, trimethylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum Chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like.

The above-mentioned catalyst can be used as the component (A) and the component (B) [(B-1) or (B-2)], or the component (A) and the component (B) [(B-1)]. Component and component (C) as main components. In this case, the use conditions of the component (A) and the component (B-1) are not limited,
Component: The ratio (molar ratio) of component (B-1) is 1: 0.01 to
The ratio is preferably set to 1: 100, particularly 1: 1 to 1:10. The conditions for using the component (A) and the component (B-2) are as follows: component (A): component (B-2) (molar ratio as a metal atom) in the range of 1:10 to 1: 10,000, particularly 1 : 20 ~
The ratio is preferably set to 1: 5,000. The working temperature is preferably in the range of -100 to 250 ° C, and the pressure and time can be set arbitrarily. Also, (C)
The amount of the component is usually from 0 to 2 per mole of the component (A).
000 mol. When the component (C) is used, the polymerization activity can be improved. However, when the content is too large, a large amount of the organic aluminum compound remains in the copolymer, which is not preferable. The components (A) and (B) may be brought into contact in advance, and the contact product may be separated and washed before use, or may be used after being brought into contact in a polymerization system. The component (C) is a component (A),
It may be used in contact with the component (B) or the contact product of the component (A) and the component (B). The contact may be made in advance, or may be brought into contact in the polymerization system.

The polymerization methods include bulk polymerization, solution polymerization,
Any method such as suspension polymerization may be used. Further, a batch method or a continuous method may be used. Regarding the polymerization conditions, the polymerization temperature is preferably -100 to 250C, particularly preferably -50 to 200C. The ratio of the catalyst to the reaction raw material is such that the raw material monomer / component (A) (molar ratio) or the raw material monomer / component (B) (molar ratio) is 1 to 1.
0 ^8, it is preferable that the particular 100 to 10 ^5. Further, the polymerization time is usually from 5 minutes to 10 hours, and the reaction pressure is from normal pressure to
100 kg / cm ² G, preferably normal pressure to 50 kg / c
m ² G. As a method of adjusting the molecular weight of the copolymer,
The amount of each catalyst component, the selection of the polymerization temperature, and the polymerization reaction in the presence of hydrogen can be used.

When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, and fats such as pentane, hexane, heptane and octane Group hydrocarbons, halogenated hydrocarbons such as chloroform, dichloromethane and the like can be used. These solvents may be used alone or in a combination of two or more. Also, α-
A monomer such as an olefin may be used as a solvent.

[0038]

[0039]

[0040]

2. Thermoplastic Resin (b) The kind of the thermoplastic resin (b) used in the present invention is not particularly limited. For example, at least the following general formula CH ₂ ＣＨCHR ¹³ (wherein R ¹³ is a hydrogen atom or a carbon atom having 1 to 1 carbon atoms) And an α-olefin homopolymer or copolymer containing an α-olefin represented by the formula (1) as one component, other than the above-mentioned cyclic olefin copolymer.

Specific examples of the thermoplastic resin (b) include high-density polyethylene, low-density polyethylene,
Polyethylene such as linear low-density polyethylene, ethylene
1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene / 1-hexene copolymer, ethylene / cyclic olefin copolymer (Tg exceeding 70 ° C), ethylene / vinyl acetate copolymer Polymer, ethylene / acrylic acid copolymer and metal salt thereof, polypropylene, ethylene / propylene copolymer, propylene / 1-butene copolymer, poly 1-butene, 1-butene / propylene copolymer, 1-butene -4-methyl-1-pentene copolymer, poly 4-methyl-1-pentene, poly 3-methyl-
1-butene and the like can be mentioned. Particularly preferred as the thermoplastic resin (b) are HDPE, LDPE,
L-LDPE, polypropylene, ethylene / propylene copolymer, cyclic olefin ring-opening polymer and the like. In addition,
If necessary, two or more kinds of thermoplastic resins can be used in combination.

Other thermoplastic resins include those obtained by blending an elastomer with the above thermoplastic resin. As a result, the effect of improving the impact resistance particularly at low temperatures can be obtained. Here, the kind of the elastomer is not particularly limited, but a thermoplastic elastomer or other rubbers can be suitably used. The compounding amount of the thermoplastic elastomer or other rubber is preferably 0.1 to 500 parts by weight, more preferably 0.5 to 300 parts by weight, based on 100 parts by weight of the thermoplastic resin. Specific examples of the thermoplastic elastomer include thermoplastic polyurethane, styrene / butadiene block copolymer, and styrene / isoprene block copolymer. Specific examples of other rubbers include natural rubber, styrene / butadiene rubber, butadiene rubber, isoprene rubber, chloroprene rubber, butyl rubber, ethylene / propylene rubber (EPR), EPDM, and chlorinated polystyrene rubber. it can. Particularly preferred elastomers include ethylene propylene rubber (EPR), E
PDM is styrene-butadiene rubber. Further, the elastomer component may be crosslinked as needed. Also,
Wax, atactic polypropylene, asphalt, petroleum resin and the like can also be added.

The mixing ratio of the thermoplastic resin (b) is as follows:
The amount is preferably 1 to 90 parts by weight, more preferably 2 to 80 parts by weight, based on 99 to 10 parts by weight of the cyclic olefin copolymer (a). If it is more than 90 parts by weight, the flexibility of the sheet is lost, and if it is less than 10 parts by weight, the impact resistance is reduced.

3. Filler (c) The filler (c) used in the present invention includes inorganic fillers such as calcium carbonate, clay, talc, white carbon, magnesium silicate, calcium silicate, and asbestos powder, polyester, propylene, cotton, and glass. Short fiber materials such as sen and asbestos can be mentioned, and the amount thereof is determined according to the required physical properties. Also,
Examples of the flame retardant used in the present invention include magnesium chloride, antimony trioxide, chlorinated paraffin, polybrominated bisphenol A and derivatives thereof. Further, titanium oxide and pigments may be used as weathering agents, process oils and the like may be used as processing aids, and phosphorus-based antioxidants and phenolic antioxidants may be used as stabilizers.
Stearic acid, zinc oxide and vulcanizing agents may be added. The waterproof sheet of the present invention may further be crosslinked (reticulated) in order to increase physical properties such as strength and durability. Crosslinking can be performed by a method using a radical generator or irradiation with high energy such as an electron beam or radiation. Known radical generators such as organic peroxides and diazo compounds can be used as the radical generator. Specifically, benzoyl peroxide, dicumyl peroxide, di-t
Examples thereof include tert-butyl peroxide, tert-butyl cumyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, and azobisisobutylnitrile. The amount of the radical generator used is preferably at least 0.01 part by weight, particularly preferably 0.03 to 1 part by weight, based on the copolymer.

As the waterproofing sheet of the present invention, a film or sheet-like material such as woven or non-woven fabric is used as a filler.
It may be a sheet having a structure in which a resin is impregnated or laminated thereon, or may be a film of another resin, a resin composition, or a laminate with the sheet.

4. Production Method The method for producing the waterproof sheet of the present invention is not particularly limited, but it can be favorably performed by kneading the components in a molten state and then forming the sheet. As the melt kneading device, a Banbury mixer, a single screw extruder, a twin screw extruder, or the like can be used. About 150 ° C-25
0 ° C, preferably 1 to 30 at a temperature of 190 ° C to 220 ° C.
It can be carried out by melt-kneading for minutes. There is no particular limitation on the order of kneading. For sheet molding from these compositions, a general sheet forming method can be used. For example, a method in which a molten resin composition is extruded from a T-die at a temperature of 180 ° C. to 250 ° C., or a resin composition heated and melted to a softening temperature or higher with a Banbury mixer, a kneader, or the like, is formed into a sheet by a calender roll or the like. Methods can be mentioned. The extruder for forming the T-die sheet is preferably an apparatus equipped with a vacuum vent mechanism.

[0048]

EXAMPLES The present invention will be described more specifically with reference to the following examples. Reference Example (Copolymerization of ethylene and 2-norbornene) Under a nitrogen atmosphere, at room temperature, 15 liters of toluene, 23 mmol of triisobutylaluminum (TIBA), 38 micromol of zirconium tetrachloride, tetrakis (pentafluorophenyl) in a 30 liter autoclave at room temperature. ) 60 micromoles of anilinium borate are charged in this order, followed by 2.9 liters of a toluene solution containing 70% by weight of 2-norbornene (19 liters as 2-norbornene).
Mol) was added. After the temperature was raised to 80 ° C., the reaction was carried out for 110 minutes while continuously introducing ethylene so that the ethylene partial pressure became 7.5 kg / cm ² . After the completion of the reaction, the polymer solution was poured into 15 liters of methanol to precipitate the polymer. The polymer is filtered and dried,
A cyclic olefin copolymer (a1) was obtained. The yield of the cyclic olefin copolymer (a1) was 3.21 kg. The polymerization activity was 928 kg / gZr.

The obtained cyclic olefin copolymer (a)
Were as follows. 30 pp of ¹³ C-NMR
m, the sum of the peaks based on ethylene and the peaks based on methylene at the 5- and 6-positions of norbornene, and 32.
The norbornene content determined from the ratio to the peak based on the methylene group at the 7-position of norbornene appearing at around 5 ppm was 10.1 mol%. The intrinsic viscosity [η] measured in decalin at 135 ° C. was 1.03 dl / g, and the crystallinity determined by X-ray diffraction was 2.0%. Using a Vibron 11-EA type manufactured by Toyo Boulding Co., Ltd. as a measuring device, a measuring piece having a width of 4 mm, a length of 40 mm, and a thickness of 0.1 mm was measured at a heating rate of 3 ° C./min and a frequency of 3.5 Hz. The glass transition temperature (Tg) was determined from the peak of the loss modulus of elasticity (E ") of the sample , Tg was 4 ° C. ALC / GPC150C manufactured by Waters [column: TSK HM + GMH manufactured by Tosoh Corporation] was used as a measuring device . −6 × 2], 1,2,4-trichlorobenzene solvent, 135 ° C.
The weight average molecular weight Mw, number average molecular weight Mn, and molecular weight distribution (Mw / Mn) were calculated in terms of polyethylene.
Mw is 62,300, Mn is 33,900, Mw / Mn
= 1.84. Using a Perkin-Elmer 7 series DSC at a rate of 10 ° C./min, -50 ° C.
When the melting point (Tm) was measured in the range of 150 ° C., the Tm
Was 78 ° C (broad peak).

Examples 1 to 6 and Comparative Examples 1 to 2 The cyclic olefin polymer (a) obtained in the above reference example and other components were melt-kneaded using a Banbury mixer in accordance with the composition shown in Table 1. This melt-kneaded product was formed into a sheet using a roll, and formed into a pellet using a cutting machine. Using the above composition, a sheet having a thickness of 1 mm was obtained with a T-die sheet processing machine. Table 2 shows the measurement results of the physical properties of the obtained sheet. In addition, the physical property measurement in these Examples etc. was evaluated in accordance with JIS A-6008 (1986). As for the shear peel strength of the heat-sealed sheet, two sheets each having a thickness of 1 mm obtained by T-die extrusion were laminated, a Teflon sheet having a thickness of 0.1 mm on the upper surface of the sheet, and a silicon rubber sheet having a thickness of 3 mm were laminated on the lower surface of the sheet. Using a “heat seal tester” (manufactured by Tester Sangyo Co., Ltd.), the temperature was 140 ° C. and the load was 1 kg /
cm ² for 30 seconds, and after 24 hours, a 20 mm wide strip specimen was pulled at a pulling speed of 50 mm.
Per minute, a 180 degree shear peel test was performed to measure the peel strength.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

According to the present invention, water resistance and durability are excellent, and since there is no elution of plasticizers and stabilizers, the environment is not adversely affected, and the weather resistance and flexibility are good. In addition, it is possible to provide a waterproof sheet excellent in workability at the time of bonding and the like.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI E04C 2/20 E04C 2/20 (56) References JP-A-5-239290 (JP, A) JP-A-6-116647 (JP) JP-A-6-240066 (JP, A) JP-A-2-196832 (JP, A) JP-A-62-252407 (JP, A) Komatsu Koei, Susumu Ono, Fumitake Imaizumi, metallocene catalyst New Polymer, Tsukuri, Japan, Industrial Research Institute Co., Ltd., April 20, 1999, Chapter 8 (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 23/00-23/36 C08L 45 / 00-45/02 C08L 101/00-101/16 C08J 5/18 E04C 2/20 C08F 4/64

Claims (2)

(57) [Claims] (1)The following compounds (A) and (B) as main components
Or the following compounds (A), (B) and (C)
Manufactured using a catalyst as a main component,α-olefin and
And a repeating unit derived from a cyclic olefin,
And a ring having a glass transition temperature (Tg) of 70 ° C. or less.
It is characterized by containing an olefin copolymer as a main component.
The waterproof sheet to be used as a sign.(A) containing a transition metal selected from Group IVB of the periodic table
Transition metal compounds (B) a transition metal compound (A) or a derivative thereof
Complex Compounds (C) Organoaluminum compound 2. The waterproof sheet according to claim 1, comprising the following components (a), (b) and (c). (A) 99 to 10 parts by weight of the cyclic olefin-based copolymer (b) 1 to 90 parts by weight of the thermoplastic resin (c) 0.1 to 400 parts by weight of the filler ((a) the cyclic olefin-based copolymer, And when the total of the thermoplastic resins of (b) is 100 parts by weight)