JP3221721B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having excellent impact resistance and heat sealing properties, which can be effectively used in various fields such as automobiles, home appliances and films.

[0002]

2. Description of the Related Art Generally, thermoplastic resins are excellent in moldability and have sufficient rigidity as compared with other materials.
It is widely used as a molding material for various products such as electric products and industrial products. However, although the thermoplastic resin has the above-mentioned excellent properties, it cannot be said that the thermoplastic resin has sufficient impact resistance. In contrast, JP-A-1-96234 discloses a composition comprising an ethylene / cycloolefin random copolymer and an ethylene / α-olefin random copolymer as a resin composition having improved impact resistance. Have been. Here, the ethylene / cyclic olefin random copolymer has a glass transition temperature (Tg) of 50 to 250 ° C., and has a problem in impact resistance. In the invention of JP-A-1-96234, an ethylene / α-olefin random copolymer is blended in order to improve the impact resistance of the ethylene / cyclic olefin random copolymer.
Therefore, the present invention does not generally improve the impact resistance of a thermoplastic resin. The present invention has been made in view of the above circumstances, and has as its object to provide a resin composition having improved impact resistance of a thermoplastic resin.

[0003]

Means and Action for Solving the Problems The present inventors have
As a result of intensive studies, it has been found that when a cyclic olefin-based copolymer having a specific structure having a specific glass transition temperature (Tg) and a tensile modulus is blended with a thermoplastic resin, the impact resistance of the thermoplastic resin and the heat resistance The inventors have found that the sealing characteristics are improved, and have accomplished the present invention. That is, the resin composition of the present invention is a copolymer obtained by copolymerizing (a) ethylene and a cyclic olefin giving a repeating unit represented by the following general formula [Y], and has a glass transition temperature (T
g) is 30 ° C. or less, and the tensile modulus is 3,000 Kg.
/ 98 ² or less cyclic olefin copolymer
% By weight and (b) 98 to 2% by weight of a thermoplastic resin.

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 1. 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. )

As a resin composition comprising a cyclic olefin copolymer and a thermoplastic resin, a composition comprising a crystalline polyolefin resin and an ethylene / cyclic olefin random copolymer (an improvement in heat resistance and the like: JP-A-1-31
No. 8052, improvement of moldability, etc .: JP-A-3-122148)
Is known. However, the random copolymer used in these compositions has a glass transition (Tg) of 50 to 230 ° C., and it is not possible to improve the impact resistance of the thermoplastic resin by blending such a random copolymer. Can not.

Hereinafter, the present invention will be described in more detail.
First, each component will be described in detail. (A) Cyclic olefin copolymer (a) The component (a) is a copolymer obtained by copolymerizing ethylene and a cyclic olefin that gives a repeating unit represented by the following general formula [Y], Glass transition temperature (T
g) is 30 ° C. or less, and the tensile modulus is 3,000 Kg.
/ Cm ² or less is used.

[0006]

Embedded image

(In the formula [Y], R ^{b to} R ^m each represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a substituent containing a halogen atom, an oxygen atom or a nitrogen atom, and n is 0 or 1 integer may be formed with each other ring and .R ^j or R ^k and R ^l or R ^m indicates a. Further, R ^b to R ^m are each may be the same or different from each other.)

In the repeating unit represented by the general formula [Y], R ^{b to} R ^m each represent a hydrogen atom and a carbon atom of 1
To 20 to 20 hydrocarbon groups or substituents containing a halogen atom, an oxygen atom or a nitrogen atom. Here, as the hydrocarbon group having 1 to 20 carbon atoms, specifically, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
Alkyl groups having 1 to 20 carbon atoms such as -butyl group, isobutyl group, t-butyl group, hexyl group, etc .; aryl groups having 6 to 20 carbon atoms such as phenyl group, tolyl group, benzyl group, alkylaryl group or arylalkyl. , A methylidene group, an ethylidene group, a propylidene group, etc.
Carbon number 2 such as alkylidene group, vinyl group, allyl group of 0
And -20 alkenyl groups. However,
R ^b , R ^c , R ^f and R ^g exclude an alkylidene group. Note that R
^{When any of d} , R ^e , and R ^{h to} R ^m is an alkylidene group,
The carbon atom to which it is attached has no other substituents.

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. Specifically as a substituent containing a nitrogen atom,
Examples thereof 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 cyclic olefin giving the repeating unit represented by the general formula [Y] include, for example, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, -Methylnorbornene, 7-methylnorbornene, 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-dimetano-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 copolymer used in the present invention is basically obtained by copolymerizing the above-mentioned ethylene with a cyclic olefin giving a repeating unit represented by the above general formula [Y]. However, as long as the object of the present invention is not impaired, other copolymerizable unsaturated monomer components may be used, if necessary, in addition to these two essential components. As the unsaturated monomer which may be optionally copolymerized, specifically, α-olefins other than ethylene, such as propylene and 1-butene, and the above-mentioned cyclic olefin components which are used earlier. None, cyclic dienes such as dicyclopentadiene and norbornadiene,
Examples include chain dienes such as butadiene, isoprene, and 1,5-hexadiene, and monocyclic olefins such as cyclopentene and cycloheptene.

The cyclic olefin copolymer must have a glass transition temperature (Tg) of 30 ° C. or less. If such a copolymer is used, the impact resistance of the thermoplastic resin,
Heat sealing characteristics can be improved. A more preferred glass transition temperature (Tg) is -30 to 30C, particularly -3.
0-20 ° C. In this case, the cyclic olefin-based copolymer used in the present invention can control the glass transition temperature (Tg) arbitrarily by changing the type and composition of the monomer. Other thermoplastics,
The glass transition temperature (Tg) can be arbitrarily changed according to the temperature used or the like.

Further, the cyclic olefin-based copolymer is
The melting point by SC is preferably 90 ° C. or lower, particularly preferably 10 to 85 ° C., particularly preferably 20 to 80 ° C. In this case, the cyclic olefin-based copolymer preferably has a broad melting peak of less than 90 ° C. by DSC. Copolymers whose DSC has a sharp melting peak at 90 ° C. or higher have a non-uniform composition distribution of the copolymer of cyclic olefin and ethylene, and do not have an effect of improving the resulting composition such as impact resistance. May be sufficient. In the DSC measurement, the melting point (melting peak) of the cyclic olefin-based copolymer used in the present invention is not sharply observed. No peak. Furthermore, it is preferable that the cyclic olefin-based copolymer has a relatively small sub-peak (one or more) on the high temperature side of the main peak in the crystallization peak by DSC (measuring temperature drop). Due to these characteristics of thermal properties, the effect of improving the impact resistance and the like of the composition can be obtained in a wide use temperature range.

In the cyclic olefin copolymer used in the present invention, the ratio of the content of repeating units derived from ethylene [ethylene] and the content of repeating units derived from cyclic olefin [y] ([ethylene]: [y ]) Is usually 80 to 99.9 mol%: 20 to 0.1 mol%, preferably 82 to 99.5 mol%: 18 to 0.5 mol%, particularly preferably 85 to 98 mol%: 15 to 15 mol%. 2 mol%.
When the content [y] of the cyclic olefin repeating unit exceeds 20 mol%, the glass transition point and the tensile modulus of the copolymer become high, and the impact resistance and toughness of the composition and the molded product become insufficient. When the content is less than 0.1 mol%, the crystallinity of the copolymer becomes too high, and the impact resistance of the composition and the molded product may be insufficient.

The cyclic olefin copolymer is a substantially linear copolymer in which repeating units derived from ethylene and repeating units derived from a cyclic olefin are linearly arranged, and has a gel-like crosslinked structure. It is preferable that it does not have. The absence of a gel-like crosslinked structure can be confirmed by the fact that the copolymer is completely dissolved in decalin at 135 ° C.

The cyclic olefin copolymer has an intrinsic viscosity [η] of 0.01 to 20 measured in decalin at 135 ° C.
It is preferably dl / g. When the intrinsic viscosity [η] is 0.
If it is less than 01 dl / g, the strength of the molded article may decrease, and if it exceeds 20 dl / g, the moldability of the composition may deteriorate. More preferable intrinsic viscosity [η] is 0.0
5 to 10 dl / g.

The molecular weight of the cyclic olefin copolymer is not particularly limited, but the weight average molecular weight Mw measured by gel permeation chromatography (GPC) is 1,000 to 2,000,000, Especially 5,000 to 1,000,000, number average molecular weight Mn
Is 500 to 1,000,000, especially 2,000 to 80
000, and a molecular weight distribution (Mw / Mn) of 1.3.
To 4, particularly preferably 1.4 to 3. When the molecular weight distribution (Mw / Mn) is more than 4, the content of the low molecular weight substance increases, which may cause bleed out from the molded product.

The cyclic olefin copolymer preferably has a crystallinity of 0 to 40% as measured by an X-ray diffraction method. If the crystallinity exceeds 40%, the impact resistance of the molded product may be insufficient. A more preferred crystallinity is 0 to 30%, particularly 0 to 25%.

The cyclic olefin copolymer used in the present invention has a tensile modulus of not more than 3,000 kg / cm ² . When the tensile modulus exceeds 3,000 kg / cm ² , the toughness of the molded product may be insufficient. A more preferred tensile modulus is 50 to 2,000 Kg / cm ² , particularly 100 to 1,500 Kg / cm ² .

The cyclic olefin copolymer used in the present invention may be a copolymer consisting of only those having the above-mentioned physical properties. In this case, the copolymer has a glass transition temperature (Tg) of 30 ° C. or lower. It may be a mixture of copolymers having certain different Tg. Further, the copolymer may partially contain a copolymer having physical properties outside the above range. In the latter case, it is sufficient that the entire physical property value is included in the above range.

The cyclic olefin copolymer used in the present invention can be produced by using a compound (A) represented by the following general formulas (I) to (IV) as a catalyst.

[0022] ^{_{CpM 1 R 1 a R 2 b}} R 3 c ... (I) Cp 2 M 1 R 1 a R 2 b ... (II) (Cp-A e -Cp) M 1 R 1 a R 2 b ... ( III) M ¹ R ¹ _a R ² _b R ³ _c R ⁴ _d ... (IV)

[In the formulas (I) to (IV), M ¹ represents a Ti, Zr or Hf atom, and Cp represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group. A cyclic unsaturated hydrocarbon group or a chain unsaturated hydrocarbon group such as a phenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group. R ¹ , R ² , R ³ and R ⁴ each represent a σ-binding ligand, a chelating ligand, a ligand such as a Lewis base, etc. Hydrogen atom, oxygen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Aryl group, alkylaryl group or arylalkyl group, an acyloxy group having 1 to 20 carbon atoms, an allyl group, a substituted allyl group, a substituent containing a silicon atom, etc., and the chelating ligand is acetyl. Examples thereof include an acetonate group and a substituted acetylacetonate group.
A represents a covalent crosslink. a, b, c, and d each represent an integer of 0 to 4, and e represents an integer of 0 to 6. R ¹ ,
Two or more of 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), the two Cp's may be the same or different from each other. ]

Further, the cyclic olefin copolymer used in the present invention comprises a catalyst containing the following compounds (A) and (B) as main components or a compound containing the following compounds (A), (B) and (C) as main components. The catalyst can be efficiently produced by using a catalyst. (A) a transition metal compound (B) a compound which reacts with a transition metal compound to form an ionic complex (C) an organoaluminum compound

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
4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group and the like. In addition, the above (I) to (I
Specific examples of R ^{1 to} R ^{4 in} the formula V) include, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom as a halogen atom; a methyl group, an ethyl group, and an n-propyl group as an alkyl group having 1 to 20 carbon atoms. Group, iso-propyl group,
n-butyl group, octyl group, 2-ethylhexyl group; methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group as C1-C20 alkoxy group; C6-C20 aryl group, alkylaryl group or A phenyl group, a tolyl group, a xylyl group, or a benzyl group as an arylalkyl group; a heptadecylcarbonyloxy group as an acyloxy group having 1 to 20 carbon atoms; a trimethylsilyl group or a (trimethylsilyl) methyl group as a substituent containing a silicon atom: Lewis base As dimethyl ether,
Ethers such as diethyl ether and tetrahydrofuran, thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, nitriles such as acetonitrile and benzonitrile, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 2,2 Amines such as 2'-bipyridine and phenanthroline; phosphines such as triethylphosphine and triphenylphosphine; linear unsaturated hydrocarbons such as ethylene, butadiene, 1-pentene, isoprene, pentadiene, 1-hexene and derivatives thereof;
Examples of the cyclic unsaturated hydrocarbon include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene, and derivatives thereof. Examples of the crosslink by a covalent bond of A in the above formula (III) include a methylene bridge, a dimethylmethylene bridge, an ethylene bridge,
Examples include a cyclohexylene cross-link, a dimethylsilylene cross-link, a dimethylgermylene cross-link, and a dimethylstannylene cross-link.

Examples of such compounds include the following 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) dimethylzirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dichlorozirconium , [Phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, diphenylmethylene Tadienyl)
(9-fluorenyl) dimethyl zirconium, ethylene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclohexylidene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium,
Cyclopentylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclobutylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium,
Dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dimethylzirconium, dimethylsilylenebis (indenyl) dichlorozirconium

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). Examples include zirconium compounds, hafnium compounds, and titanium compounds 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. Tetramethyl zirconium, tetrabenzyl zirconium, tetramethoxy zirconium, tetraethoxy zirconium, tetrabutoxy zirconium, tetrachloro zirconium, tetrabromo zirconium, butoxytrichloro zirconium, dibutoxy dichloro zirconium, bis (2,5-di-t-butylphenoxy) Dimethyl zirconium, bis (2,5-di-t-butylphenoxy) dichlorozirconium, zirconium bis (acetylacetonate),

The transition metal compound containing a VB-VIII group transition metal is not particularly limited. Specific examples of the chromium compound include, for example, tetramethylchromium, tetra (t
-Butoxy) chromium, bis (cyclopentadienyl) chromium, hydridetricarbonyl (cyclopentadienyl) chromium, hexacarbonyl (cyclopentadienyl) chromium, bis (benzene) chromium, tricarbonyltris (triphenylphosphonate) Chromium, tris (allyl) chromium, triphenyltris (tetrahydrofuran) chromium, chromium tris (acetylacetonate) and the like can be mentioned.

Specific examples of the manganese compound include, for example, tricarbonyl (cyclopentadienyl) manganese, pentacarbonylmethylmanganese, bis (cyclopentadienyl) manganese, manganese bis (acetylacetonate) and the like.

Specific examples of the nickel compound include, for example, dicarbonylbis (triphenylphosphine) nickel, dibromobis (triphenylphosphine) nickel, dinitrogenbis (bis (tricyclohexylphosphine) nickel), chlorohydridobis (tricyclohexyl) Phosphine) nickel, chloro (phenyl) bis (triphenylphosphine) nickel, dimethylbis (trimethylphosphine) nickel, diethyl (2,
2'-bipyridyl) nickel, bis (allyl) nickel, bis (cyclopentadienyl) nickel, bis (methylcyclopentadienyl) nickel, bis (pentamethylcyclopentadienyl) nickel, allyl (cyclopentadienyl) Nickel, (cyclopentadienyl)
(Cyclooctadiene) nickel tetrafluoroborate, bis (cyclooctadiene) nickel, nickel bisacetylacetonate, allylnickel chloride,
Tetrakis (triphenylphosphine) nickel, nickel _{chloride, (C 6 H 5) Ni} {OC (C 6 H 5) CH = P (C 6 H 5) 2} {P (C 6 H 5) 3}, ( _{C 6 H 5) Ni {OC} (C 6 H 5) C (SO 3 Na) = P (C 6 H 5) 2} {P (C 6 H 5) 3} and the like.

Specific examples of the palladium compound include, for example, dichlorobis (benzonitrile) palladium, carbonyltris (triphenylphosphine) palladium,
Dichlorobis (triethylphosphine) palladium, bis (t-butyl isocyanate) palladium, palladium bis (acetylacetonate), dichloro (tetraphenylcyclobutadiene) palladium, dichloro (1,5
-Cyclooctadiene) palladium, allyl (cyclopentadienyl) palladium, bis (allyl) palladium, allyl (1,5-cyclooctadiene) palladium tetrafluoroborate, (acetylacetonate)
(1,5-cyclooctadiene) palladium tetrafluoroborate, tetrakis (acetonitrile) palladium ditetrafluoroborate and the like can be mentioned.

Next, as the compound (B), any compound can be used as long as it reacts with the transition metal compound (A) to form an ionic complex. A compound comprising a bound anion, particularly a coordination complex compound comprising a cation and an anion having a plurality of groups bound to an element, can be suitably used. As a compound comprising such a cation and an anion in which a plurality of groups are bonded to an element, the following formula (V) or (VI)
The compound shown by can be used suitably. ^{([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⁾

In the formulas (V) and (VI), L ¹ is a Lewis base, and M ³ and M ⁴ are VB group, VIB group and V
IIB, VIII, IB, IIB, IIIA, IVA and
Element selected from Group VA, preferably, a Group IIIA, elements selected from Group IVA, and group VA, IIIB group of M ⁵ and M ^6, respectively Periodic Table, IVB group, VB group, VIB group, VIIB group, V
Group III, IA Group, IB, Group IIA, 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, 6 to 20 carbon atoms Aryloxy group, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group, arylalkyl group, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, acyloxy having 1 to 20 carbon atoms group, an organometalloid 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,
20 aryl group, an alkyl group, or an arylalkyl group, each R ⁸ and R ⁹ are a cyclopentadienyl group, substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, R ¹⁰ is 1 to 20 carbon atoms It represents an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group. R ¹¹ is tetraphenylporphyrin,
It shows a macrocyclic ligand such as phthalocyanine. m is M ³ , M
A valence of ⁴ and an integer of 1 to 7, n is an integer of 2 to 8 and k is an integer of 1 to 7 of an ionic valence of [L ¹ -R ⁷ ] and [L ² ];
p is an integer of 1 or more, and 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, and triethylphosphine Phosphines such as triphenylphosphine and diphenylphosphine; ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane; thioethers such as diethylthioether and tetrahydrothiophene; and esters such as ethylbenzoate. Specific examples of M ³ and M ⁴ are B, Al, Si, P, As, Sb and the like, preferably B or P, and specific examples of M ⁵ are Li, Na, A
g, Cu, Br, I, I 3 , etc., specific examples of M ⁶ M
n, Fe, Co, Ni, Zn and the like.

Specific examples of Z ^{1 to} Z ⁿ include, for example, a dimethylamino group and a diethylamino group as a dialkylamino group; a methoxy group, an ethoxy group and 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 from 20 to 20; a methyl group, an ethyl group, an n-propyl group as an alkyl group having from 1 to 20 carbon atoms;
iso-propyl group, n-butyl group, n-octyl group,
2-ethylhexyl group; an aryl group having 6 to 20 carbon atoms,
A phenyl group, 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 as a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, Pentachlorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group; F, Cl, Br,
I; Examples of the organic metalloid group include a pentamethylantimony group, a trimethylsilyl group, a trimethylgermyl group, a diphenylarsine group, a dicyclohexylantimony group, and a diphenylboron group. Specific examples of R ⁷ and R ¹⁰ include:
The same ones as mentioned above can be mentioned. R ⁸ and R ⁹
Specific examples of the substituted cyclopentadienyl group include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. 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 5. (V), (V
Among the compounds of the formula (I), those in which M ³ and M ⁴ are boron are preferred.

Among the compounds of the formulas (V) and (VI), 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, benzyltributyltetraphenylborate (N-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyltetraphenylborate (2-cyanopyridinium ), Trimethylsulfonium tetraphenylborate, benzyldimethylsulfonium tetraphenylborate ,

Triethylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate
Tetrabutylammonium borate, tetrakis (pentafluorophenyl) borate (tetraethylammonium),
Tetrakis (pentafluorophenyl) borate (methyltri (n-butyl) ammonium), tetrakis (pentafluorophenyl) borate (benzyltri (n-butyl))
Ammonium), methyldiphenylammonium tetrakis (pentafluorophenyl) borate, methyltriphenylammonium tetrakis (pentafluorophenyl) borate, dimethyldiphenylammonium tetrakis (pentafluorophenyl) borate, anilinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluoro) Phenyl) methylanilinium borate,
Dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, dimethyltetrakis (pentafluorophenyl) borate (m-nitroanilinium), dimethyltetrakis (pentafluorophenyl) borate (p-bromo) Anilinium),

Pyridinium tetrakis (pentafluorophenyl) borate, p-cyanopyridinium tetrakis (pentafluorophenyl) borate, N-methylpyridinium tetrakis (pentafluorophenyl) borate, N-methylpyridinium tetrakis (pentafluorophenyl) borate Benzylpyridinium), tetrakis (pentafluorophenyl) borate (O-cyano-N-methylpyridinium), tetrakis (pentafluorophenyl) borate (p-cyano-N-methylpyridinium), tetrakis (pentafluorophenyl) borate (p- Cyano-N-benzylpyridinium), trimethylsulfonium tetrakis (pentafluorophenyl) borate, benzyldimethylsulfonium tetrakis (pentafluorophenyl) borate, tetrakis ( Pentafluorophenyl) borate, tetraphenylphosphonium tetrakis (pentafluorophenyl) borate triphenylphosphonium tetrakis [3,5-bis (trifluoromethylphenyl)] borate dimethylanilinium, triethylammonium hexafluoroarsenate,

Compound of formula (VI) Ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, manganese tetraphenylborate (ferromanganese tetraphenylporphyrin), ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (1,1'-
Dimethylferrocenium), decamethylferrocenium tetrakis (pentafluorophenyl) borate, acetylferrocenium tetrakis (pentafluorophenyl) borate, formylferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate Cyanoferrocenium, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (tetra Phenylporphyrin manganese), tetrakis (pentafluorophenyl) borate (tetraphenylporphyrin iron chloride), tetrakis (pentafluoro) Phenyl) borate (tetraphenylporphyrin zinc), silver tetrafluoroborate, hexafluoroarsenate, silver hexafluoroantimonate, silver

Compounds other than those of the formulas (V) and (VI), for example, tris (pentafluorophenyl) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, triphenylboron and the like can also be used. is there.

Examples of the organoaluminum compound as the component (C) include compounds represented by the following general formulas (VII), (VIII) or (IX). 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 an alkoxy group having 1 to 20 carbon atoms or a halogen atom, and r is in the range of 1 ≦ r ≦ 3.) As the compound of the formula (VII), specifically, trimethylaluminum, triethylaluminum, triisopropyl Examples include aluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, and ethylaluminum sesquichloride.

[0044]

Embedded image (R ¹² is the same as in formula (VII). S indicates the degree of polymerization, and is usually 3 to 50, preferably 7 to 40.)

[0045]

Embedded image (R ¹² is the same as in formula (VII). S represents the degree of polymerization, and the number of repeating units is preferably from 3 to 50, and preferably from 7 to 40.) Aluminoxane. Among the compounds of the formulas (VII) to (IX), preferred are an alkyl group having 3 or more carbon atoms, especially an alkyl group-containing aluminum compound having at least one or more branched alkyl group or an aluminoxane. Particularly preferred is triisobutylaluminum or an aluminoxane having a degree of polymerization of 7 or more. When this triisobutylaluminum, aluminoxane having a polymerization degree of 7 or more, or a mixture thereof, high activity can be obtained. Further, a modified aluminoxane which is insoluble in a usual solvent obtained by modifying the aluminoxane represented by the formulas (VIII) to (IX) with a compound having active hydrogen such as water can be used.

The method for producing the aluminoxane includes a method in which an alkylaluminum is brought into contact with a condensing agent such as water. The method is not particularly limited, and the reaction may be carried out according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, a method in which an organoaluminum compound is added at the beginning of polymerization and water is added later, a crystal water contained in a metal salt or the like, A method of reacting water adsorbed on inorganic or organic substances with an organoaluminum compound, a method of reacting a trialkylaluminum with a tetraalkyldialuminoxane, and further reacting water.

The catalyst used in the production of the cyclic olefin-based copolymer has the above components (A) and (B) or the above components (A), (B) and (C) as main components. is there. In this case, the use conditions of the component (A) and the component (B) are not limited, but the ratio (molar ratio) of the component (A) to the component (B) is 1: 0.01 to 1: 100, particularly 1: 1: 0.
5 to 1:10, preferably 1: 1 to 1: 5. The working temperature is preferably in the range of -100 to 250 ° C, and the pressure and time can be set arbitrarily.

The component (C) is used in an amount of usually from 0 to 2,000 mol, preferably from 5 to 2,000 mol, per mol of the component (A).
It is 1,000 mol, particularly preferably 10 to 500 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 polymer, which is not preferable. The use form of the catalyst is not limited. For example, the components (A) and (B) may be brought into contact with each other in advance, or the contact product may be separated and washed before use. May be used.
Further, the component (C) may be used in contact with the component (A), the component (B) or a contact product of the component (A) and the component (B) in advance. The contact may be made in advance, or may be brought into contact in the polymerization system. Further, the catalyst component can be added in advance to the monomer and the polymerization solvent, or can be added to the polymerization system.

The polymerization methods include bulk polymerization, solution polymerization,
Any method such as suspension polymerization and gas phase polymerization may be used.
Further, a batch method or a continuous method may be used. Regarding the polymerization conditions,
Polymerization temperature is -100 to 250C, especially -50 to 200C
It is preferable that The ratio of the catalyst used to the reaction raw material is expressed by: raw material monomer / component (A) (molar ratio)
Alternatively, the raw material monomer / the component (B) (molar ratio) is 1
It is preferably from 10 to 10 ⁹ , particularly preferably from 100 to 10 ⁷ . Further, the polymerization time is usually 1 minute to 10 hours, and the reaction pressure is normal pressure to 100 kg / cm ² G, preferably normal pressure to 50 kg / cm ^2.
cm ² G. As a method of adjusting the molecular weight of the polymer,
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, pentane, hexane,
Aliphatic hydrocarbons such as heptane and octane, and halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. Further, a monomer such as an α-olefin may be used as the solvent.

(B) Thermoplastic Resin The type of the thermoplastic resin used as the component (b) 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 carbon atom) Α-olefin-based homopolymer or copolymer containing an α-olefin represented by the following formula (1) as an ingredient, and other than the above-mentioned cyclic olefin-based copolymer can be used. .

Specific examples of such a thermoplastic resin include polyethylene such as high-density polyethylene, low-density polyethylene, and linear low-density polyethylene, ethylene / 1-butene copolymer, and ethylene / 4-methyl-1-. Pentene copolymer, ethylene / 1-hexene copolymer, ethylene
Cyclic olefin copolymer (Tg exceeding 30 ° C.), ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer and its metal salt, polypropylene, ethylene /
Propylene copolymer, propylene / 1-butene copolymer, poly 1-butene, 1-butene / ethylene copolymer,
Examples thereof include 1-butene / propylene copolymer, 1-butene / 4-methyl-1-pentene copolymer, poly-4-methyl-1-pentene, and poly3-methyl-1-butene.

In addition, as the thermoplastic resin,
Polystyrene, ABS resin, AS resin, polyvinyl alcohol, polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, fluorine resin (polytetrafluoroethylene, etc.), polycarbonate, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, poly Ether sulfone, polyamide, polyimide, polyphenylene oxide, polyacetal, and the like can be used. Particularly preferred thermoplastic resins are HDPE, LDPE,
L-LDPE, polypropylene, ethylene-propylene copolymer, cyclic olefin ring-opening polymer, polystyrene,
Such as polyvinyl chloride. In addition, two or more kinds of thermoplastic resins can be used in combination as needed.

In the thermoplastic resin composition of the present invention,
The amount of component (a) is 2 to 98% by weight, preferably 5 to 95% by weight, particularly preferably 10 to 90% by weight, and the amount of component (b) is 98 to 2% by weight of the whole. , Preferably 95 to 5% by weight, particularly preferably 90 to 10% by weight. When the blending amount of the component (a) exceeds 98% by weight, the properties of the thermoplastic resin become insufficient. When the blending amount of the component (b) exceeds 98% by weight, the effect of improving impact resistance and the like becomes insufficient. .

Optional Components Elastomers can be added to the resin composition of the present invention, if necessary, whereby the effect of improving impact resistance particularly at low temperatures can be obtained. Here, the type of the elastomer is not limited, but a thermoplastic elastomer, another rubber, or the like can be suitably used. 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 (EPM), EPDM, and chlorinated polystyrene rubber. Particularly preferred as the elastomer are ethylene-propylene rubber (EPM), EPDM, styrene-butadiene rubber and the like. When the elastomer is blended, the blending amount is 2 parts per 100 parts by weight of the thermoplastic resin.
Not less than 200 parts by weight, especially not less than 5 parts by weight and not more than 100 parts by weight
It is preferable that the content be not more than part by weight. If the amount of the elastomer is less than 2 parts by weight, the effect of improving the low-temperature impact resistance becomes insufficient, and if it is more than 200 parts by weight, the properties of the thermoplastic resin become insufficient. The resin composition of the present invention may further contain various additives as necessary, for example, stabilizers such as antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, antistatic agents, anti-blocking agents, lubricants, Slip agent, anti-fog agent, foaming agent,
Flame retardants, inorganic fillers, organic fillers, dyes, pigments and the like can be blended.

Production Method The production method of the thermoplastic resin composition of the present invention is not limited. For example, the thermoplastic resin composition can be favorably produced by kneading each component in a molten state. As the melt-kneading device, an open-type mixing roll, a non-open-type Banbury mixer,
Conventionally known ones such as an extruder, a kneader and a continuous mixer can be used.

Molding Method The thermoplastic resin composition of the present invention can be molded by a conventional method. For example, single screw extruder, vented extruder,
Twin screw extruder, conical twin screw extruder, co-kneader, plasticizer, mixtruder,
Extrusion molding, injection molding, compression molding, blow molding, rotational molding, or thermoforming from a sheet is performed using a twin-screw conical screw extruder, a planetary screw extruder, a gear type extruder, a screwless extruder, or the like. Among these, injection molding can be particularly preferably employed. The molded products obtained in this way, for example, films, sheets, molded products, etc., are excellent in impact resistance and heat sealing properties, and therefore are used in various applications in the fields of automobiles, home appliances, films, and the like. can do.

[0058]

EXAMPLES Next, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to the following examples. First, prior to the production of the thermoplastic resin composition, a cyclic olefin-based copolymer of the following reference example was produced.

REFERENCE EXAMPLE At room temperature under nitrogen atmosphere, 15 liters of toluene, 23 mmol of triisobutylaluminum (TIBA), 38 micromol of zirconium tetrachloride and 60 micromol of anilinium tetrakis (pentafluorophenyl) borate were placed in a 30 liter autoclave at room temperature. Then, 2.4 liters of a toluene solution containing 70% by weight of 2-norbornene (16% as 2-norbornene) was added.
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 8 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 was collected by filtration and dried to obtain a cyclic olefin copolymer (a1). The yield of the cyclic olefin-based copolymer (a1) was 2.93 Kg. The polymerization activity was 845 Kg / gZr.

The obtained cyclic olefin copolymer (a)
Physical properties of 1) were as described below. 30 of ¹³ C-NMR
The sum of the peak based on ethylene and the peak based on methylene at the 5- and 6-positions of norbornene, which appears around ppm, and 3
The norbornene content determined from the ratio to the peak based on a methylene group at the 7-position of norbornene appearing at around 2.5 ppm was 7.7 mol%. The intrinsic viscosity [η] measured in decalin at 135 ° C. was 1.20 dl / g, and the crystallinity determined by X-ray diffraction was 1.0%. 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, and the Tg was 0 ° C. ALC / GPC150C manufactured by Waters Co., Ltd. was used as a measuring device, and 1,2,4-trichlorobenzene solvent was used. 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 69,600, Mn is 35,900, Mw / Mn
= 1.94. 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 72 ° C (broad peak) ° C.

Next, Examples and Comparative Examples using the cyclic olefin-based copolymer a1 obtained in the above Reference Example and other resins will be described. Examples 1 to 6 and Comparative Examples 1 to 4 Resin pellets having the compositions shown in Table 1 were produced. Next, using the obtained pellets, using an injection molding machine (IS25EP manufactured by Toshiba Corporation), set temperature 150 ° C., mold temperature 30 ° C., injection pressure (primary / secondary) 80/40 Kg / c.
Injection molding was performed under the conditions of m ² to obtain a test piece. Table 1 shows the results of measuring physical properties such as tensile properties, bending properties, and impact properties of the obtained test pieces.

Here, the measurement of each item was performed as follows. Tensile modulus: Measured according to JIS-K7113. Flexural strength and flexural modulus: Measured according to JIS-K7200. Izod impact strength: Measured according to JIS-K7110. Heat sealability: 1K between 0.1mm thick films
The results are shown by the feasibility of fusion when heat sealing at a pressure of g / cm ² at a predetermined temperature for 10 seconds.

[0063]

[Table 1]

[0064]

As described above, the thermoplastic resin composition of the present invention has excellent impact resistance and heat sealing properties.

Continuation of front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 23/08 C08L 45/00 C08L 101/00

Claims (1)

(57) [Claims] 1. A copolymer obtained by copolymerizing (a) ethylene and a cyclic olefin giving a repeating unit represented by the following general formula [Y], wherein the copolymer has a glass transition temperature (T
g) is 30 ° C. or less, and the tensile modulus is 3,000 Kg.
/ 98 ² or less cyclic olefin copolymer
A thermoplastic resin composition comprising: (b) 98 to 2% by weight of a thermoplastic resin. 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 1. 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. )