JP2014125496A - Thermoplastic resin composition and film of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition yielding a film excellent in terms of lubricity and blocking resistance and also having an excellent dropout resistance and a film obtained from the composition.SOLUTION: The provided problem-solving thermoplastic resin composition comprises, with respect to 100 parts.wt. of (A) a thermoplastic resin, at least 0.05 part.wt. and no more than 50 parts.wt. of (B) a 4-methyl-1-pentene copolymer satisfying the following requisites (1) through (5): (1) that a constituent unit derived from 4-methyl-1-pentene accounts for 99-80 mol% and that the sum of constituent units derived from olefins including 2-20 carbon atoms (excluding 4-methyl-1-pentene) accounts for 1-20 mol% (the total of the constituent unit derived from 4-methyl-1-pentene and constituent units derived from olefins including 2-20 carbon atoms is 100 mol%); (2) that the limiting viscosity [η] is 0.5-5.0 dL/g; (3) that the molecular weight distribution (Mw/Mn) is 1.0-3.5; (4) that the density is 825-860 kg/m3; and (5) that the melting point (Tm) is 125°C to 199°C.

Description

  The present invention relates to a thermoplastic resin composition suitable for efficiently producing a film excellent in slipping property and blocking resistance and further excellent in anti-blocking agent removal resistance, and a film using the same.

  Thermoplastic resin films, particularly polypropylene films, are used in a wide range of applications such as food packaging and insulating materials because of their excellent transparency and mechanical properties. However, the polypropylene-based film has a problem that a so-called blocking phenomenon occurs in which the films are brought into close contact with each other and the packaging workability and the winding workability are remarkably lowered.

  Conventionally, in order to improve the slipperiness and blocking resistance of a polypropylene film, a method for improving blocking resistance by adding zeolite, magnesium silicate, etc. (for example, see Patent Documents 1 and 2), adding fine silica. In addition, a method of kneading a fine powdery inorganic substance as an antiblocking agent (AB agent) into a polypropylene resin, such as a method of improving blocking resistance (for example, see Patent Documents 3 and 4) has been proposed.

  However, finely divided inorganic substances tend to agglomerate, and due to insufficient affinity between the polypropylene resin and the inorganic substance, voids are generated during stretching with the inorganic substance at the core, resulting in poor transparency or film surface Therefore, there was a problem that the AB agent dropped out and the appearance was poor.

  In order to make up for the shortcomings of films in which these finely divided inorganic substances are added as AB agents, a method of obtaining a film by dispersing a polymer AB agent such as a polymer substance or crosslinked polymer particles in a polypropylene resin (for example, Patent Documents 5 to 10) have been proposed.

  However, in these methods, since the affinity between the polypropylene resin and the polymer AB agent is insufficient, the appearance of the film is impaired, the mechanical properties of the film are deteriorated, and voids are generated during stretching. Therefore, there is a problem that the transparency of the film is deteriorated or the AB agent is dropped from the surface of the film, resulting in a poor appearance, and the effect as an AB agent is not necessarily exhibited.

Japanese Patent Publication No. 52-16134 Japanese Patent Publication No. 48-14423 Japanese Patent Publication No. 63-58170 JP-A-4-288353 JP 57-64522 A JP-A-5-214120 JP-A-6-107868 JP-A-7-178805 JP-A-7-196819 JP-A-9-22827

  The problem to be solved by the present invention is a thermoplastic resin composition that gives a film that not only has excellent slipperiness and blocking resistance, but also has excellent dropout resistance, in view of the various problems of the background art described above. It is to provide a film obtained from the composition.

  In order to solve the above-mentioned problems, the inventor has intensively studied an AB agent added to a thermoplastic resin. As a result, by combining a 4-methyl-1-pentene copolymer having specific physical properties with a thermoplastic resin, a film having not only excellent slipperiness and blocking resistance but also excellent dropout resistance is obtained. It has been found that a thermoplastic resin composition can be obtained.

That is, the thermoplastic resin composition of the present invention and the film obtained from the composition have the following constitution.
[1] (A) 100 parts by weight of a thermoplastic resin;
(B) 0.05 part by weight or more and 50 parts by weight or less of 4-methyl-1-pentene copolymer satisfying the following (1) to (5):
And a thermoplastic resin composition.
(1) 99 to 80 mol% of structural units derived from 4-methyl-1-pentene and 1 to 1 of total structural units derived from olefins having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) (2) 135 ° C. in decalin (2 to 135 ° C.) (the total of the structural unit derived from 4-methyl-1-pentene and the structural unit derived from an olefin having 2 to 20 carbon atoms is 100 mol%) (3) The ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 0.5 to 5.0 dl / g. The molecular weight distribution (Mw / Mn) is 1.0 to 3.5 (4) The density is 825 to 860 kg / m ³ (5) The melting point (T _m ) measured by DSC is 125 ° C. to 199 ° C. In the range [ Thermoplastic resin composition according to the thermoplastic resin (A) is a polyolefin-based resin [1].
[3] The thermoplastic resin composition according to [1] or [2], wherein the thermoplastic resin (A) is a polypropylene resin.
[4] A film comprising the thermoplastic resin composition according to any one of [1] to [3].

  The thermoplastic resin composition of the present invention is excellent in slipping property and blocking resistance, and exhibits extremely excellent AB agent drop-off resistance. In addition, because the film is excellent in stretchability, the film provided by the present invention makes use of excellent slipperiness, good handling properties based on blocking resistance, low roll contamination based on excellent slip-off resistance, and hygiene. It can be used in a wide range of applications such as industrial members such as food packaging, industrial members, automobile members, designable members, insulating members, and release films.

Hereinafter, the thermoplastic resin composition according to the present invention and the film comprising the composition will be described in detail.
[Thermoplastic resin composition]
The thermoplastic resin composition of the present invention contains a thermoplastic resin (A) and a 4-methyl-1-pentene copolymer (B).
<Thermoplastic resin (A)>
The thermoplastic resin (A) used in the present invention includes, for example, low density, medium density, high density polyethylene, ultrahigh molecular weight polyethylene, high pressure method low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene, Poly 1-butene, poly 4-methyl-1-pentene, poly 3-methyl-1-butene, ethylene / α-olefin copolymer, propylene / α-olefin copolymer, 1-butene / α-olefin copolymer Polymer, Cyclic olefin copolymer, Styrenic elastomer, Ethylene / vinyl alcohol copolymer, Ethylene / vinyl acetate copolymer, Ethylene / acrylic acid copolymer, Ethylene / methacrylic acid copolymer, Ethylene / methacrylic acid acrylate copolymer Polymer, ethylene acrylate acrylate Polymer, ionomer, fluorine resin, rosin resin, terpene resin and petroleum resin, polyvinyl chloride, chlorinated polyethylene, chlorinated polypropylene, polystyrene, styrene / acrylonitrile copolymer, polyacrylonitrile, polyethylene terephthalate, polybutylene terephthalate, Polycyclohexanedimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polylactic acid, polycaprolactone, polybutylene succinate, polyamino acid, polydimethylsiloxane, polytetramethylene glycol, polyhydroxyethyl methacrylate, polyphenylene terephthalamide, polyacrylamide, Polyurethane, polyamide, polyoxymethylene, polycarbonate, polyphenylene ether, poly Enylene sulfide, polysulfone, polyether ether ketone, polyether ketone, polyethylene oxide, polymethyl methacrylate, polyimide, liquid crystal polymer, polyamideimide, polyaminobismaleimide, polyarylate, polyetherimide, polyketone, polybenzimidazole, silicone resin , Polybutadiene, ABS resin, ACS resin, AES resin, ASA resin, cellulose resin, and a mixture of these polymers. Among them, it is preferable to use a polyolefin-based resin.

Among the polyolefin resins, it is particularly preferable to use a polypropylene resin. Polypropylene resins are known propylene-based polymers, and examples thereof include propylene homopolymers, copolymers of propylene and other α-olefins such as propylene / ethylene copolymers, propylene. A 1-butene copolymer, a propylene / ethylene / 1-butene copolymer, a mixture thereof, and the like can be given. In addition, polyolefin polymers such as polyethylene, poly 1-butene, styrene resin, ethylene / propylene rubber, and ethylene / propylene / diene copolymer rubber can be added to these polymers as necessary. is there.
<(B) 4-methyl-1-pentene copolymer>
The 4-methyl-1-pentene polymer (B) used in the present invention satisfies the following requirements (1) to (5).
(1) 99 to 80 mol% of structural units derived from 4-methyl-1-pentene and 1 to 1 of total structural units derived from olefins having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) (2) 135 ° C. in decalin (2 to 135 ° C.) (the total of the structural unit derived from 4-methyl-1-pentene and the structural unit derived from an olefin having 2 to 20 carbon atoms is 100 mol%) (3) The ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 0.5 to 5.0 dl / g. The molecular weight distribution (Mw / Mn) is 1.0 to 3.5 (4) The density is 825 to 860 kg / m ³ (5) The melting point (T _m ) measured by DSC is 125 ° C. to 199 ° C. In the range , Described the requirements (1) to (5).
・ Requirement (1)
In the present invention, the 4-methyl-1-pentene copolymer (B) is composed of 99 to 80 mol% of structural units derived from 4-methyl-1-pentene and olefins having 2 to 20 carbon atoms ( The structural unit derived from (excluding 4-methyl-1-pentene) is 1 to 20 mol%.

  Here, the upper limit of the structural unit derived from 4-methyl-1-pentene is preferably 98 mol%, more preferably 96 mol%, still more preferably 95 mol%, and the lower limit is preferably 82 mol%, more preferably. Is 83 mol%. The upper limit of the structural unit derived from an olefin having 2 to 20 carbon atoms is preferably 18 mol%, more preferably 17 mol%, and the lower limit is preferably 2 mol%, more preferably 4 mol%, and even more preferably 5 mol%. Mol%.

  When each structural unit is in the above range, the polymer composition containing the 4-methyl-1-pentene copolymer (B) is preferable from the viewpoint of dispersibility in the thermoplastic resin (A) including polypropylene.

  The 4-methyl-1-pentene copolymer (B) is at least one selected from 4-methyl-1-pentene and olefins having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene). Even if it is a random copolymer containing a structural unit, at least 1 sort (s) chosen from 4-methyl-1- pentene structural unit chain | strand and a C2-C20 olefin (except 4-methyl-1- pentene). It may be a block copolymer containing structural unit chains. From the viewpoint of moldability, a random copolymer of 4-methyl-1-pentene and an olefin having 2 to 20 carbon atoms is preferable.

  Examples of the olefin having 2 to 20 carbon atoms contained in the 4-methyl-1-pentene copolymer (B) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 3-methyl-1-butene. , 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-eicosene and the like are preferable examples.

  Of these, ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, and 1 are preferable from the viewpoints of copolymerizability and physical properties of the obtained copolymer. -Octene, 1-decene, 1-hexadecene, 1-heptadecene, 1-octadecene, and more preferably ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-hexadecene, 1-heptadecene and 1-octadecene are more preferable, and 1-octene, 1-decene, 1-hexadecene, 1-heptadecene and 1-octadecene are more preferable.

  Of these, α-olefins having 2 to 4 carbon atoms are preferable, and specific examples include ethylene, propylene, and 1-butene.

  These olefins having 2 to 20 carbon atoms can be used alone or in combination of two or more.

  Of these, propylene is particularly preferably used from the viewpoint of copolymerizability.

  The 4-methyl-1-pentene copolymer (B) may contain structural units derived from other polymerizable compounds as long as the object of the present invention is not impaired.

  Examples of such other polymerizable compounds include vinyl compounds having a cyclic structure such as styrene, vinylcyclopentene, vinylcyclohexane, and vinylnorbornane; vinyl esters such as vinyl acetate; unsaturated organic acids such as maleic anhydride or the like Derivatives; Conjugated dienes such as butadiene, isoprene, pentadiene, 2,3-dimethylbutadiene; 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5- Heptadiene, 7-methyl-1,6-octadiene, dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylene norbornene, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5- Isopropylidene-2-norbol , 6-chloromethyl-5-isopropylene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, etc. Non-conjugated polyenes.

The 4-methyl-1-pentene copolymer (B) in the present invention includes units derived from such other polymerizable compounds in the 4-methyl-1-pentene copolymer (B). It may be contained in an amount of 10 mol% or less, preferably 5 mol% or less, more preferably 3 mol% or less, based on all polymerizable compound structural units.
・ Requirement (2)
In the present invention, the intrinsic viscosity [η] of the 4-methyl-1-pentene copolymer (B) measured in decalin at 135 ° C. is 0.5 to 5.0 dL / g.

  Here, the intrinsic viscosity [η] is preferably 1.0 to 4.0 dL / g, and more preferably 1.2 to 3.5 dL / g.

  The value of the intrinsic viscosity [η] can be adjusted by the amount of hydrogen added during the polymerization when the 4-methyl-1-pentene copolymer (B) is produced.

The 4-methyl-1-pentene copolymer (B) having an intrinsic viscosity [η] in the above range exhibits good fluidity at the time of resin composition production and various moldings, and includes polypropylene and the like. Therefore, the dispersibility in the thermoplastic resin (A) is improved, and a molded article having a beautiful appearance tends to be obtained.
・ Requirement (3)
Molecular weight distribution which is the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of the 4-methyl-1-pentene copolymer (B) in the present invention. (Mw / Mn) is 1.0 to 3.5.

  Here, the molecular weight distribution (Mw / Mn) is preferably 1.0 to 3.0, more preferably 1.5 to 2.5.

  The value of the molecular weight distribution (Mw / Mn) can be controlled and adjusted according to the type of olefin polymerization catalyst described later.

The polymer composition containing the 4-methyl-1-pentene copolymer (B) having a molecular weight distribution (Mw / Mn) value in the above range tends to have a relatively low content of the molecular weight component. The low molecular weight body is preferable from the viewpoint that the possibility of a decrease in blocking property due to bleed-out is reduced, and there is a favorable influence on overall film physical properties, particularly mechanical strength and appearance.
・ Requirement (4)
The density of the 4-methyl-1-pentene copolymer (B) in the present invention is 825 to 860 kg / m ³ .

Here, a density becomes like this. Preferably it is 830-855 kg / m < ³ >, More preferably, it is 830-850 kg / m < ³ >, More preferably, it is 830-845 kg / m < ³ >.

  The density value can be adjusted by selecting the type and blending amount of other α-olefins to be polymerized with 4-methyl-1-pentene.

A polymer composition containing a 4-methyl-1-pentene copolymer (B) having a density value in the above range is preferable from the viewpoints of heat resistance and lightness.
・ Requirement (5)
The melting point ( _Tm ) measured by DSC of the 4-methyl-1-pentene copolymer (B) in the present invention is 125 to 199 ° C.

Here, melting | fusing point ( _Tm ) becomes like this. Preferably it is 130-197 degreeC, More preferably, it is 135-195 degreeC, More preferably, it is 140-190 degreeC.

The melting point (T _m ) is a value that varies depending on the stereoregularity of the polymer and the amount of α-olefin polymerized together, and is controlled and adjusted to a desired composition using an olefin polymerization catalyst described later. Is possible.

A polymer composition containing a 4-methyl-1-pentene copolymer (B) having a melting point (T _m ) in the above-mentioned range is less sticky and therefore has good handling properties, such as good handleability. To preferred.
<Method for Producing 4-Methyl-1-pentene Copolymer (B)>
The 4-methyl-1-pentene copolymer (B) in the present invention, in the presence of an olefin polymerization catalyst, 4-methyl-1-pentene and the above-mentioned specific α-olefin, and if necessary, the other It can obtain by polymerizing the polymerizable compound.

  Among the above-mentioned olefin polymerization catalysts, a metallocene catalyst can be mentioned as a preferred embodiment of the catalyst for producing the 4-methyl-1-pentene copolymer (B).

  Preferred metallocene catalysts include those described in WO 01/53369, WO 01/27124, JP-A-3-19396, JP-A-02-41303, or WO 06/025540. And metallocene catalysts described in the above.

  Hereinafter, the metallocene catalyst preferably used for production of the 4-methyl-1-pentene copolymer (B) in the present invention will be described.

In the production of the 4-methyl-1-pentene copolymer (B) in the present invention,
(Α) a metallocene compound represented by the following general formula (1) or (2);
(Β) (β-1) an organometallic compound, (β-2) an organoaluminum oxy compound, and (β-3) a compound that reacts with the metallocene compound (α) to form an ion pair,
At least one compound selected from:
If necessary,
A metallocene catalyst composed of (γ) a particulate carrier is preferably used.
[(Α) metallocene compound]
In the present invention, examples of the metallocene compound that can be used for the production of the 4-methyl-1-pentene copolymer (B) include compounds represented by the following general formula (1) or (2).

(In the general formula (1) or (2), the substituent represented by R ^{1 to} R ¹⁴ is selected from a hydrogen atom, a hydrocarbon group, and a silicon-containing hydrocarbon group, and may be the same or different, Adjacent substituents from R ¹ to R ⁴ may be bonded to each other to form a ring, adjacent substituents from R ⁵ to R ¹² may be bonded to each other to form a ring, and A is A divalent hydrocarbon group having 2 to 20 carbon atoms which may partially contain an unsaturated bond and / or an aromatic ring, and A represents two or more ring structures including a ring formed with Y; M is a metal selected from Group 4 of the periodic table, Y is carbon or silicon, and Q can be coordinated by a halogen, a hydrocarbon group, an anionic ligand or a lone electron pair. Neutral ligands may be selected in the same or different combinations, and j is an integer from 1 to 4. Number.)
In R ^{1 to} R ^{14 of the} above general formula (1) or (2), the hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or the number of carbon atoms. It is a 6-20 aryl group or a C7-20 alkylaryl group, and may contain one or more ring structures. Further, a part or all of the hydrocarbon group may be substituted with a functional group such as a hydroxyl group, an amino group, a halogen group, or a fluorine-containing hydrocarbon group. Specific examples include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl 1-adamantyl, 2-adamantyl, 2-methyl-2-adamantyl, menthyl, norbornyl, benzyl, 2-phenylethyl, 1-tetrahydronaphthyl, 1-methyl-1-tetrahydronaphthyl, phenyl, biphenyl, naphthyl, tolyl, Chlorophenyl, chlorobiphenyl, chlorona Chill, and the like.

In R ^{1 to} R ^{14 of the} above general formula (1) or (2), the silicon-containing hydrocarbon group is preferably an alkylsilyl group or arylsilyl group having 1 to 4 silicon atoms and 3 to 20 carbon atoms. Specific examples thereof include trimethylsilyl, tert-butyldimethylsilyl, triphenylsilyl and the like.

Adjacent substituents from R ⁵ to R ¹² on the fluorene ring may be bonded to each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl, dibenzofluorenyl, octahydrodibenzofluorenyl, octamethyloctahydrodibenzofluorenyl and the like.

The substituents R ⁵ to R ¹² on the fluorene ring are symmetrical from the viewpoint of ease of synthesis, that is, R ⁵ = R ¹² , R ⁶ = R ¹¹ , R ⁷ = R ¹⁰ , R ⁸ = R ⁹ . Preferably, it is unsubstituted fluorene, 3,6-disubstituted fluorene, 2,7-disubstituted fluorene or 2,3,6,7-tetrasubstituted fluorene. Here, the 3rd, 6th, 2nd and 7th positions on the fluorene ring correspond to R ⁷ , R ¹⁰ , R ⁶ and R ¹¹ , respectively.

R ¹³ and R ^{14 in} the general formula (1) are selected from a hydrogen atom or a hydrocarbon group, and may be the same or different from each other. Specific examples of preferred hydrocarbon groups include those similar to the above R ^{1 to} R ¹⁴ .

Y is a carbon atom or a silicon atom. In the case of the general formula (1), R ¹³ and R ¹⁴ are bonded to Y to form a substituted methylene group or a substituted silylene group as a bridging part. Preferred examples include, for example, methylene, dimethylmethylene, diisopropylmethylene, methyl tert-butylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, fluoromethylphenylmethylene, chloromethylphenylmethylene, diphenylmethylene, dichlorophenylmethylene, difluorophenyl. Methylene, methylnaphthylmethylene, dibiphenylmethylene, di-p-methylphenylmethylene, methyl-p-methylphenylmethylene, ethyl-p-methylphenylmethylene, dinaphthylmethylene or dimethylsilylene, diisopropylsilylene, methyl-tert-butylsilylene, Dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylsilylene, fluoro Chill silylene, chloromethyl silylene, diphenyl silylene, mention may be made of di-p- methylphenyl silylene, methyl -p- methylphenyl silylene, ethyl -p- methylphenyl silylene, methyl naphthyl silylene, a dinaphthyl silylene like.

  In the case of the general formula (2), Y is bonded to a divalent hydrocarbon group A having 2 to 20 carbon atoms which may partially contain an unsaturated bond and / or an aromatic ring, and a cycloalkylidene group or It constitutes a cyclomethylenesilylene group and the like. Preferable specific examples include, for example, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, dihydroin Examples include danylidene, cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, cycloheptamethylenesilylene, and the like.

  M in the general formulas (1) and (2) is a metal selected from Group 4 of the periodic table, and examples of M include titanium, zirconium, and hafnium.

Q is selected from the same or different combinations from halogen, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair. Specific examples of the halogen include fluorine, chlorine, bromine, and iodine. Specific examples of the hydrocarbon group include the same as those described above. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of the neutral ligand that can coordinate with a lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane. Among these, Q may be the same or different combinations, but at least one is preferably a halogen or an alkyl group.
(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ are hydrogen and hydrocarbon. group, selected from a silicon-containing hydrocarbon group, each may be the same or different, they may form a ring adjacent substituents, taken together from R1 to R4, adjacent to R ⁵ to R ¹² The substituents may be bonded to each other to form a ring, and A is a divalent hydrocarbon group having 2 to 20 carbon atoms which may partially contain an unsaturated bond and / or an aromatic ring. , A may contain two or more ring structures including a ring formed with Y, M is a metal selected from Group 4 of the periodic table, Y is carbon or silicon, and Q is halogen. , Hydrocarbon groups, anionic ligands or neutral ligands that can coordinate with lone pairs Alternatively, j may be selected from different combinations, and j is an integer of 1 to 4.) For the production of the olefin polymer according to the present invention, it is more preferably represented by the following general formula (3) or (4). Metallocene compounds are used.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , in the above general formula (1) or (2) R ¹⁴ is selected from hydrogen, a hydrocarbon group, and a silicon-containing hydrocarbon group, and may be the same or different.

  The hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms. And may contain one or more ring structures. Further, a part or all of the hydrocarbon group may be substituted with a functional group such as a hydroxyl group, an amino group, a halogen group, or a fluorine-containing hydrocarbon group. Specific examples include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl 1-adamantyl, 2-adamantyl, 2-methyl-2-adamantyl, menthyl, norbornyl, benzyl, 2-phenylethyl, 1-tetrahydronaphthyl, 1-methyl-1-tetrahydronaphthyl, phenyl, biphenyl, naphthyl, tolyl, Chlorophenyl, chlorobiphenyl, chlorona Chill, and the like.

  The silicon-containing hydrocarbon group is preferably an alkylsilyl group or arylsilyl group having 1 to 4 silicon atoms and 3 to 20 carbon atoms. Specific examples thereof include trimethylsilyl, tert-butyldimethylsilyl, triphenylsilyl. Etc.

The adjacent substituents from R ^{5 to} R ¹² on the fluorene ring may be bonded to each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl, dibenzofluorenyl, octahydrodibenzofluorenyl, octamethyloctahydrodibenzofluorenyl and the like.

The substituents R ^{5 to} R ¹² on the fluorene ring are symmetrical from the viewpoint of ease of synthesis, that is, R ⁵ = R ¹² , R ⁶ = R ¹¹ , R ⁷ = R ¹⁰ , R ⁸ = R ⁹ . Preferably, it is unsubstituted fluorene, 3,6-disubstituted fluorene, 2,7-disubstituted fluorene or 2,3,6,7-tetrasubstituted fluorene. Here, the 3rd, 6th, 2nd and 7th positions on the fluorene ring correspond to R ⁷ , R ¹⁰ , R ⁶ and R ¹¹ , respectively.

R ¹³ and R ^{14 in} the general formula (1) are selected from hydrogen and a hydrocarbon group, and may be the same or different. Specific examples of preferred hydrocarbon groups include the same as those described above.

Y is carbon or silicon. In the case of the general formula (1), R ¹³ and R ¹⁴ are bonded to Y to form a substituted methylene group or a substituted silylene group as a bridging part. Preferred examples include, for example, methylene, dimethylmethylene, diisopropylmethylene, methyl tert-butylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, fluoromethylphenylmethylene, chloromethylphenylmethylene, diphenylmethylene, dichlorophenylmethylene, difluorophenyl. Methylene, methylnaphthylmethylene, dibiphenylmethylene, di-p-methylphenylmethylene, methyl-p-methylphenylmethylene, ethyl-p-methylphenylmethylene, dinaphthylmethylene or dimethylsilylene, diisopropylsilylene, methyl-tert-butylsilylene, Dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylsilylene, fluoro Chill silylene, chloromethyl silylene, diphenyl silylene, mention may be made of di-p- methylphenyl silylene, methyl -p- methylphenyl silylene, ethyl -p- methylphenyl silylene, methyl naphthyl silylene, a dinaphthyl silylene like.

  In the case of the general formula (2), Y is bonded to a divalent hydrocarbon group A having 2 to 20 carbon atoms which may partially contain an unsaturated bond and / or an aromatic ring, and a cycloalkylidene group or It constitutes a cyclomethylenesilylene group and the like. Preferable specific examples include, for example, cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, dihydroin Examples include danylidene, cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, cycloheptamethylenesilylene, and the like.

  M in the general formulas (1) and (2) is a metal selected from Group 4 of the periodic table, and examples of M include titanium, zirconium, and hafnium.

Q is selected from the same or different combinations from halogen, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair. Specific examples of the halogen include fluorine, chlorine, bromine, and iodine. Specific examples of the hydrocarbon group include the same as those described above. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of the neutral ligand that can coordinate with a lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane. Among these, Q may be the same or different combinations, but at least one is preferably a halogen or an alkyl group.
[Compound (β)]
The compound (β) is selected from an organoaluminum compound (β-1), an organoaluminum oxy compound (β-2), and a compound (β-3) that reacts with the metallocene compound (α) to form an ion pair. It is composed of at least one compound.

Hereinafter, each component will be specifically described.
-(Β-1) Organometallic compound As (β-1) organometallic compound used as necessary in the present invention, specifically, the following periodic table groups 1, 2, and 12, 13 Examples of the organic metal compound include (β-1a), (β-1b), and (β-1c) described below. In the present invention, the (β-1) organometallic compound does not include the (β-2) organoaluminum oxy compound described later.

(Β-1a) An organoaluminum compound represented by the general formula R ^a _m Al (OR ^b ) _n H _p X _q .
(Wherein R ^a and R ^b represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, which may be the same or different from each other, X represents a halogen atom, and m represents 0 < m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3)
(Β-1b) A complex alkylated product of a Group 1 metal of the periodic table represented by the general formula M ² AlR ^a ₄ and aluminum.
(Wherein M ² represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms)
(Β-1c) A dialkyl compound of Group 2 or Group 12 metal represented by the general formula R ^a R ^b M ³ .
(Wherein R ^a and R ^b represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms which may be the same or different from each other, and M ³ is Mg, Zn or Cd)
Examples of the organoaluminum compound belonging to (β-1a) include the following compounds.

General formula R ^a _m Al (OR ^b ) _3-m (wherein R ^a and R ^b represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms which may be the same or different from each other). M is preferably a number of 1.5 ≦ m ≦ 3.), An organoaluminum compound represented by the general formula R ^a _m AlX _3-m (wherein R ^a is 1 to 1 carbon atoms) 15, preferably 1 to 4 hydrocarbon groups, X represents a halogen atom, and m is preferably 0 <m <3.), An organoaluminum compound represented by the general formula R ^a _m AlH _{3 − m} (wherein R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 2 ≦ m <3), a general formula during _{^{R a m Al (oR b)}} n X q ( wherein, ^{R a} and ^{R b} are identical to each other May represent different hydrocarbon groups having 1 to 15, preferably 1 to 4, carbon atoms, X represents a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n <3, q Is a number of 0 ≦ q <3 and m + n + q = 3).

More specifically, as the organoaluminum compound belonging to (β-1a), trimethylaluminum, triethylaluminum, tri (n-butyl) aluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecyl Tri (n-alkyl) aluminum such as aluminum; triisopropylaluminum, triisobutylaluminum, tri (sec-butyl) aluminum, tri (tert-butyl) aluminum, tri (2-methylbutyl) aluminum, tri (3-methylbutyl) aluminum , Tri (2-methylpentyl) aluminum, tri (3-methylpentyl) aluminum, tri (4-methylpentyl) aluminum, tri (2-methylhexyl) Tri-branched alkylaluminums such as luminium, tri (3-methylhexyl) aluminum, tri (2-ethylhexyl) aluminum; tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; triphenylaluminum, tritolylaluminum and the like triaryl aluminum diethyl hydride, dialkylaluminum hydride such as diisobutylaluminum _{hydride; (iC 4 H 9) x} Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, z ≧ 2x .iC ₄ H ₉ is represents a isobutyl group) alkenyl aluminum such as isoprenyl aluminum represented by like;. triisobutylaluminum methoxide, isobutylene Alkylaluminum alkoxides such as rualuminum ethoxide and isobutylaluminum isopropoxide; dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; alkylaluminum sesquioxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide R ^a _2.5 Al (OR ^b ) _0.5 (wherein R ^a and R ^b may be the same or different and each have 1 to 15 carbon atoms, preferably 1 to 4 hydrocarbons) A partially alkoxylated alkylaluminum having an average composition such as: diethylaluminum phenoxide, diethylaluminum (2,6-di-ter -Butyl 4-methylphenoxide), ethylaluminum bis (2,6-di-tert-butyl 4-methylphenoxide), diisobutylaluminum (2,6-di-tert-butyl 4-methylphenoxide), isobutylaluminum bis (2 , 6-di-tert-butyl 4-methylphenoxide); dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; ethylaluminum sesquichloride , Alkylaluminum sesquihalides such as butylaluminum sesquichloride and ethylaluminum sesquibromide; ethylaluminium Partially halogenated alkylaluminums such as alkylaluminum dihalides such as dichloride, propylaluminum dichloride, butylaluminum dibromide; Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as; partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxycyclide, ethylaluminum ethoxybromide, etc. It is done.

Moreover, the compound similar to ((beta) -1a) can also be used, for example, the organoaluminum compound which two or more aluminum compounds couple | bonded through the nitrogen atom is mentioned. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

Examples of the compound belonging to (β-1b) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

  Examples of the compound belonging to (β-1c) include dimethylmagnesium, diethylmagnesium, dibutylmagnesium, and butylethylmagnesium.

  Examples of (β-1) organometallic compounds other than the above (β-1a) to (β-1c) include methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethyl Magnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, butylmagnesium chloride and the like can also be used.

  A compound that can form the organoaluminum compound in the multimerization reaction system, for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium can also be used.

Among the (β-1) organometallic compounds, organoaluminum compounds are preferred. The (β-1) organometallic compounds as described above are used singly or in combination of two or more.
-(Β-2) Organoaluminum Oxy Compound The (β-2) organoaluminum oxy compound used as necessary in the present invention may be a conventionally known aluminoxane, and is exemplified in JP-A-2-78687. It may be a benzene insoluble organoaluminum oxy compound.

  A conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally obtained as a solution of a hydrocarbon solvent. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the suspension of the hydrocarbon. (2) A method of allowing water, ice or water vapor to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.

  The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, it may be redissolved in a solvent or suspended in a poor aluminoxane solvent.

  Specific examples of the organoaluminum compound used when preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the above (β-1a).

  Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.

  The organoaluminum compounds as described above are used singly or in combination of two or more.

  Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane, and cyclopentane. , Cycloaliphatic hydrocarbons such as cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, especially chlorine And hydrocarbon solvents such as bromide and bromide. Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.

  The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component dissolved in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, That is, those which are insoluble or hardly soluble in benzene are preferred.

  Examples of the organoaluminum oxy compound used in the present invention also include an organoaluminum oxy compound containing boron represented by the following general formula (i).

In formula (i), R ¹⁵ represents a hydrocarbon group having 1 to 10 carbon atoms. R ¹⁶ represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms, which may be the same as or different from each other.

  The organoaluminum oxy compound containing boron represented by the general formula (i) includes an alkyl boronic acid represented by the following general formula (ii) and an organoaluminum compound in an inert solvent under an inert gas atmosphere. In particular, it can be produced by reacting at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours.

R ¹⁵ -B (OH) ₂ (ii)
(In the formula (ii), R ¹⁵ is selected from the same group as in the above formula (i).)
Specific examples of the alkyl boronic acid represented by the general formula (ii) include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, and n-hexyl boron. Examples include acid, cyclohexyl boronic acid, phenyl boronic acid, 3,5-difluorophenyl boronic acid, pentafluorophenyl boronic acid, 3,5-bis (trifluoromethyl) phenyl boronic acid, and the like. Among these, methyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, 3,5-difluorophenyl boronic acid, and pentafluorophenyl boronic acid are preferable.

  These may be used alone or in combination of two or more.

  Specific examples of the organoaluminum compound to be reacted with such an alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to (β-1a). Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.

The (β-2) organoaluminum oxy compounds as described above are used singly or in combination of two or more.
Compound that reacts with (β-3) metallocene compound (α) to form an ion pair Used as needed in the present invention to react with (β-3) metallocene compound (α) to form an ion pair The compound is a compound that reacts with the metallocene compound (α) to form an ion pair. Therefore, what forms an ion pair by making it contact with a metallocene compound ((alpha)) at least is contained in this compound.

  Examples of such compounds include JP-A-1-501950, JP-A-1-502036, JP-A-3-179905, JP-A-3-179006, JP-A-3-207703, and JP-A-3. And Lewis acids, ionic compounds, borane compounds and carborane compounds described in US Pat. No. 207704 and US Pat. No. 5,321,106. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

Specifically, as the Lewis acid, a compound represented by BR ₃ (R is a phenyl group which may have a substituent such as a fluorine, a methyl group, a trifluoromethyl group, or fluorine) can be mentioned. For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (P-Tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like can be mentioned.

  Examples of the ionic compound include compounds represented by the following general formula (iii).

In the formula (iii), ^examples of R ¹⁷⁺ include H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal.

R ^{18 to} R ²¹ are organic groups which may be the same as or different from each other, preferably an aryl group or a substituted aryl group.

  Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.

  Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri (n-propyl) ammonium cation, and tri (n-butyl) ammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-diphenylanilinium cation such as N, N, 2,4,6-pentamethylanilinium cation; dialkylammonium cation such as di (isopropyl) ammonium cation and dicyclohexylammonium cation Etc.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

R ¹⁷⁺ is preferably a carbonium cation, an ammonium cation or the like, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation or an N, N-diethylanilinium cation.

  Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

  Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetraphenylborate, tri (n-propyl) ammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetra (p-tolyl) borate, Trimethylammonium tetra (o-tolyl) borate, tri (n-butyl) ammonium tetra (pentafluorophenyl) borate, tri (n-propyl) ammonium tetra (o, p-dimethylphenyl) borate, tri (n-butyl) ammonium Tetra (m, m-dimethylphenyl) borate, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) borate, tri (n-butyl) ammonium tetra (3,5-dito Trifluoromethylphenyl) borate, tri (n- butyl) ammonium tetra (o-tolyl) borate.

  Specific examples of N, N-dialkylanilinium salts include, for example, N, N-dimethylanilinium tetraphenylborate, N, N-diethylanilinium tetraphenylborate, N, N, 2,4,6-pentamethylaniline. Examples thereof include nium tetraphenylborate.

  Specific examples of the dialkylammonium salt include di (n-propyl) ammonium tetra (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.

  Further, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl Examples thereof include cyclopentadienyl complexes, N, N-diethylanilinium pentaphenylcyclopentadienyl complexes, and boron compounds represented by the following formula (iv) or (v).

(In the formula (iv), Et represents an ethyl group.)

  Specific examples of the borane compound include decaborane (14); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undeca. Salts of anions such as borate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate; Of metal borane anions such as tri (n-butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickate (III) Examples include salt.

  Specific examples of the carborane compound include, for example, 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecarborane (14), dodecahydride-1-phenyl-1, 3-dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane (13), 2,7-dicarboundecarborane (13), undecahydride-7,8-dimethyl-7,8-dicarboundecarborane, dodecahydride-11-methyl-2,7-dicarboundecarborane , Tri (n-butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carbaundecaborate, tri n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl) ammonium 7 carbaundecaborate (13), tri (n-butyl) ammonium 7, 8-dicarbaundecaborate (12), tri (n-butyl) ammonium 2,9-dicarbaundecaborate (12), tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarboundeca Borate, tri (n-butyl) ammonium undecahydra Do-8-ethyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride 8-allyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4, Salts of anions such as 6-dibromo-7-carbaundecaborate; tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) Ammonium bis (undecahydride-7,8-dicarbaoundebore G) Ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride) -7,8-dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cuprate (III), tri (n- (Butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundeca) Borate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl) -7,8-dicarbaundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarboundeborate) cobaltate (III), tris [ Tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate ) Manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis ( Metal carbo such as undecahydride-7-carbaundecaborate) nickelate (IV) The salt of a runanion etc. are mentioned.

  The heteropoly compound is composed of atoms composed of silicon, phosphorus, titanium, germanium, arsenic or tin and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, lintongost vanadic acid, germanotangostovanadic acid, phosphomolybdotangostobanamic acid, germanomolybdo tungstovanadate, phosphomolybdo Tungstic acid, phosphomolybniobic acid, salts of these acids, such as metals of Group 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium , With barium etc. Salts, and organic salts such as triphenylethyl salt, and isopoly compound can be used but not limited thereto.

  The heteropoly compound and the isopoly compound are not limited to one of the above compounds, and two or more of them can be used.

The compounds that react with the (β-3) metallocene compound (α) to form an ion pair are used singly or in combination of two or more.
[(Γ) particulate carrier]
In the present invention, the metallocene catalyst preferably used for the production of the 4-methyl-1-pentene copolymer (B) may contain a (γ) fine particle carrier, if necessary.

  In the method for producing the 4-methyl-1-pentene copolymer (B) of the present invention, the above-mentioned olefin polymerization catalyst may be used by being supported on a (γ) particulate carrier. In particular, in bulk polymerization using a supported catalyst described later, the form (γ) supported on a particulate carrier is preferably used.

  (Γ) The particulate carrier is an inorganic or organic compound and is a granular or particulate solid.

Among these, as the inorganic compound, a porous oxide, an inorganic halide, clay, clay mineral, or an ion-exchange layered compound is preferable. As the porous oxide, specifically, SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO _{2 and the} like, or a composite or mixture containing these, for example, using natural or synthetic _zeolites, SiO _{2 -MgO,} a _{SiO 2 -Al 2 O 3, SiO} 2 -TiO 2, SiO 2 -V 2 O 5, SiO 2 -Cr 2 O 3, SiO 2 -TiO 2 -MgO , etc. can do. Of these, those containing SiO ₂ and / or Al ₂ O ₃ as main components are preferred.

The inorganic oxide includes a small amount of Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ). ₂ , carbonates such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, and Li ₂ O, sulfates, nitrates, and oxide components may be contained.

As the inorganic halide, MgCl ₂ , MgBr ₂ , MnCl ₂ , MnBr ₂ or the like is used. The inorganic halide may be used as it is or after being pulverized by a ball mill or a vibration mill. Further, it is also possible to use a material obtained by dissolving an inorganic halide in a solvent such as alcohol and then precipitating the fine particles with a precipitating agent.

  Clay is usually composed mainly of clay minerals. The ion-exchangeable layered compound is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with a weak binding force, and the ions contained therein can be exchanged. Most clay minerals are ion-exchangeable layered compounds. In addition, these clays, clay minerals, and ion-exchange layered compounds are not limited to natural products, and artificial synthetic products can also be used.

Further, as clay, clay mineral or ion-exchangeable layered compound, clay, clay mineral, ionic crystalline compound having a layered crystal structure such as hexagonal fine packing type, antimony type, CdCl ₂ type, CdI ₂ type, etc. It can be illustrated.

Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrome clay, allophane, hysinger gel, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokdeite group, palygorskite, kaolinite, nacrite, dickite , Halloysite and the like, and as the ion-exchangeable layered compound, α-Zr (HAsO ₄ ) ₂ .H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KPO ₄ ) ₂ .3H ₂ O, α-Ti (HPO ₄ ) ₂ , α-Ti (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂ .H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO ₄ ) ₂ and crystalline acid salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.

Such a clay, clay mineral, or ion-exchange layered compound preferably has a pore volume of 0.1 cc / g or more and a diameter of 0.3 to 5 cc / g measured by mercury porosimetry. Particularly preferred. Here, the pore volume is measured in the range of pore radius of 20 to 3 × 10 ⁴に よ り by mercury porosimetry using a mercury porosimeter.

  When a carrier having a pore volume with a radius of 20 mm or more and smaller than 0.1 cc / g is used as a carrier, high polymerization activity tends to be difficult to obtain.

  It is also preferable to subject the clay and clay mineral to chemical treatment.

  As the chemical treatment, any of a surface treatment that removes impurities adhering to the surface and a treatment that affects the crystal structure of clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, and organic matter treatment. In addition to removing impurities on the surface, the acid treatment increases the surface area by eluting cations such as Al, Fe, and Mg in the crystal structure. Alkali treatment destroys the crystal structure of the clay, resulting in a change in the structure of the clay.

  In the salt treatment and the organic matter treatment, an ion complex, a molecular complex, an organic derivative, and the like can be formed, and the surface area and interlayer distance can be changed.

  The ion-exchangeable layered compound may be a layered compound in which the layers are expanded by exchanging the exchangeable ions between the layers with another large and bulky ion using the ion-exchangeability.

Such a bulky ion plays a role of a column supporting the layered structure and is usually called a pillar. Moreover, introducing another substance between the layers of the layered compound in this way is called intercalation. Examples of guest compounds to be intercalated include cationic inorganic compounds such as TiCl ₄ and ZrCl ₄ , metal alkoxides such as Ti (OR) ₄ , Zr (OR) ₄ , PO (OR) ₃ , and B (OR) ₃ ( R is a hydrocarbon group), metal hydroxide ions such as [Al ₁₃ O ₄ (OH) ₂₄ ] ⁷⁺ , [Zr ₄ (OH) ₁₄ ] ²⁺ , and [Fe ₃ O (OCOCH ₃ ) ₆ ] ⁺ Can be mentioned. These compounds are used alone or in combination of two or more. Moreover, when intercalating these compounds, obtained by hydrolyzing metal alkoxides such as Si (OR) ₄ , Al (OR) ₃ , Ge (OR) ₄ (R is a hydrocarbon group, etc.) Polymers, colloidal inorganic compounds such as SiO _2, and the like can also coexist. Examples of the pillar include oxides produced by heat dehydration after intercalation of the metal hydroxide ions between layers.

  Clay, clay mineral, and ion-exchangeable layered compound may be used as they are, or may be used after a treatment such as ball milling or sieving. Further, it may be used after newly adsorbing and adsorbing water or after heat dehydration treatment. Furthermore, you may use individually or in combination of 2 or more types.

  When ion exchange layered silicate is used, in addition to its function as a carrier, it can also reduce the amount of organoaluminum oxy compounds such as alkylaluminoxane by utilizing its ion exchange properties and layer structure. Is possible. The ion-exchange layered silicate is naturally produced mainly as a main component of clay mineral, but is not limited to a natural product, and may be a synthetic product. Specific examples of clay, clay mineral, and ion-exchange layered silicate include kaolinite, montmorillonite, hectorite, bentonite, smectite, vermiculite, teniolite, synthetic mica, synthetic hectorite, and the like.

Examples of the organic compound include granular or fine particle solids having a particle size in the range of 5 to 300 μm. Specifically, a (co) polymer produced mainly from an α-olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, styrene (Co) polymers or copolymers produced with a main component as a main component, or polar functional groups obtained by copolymerizing or graft polymerizing polar monomers such as acrylic acid, acrylic acid ester, and maleic anhydride to these polymers A polymer or modified product having These particulate carriers can be used alone or in combination of two or more.
(Polymerization conditions)
In the present invention, the polymerization of 4-methyl-1-pentene with a specific olefin for obtaining the 4-methyl-1-pentene copolymer (B) is a liquid phase polymerization method such as solution polymerization or suspension polymerization, or Any gas phase polymerization method can be used. In the liquid phase polymerization method, an inert hydrocarbon solvent may be used. Specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclopentane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane, lichloromethane and tetrachloromethane or mixtures thereof And so on. Bulk polymerization using olefins containing 4-methyl-1-pentene as a solvent can also be carried out.

  In addition, so-called multistage polymerization in which the polymerization conditions are changed stepwise can also be performed. For example, a desired broad molecular weight distribution or a broad composition distribution of 4-methyl- can be obtained by performing polymerization stepwise under two conditions with different amounts of hydrogen or 4-methyl-1-pentene and olefin. It is also possible to obtain a 1-pentene copolymer (B). In addition, 4-methyl-1-pentene system in which the composition distribution is controlled by performing stepwise homopolymerization of 4-methyl-1-pentene and copolymerization of 4-methyl-1-pentene with other olefins. It is also possible to obtain a copolymer (B).

In carrying out the polymerization, the component (α) is usually 10 ⁻⁸ to 10 ⁻² mol, preferably 10 ⁻⁷ to 10 ⁻³ mol in terms of Group 4 metal atom in the periodic table per liter of reaction volume. Used in various amounts.

  When the component (β) is used, the component (β-1) is a molar ratio of the component (β-1) to the transition metal atom (M) in the component (α) [(β-1) / M. ] Is usually used in an amount of 0.01 to 100,000, preferably 0.05 to 50,000.

  In the component (β-2), the molar ratio [(β-2) / M] of the aluminum atom in the component (β-2) and the transition metal atom (M) in the component (α) is usually 10 to 10. The amount used is 500,000, preferably 20 to 100,000.

  The component (β-3) has a molar ratio [(β-3) / M] of the component (β-3) and the transition metal atom (M) in the component (α) of usually 1 to 10, preferably It is used in such an amount as to be 1-5.

  The polymerization temperature is usually in the range of −50 to 200 ° C., preferably 0 to 100 ° C., more preferably 20 to 100 ° C. If the polymerization temperature is too low, there is an industrial disadvantage in terms of polymerization activity per unit catalyst and heat recovery efficiency.

The polymerization pressure is usually from normal pressure to 10 MPa gauge pressure, preferably from normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.
In the polymerization, hydrogen can be added for the purpose of controlling the molecular weight and polymerization activity of the produced polymer, and the amount is suitably about 0.001 to 100 NL per kg of olefin.
<Method for producing thermoplastic resin composition>
The thermoplastic resin composition contains the above-described thermoplastic resin (A) and each component of the 4-methyl-1-pentene copolymer (B) in specific amounts, and further described later if necessary. It can be obtained by blending and mixing additives.

  The thermoplastic resin composition of the present invention comprises 0.05 parts by weight or more and less than 50 parts by weight of 4-methyl-1-pentene copolymer (B) with respect to 100 parts by weight of the thermoplastic resin (A). Preferably, it comprises 0.075 parts by weight or more and less than 40 parts by weight, more preferably 0.1 parts by weight or more and less than 30 parts by weight.

  If the amount of 4-methyl-1-pentene copolymer (B) added is in the above range, the affinity with the thermoplastic resin (A) is high. Since the polymer (B) can be finely dispersed, the 4-methyl-1-pentene copolymer (B) falls off when a film is produced using the thermoplastic resin composition. The anti-blocking property can be maintained over a long period of time. Furthermore, the film formability and stretchability are not impaired, and the resulting film has high mechanical strength.

  The surface tension of the 4-methyl-1-pentene copolymer (B) is lower than that of a general thermoplastic resin (A) such as polypropylene (4-methyl-1-pentene copolymer: 24 mN / m). , Polypropylene 32 mN / m), in the film of the present invention, the dispersed phase of the 4-methyl-1-pentene copolymer (B) tends to localize in the film surface layer, which is This is considered to be the reason why blocking resistance can be imparted. Moreover, although the reason is not certain, in order to appropriately localize the 4-methyl-1-pentene copolymer (B) on the film surface layer portion, a 4-methyl-1-pentene copolymer ( It is considered that the addition amount of B) is preferably in the above range.

  By the way, the surface tension of poly-4-methyl-1-pentene is 24 mN / m similarly to the 4-methyl-1-pentene copolymer (B), and it is the same as that of the present invention when added to the thermoplastic resin (A). The effect of can be expected. However, the melting point of poly-4-methyl-1-pentene is 220 to 240 ° C., and for example, it is problematic that it is too high for the molding processing temperature (200 to 230 ° C.) of polypropylene resin. Specifically, when poly-4-methyl-1-pentene is added to a polypropylene resin, the film forming temperature needs to be 260 ° C. or higher in order to keep the dispersibility of poly-4-methyl-1-pentene good. is there. However, when molded under such high temperature conditions, the heat resistance of polypropylene is insufficient, so a large amount of pyrolytic degradation products are generated, foreign matter is mixed in the film, die lip is burned, burned, etc. The moldability becomes extremely poor, such as the occurrence of On the other hand, if the film forming temperature is lowered to 230 to 240 ° C. in order to suppress the thermal decomposition deterioration of polypropylene, this will cause a problem of insufficient melting of poly-4-methyl-1-pentene. As a result of the contamination of the unmelted foreign matter, poor film appearance becomes a problem.

However, since the melting point of the 4-methyl-1-pentene copolymer (B) of the present invention is lower than that of poly-4-methyl-1-pentene, it is within the optimum molding temperature region (200 to 230 ° C.) of the polypropylene resin. Even if film forming is performed, the above-described problems do not occur. This point is also considered to be one of the characteristics when using the 4-methyl-1-pentene copolymer (B) as an AB agent of a polypropylene film, and various known methods, for example, Multi-stage polymerization method, plast mill, Henschel mixer, V-blender, ribbon blender, tumbler, blender, kneader ruder, etc., or after mixing, melt-kneaded with single screw extruder, twin screw extruder, kneader, Banbury mixer, etc. A method of granulating or pulverizing can be employed. By this method, it is possible to obtain a high-quality thermoplastic resin composition in which each component and additive are uniformly dispersed and mixed.

In the present invention, in particular, a master batch containing about 1 to 50 parts by weight of 4-methyl-1-pentene copolymer (B) in 100 parts by weight of the thermoplastic resin (A) is prepared in advance and appropriately blended with it. And it can also be used as the concentration of a predetermined 4-methyl-1-pentene copolymer (B).
〔Additive〕
The thermoplastic resin composition in the present invention may contain a nucleating agent as a specific optional component in order to further improve the moldability, that is, to increase the crystallization temperature and increase the crystallization speed. In this case, for example, the nucleating agent is dibenzylidene sorbitol nucleating agent, phosphate ester nucleating agent, rosin nucleating agent, benzoic acid metal salt nucleating agent, fluorinated polyethylene, 2,2-methylenebis (4,6-di- -T-butylphenyl) sodium phosphate, pimelic acid and salts thereof, 2,6-naphthalene dicarboxylic acid dicyclohexyl amide, etc., and the amount is not particularly limited, but 100 parts by weight of the (co) polymer composition On the other hand, it is preferably about 0.1 to 1 part by weight. There is no restriction | limiting in particular in a mixing | blending timing, It can add during superposition | polymerization, after superposition | polymerization, or a shaping | molding process.

  In the thermoplastic resin composition, a secondary antioxidant, a heat stabilizer, a weather stabilizer, an antistatic agent, a slip agent, an antifogging agent, if necessary, as long as the object of the present invention is not impaired. Lubricants, dyes, pigments, natural oils, synthetic oils, waxes, fillers, hydrochloric acid absorbents, other olefin polymers, and the like can be blended. The amount is not particularly limited, but is usually 0 to 50 parts by weight, preferably 0 to 30 parts by weight, more preferably 0 to 10 parts by weight, particularly preferably 100 parts by weight of the (co) polymer composition. 0 to 1 part by weight.

  A known antioxidant can be used as the antioxidant. Specifically, a hindered phenol compound, a sulfur-based antioxidant, a lactone-based antioxidant, an organic phosphite compound, an organic phosphonite compound, or a combination of these can be used.

  Examples of the lubricant include sodium, calcium and magnesium salts of saturated or unsaturated fatty acids such as lauric acid, palmitic acid, oleic acid and stearic acid, and these may be used alone or in combination of two or more. it can. The blending amount of the lubricant is usually 0.1 to 3 parts by weight, preferably about 0.1 to 2 parts by weight, based on 100 parts by weight of the (co) polymer composition.

  As the slip agent, it is preferable to use amides of saturated or unsaturated fatty acids such as lauric acid, palmitic acid, oleic acid, stearic acid, erucic acid and hebenic acid, or bisamides of these saturated or unsaturated fatty acids. Of these, erucic acid amide and ethylene bisstearamide are particularly preferred. These fatty acid amides are preferably blended usually in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the polymer composition of the present invention.

Examples of other olefin polymers include known ethylene polymers, propylene polymers, pentene polymers, and cyclic olefin copolymers. The ethylene polymer is an ethylene / propylene copolymer, an ethylene / butene copolymer, an ethylene / hexene copolymer, an ethylene / octene copolymer or the like, and the propylene polymer is a propylene / propylene copolymer. Copolymers such as ethylene copolymers, propylene / butene copolymers, propylene / butene / ethylene copolymers, and butene-based polymers are copolymers of butene / propylene copolymers and butene / ethylene copolymers. A polymer is included.
[Film made of thermoplastic resin composition]
The film of the present invention can be obtained by melt-extruding the above-described thermoplastic resin composition usually in the range of 180 to 300 ° C. Since the 4-methyl-1-pentene copolymer (B) is present in the film of the present invention with high affinity to the thermoplastic resin (A), the 4-methyl-1-pentene copolymer ( B) is less likely to fall off and has excellent blocking resistance over a long period of time.

  In the present invention, “film” is a convenient name for indicating the appearance structure of the thermoplastic resin composition, and “film” is a general term for a molded product on a plane, and this includes the film. Other concepts include sheets, membranes (membranes), tapes, and the like.

  The film of the present invention is also preferably obtained by further uniaxially or biaxially stretching a molded product obtained by molding into a film or sheet by a T-die extrusion method or the like.

  In addition to the single-layer film obtained from the thermoplastic resin composition described above, the film of the present invention is preferably a laminated film in which the thermoplastic resin composition is contained in any one layer. The method for obtaining such a laminated film is not particularly limited, but a method of laminating by a known laminating method such as extrusion lamination or extrusion coating on a surface layer film obtained in advance by T-die molding or inflation molding. Or a method of laminating each film by dry lamination after independently molding a plurality of films, etc. From the viewpoint of productivity, coextrusion in which a plurality of components are subjected to a multilayer extruder for molding. Molding is preferred.

  As the above-mentioned preferable form, it can be suitably used for a multi-layered surface protective film and a multi-layer release film containing the film of the present invention in the film surface layer.

  In addition, although the film in this invention has high blocking resistance as mentioned above, the said performance is a normal temperature use, for example, the film in this invention and other films like the said laminated | multilayer film When the 4-methyl-1-pentene copolymer (B) of the present invention is bonded at a temperature equal to or higher than the melting point in a heat-melted state, the adhesive interface between the two films is firmly attached, so that the surface of the 4-methyl-1-pentene copolymer (B) The blocking resistance which is the effect of the invention is not exhibited. On the other hand, the laminated film in which the film of the present invention is located on the outermost surface still has excellent blocking resistance.

  Although the thickness of the film which consists of a thermoplastic resin composition of this invention is not specifically limited, Usually, it is 500 micrometers or less, 1-250 micrometers is preferable, More preferably, it is 2-100 micrometers.

  Specific examples of such a film include the following general film applications.

  Packaging film; for example, food packaging film, stretch film, wrap film, shrink film, easy peel film, aluminum vapor deposition film, PVDC coat film, etc.

  Breathable film; for example, disposable diapers, sanitary products, surgical clothing, surgical gloves, surgical down, house wrap (breathable waterproof sheet), disposable warmers, household dehumidifiers, desiccants, oxygen absorbers, freshness-keeping agents, compost Sheet, simple jumper, etc.

  Rust prevention film; for example, automotive parts, knockdown parts, machinery / machine parts, iron / chrome products, steel pipes, wire rods, bolts / nuts, bearings, dies, tools, blades, cutting tools, building tools, etc. Storage packing, export packing, etc.

  Anti-fogging film; for example, film for fruits and vegetables, film for processed foods, etc.

  Directional films: confectionery twist packaging, agricultural materials, laminate substrates, coin packaging, wire bundling materials, fruit and vegetable packaging, cardboard cut tape, detergent refill containers, rice ball packaging, pillow packaging, stick packaging, boil and retort packaging, Aquatic food packaging, infusion bag, etc.

  Self-cleaning film; for example, road signs, general signs, signboards, window glass, road materials, side mirrors, etc.

  Separator; for example, battery separator, lithium ion battery separator, fuel cell electrolyte membrane, adhesive / adhesive separator, etc.

  Stretched film; for example, film for film capacitor, capacitor film, capacitor film for fuel cell, etc.

  Semiconductor process film; for example, dicing tape, back grind tape, die bonding film, polarizing film, etc.

  Surface protective films; for example, protective films for polarizing plates, protective films for liquid crystal panels, protective films for optical parts, protective films for lenses, protective films for electrical parts and electrical appliances, protective films for mobile phones, protective films for personal computers, masking Film, protective film for touch panel, etc.

  Film for electronic members; for example, diffusion film, reflection film, radiation resistant film, gamma ray resistant film, porous film, etc.

  Building material films; for example, building material window films, laminated glass films, bulletproof materials, bulletproof glass films, thermal insulation sheets, thermal insulation films, and the like.

  Release film; for example, release film for flexible printed circuit board, release film for ACM board, release film for rigid flexible board, release film for advanced composite material, release film for curing carbon fiber composite material, glass fiber composite Release film for curing material, Release film for curing aramid fiber composite material, Release film for curing nanocomposite material, Release film for curing filler filler, Release film for semiconductor sealing, Release film for polarizing plate, Release film for diffusion sheet, release film for prism sheet, release film for reflection sheet, cushion film for release film, release film for fuel cell, release film for various rubber sheets, release film for urethane curing, Release film for epoxy curing (manufacturing process members such as metal bats and golf clubs), etc.

  Green plastic film; for example, agricultural multi-film, vegetable packaging bag, fruit packaging bag, household wrap film, scratch card, blister pack, fusing seal bag, cup lid, caramel packaging film, cap seal, cooked rice packaging, envelope Windows, point cards, IC cards, health insurance card cards, membership cards, ID cards, employee ID cards, nameplates, catalogs and other surface laminates, adhesive labels, tapes, clear folders, carrier tapes, stickers, laminate bags, tea bags, Garbage bags, grass protection sheets, handbags, compost bags, etc.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention does not receive a restriction | limiting in particular by the following Examples.

The detailed description of the present invention and the measured values of each item in the examples were measured by the following methods.
<Evaluation of 4-methyl-1-pentene copolymer (B)>
(1) 4-methyl-1-pentene and α-olefin content The 4-methyl-1-pentene and α-olefin content of the 4-methyl-1-pentene copolymer was quantified by the following apparatus and conditions. ^It was carried out from the result measured by ¹³ C-NMR.

Using an ECP500 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd., a mixed solvent of orthodichlorobenzene / heavy benzene (80/20 vol%) as a solvent, sample concentration 55 mg / 0.6 mL, measurement temperature 120 ° C., observation nucleus 13C (125 MHz), sequence is single pulse proton decoupling, pulse width is 4.7 μs (45 ° pulse), repetition time is 5.5 seconds, integration number is 10,000 times or more, and 27.50 ppm is the reference value for chemical shift As measured. From the obtained ¹³ C-NMR spectrum, the composition of 4-methyl-1-pentene and α-olefin was quantified.
(2) Melting point (Tm)
Using a DSC measuring device (DSC220C) manufactured by Seiko Instruments Inc., a sample of about 5 mg was put in an aluminum pan for measurement, heated to 290 ° C. at 100 ° C./min, held at 290 ° C. for 5 minutes, 10 ° C. / The melting point (Tm) was calculated from the peak apex of the crystal melting peak in the calorimetric curve when the temperature was lowered to −100 ° C. in min and then raised to −290 ° C. from −100 ° C. to 10 ° C./min.
(3) Molecular weight distribution (Mw / Mn)
Measurement was carried out as follows using a gel permeation chromatograph Alliance GPC-2000 manufactured by Waters. The separation columns are two TSKgel GNH6-HT and two TSKgel GNH6-HTL, the column size is 7.5 mm in diameter and 300 mm in length, the column temperature is 140 ° C., and the mobile phase is o -Using dichlorobenzene (Wako Pure Chemical Industries) and 0.025 wt% BHT (Takeda Pharmaceutical) as an antioxidant, moving at 1.0 ml / min, sample concentration 15 mg / 10 mL, sample injection volume 500 micron A differential refractometer was used as a detector. Standard polystyrene used was manufactured by Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and used by Pressure Chemical Co. for 1000 ≦ Mw ≦ 4 × 10 ⁶ .
(4) Intrinsic viscosity [η]
It is a value measured at 135 ° C. using a decalin solvent. That is, about 20 mg of polymer powder, pellets or resin mass was dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath at 135 ° C. After diluting the decalin solution with 5 ml of decalin solvent, the specific viscosity ηsp was measured in the same manner. This dilution operation was further repeated twice, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was obtained as the intrinsic viscosity (see the following formula).
[Η] = lim (ηsp / C) (C → 0)
(5) MFR
Based on JIS K7210, the measurement was performed at 230 ° C. and a load of 2.16 kg.
(6) Density was set to 230 ° C using a hydraulic hot press machine (NS-50) manufactured by Shindo Metal Industry Co., Ltd., the residual heat was reduced to about 5 to 7 minutes, and the pressure was increased to 10 minutes with a gauge pressure of 10 MPa, and then 20 ° C. Using another hydraulic heat press machine manufactured by Shinfuji Metal Industry Co., Ltd., set to a gauge pressure of 10 MPa and cooled for about 5 minutes to prepare a measurement sample. A 5 mm thick brass plate was used as the hot plate.

The 1 mm thick press sheet obtained by the above method was cut into 30 mm squares, and measured by an underwater substitution method using an electronic hydrometer according to JIS K6268.
<Film physical property evaluation>
The following measurements (7) to (10) were performed using a film having a thickness of 20 μm or 5 μm manufactured in the following examples and comparative examples.
(7) Internal HAZE (unit:%)
Measured according to ASTM D-1003.
(8) Sliding property The static friction coefficient (μs) and the dynamic friction coefficient (μd) were measured according to ASTM D-1894.
(9) Blocking resistance (unit: mN)
Using a 80 mm × 120 mm film, the corona-treated surfaces of the film that were combined 100 mm in the longitudinal direction were sandwiched between glass plates, and conditioned at 80 ° C. for 72 hours under a load of 20 kg. Thereafter, the sample was left for 30 minutes or more in an atmosphere of 23 ° C. and 50% humidity, the sample was cut to a width of 20 mm in the longitudinal direction, and the shearing tension test was performed at a speed of 200 mm / min to evaluate the blocking force.
(10) Dropout resistance (powder adhesion amount)
In Examples and Comparative Examples, film formation was continued for 10 minutes, and the powder adhering to the nip roll immediately before the winder (dropping of the AB agent) was wiped off with a black cloth, and the amount of powder adhered was visually confirmed.

  The result was determined according to the following criteria.

○: Almost no powder is attached and the drop-off resistance is good. Δ: A small amount of powder is attached and the drop-out resistance is poor.

X: A large amount of powder adheres and the drop-out resistance is very poor.
<Thermoplastic resin (A)>
(A-1) Polypropylene (trade name; Prime Polypro, Grade F107)
(A-2) Polypropylene (trade name; Prime Polypro, Grade F327)
(A-3) Polypropylene (trade name; Prime Polypro, Grade J704LB)
(A-4) Linear low density polyethylene (trade name; Evolue, grade SP2540)
(A-5) Poly-4-methyl-1-pentene (trade name; TPX, grade MX002)
<Synthesis of 4-methyl-1-pentene copolymer (B)>
[Synthesis Example 1] Production of 4-methyl-1-pentene copolymer (B-1) In a SUS autoclave with a stirring blade having a capacity of 1.5 liters sufficiently purged with nitrogen, 300 ml of normal hexane (dry nitrogen) at 23 ° C. Atmosphere, dried on activated alumina), and 450 ml of 4-methyl-1-pentene was charged. The autoclave was charged with 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL), and the stirrer was rotated.

  Next, the autoclave was heated to an internal temperature of 60 ° C. and pressurized with propylene so that the total pressure was 0.19 MPa (gauge pressure). Subsequently, 1 mmol of methylaluminoxane prepared in advance, diphenylmethylene (1-ethyl-3-tert-butyl-cyclopentadienyl) (2,7-di-tert-butyl-fluorenyl) zirconium in terms of Al Polymerization was initiated by injecting 0.34 ml of a toluene solution containing 0.01 mmol of dichloride into the autoclave with nitrogen. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C. Sixty minutes after the start of polymerization, 5 ml of methanol was injected into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution with stirring.

The obtained powdered polymer containing the solvent was dried at 100 ° C. under reduced pressure for 12 hours. The obtained polymer was 44.0 g, and the 4-methyl-1-pentene content in the polymer was 84 mol% and the propylene content was 16 mol%. The melting point (Tm) of the polymer was 130 ° C., and the intrinsic viscosity [η] was 1.4 dl / g. Table 1 shows the measurement results of various physical properties.
[Synthesis Example 2] Production of 4-methyl-1-pentene copolymer (B-2) To a 1.5-liter SUS autoclave with a stirring blade sufficiently purged with nitrogen, was added 4-methyl-1- 750 ml of pentene was charged. The autoclave was charged with 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL), and the stirrer was rotated.

  Next, the autoclave was heated to an internal temperature of 60 ° C. and pressurized with propylene so that the total pressure was 0.15 MPa (gauge pressure). Subsequently, 1 mmol of methylaluminoxane prepared in advance, diphenylmethylene (1-ethyl-3-tert-butyl-cyclopentadienyl) (2,7-di-tert-butyl-fluorenyl) zirconium in terms of Al Polymerization was initiated by injecting 0.34 ml of a toluene solution containing 0.005 mmol of dichloride into an autoclave with nitrogen. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C. Sixty minutes after the start of polymerization, 5 ml of methanol was injected into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution with stirring.

  The obtained powdery polymer containing the solvent was dried at 130 ° C. under reduced pressure for 12 hours. The obtained polymer was 45.9 g, and the 4-methyl-1-pentene content in the polymer was 92 mol% and the propylene content was 8 mol%. The melting point (Tm) of the polymer was 180 ° C., and the intrinsic viscosity [η] was 1.7 dl / g. Table 1 shows the measurement results of various physical properties.

[Example 1]
0.1 parts by weight of 4-methyl-1-pentene copolymer (B-2) is dry blended with respect to 100 parts by weight of the thermoplastic resin (A-1), and a 20 mm single screw extruder manufactured by Tanaka Tekko Co., Ltd. The film was melt-extruded at a resin temperature of 230 ° C. and quenched with a 60 ° C. cooling roll to obtain a 20 μm thick film. Table 2 shows the evaluation results of the film properties.
[Example 2]
To 100 parts by weight of the thermoplastic resin (A-1), 0.1 part by weight of 4-methyl-1-pentene copolymer (B-2) was added and dry blended, and then placed in a 30 mmφ single screw extruder. Then, melt extrusion is performed at a resin temperature of 230 ° C., and it is cooled and solidified into a sheet having a thickness of 0.2 mm by quenching with a 60 ° C. cooling roll, followed by preheating at 140 ° C. Due to the difference, the film was stretched 5 times in the machine direction (MD direction) at a stretching temperature of 155 ° C., and subsequently stretched 7 times in the transverse direction (TD direction) at a stretching temperature of 160 ° C. with a tenter type stretching machine, and heat-treated at 165 ° C. After forming a stretched film having a thickness of 5 μm, a single-sided corona treatment was performed. Table 2 shows the evaluation results of the film properties.
[Example 3]
A film having a thickness of 20 μm was obtained in the same manner as in Example 1 except that the amount of the 4-methyl-1-pentene copolymer (B-2) was changed to 0.05 parts by weight. Table 2 shows the evaluation results of the film properties.
[Example 4]
A film having a thickness of 20 μm was obtained in the same manner as in Example 1 except that the amount of the 4-methyl-1-pentene copolymer (B-2) was changed to 0.5 parts by weight. Table 2 shows the evaluation results of the film properties.
[Example 5]
A film having a thickness of 20 μm was obtained in the same manner as in Example 1 except that the amount of the 4-methyl-1-pentene copolymer (B-2) was changed to 1 part by weight. Table 2 shows the evaluation results of the film properties.
[Example 6]
A stretched film having a thickness of 5 μm was obtained in the same manner as in Example 2 except that the amount of the 4-methyl-1-pentene copolymer (B-2) was changed to 1 part by weight. Table 2 shows the evaluation results of the film properties.
[Example 7]
A film having a thickness of 20 μm was obtained in the same manner as in Example 1 except that the amount of the 4-methyl-1-pentene copolymer (B-2) was changed to 10 parts by weight. Table 2 shows the evaluation results of the film properties.
[Example 8]
A film having a thickness of 20 μm was obtained in the same manner as in Example 1 except that the amount of the 4-methyl-1-pentene copolymer (B-2) was changed to 30 parts by weight. Table 2 shows the evaluation results of the film properties.
[Example 9]
A film having a thickness of 20 μm was obtained in the same manner as in Example 1 except that (A-2) was used as the thermoplastic resin. The evaluation results of film properties are shown in Table 3.
[Example 10]
A film having a thickness of 20 μm was obtained in the same manner as in Example 1 except that (A-3) was used as the thermoplastic resin. The evaluation results of film properties are shown in Table 3.
[Example 11]
A film having a thickness of 20 μm was obtained in the same manner as in Example 1 except that (A-4) was used as the thermoplastic resin and (B-1) was used as the 4-methyl-1-pentene copolymer. . The evaluation results of film properties are shown in Table 3.
[Example 12]
A film having a thickness of 20 μm was obtained in the same manner as in Example 1 except that (A-5) was used as the thermoplastic resin, the resin temperature during film formation was 260 ° C., and the cooling roll temperature was 80 ° C. The evaluation results of film properties are shown in Table 3.
[Comparative Example 1]
A film having a thickness of 20 μm was obtained in the same manner as in Example 1 except that the 4-methyl-1-pentene copolymer (B) was not added. The results of film physical property evaluation are shown in Table 4.
[Comparative Example 2]
A film having a thickness of 5 μm was obtained in the same manner as in Example 2 except that 4-methyl-1-pentene copolymer was not added. The results of film physical property evaluation are shown in Table 4.
[Comparative Example 3]
A film having a thickness of 20 μm was obtained in the same manner as in Example 9 except that 4-methyl-1-pentene copolymer was not added. The results of film physical property evaluation are shown in Table 4.
[Comparative Example 4]
A film having a thickness of 20 μm was obtained in the same manner as in Example 10 except that 4-methyl-1-pentene copolymer was not added. The results of film physical property evaluation are shown in Table 4.
[Comparative Example 5]
A film having a thickness of 20 μm was obtained in the same manner as in Example 11 except that 4-methyl-1-pentene copolymer was not added. The results of film physical property evaluation are shown in Table 4.
[Comparative Example 6]
A film having a thickness of 20 μm was obtained in the same manner as in Example 12 except that 4-methyl-1-pentene copolymer was not added. The results of film physical property evaluation are shown in Table 4.
[Comparative Example 7]
As an AB agent, the weight average particle diameter measured with a Coulter counter was 1.9 μm, the BET specific surface area was 321 m ² / g, the pore volume measured by the N ₂ adsorption method was 1.25 ml / g, and the whiteness was 97 A stretched film having a thickness of 5 μm was obtained in the same manner as in Example 2 except that silica fine particles (trade name: Siricia 420 (manufactured by Fuji Silysia Co., Ltd.)) were used. The results of film physical property evaluation are shown in Table 4.
[Comparative Example 8]
In a flask equipped with a stirrer, 40 parts by weight of a monomer mixture consisting of 60% by weight of 2-ethylhexyl acrylate, 30% by weight of styrene and 10% by weight of divinylbenzene, 200 parts by weight of ethanol, 1 part by weight of benzoyl peroxide, and 1 part by weight of hydroxypropylcellulose. After being charged and dissolved, it was polymerized at 77 ° C. for 8 hours and dried to obtain crosslinked polymer beads. 10 parts by weight of the solid content of the crosslinked polymer beads, 0.1 parts by weight of calcium stearate as a stabilizer, BHT (2,6-ditertiary butyl) with respect to 100 parts by weight of polypropylene powder (trade name: Prime Polypro, Grade F103WP) Hydroxytoluene) 0.2 parts by weight and trade name Irganox 1010 (antioxidant manufactured by Ciba Geigy) 0.05 parts by weight were mixed with a Henschel mixer, and then 30 mmφ twin screw extruder (BT-30 manufactured by Plastic Engineering Co., Ltd.). Granulation and pelletization were performed to obtain a master batch of crosslinked polymer beads.

  A thickness of 5 μm was obtained in the same manner as in Example 2 except that 10 parts by weight of the master batch of the crosslinked polymer beads was used as an AB agent instead of the 4-methyl-1-pentene copolymer (B-1). A stretched film was obtained. The results of film physical property evaluation are shown in Table 4.

  When Examples 1-12 are compared with Comparative Examples 1-6, the blocking force is reduced to 20 mN / cm or less in Examples 1-12, and it can be seen that the effect of adding the AB agent is expressed. Moreover, when the said Examples 1-12 and Comparative Examples 7-8 are contrasted, in Examples 1-12, not only is it excellent in the improvement degree of blocking power, but even if AB agent is added, removal of AB agent will be from the film surface. It can be seen that a film with a beautiful appearance can be obtained.

  Since the thermoplastic resin composition of the present invention contains a 4-methyl-1-pentene copolymer (B), the copolymer acts as an antiblocking agent (AB agent) in the composition. A film made of the thermoplastic resin composition has excellent blocking resistance. Moreover, the said copolymer (B) is remarkably excellent in the fall-off resistance of the AB agent from the film surface in a manufacturing process unlike the conventional AB agent. Therefore, since the yield in film production can be improved, the industrial applicability is considered high.

Claims (4)

(A) 100 parts by weight of a thermoplastic resin;
(B) 0.05 part by weight or more and 50 parts by weight or less of 4-methyl-1-pentene copolymer satisfying the following (1) to (5):
And a thermoplastic resin composition.
(1) 99 to 80 mol% of structural units derived from 4-methyl-1-pentene and 1 to 1 of total structural units derived from olefins having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) (2) 135 ° C. in decalin (2 to 135 ° C.) (the total of the structural unit derived from 4-methyl-1-pentene and the structural unit derived from an olefin having 2 to 20 carbon atoms is 100 mol%) (3) The ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 0.5 to 5.0 dl / g. The molecular weight distribution (Mw / Mn) is 1.0 to 3.5 (4) The density is 825 to 860 kg / m ³ (5) The melting point (T _m ) measured by DSC is 125 ° C. to 199 ° C. Is in the range The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (A) is a polyolefin resin. The thermoplastic resin composition according to claim 1 or 2, wherein the thermoplastic resin (A) is a polypropylene resin. The film which consists of a thermoplastic resin composition in any one of Claims 1-3.