WO2007043188A1 - Process for producing injection-molded object - Google Patents

Abstract

A process for producing an injection-molded object, characterized by injection-molding a mixture which comprises a thermoplastic resin and a polyolefin wax and in which the ratio of the flow length (L) of the mixture containing the polyolefin wax as measured with a spiral flow mold having a thickness of 1 mm and a width of 10 mm under the conditions of a resin temperature of Tr which is determined with the following equation: Tr = 3/4 × Tm + 100 (wherein Tm indicates the melting temperature (°C) of the thermoplastic resin) and a mold temperature of 40°C to the flow length (L0) of the mixture not containing the polyolefin wax as measured likewise, L/L0, is not lower than 1.05. According to the process, the injection moldability, especially releasability and flowability, of a thermoplastic resin can be improved without reducing the properties of injection-molded objects of the resin. The thermoplastic resin can be molded by thin-wall molding or precision molding.

Description

 Specification

 Manufacturing method of injection molded body

 Technical field

 [0001] The present invention relates to a method for producing an injection molded article of thermoplastic resin. More specifically, the present invention relates to a method for producing an injection molded article from a mixture containing a thermoplastic resin and polyolefin wax.

 Background art

 [0002] Thermoplastic resin is a resin resin that is plasticized by heating and has fluidity, and various molded products are produced by various molding methods. However, when thermoplastic resin is thin-molded or precision-molded by injection molding, the molded product may stick to the mold or the mold shape may not be faithfully reproduced. For this reason, the releasability and fluidity of thermoplastic resin have had a great influence on the productivity of thermoplastic resin injection molding, particularly the yield.

 [0003] In general, when molding a resin, a plasticizer and a lubricant are used in order to improve mold release and fluidity. However, while this plasticizer and lubricant improve moldability, there is also a problem that the properties of the obtained molded product, particularly mechanical strength and heat resistance are lowered. For this reason, there has been proposed a thermoplastic resin composition for the purpose of improving mold release properties and fluidity in injection molding of thermoplastic resin and preventing deterioration of properties of the obtained molded product. (For example, see Patent Documents 1 to 4).

 Patent Document 1: JP-A-5-209129

 Patent Document 2: JP-A-9-111067

 Patent Document 3: Japanese Patent Laid-Open No. 2000-226478

 Patent Document 4: Japanese Unexamined Patent Application Publication No. 2004-189864

 Disclosure of the invention

 Problems to be solved by the invention

[0004] The present invention is intended to solve the problems associated with the prior art as described above, and is an injection moldability, particularly a mold release property, which does not deteriorate the properties of the injection molded product of the thermoplastic resin. A thermoplastic resin injection molding method that improves fluidity and fluidity, and enables thin-wall molding and precision molding. The purpose is to serve.

 Means for solving the problem

 [0005] As a result of diligent research to solve the above problems, the present inventor has mixed a polyolefin wax with thermoplastic resin, has a longer flow length than thermoplastic resin, and has a mold release. The present invention has found that a thermoplastic resin can be thin-walled and precision molded by preparing a mixture containing excellent properties of thermoplastic resin and polyolefin wax, and performing main molding using this mixture. It came to be completed.

 [0006] That is, the method for producing an injection-molded article according to the present invention is obtained by the following formula using a spiral flow mold having a thickness of lmm and a width of 10mm, which includes thermoplastic resin and polyolefin wax. The ratio between the flow length L when the polyolefin wax is included and the flow length L when the polyolefin wax is not included is LZL≥1. A mixture which is 05 is injection-molded.

 0 0

 [0007] Tr = 3/4 XTm + 100

 (In the formula, Tm indicates the melting temperature (° C) of thermoplastic resin.)

 In the above production method, it is preferable to contain 0.5 to 15 parts by weight of the polyolefin wax with respect to 100 parts by weight of the thermoplastic resin. The polyolefin wax is preferably a polyethylene wax, and the thermoplastic resin is preferably polypropylene or polyethylene. The invention's effect

 [0008] According to the present invention, by adding polyolefin wax, the flow length of the thermoplastic resin can be increased, the releasability can be improved, and the properties of the obtained molded product can be improved. Thin film molding and precision molding can be performed by injection molding of thermoplastic resin without lowering.

 BEST MODE FOR CARRYING OUT THE INVENTION

[0009] The method for producing an injection-molded article according to the present invention uses a spiral flow mold having a thickness of lmm and a width of 10mm by adding a polyolefin wax to a thermoplastic resin, and using the following formula:

Tr = 3/4 XTm + 100

(In the formula, Tm is the melting temperature (° C) of thermoplastic resin, especially in the case of crystalline resin. Indicates solution temperature (° C). )

 The ratio of the flow length L when the polyolefin wax is included and the flow length L when the polyolefin wax is not included is L / L≥ 1. 05, preferably in the range of 1.05≤L / L≤ 1.30 and more preferred

0 0 0

 Prepare a mixture in the range of 1.05≤LZL≤ 1.20 and injection mold this mixture

 0

 Is the method.

 [0010] The mixture having L / L in the above range is excellent in fluidity.

 0

 Fills every corner of the mold so that the resin does not leak through the gaps in the mold, and can faithfully reproduce the shape of the mold. Therefore, the mixture can be suitably used for thin film molding and precision molding.

 Hereinafter, the thermoplastic resin and polyolefin wax used in the production method of the present invention will be described.

 [0011] [Thermoplastic resin]

 Examples of the thermoplastic resin used in the present invention include polyolefins such as low-density polyethylene such as linear linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, and ethylene-propylene copolymer; ethylene acrylic acid copolymer , Ethylene-methacrylic acid copolymers and esterified products thereof, olefin butyl compound copolymers such as ethylene acetate butyl copolymer, ethylene butyl alcohol copolymer; polyester salts such as polyvinyl chloride, polystyrene, polyethylene terephthalate, etc. Fat and polyamide rosin can be mentioned. In addition, these graft copolymers, block copolymers, and random copolymers can also be used. In addition, use a blend of two or more of these types of fats.

 [0012] The MI (190 ° C) of the high-density polyethylene is preferably in the range of 3.0 to 20 gZlO, more preferably in the range of 4.0 to 15 gZlO. When the Ml of the high-density polyethylene is in the above range, it is possible to obtain a molded article excellent in texture, rigidity, impact strength, chemical resistance, and the like.

As the density of the high density polyethylene, rather preferably in the range of 942~970kg / m ^3, and more preferably in a range of from 950~965kg / m ^3. The density of high density polyethylene is in the above range. If it is, it is possible to obtain a molded article excellent in texture, rigidity, impact strength, chemical resistance and the like.

 [0013] As the MI (230 ° C) of the polypropylene, a range of 3.0 to 60 gZlO is preferable, and a range of 5.0 to 55 is more preferable. When the Ml of polypropylene is in the above range, a molded product excellent in heat resistance, rigidity, etc. can be obtained.

 [Polyolefin wax]

 The polyolefin wax used in the present invention is an α-olefin homopolymer or olefin oligomer having a copolymer power, and can be produced using a Ziegler catalyst or a metalocene catalyst. Of these, polyethylene waxes such as ethylene homopolymers and copolymers of ethylene and α-olefins having 3 to 20 carbon atoms are preferred. Particularly, polyethylene waxes prepared using a metallocene catalyst (hereinafter referred to as “ It is preferable to abbreviate it as “meta-orthene-based polyethylene wax”!

 [0014] In the copolymer of ethylene and 3 to 20 carbon at-olefins, the at-olefin has 3 to 10 carbon atoms, preferably 3 to 3 propylene and 4 to 1 carbon atoms. 1-pentene with 5 carbon atoms, 1-hexene with 6 carbon atoms and 4-methyl-1 pentene, 1-octene with 8 carbon atoms, and more preferred propylene, 1-butene, 1-hexene, 4 methyl 1 Penten is especially preferred.

 [0015] The polyolefin wax is a polystyrene-reduced number average molecular weight (Μη) force measured by gel permeation chromatography, usually 400 to 5,000, preferably 1,000 to 4,000, more preferably It is in the range of 1,500 to 4,000. If 才 η of the positive age refin status is in the above range, the flow improvement effect is great, the flow length becomes long, and precision molding becomes easy. In addition, it exhibits a good mold release effect, has excellent mold releasability, and can suppress mold contamination.

 [0016] The ratio (MwZMn) of the weight average molecular weight (Mw) and the number average molecular weight (Μη) in terms of polystyrene measured by gel permeation chromatography is usually 1.2 to 4.0, It is preferably in the range of 1.5 to 3.5, and more preferably in the range of 1.5 to 3.5. Mw / Mn force Within the above range, mold releasability is excellent and mold contamination can be suppressed.

The melting point measured with a differential scanning calorimeter (DSC) is usually 65-130 ° C, preferably 70-13. It is in the range of 0 ° C, more preferably 75-130 ° C. When the melting point is in the above range, mold releasability is excellent and mold contamination can be suppressed.

[0017] The density measured by the density gradient tube method is usually 850 to 980 kg / m ³ , preferably 870 to 980.

More preferably, it is in the range of 890 to 980 kgZm ³ . When the density is in the above range, mold releasability is excellent and mold contamination can be suppressed.

In addition, the polyolefin wax described above has a crystallization temperature (Tc (° C), measured at a temperature drop rate of 2 ° CZ) measured with a differential scanning calorimeter (DSC), and a density (D ( kg / m ³ )) satisfy the following formula (1), preferably the following formula (la), more preferably the following formula (lb).

[0018] 0. 501 X D- 366≥ Tc · '· (Ι)

 0. 501 X D- 366. 5 ≥ Tc "-(la)

 0. 501 X D- 367≥ Tc "-(lb)

 When the crystallization temperature (Tc) and density (D) of the polyolefin wax satisfy the relationship of the above formula, the comonomer composition of the polyolefin wax becomes more uniform, and as a result, the thermoplastic resin, especially the sticky component of the polyolefin, decreases. However, the tackiness of the mixture or composition containing thermoplastic rosin and polyolefin wax tends to be reduced.

[0019] The penetration is usually 30 dmm or less, preferably 25 dmm or less, more preferably 20 dmm or less, and even more preferably 15 dmm or less. This is a value measured in accordance with the above-mentioned penetration degree IS K2207. When the penetration is in the above range, a molded article having sufficient strength can be obtained.

 The amount of acetone extracted is preferably in the range of 0 to 20% by weight, more preferably 0 to 15% by weight. When the amount of acetone extracted is in the above range, mold releasability is excellent and mold contamination can be suppressed. In addition, the acetone extraction amount is a value measured as follows. Using a filter (made by ADVANCE, No. 84) in a Sotshlet extractor (made of glass), 200 ml of acetone was placed in the bottom round bottom flask (300 ml) and placed in a 70 ° C water bath for 5 hours. Perform extraction. Set 10g of the first wax on the filter.

[0020] The polyolefin wax is solid at room temperature and becomes a low-viscosity liquid at 65 to 130 ° C. The polyolefin wax is, for example,

 (A) a metallocene compound of a transition metal in which the Group 4 force of the periodic table is also selected, and

 (B) (b—1) an organoaluminum oxide compound, (b—2) a compound that reacts with the above-mentioned meta-mouth compound (A) to form an ion pair, and (b-3) Organoaluminum compound power with at least one compound selected

 It is preferable to produce the catalyst using an olefin polymerization catalyst that also has strength. In particular, in the case of producing polyolefin wax having a small MwZMn, a meta-cene catalyst is effective.

[0021] (A) Meta-metallic compound of transition metal in which periodic group 4 forces are also selected:

The meta-octane compound forming the meta-catalyst-based catalyst is a meta-metallic compound of a transition metal selected from Group 4 of the periodic table. A specific example is represented by the following formula (1). Compounds. Here, M ¹ is a transition metal selected from Group 4 force of the periodic table, X is a valence of transition metal M ¹ , and L is a ligand. Examples of the transition metals indicated by M ^1, zirconium, titanium and Hafuyuu beam. L is a ligand coordinated to the transition metal M ^1, and at least one of the ligands L is a ligand having a cyclopentagel skeleton, and the coordination having this cyclopentaphenyl skeleton The child may have a substituent. Examples of the ligand L having a cyclopentagenyl skeleton include a cyclopentagel group, a methylcyclopentaenyl group, an ethylcyclopentagel group, n- or i-propyl cyclopentagel. Group, ni sec— or t-butylcyclopentagel group, dimethylcyclopentagel group, methylpropyl cyclopentagel group, methylbutylcyclopentaenyl group, methylbenzylcyclopentagel group And alkyl- or cycloalkyl-substituted cyclopentagel groups such as Indur, 4, 5, 6, 7-tetrahydroindenyl, fluorenyl and the like. The hydrogen of the ligand having a cyclopentagel skeleton may be substituted with a halogen atom or a trialkylsilyl group.

[0022] In the case of having two or more ligands having a cyclopentagel skeleton as the ligand L, the ligand having the cyclopentagel skeleton is included. The ligands are linked via an alkylene group such as ethylene or propylene; a substituted alkylene group such as isopropylidene or diphenylmethylene; a substituted silylene group such as a silylene group, a dimethylsilylene group, a diphenylsilylene group, or a methylphenylsilylene group. Can be combined.

[0023] A ligand other than a ligand having a cyclopentagel skeleton (a ligand not having a cyclopentagel skeleton) L is a hydrocarbon group having 1 to 12 carbon atoms, alkoxy Group, aryloxy group, sulfonic acid-containing group (one SO R ¹ ), halogen atom or hydrogen atom (here

 Three

R ¹ is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, an aryl group substituted with a halogen atom, or an aryl group substituted with an alkyl group. ).

 [Example 1 of meta-orthane compound]

 For example, when the valence of the transition metal is 4, it is more specifically represented by the following formula (2).

R ² R ³ R ⁴ R ⁵ M ¹ -"(2)

 k 1 m n

Where M ¹ is a transition metal selected from Group 4 force of the periodic table, R ² is a group (ligand) having a cyclopentagel skeleton,

R ⁴ and R ⁵ are each independently a group having a cyclopentadenyl skeleton or a group (ligand) having no cyclopentagenyl skeleton. k is an integer of 1 or more, and k + l + m + n = 4.

[0025] Examples of meta-orthocene compounds in which M ¹ is zirconium and contains at least two ligands having a cyclopentagel skeleton are given below. Bis (cyclopentagel) zirconium monochloride monohydride, bis (cyclopentagel) zirconium dichloride, bis (1-methyl-3-butylcyclopentagel) zirconium bis (trifluoromethanesulfonate), bis (1, 3 dimethylcyclopentagel) zirconium dichloride and the like.

 [0026] Among the above compounds, compounds obtained by replacing the 1,3-position substituted cyclopentagel group with a 1,2-position substituted cyclopentagel group can also be used.

Further, as another example of the meta-mouth compound, in the above formula (2), R ² ,

At least two of R ⁴ and R ⁵ , for example, R ² and R ³ are groups (ligands) having a cyclopentagel skeleton. It is also possible to use a bridge type meta-orthene compound in which at least two groups are bonded via an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group or the like. At this time, R ⁴ and R ⁵ are each independently the same as the ligand L other than the ligand having the cyclopentagel skeleton described above.

 [0027] Such bridge type meta-octene compounds include ethylenebis (indul) dimethylzirconium, ethylenebis (indur) zirconium dichloride, isopropylidene (cyclopentagel monofluorenyl) zirconium dichloride, diphenylsilylene biphenyl. Sulfur (Indur) Zirconium Dichloride, Methylphenol Silylene Bis (Indur) Zirconium Dichloride and the like.

 [0028] (Example 2 of metaguchicene compound)

 Another example of the meta-mouth compound is a meta-mouth compound of the following formula (3) described in JP-A-4-268307.

 [0029] [Chemical 1]

Here, M ¹ is a Group 4 transition metal of the periodic table, and specifically includes titanium, zirconium, and hafnium.

R ¹¹ and R ¹² may be the same or different from each other; a hydrogen atom that may be the same as or different from each other; an alkyl group having 1 to carbon atoms; an alkyl group having 1 to LO; an alkoxy group having 1 to carbon LO; an alkoxy group having 6 to carbon atoms; Carbon atom number 6 to 10 aryloxy group; carbon atom number 2 to: LO alkyl group; 7 to 40 carbon atom alkyl group; 7 to 40 carbon atom alkyl group An arylalkyl group having 8 to 40 carbon atoms; or a halogen atom, and R ¹¹ and R ¹² are preferably chlorine atoms. [0031] R ¹³ and R ¹⁴ may be the same or different from each other; a hydrogen atom; a halogen atom; an optionally halogenated alkyl group having 1 to 10 carbon atoms; and a carbon atom number 6 to 10 Aryl groups of —N (R ² °), —SR ² °, —OSi (R ² °), —Si (R ² °) or —P (R ² °). here

 2 3 3 2

R ^2Q is a halogen atom, preferably a chlorine atom; an alkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms; or an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms. R ¹³ and R ¹⁴ are particularly preferably hydrogen atoms.

[0032] R ¹⁵ and R ¹⁶ are the same as R ¹³ and R ¹⁴ except that they do not include a hydrogen atom, and are preferably the same or different from each other. is there. R ¹⁵ and R ¹⁶ are preferably halogenated alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, trifluoromethyl and the like. In particular, methyl is preferred.

In the above formula (3), the following group force is also selected for R ¹⁷ .

[0033] [Chemical 2] 3) ₂ ) —,

BR '= A1R: Ge- -Sn- OS—, = SO, = SO, = NR ²¹ , = C

 2

0, = PR ²¹ , = P (0) R ²¹ etc.

M ² is silicon, germanium or tin, preferably silicon or germanium. Here, R ²¹ , R ²² and R ²³ may be the same or different from each other; a hydrogen atom; a halogen atom; an alkyl group having 1 to 10 carbon atoms; a fluoroalkyl group having 1 to 10 carbon atoms; Aryl group having 6 to 10 atoms; a fluoroaryl group having 6 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; a alkenyl group having 2 to 10 carbon atoms; an aryl having 7 to 40 carbon atoms An alkyl group; an arylalkenyl group having 8 to 40 carbon atoms; or a carbon atom number 7 to 40 alkylaryl groups. “R ²¹ and R ²² ” or “R ²¹ and R ²³ ” may be combined with the atoms to which they are bonded to form a ring. Also, R ¹⁷ can be = CR ²¹ R ²² , = Si R2i _R 22, = GeR ²¹ R ²² , — O—, — S—, = SO, = PR ²¹ or = P (O) R ²¹ preferable. R ¹⁸ and R ¹⁹ may be the same as or different from each other, and examples thereof include the same as R ²¹ . m and n may be the same or different and are each 0, 1 or 2, preferably 0 or 1, and m + n is 0, 1 or 2, preferably 0 or 1.

 [0035] Examples of the meta-mouth compound represented by the above formula (3) include the following compounds. ra c -Ethylene (2-methyl-1-indul) 2-zirconium dichloride, rac-dimethylsilylene (2-methyl 1-indenyl) 2-zirconium dichloride, etc. These meta-mouth compounds can be produced, for example, by the method described in JP-A-4-268307.

 [0036] (Example 3 of metaguchicene compound)

 In addition, as a meta-mouth compound, a meta-mouth compound represented by the following formula (4) is used.

 [0037] [Chemical 3]

[0038] In formula (4), M ³ represents a transition metal atom of Group 4 of the periodic table, specifically titanium, zirconium, hafnium, or the like. R ²⁴ and R ²⁵ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, Oxygen-containing group, xio-containing group, nitrogen-containing group or phosphorus-containing group. R ²⁴ is preferably a hydrocarbon group, particularly preferably an alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl or propyl. R ²⁵ is preferably a hydrogen atom or a hydrocarbon group, particularly preferably a hydrogen atom, or an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl or propyl.

R ²⁸ and R ²⁹ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, or a carbon atom having 1 to 20 carbon atoms. A hydrocarbon group and a halogenated hydrocarbon group having 1 to 20 carbon atoms are shown. Among these, a hydrogen atom, a hydrocarbon group, or a halogenated hydrocarbon group is preferable. At least one pair of R ²⁶ and R ²⁷ , R 2 ⁷ and R ²⁸ , R ²⁸ and R ²⁹ together with the carbon atom to which they are bonded forms a monocyclic aromatic ring. Also good. In addition, when there are two or more hydrocarbon groups or halogenated hydrocarbon groups other than the group forming the aromatic ring, they may be bonded to each other to form a ring. When R ²⁹ is a substituent other than an aromatic group, it is preferably a hydrogen atom. X ¹ and X ² may be the same or different from each other, hydrogen atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms, halogenated hydrocarbon group having 1 to 20 carbon atoms, oxygen atom-containing group Or a thio atom-containing group. Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, a divalent Tin-containing group, O, one CO one, S, one SO, one SO —, one NR ³⁰ —, one P (R ³⁰ ) —, -P (O) (R ³ °) one, -BR ³⁰

 2

Or A1R ^3Q — (where R ^3Q is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms).

[0039] In the formula (4), at least one pair of R ²⁶ and R ²⁷ , R ²⁷ and R ²⁸ , R ²⁸ and R ²⁹ is bonded to each other and includes a monocyclic aromatic ring, and M ³ Examples of the ligand coordinated to the ligand include those represented by the following formula.

[0040] [Chemical 4]

 [0041] In the formula, Y is the same as that shown in formula (4).

 (Example 4 of metaguchisen compound)

 In addition, the meta-mouth compound may be a meta-mouth compound represented by the following formula (5).

[0042] [Chemical 5]

In the formula (5), M ³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ are the same as the above formula (4). Of R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ , it is preferred that two groups including R ²⁶ are alkyl groups. R ²⁶ and R ²⁸ , or R ²⁸ and R ²⁹ are alkyl groups. Is preferred. This alkyl group is preferably a secondary or tertiary alkyl group. In addition, the alkyl group includes a halogen atom and a halogen-containing group which may be substituted with a silicon-containing group, and examples of the halogen-containing group include the substituents exemplified for R ²⁴ and R ²⁵ . R ²⁶ ,

Of R ²⁸ and R ²⁹ , groups other than alkyl groups are preferably hydrogen atoms. Further, ⁶ , R ²⁷ , R ²⁸ and R ²⁹ may be such that two groups selected from these forces are bonded to each other to form a monocyclic or polycyclic ring other than an aromatic ring. Examples of the halogen atom include those similar to the above R ²⁴ and R ²⁵ . Examples of X ¹ , X ² and Y are the same as described above.

 A specific example of the meta-mouth compound represented by the above formula (5) is shown below. rac dimethylsilylene-bis (4,7 dimethyl-1-indul) zirconium dichloride, rac dimethylsilylene monobis (2,4,7 trimethyl1-indul) zirconium dichloride, ra c dimethylsilylene monobis (2,4,6 trimethyl 1 —Indules) Zirconium dichloride.

 In these compounds, transition metal compounds in which zirconium metal is replaced with titanium metal or hafnium metal can also be used. As the transition metal compound, a force R type or S type generally used as a racemate can also be used.

 (Example 5 of metaguchisen compound)

 In addition, a meta-mouth compound represented by the following formula (6) can be used as a meta-mouth compound.

[0046] [Chemical 6] K

In the formula (6), M ³ , R ²⁴ , X ¹ , X ² and Y are the same as in the above formula (4). R ²⁴ is preferably a hydrocarbon group, particularly preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl or butyl. R ²⁵ represents an aryl group having 6 to 16 carbon atoms. R ²⁵ is preferably phenyl or naphthyl. The aryl group may be substituted with a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. X ¹ and X ² are preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

[0048] Specific examples of the meta-mouth compound represented by the above formula (6) are shown below. rac dimethylsilylene monobis (4-phenol 1-indul) zirconium dichloride, rac dimethylsilylene-bis (2-methyl-4-phenol-1-diuryl) zirconium dichloride, _r ac dimethylsilylene bis (2-methyl-4) 1 (a naphthyl) 1 indul) dirucum-dichloride, rac dimethylsilylene bis (2-methyl-4) (1-indul) zirconium dichloride, rac dimethylsilylene monobis (2—methyl 1 4— (1— Anthryl) —1-indul) zirconium dichloride and the like. In these compounds, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal can also be used.

 [0049] (Example 6 of metaguchicene compound)

 In addition, as a meta-mouth compound, a meta-mouth compound represented by the following formula (7) is used.

LaM ⁴ X ³ ---(7)

 2

Here, M ⁴ is a group ⁴ of the periodic table or a lanthanide series metal. La is a derivative of a delocalized π bond group, and is a group that imparts a constrained geometry to the metal Μ ⁴ active site. X 3 may be the same or different from each other, and may be a hydrogen atom, a halogen atom or a carbon atom number of 20 or more. The lower hydrocarbon group, a silyl group containing 20 or less silicon, or a germanyl group containing 20 or less germanium.

[0050] Among these compounds, the compound represented by the following formula (8) is preferred! /.

[0051] [Chemical 7]

In formula (8), M ⁴ is titanium, zirconium or hafnium. X ³ is the same as that described in Equation (7) above. Cp is a substituted cyclopentadenyl group having a π bond to M ⁴ and having a substituent Ζ. Ζ is oxygen, iow, boron, or an element of group 4 of the periodic table (eg, silicon, germanium, or tin). Υ is a ligand containing nitrogen, phosphorus, oxygen or io, and Ζ and Υ may form a condensed ring. A specific example of the meta-mouth compound represented by equation (8) is shown below. (Dimethyl (t-butylamide) (tetramethyl-7} 5-cyclopentagel) silane) titanium dichloride, ((t-butylamide) (tetramethyl-η 5 cyclopentagel) 1,2 ethanediyl) titanium dichloride, and the like. In addition, in this meta-octene compound, a compound in which titanium is replaced with zirconium or hafnium can also be mentioned.

 [0053] (Example 7 of metaguchisen compound)

 In addition, a meta-mouth compound represented by the following formula (9) is used as the meta-mouth compound.

 [0054] [Chemical 8]

... (9)

In formula (9), M ³ is a transition metal atom of Group 4 of the periodic table, specifically titanium, zirconium or hafnium, preferably zirconium. R ³¹ may be the same or different from each other, at least one of which is an aryl group having 11 to 20 carbon atoms, an aryl alkyl group having 12 to 40 carbon atoms, or an aryl hydrocarbon group having 13 to 40 carbon atoms. , A force which is an alkylaryl group having 12 to 40 carbon atoms or a group containing a key group, or a group represented by R ³¹ , and at least two adjacent groups together with the carbon atoms to which they are bonded are singular or A plurality of aromatic rings or aliphatic rings are formed. In this case, the ring formed by R ³¹ as a whole number of carbon atoms including carbon atoms to which R ³¹ is bonded is from 4 to 20. Ariru group, § reel alkyl group, Ariruaruke - R ³¹ except R ³¹ that group, Arukiruari Lumpur group and an aromatic ring to form an aliphatic ring is a hydrogen atom, halogen atom, 1 to carbon atoms 10 alkyl groups or a group containing silicon. R ³² may be the same or different from each other, a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to carbon atoms: LO, 7 to 40 carbon atom alkyl group, 8 to 40 carbon atom alkyl group, 7 to 40 carbon atom alkyl group, key group, oxygen group, nitrogen group, nitrogen group An element-containing group or a phosphorus-containing group. Further, at least two adjacent groups out of the groups represented by R ³² may form one or more aromatic rings or aliphatic rings together with the carbon atoms to which they are bonded. In this case, the ring formed by R ³² as a whole number of carbon atoms including carbon atoms to which R ³² is bonded is from 4 to 20, except R ³² that forms form an aromatic ring, an aliphatic ring R ³² in the formula is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a key group containing silicon. The group in which the two groups represented by R ^{32 form} one or more aromatic rings or aliphatic rings includes an embodiment in which the fluorenyl group has a structure as shown in the following formula.

[0056] [Chemical 9]

[0057] R is preferably a hydrogen atom or an alkyl group, particularly a hydrogen atom or a methyl group. A hydrocarbon group having 1 to 3 carbon atoms of ru, ethyl and propyl is preferable. A suitable example of such a fluorenyl group having R ³² as a substituent is a 2,7 dialkyl fluoryl group. In this case, the 2,7 dialkyl alkyl group has 1 to 5 carbon atoms. Of the alkyl group. R ³¹ and R ³² may be the same as or different from each other. R ³³ and R ³⁴ may be the same or different from each other, and are the same as described above. Hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 20 carbon atoms, carbon atom number 2 ~ 10 alkyl group, 7 to 40 carbon atoms alkyl group, 8 to 40 carbon atoms alkyl group, 7 to 40 carbon atoms alkyl group, silicon containing group, oxygen containing group , Io group, nitrogen group or phosphorus group. Of these, at least one of R ³³ and R ³⁴ is preferably an alkyl group having 1 to 3 carbon atoms. X ¹ and X ² may be the same or different from each other; a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, Conjugated residue formed from a containing group or a nitrogen-containing group, or X ¹ and X ² . Preferred conjugation residues formed from X ¹ and X ² are residues of 1, 3 butadiene, 2, 4 monohexagen, 1 phenenole 1, 3 pentagen, and 1, 4 diphenyl butadiene. These residues may be further substituted with a hydrocarbon group having 1 to 10 carbon atoms. X ¹ and X ² are preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a X-containing group. Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, a divalent Tin-containing group, O, 1 CO—, — S—, — SO—, —SO —, — NR ³⁵ —, — P (R ³⁵ ) —, — P (O) (R ³⁵ ) —, —BR ³⁵ Ma

 2

Or AIR ³⁵ (wherein R ³⁵ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms). Among these divalent groups, those in which the shortest linking part of Y— is composed of one or two atoms are preferred. R ³⁵ is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. Y is preferably a divalent hydrocarbon group having 1 to 5 carbon atoms, a divalent silicon-containing group, or a divalent germanium-containing group. Preferred alkylsilylene, alkylarylsilylene or Especially preferred to be arylsilylene.

 [0058] (Example 8 of metaguchicene compound)

 In addition, as the meta-mouth compound, the meta-mouth compound represented by the following formula (10) is used.

[0059] [Chemical 10]

In formula (10), M ³ is a transition metal atom of Group 4 of the periodic table, specifically titanium, zirconium or hafnium, preferably zirconium. R ³⁶ may be the same or different from each other, hydrogen atom, halogen atom, carbon atom number 1 to: LO alkyl group, carbon atom number 6 to: LO aryl group, carbon atom number 2 to: LO alkke Group, a group containing silicon, a group containing oxygen, a group containing nitrogen, a group containing nitrogen, or a group containing phosphorus. The above alkyl group and alkenyl group may be substituted with a halogen atom. Of these, R ³⁶ is preferably an alkyl group, an aryl group or a hydrogen atom, particularly a hydrocarbon group having 1 to 3 carbon atoms, such as methyl, ethyl, n-propyl and i-propyl, a phenol, a An aryl group such as naphthyl or 13 naphthyl or a hydrogen atom is preferred. R ³⁷ may be the same or different and each may be a hydrogen atom, halogen atom, carbon atom number 1 to: LO alkyl group, carbon atom number 6 to 20 aryl group, carbon atom number 2 to 10 alkyl group. An arylalkyl group having 7 to 40 carbon atoms, an arylalkyl group having 8 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, a kale-containing group, an oxygen-containing group, an i-containing group, A nitrogen-containing group or a phosphorus-containing group. The alkyl group, aryl group, alkyl group, aryl alkyl group, arylalkyl group, and alkylaryl group may be substituted with a halogen. R ³⁷ is a hydrogen atom or an alkyl group. In particular, a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, and tert-butyl is preferable. R ³⁶ and R ³⁷ may be the same as or different from each other. One of R ³⁸ and R ³⁹ is an alkyl group having 1 to 5 carbon atoms, and the other is a hydrogen atom, a halogen atom, or a carbon atom number 1 to: an L0 alkyl group, or a carbon atom number 2 to: L0 is an alkenyl group, a silicon-containing group, an oxygen-containing group, a X-containing group, a nitrogen-containing group or a phosphorus-containing group. Among these, R ³⁸ and R ³⁹ are preferably one of the alkyl groups having 1 to 3 carbon atoms such as S methyl, ethyl, propyl, etc., and the other is preferably a hydrogen atom. X ¹ and X ² may be the same or different from each other, a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group A X-containing group or a nitrogen-containing group, or a conjugation residue formed from X ¹ and X ² . Of these, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms is preferable. Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, a divalent Tin-containing group, O, One CO—, — S—, — SO—, —SO One, NR ⁴⁰ —, — P (R ⁴⁰ ) —, —P (O) (R ⁴⁰ ) —, —BR ⁴⁰ — Ma

 2

Or A1R ^4Q — (where R ^4Q is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms). Of these, Y is a divalent hydrocarbon-containing group having 1 to 5 carbon atoms, preferably a divalent hydrocarbon-containing group or a divalent germanium-containing group. Particularly preferred are alkylsilylene, alkylarylsilylene or arylylsilylene, which are more preferred.

 [0061] (Example 9 of metaguchicene compound)

 In addition, the meta-mouth composite compound represented by the following formula (11) is used.

[0062] [Chemical 11]

[0063] In the formula (11), Y is selected from carbon, silicon, germanium and tin nuclear power, M is Ti, Zr or Hf,

R ¹⁰ , R ^U and R ¹² are selected from hydrogen, a hydrocarbon group and a silicon-containing group, and may be the same or different, and adjacent substituents from R ⁵ to R ¹² are bonded to each other to form a ring. R ¹³ and R ″ may be selected from hydrocarbon groups and silicon-containing forces, which may be the same or different, and R ¹³ and R ¹⁴ may be bonded to each other to form a ring. Q may be selected from a halogen, a hydrocarbon group, an anion ligand, or a neutral ligand capable of coordinating with a lone pair, in the same or different combination, and j is an integer of 1 to 4.)

 Hereinafter, after the cyclopentadenyl group, the fluorenyl group, the cross-linking part, and other characteristics, which are the characteristics of the chemical structure of the metamouth compound used in the present invention, will be described in order, the preferred meta mouthsenic compound having these characteristics together. Explain the compound.

 [0064] (Cyclopentagel group)

The cyclopentagel group may or may not be substituted. A substituted or unsubstituted cyclopentagenyl group is possessed by the cyclopentagel group in the above formula (11).

A force in which R ² , R ³ and R ⁴ are all hydrogen atoms, one or more of R ² , R ³ and R ⁴ are hydrocarbon groups (fl), preferably having a total carbon number of 1 to 20 A cyclopentagel group substituted by a hydrocarbon group (fl ′) or a group containing a silicon (f 2), preferably a group containing 1 to 20 carbons (f 2,) Means.

When two or more of R ³ and R ⁴ are substituted, these substituents may be the same or different from each other. In addition, hydrocarbon groups having 1 to 20 carbon atoms are carbon and hydrogen. An alkyl group, an alkyl group, an alkyl group, and an aryl group. These include those in which any two adjacent hydrogen atoms are replaced at the same time to form an alicyclic or aromatic ring! /.

[0065] The hydrocarbon group having 1 to 20 carbon atoms in total (f 1 ') was directly bonded to these carbons other than an alkyl group, an alkenyl group, an alkynyl group and an aryl group composed only of carbon and hydrogen. A heteroatom-containing hydrocarbon group in which a part of hydrogen atoms is substituted with a halogen atom, an oxygen-containing group, a nitrogen-containing group, or a silicon-containing group, or any two adjacent hydrogen atoms form an alicyclic group. Including those that are. Such hydrocarbon groups (fl ′) include methyl, ethyl, n-propyl, allyl, n-butyl, n-pentyl, n-xyl, and n-butyl groups. , N-octyl group, n-nor group, n-dehydryl group, etc., linear hydrocarbon group; isopropyl group, t-butyl group, amyl group, 3-methylpentyl group, 1,1-benzene Branched hydrocarbon groups such as tilpropyl group, 1,1-dimethylbutyl group, 1-methyl-1 propylbutyl group, 1,1 propylbutyl group, 1,1 dimethyl-2-methylpropyl group, 1-methyl-1 isopropyl 2-methylpropyl group ; Cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, cyclic saturated hydrocarbon group such as adamantyl group; phenyl group, naphthyl group, biphenyl group, phenanthryl group, anthracene group Le group Any cyclic unsaturated hydrocarbon group and their nuclear alkyl substituents; saturated hydrocarbon groups substituted with aryl groups such as benzyl group, Tamyl group; methoxy group, ethoxy group, phenoxy group, N-methylamino group, trifluoro group Examples thereof include heteroatom-containing hydrocarbon groups such as a methyl group, tribromomethyl group, pentafluoroethyl group, and pentafluorophenyl group.

The key group containing group (f 2) is, for example, a group in which the ring carbon of the cyclopentagel group is directly covalently bonded to the key atom, specifically an alkylsilyl group or a arylsilyl group. It is a group. Examples of the C-containing group (f2 ′) having 1 to 20 carbon atoms include trimethylsilyl group and triphenylsilyl group.

 (Fluorol group)

The fluorenyl group may or may not be substituted. The substituted or unsubstituted fluorine group means R ⁵ R possessed by the fluorine group moiety in the above formula (11). ⁹ , R ¹⁰ , R ¹¹ and R ¹² are all hydrogen atoms, or one of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² At least one hydrocarbon group (f 1), preferably a hydrocarbon group having 1 to 20 carbon atoms (fl '), or a silicon-containing group (f 2), preferably having a total carbon number of 1 to 20 It means a fluorenyl group substituted with a silicon-containing group (f 2 ′). R ⁵ , R ⁶ , R

When two or more of R ¹¹ and R ¹² are substituted, these substituents may be the same or different from each other. R ⁵ ,

R ⁹ , R ^1Q , R ¹¹ and R

^{In 12} , adjacent groups may be bonded to each other to form a ring. In view of ease of catalyst production, those in which R ⁶ and R ^u , and R ⁷ and R ^1Q are the same are preferably used.

[0067] A preferred hydrocarbon group (fl) is a hydrocarbon group (fl ') having a total carbon number of 1 to 20, and examples of a preferable silicon-containing group (f 2) include those having a total carbon number of It is a group containing 1 to 20 (f 2 ').

 (Covalent cross-linking)

The main chain part of the bond connecting the cyclopentadenyl group and the fluorenyl group is a divalent covalent bond containing one carbon, silicon, germanium and tin atom. An important point in the case of high temperature solution polymerization is that the bridging atom Y of the covalent bond bridging portion has R ¹³ and R ¹⁴ which may be the same or different from each other. The preferred hydrocarbon group (fl) is the hydrocarbon group (f 1 ′) having the total carbon number of 1 to 20, and preferably the example of the silicon-containing group (f 2) has the total carbon number of 1 to 20 C-containing groups (f2 ').

[0068] (Other features of meta-orthane compounds)

In the formula (11), Q is a halogen, a hydrocarbon group having 1 to L carbon atoms, or a neutral, conjugated or nonconjugated gen, carbon-on ligand or lone electron pair having 10 or less carbon atoms. The neutral ligands that can be coordinated are selected in the same or different combinations. Specific examples of halogen are fluorine, chlorine, bromine, and iodine. Specific examples of hydrocarbon groups are methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2, 2-dimethylpropyl, 1,1-jetylpropyl, 1-ethyl-1-methylpropyl pill, 1, 1, 2, 2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1, 1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl and the like. Within 10 or less carbon atoms Specific examples of sex, conjugated or non-conjugated gens include S cis—or S trans—7? ⁴ —

1, 3 Butadiene, s-cis or s-trans 4-1, 4, Diphenenole 1, 3 Butagen, s cis 1 or s trans 1 ⁴ — 3—Methylolene 1, 3 Pentagene, s—cis or s trans ⁴ 1 , 4-dipentenoyl 1,3 Butadiene, s cis or s trans 7? ⁴ — 2, 4—Hexagene, s cis or s trans 7? ⁴ — 1, 3 Pentagen, s cis cis or s trans s 7? ⁴ —1, 4 Ditrinole 1,3 Butadiene, s cis- or s-trans 7? —I, 4 Bis (trimethylsilyl) -1,3 butadiene. Specific examples of the cation 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 neutral ligands that can be coordinated by a lone pair of electrons include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, and jetyl ether. , Ethers such as dioxane and 1,2-dimethoxyethane. j is an integer from 1 to 4, and when j is 2 or more, Qs may be the same or different.

 [0069] (Example 10 of metaguchicene compound)

 In addition, as a meta-mouth compound, a meta-mouth compound represented by the following formula (12) is used.

[0070] [Chemical 12]

[0071] where

^{R 2, R 3, R 4} , R 5, R 6, R 7, R 8, R 9, R 1Q, R U, R 12, R 13, R 14 is hydrogen, hydrocarbon Substituent substituents R ¹ to R ¹⁴ may be the same or different and may be bonded to each other to form a ring. M is Ti, Zr Or Hf, Y is a Group 14 atom, Q is halogen, hydrocarbon group, neutral with 10 or less carbon atoms, conjugated or non-conjugated gen, anion ligand, and can be coordinated by lone pair The neutral ligand force is selected from the same or different combination, n is an integer of 2 to 4, and j is an integer of 1 to 4.

 [0072] In the above formula (12), the hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, an aryl alkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a carbon number. 7-20 alkylaryl groups, which may contain one or more ring structures. Specific examples include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-jetylpropyl, 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, phenol, naphthyl, tolyl and the like.

 [0073] In the above formula (12), the hydrocarbon-containing hydrocarbon group is preferably an alkyl or aryl silyl group having 1 to 4 carbon atoms and 3 to 20 carbon atoms, and specific examples thereof include trimethylsilyl, tert Examples thereof include butyldimethylsilyl and triphenylsilyl.

In the present invention, R ¹ to R ″ in the above formula (12) are selected from hydrogen, a hydrocarbon group, and a silicon-containing hydrocarbon group, and may be the same or different from each other. Specific examples of the hydrocarbon group include those similar to the above.

[0074] The adjacent substituents from R ¹ to R ¹⁴ on the cyclopentagel ring of the above formula (12) may be bonded to each other to form a ring! /.

 M in the general formula (12) is a group 4 element of the periodic table, that is, zirconium, titanium, or hafnium, preferably zirconium.

Y is a Group 14 atom, preferably a carbon atom or a silicon atom. n is an integer from 2 to 4 A number, preferably 2 or 3, particularly preferably 2.

[0075] Q is selected from the group consisting of a halogen, a hydrocarbon group, neutral having 10 or less carbon atoms, conjugated or non-conjugated gen, a-on ligand, and a neutral ligand capable of coordination with a lone pair. Selected in the same or different combinations. When Q is a hydrocarbon group, it is more preferably a hydrocarbon group having 1 to: L0 carbon atoms.

Specific examples of halogen include fluorine, chlorine, bromine and iodine. Specific examples of hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1, 1-dimethylpropyl, 2, 2-dimethylpropyl, 1,1-jetylpropyl, 1-ethynole 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 and the like can be mentioned. Specific examples of neutral, conjugated or non-conjugated gens with less than 10 carbon atoms include s-cis or s-trans 7? '1, 3 butadiene, s-cis or s-trans 7? ⁴ —1, 4 Jifue two Lou 1, 3-butadiene, s-cis one or s trans one ^{4-3-methyl-1,} 3 pen Tajen, s-cis or s trans ⁴ 1, 4 Jipenjinore 1, 3-butadiene, s-cis or s transformer 7? ⁴ — 2, 4 Hexagen, s cis or s trans 1'—1, 3—Pentagen, s cis 1 or s trans 1 ⁴ —1, 4—Ditrinole-1, 3—Butadiene, s—cis or s—trans 7? ⁴ -1, 4-bis (Torimechinoreshiri Le) -1, 3-butadiene and the like. Specific examples of the cation 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 neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, or tetrahydrofuran and jetyl ether. And ethers such as dixanthone and 1,2-dimethoxyethane. When j is an integer of 2 or more, multiple Qs may be the same or different.

[0076] In the formula (12), Y is a force in which a plurality of 2 to 4 exist. A plurality of Y may be the same as or different from each other. The plurality of R ¹³ and the plurality of R ¹⁴ bonded to Y are the same as each other. It may be one or different. For example, a plurality of R ¹³ bonded to the same Y may be different from each other, or a plurality of R ¹³ bonded to different Y may be the same as each other. Also, R ¹³ or R ¹⁴ may form a ring with each other!

[0077] Preferable examples of the Group 4 transition metal compound represented by the formula (12) include a compound represented by the following formula (13).

 [0078] [Chemical 13]

[0079] In formula (13),

R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ^1Q , R ^U , R ¹² are selected from a hydrogen atom, a hydrocarbon group, and a silicon-containing group, and may be the same or different. ¹³ , R ", R ¹⁵ , and R ¹⁶ are hydrogen atoms or hydrocarbon groups, n is an integer of 1 to 3, and when n = l, R ¹ to R ¹⁶ are not hydrogen atoms at the same time. The adjacent substituents from R ⁵ to R ¹² may be bonded to each other to form a ring, and R ¹³ and R ¹⁵ may be bonded to each other to form a ring. In addition, R ¹³ and R ¹⁵ may be bonded to each other to form a ring, and at the same time, R ¹⁴ and R ¹⁶ may be bonded to each other to form a ring. Y ¹ and Y ² are group 14 atoms and M may be Ti, Zr, or Hf, and Q may be a halogen, a hydrocarbon group, a lone ligand, or a neutral ligand that can coordinate with a lone pair of electrons. Same or different May be selected with that combination, j is an integer of 1 to 4.

 [0080] Examples of such meta-cene compounds such as 9 and 10 are listed in JP-A-2004-175707, WO200lZ027124, WO2004 / 029062, WO2004Z083265, and the like.

The meta-mouth compounds described above can be used alone or in combination of two or more. Further, the meta mouth mixture may be diluted with a hydrocarbon or a halogenated hydrocarbon. [0081] (b-1) Organoaluminum compound:

 In the present invention, a conventionally known aluminoxane can be used as it is as the organoaluminum compound (b-1). Specific examples of such a known aluminoxane include compounds represented by the following formula (14) or the following formula (15).

 [0082] [Chemical 14]

 [In the formula, R represents a hydrocarbon group having 1 to carbon atoms: LO, and n represents an integer of 2 or more.]

 Of these compounds, those in which n is 3 or more, preferably 10 or more, particularly methylaluminoxane, which is an R-catayl group, are preferred. These aluminoxanes may be mixed with some organic aluminum compounds.

 In the case of performing high-temperature solution polymerization, a benzene-insoluble organoaluminum compound as exemplified in JP-A-2-78687 can also be applied. Also, organoaluminum compounds described in JP-A-2-167305, two or more kinds of alkyl groups described in JP-A-2-24701, JP-A-3-103407. Aluminoxane and the like having can be suitably used. The term “benzene insoluble” in an organoaluminum oxide compound means that the A1 component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of A1 atoms. It is insoluble or hardly soluble in benzene.

 [0084] Examples of the organoaluminum compound (b-1) used in the present invention also include modified methylaluminoxane having the following structure (16).

[0085] [Chemical 15]

(1 6) [0086] (where R is a hydrocarbon group having 1 to 10 carbon atoms, and m and n are integers of 2 or more.) This modified methylaluminoxane is prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. The Such modified methylaluminoxane is commonly called MMAO. Such MMAO can be prepared by the methods listed in U.S. Pat. No. 4,960,878 and U.S. Pat. No. 5041584.

 [0087] In addition, Tosoh Finechem Co., Ltd. also produced trimethylaluminum and triisobutylaluminum, and modified methylaluminoxanes, where R is an isobutyl group, are commercially produced under the names MMA O and TMAO. Talk!

 Such MMAO is an aluminoxane with improved solubility in various solvents and storage stability. Specifically, it is insoluble or hardly soluble in benzene as in the above formulas (14) and (15). However, it is soluble in aliphatic hydrocarbons and alicyclic hydrocarbons.

 [0088] Further, examples of the organoaluminum oxide compound (b-1) used in the present invention include an organoaluminum oxide compound containing boron represented by the following formula (17). You can also.

[0089] [Chemical 16]

[0090] (In the formula, R ^e represents a hydrocarbon group having 1 to LO carbon atoms. R ^d may be the same as or different from each other, a hydrogen atom, a halogen atom, or a carbon atom number power ^ ~ Represents 10 hydrocarbon groups.)

 (b 2) Compound that reacts with meta-acene compound (A) to form an ion pair:

JP-A-1-501950 discloses a compound (b-2) that reacts with the meta-orthene compound (A) to form an ion pair (hereinafter sometimes abbreviated as “ionic compound”). Japanese Laid-open Patent Publication No. 1-502036, No. 3-179005, No. 3-179006, No. 3-207703, No. 3-207704, US Pat. No. 5,321,106, etc. Lewis acids, ionic compounds, borane compounds and carborane compounds described in Things can be mentioned. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

 [0091] In the present invention, the ionic compound preferably employed is a compound represented by the following general formula (18).

[0092] [Chemical 17]

[0093] In the formula, as R ^{e +} is, H +, carbenium - Umukachion, Okiso - Umukachion, ammonium - © beam cation, phospho - Umukachion, cyclohexane Puchirutorie - Rukachion, Hue port Se for have a transition metal - such Umukachion is Can be mentioned. ~ May be the same as or different from each other, and are an organic group, preferably an aryl group.

 Specific examples of the carb cation include triphenyl carb cation, tris (methyl phen) carb cation, tri-substituted carb cation such as tris (dimethyl phen) carb cation. Can be mentioned.

 [0094] Specific examples of the ammonium cation include trimethyl ammonium cation, triethyl ammonium cation, tri (n-propyl) ammonium cation, triisopropyl ammonium cation, tri (n-butyl) ammonium cation, and tri (n-butyl) ammonium cation. N, N such as trialkyl ammonium cation such as isobutyl ammonium cation, N, N-dimethylaurium cation, N, N-jetylarium cation, N, N— 2, 4, 6-pentamethylium cation —Dialkyl ammonium cation such as dialkyl ammonium cation, diisopropyl ammonium cation and dicyclohexyl ammonium cation.

 [0095] Specific examples of the phosphonium cation include triarylphosphonium cations, such as triphenylphosphonium cation, tris (methylphenol) phosphonium cation, and tris (dimethylphenol) phosphonium cation. It is done.

Of these, R ⁰ "is preferably a carbium cation, an ammonium cation, etc., particularly a triphenyl carbium cation, an N, N-dimethylarium cation, N, N Jetylurium cation is preferred.

[0096] Specific examples of the carbaum salt include triphenyl carbe tetraphenol ruporate, triphenyl carbe tetrakis (pentafluorophenol) borate, triphenyl carbe tetrakis (3, 5 —Ditrifluoromethylphenol) borate, tris (4-methylphenyl) carbtetrakis (pentafluorophenol) borate, tris (3,5-dimethyldimethyl) carbtetrakis (Pentafluorophenol) borate and the like.

 Examples of ammonium salts include trialkyl-substituted ammonium salts, N, N dialkyl ammonium salts, dialkyl ammonium salts, and the like.

Examples of the trialkyl-substituted ammonium salt include triethyl ammonium tetraphenol ruborate, tripropyl ammonium tetraphenol porate, tri (n-butyl) ammonium tetraphenol porate, trimethyl ammonium tetrakis (p-tolyl) borate, Trimethylammonium tetrakis (o-tolyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenol) borate, triethylammonium tetrakis (pentafluorophenol) borate, tripropylammonium tetrakis (penta Fluorophenol) borate, tripropylammonium tetrakis (2,4 dimethylphenol) borate, tri (n-butyl) ammoniumtetrakis (3,5-dimethylphenol) borate, tri (n-butyl) ammonium Umutet Lakis (4 trifluoromethyl phenol) borate, tri (n-butyl) ammonium tetrakis (3,5-ditrifluoromethylphenol) borate, tri (n-butyl) ammonium tetrakis (o Tolyl) borate, dioctadecylmethylammonium tetraborate, dioctadecylmethylammonium tetrakis (p tolyl) borate, dioctadecylmethylammonium tetrakis (o tolyl) borate, dioctadecylmethylammonium -Umtetrakis (pentafluorophenol) borate, dioctadecyl methylammotetrakis (2,4 dimethylphenol) borate, dioctadecylmethyl ammoamtetrakis (3,5-dimethylphenol) borate, dioctadecyl Methyl ammonium tetrakis (4 trifluoromethyl phenol) Over DOO, di O Kuta decyl methyl ammonium - Umutetorakisu (3, 5-di-full O b methyl Hue - Le) borate, Jiokutadeshi Rumechiruanmo - © beam, and the like. [0098] Examples of the N, N dialkylayuyurumu salt include, for example, N, N dimethylayumuterutrafolate, N, N dimethylayuyumu-tetrakis (pentafluorophenol) borate, N, N dimethylayuyumu tetrakis (3,5-ditrifluoromethylphenyl) borate, N, N jetylureum tetraphenol, N, N jetyllium tetrakis (pentafluorophenyl) borate, N, N jetylureum tetrakis (3,5 ditrifluoromethylphenol) borate, N, N— 2, 4, 6 pentamethylaureum tetraphenolate, N, N- 2, 4, 6 pentamethylaurium tetrakis (pentafluoro) Lophe) borate and the like.

 [0099] Examples of the dialkyl ammonium salt include di (1 propyl) ammonium tetrakis (pentafluorophenol) borate, dicyclohexyl ammonium tetraphenol, and the like.

 Furthermore, an ionic compound disclosed by the present applicant (Japanese Patent Laid-Open No. 2004-51676) can be used without limitation.

 [0100] The ionic compound (b-2) as described above can be used in combination of two or more.

 (b 3) Organoaluminum compound:

 Examples of the organoaluminum compound that forms the olefin polymerization catalyst (b-3) include, for example, an organoaluminum compound represented by the following formula (19), a complex of a Group 1 metal represented by the following formula (20) and aluminum. Examples thereof include alkylated products.

[0101] R ^a Al (OR ^b ) HX "'(19)

 m n p q

(In the formula, R ^a and R ^b each 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 0≤q <3, and m + n + p + q = 3.) M ² AlR ^a --(20)

 Four

(In the formula, 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.)

Specific examples of the compound represented by the above formula (19) include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, trioctylaluminum; Isopropylaluminum, triisobuty Trialuminum, trisec butylaluminum, tritert butylaluminum, tri2-methylbutylaluminum, tri3 methylhexylaluminum, tri2 hexylaluminum, and other tri-branched alkylaluminums; tricyclohexylaluminum, tricycloaluminum Tricycloalkylaluminum such as octylaluminum; Triarylaluminum such as triphenyl aluminum and tolyl aluminum; Dialkylaluminum hydride such as diisopropylaluminum hydride and diisobutylaluminum hydride; ) Al (CH) (where x, y, z are positive numbers, z≤2x

 4 9 5 10

It is. ) Alkenyl aluminum such as isoprenylaluminum, etc .; alkylaluminum alkoxides such as isobutylaluminum methoxide and isobutylaluminum ethoxide; dimethylaluminum methoxide, jetylaluminum ethoxide, dibutylaluminum butoxide, etc. Dialkylaluminum alkoxides; alkylalkylene sesquialkoxides such as ethylaluminum sesquibutoxide and butylaluminum sesquibutoxide; having an average composition represented by the general formula R ^a Al (OR ^b )

 2.5 0.5

Partially alkoxylated alkylaluminum; alkylaluminum bite oxides such as jetylaluminum phenoxide and jetylaluminum (2, 6-di-tert-butyl-4-methylphenoxide); dimethylaluminum chloride and jetylaluminum -Dialkylaluminum halides such as umuchloride, dibutylaluminum chloride, jetylaluminum bromide, diisobutylaluminum chloride; Alkyl aluminums such as aluminum dichlorides Partially halogenated alkyl aluminums such as urea dihalides; Jetyl aluminum hydrides Dialkylaluminum hydrides such as dibutylaluminum hydride; Other partially hydrogenated alkylaluminums such as alkylaluminum dihydride such as ethylaluminum dihydride and propylaluminum dihydride; Mention may be made of partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxybromide.

Specific examples of the compound represented by the above formula (20) include LiAl (CH 3), LiAl (CH 3), etc. Can be illustrated. A compound similar to the compound represented by the general formula (20) can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (CH 3) A1N (CH 3) A1 (CH 3).

 2 5 2 2 5 2 5 2

 From the viewpoint of availability, trimethylaluminum and triisobutylaluminum are preferably used as the (b-3) organoaluminum compound.

 (Polymerization)

 The polyolefin wax used in the present invention can be obtained by copolymerizing ethylene or a-year-old olefin with the ability to homopolymerize ethylene or α-olefin in a normal liquid phase in the presence of the above-mentioned meta-orthocene catalyst. In the polymerization, the usage method of each component and the order of addition are arbitrarily selected. The following methods are exemplified.

[0104] A method wherein [ql] component (A) is added alone to the polymerization vessel.

 [q2] A method in which component (A) and component (B) are added to the polymerization vessel in any order. In the method [q2], at least two or more of the catalyst components may be in contact with each other in advance. In this case, a hydrocarbon solvent is generally used, but a-olefin may be used as a solvent. The monomers used here are as described above.

[0105] Polymerization methods include suspension polymerization in which polyolefin wax is present as particles in a solvent such as hexane, gas phase polymerization in which a solvent is not used, and a polymerization temperature of 140 ° C or higher. It is possible to perform solution polymerization in which polyolefin wax is polymerized in the state of coexistence with a solvent or when melted alone. Among them, solution polymerization is preferred in terms of both economy and quality. ヽ The polymerization reaction is either a batch method or a continuous method. You may go on. When the polymerization is carried out by a batch method, the above catalyst components are used under the concentration conditions described below.

[0106] using Orefin polymerization catalyst as described above, when performing polymerization of Orefin, Ingredient (A) is, per liter of the reaction volume, typically 10 ^{9-10 - 1} mol, preferably from 10 ⁸ to : LO—Used in an amount of ² moles.

Component (b— 1) is a molar ratio of component (b— 1) to all transition metal atoms (M) in component (A) [(b — 1) / M] force usually from 0.01 to 5, 000, preferably in an amount such as 0.05-2,000! /, It is done. Component (b-2) has a molar ratio [(b-2) ZM] between the ionic compound in component (b-2) and the total transition metal (M) in component (A). In general, it is used in an amount of 0.5 to 5,000, preferably 1 to 2,000. Component (b-3) has a molar ratio [(b 3) ZM] of component (b-3) to transition metal atom (M) in component (A) usually from 1 to: L0000, preferably Used in an amount of 1 to 5000.

[0107] The polymerization reaction is carried out at a temperature of usually 20 to + 200 ° C, preferably 50 to 180 ° C, more preferably 70 to 180 ° C, and a pressure of usually more than 0 7.8 MPa ( 80kgfZcm ² (gauge pressure) or less, preferably more than 0 4.

(Gauge pressure) Performed under the following conditions.

 Ethylene and Z or α-olefin are supplied to polymerize them in the presence of the above-mentioned metalocene catalyst. At this time, a molecular weight regulator such as hydrogen may be added. When polymerized in this manner, the produced polymer is usually obtained as a polymerization solution containing the polymer, so that polyolefin wax can be obtained by treatment by a conventional method.

[0108] As the above-mentioned meta-octacene catalyst, a catalyst containing a meta-caffeine compound shown in (Example 6 of meta-caffeine compound) is particularly preferable.

 <Mixture of thermoplastic rosin and polyolefin wax>

 The thermoplastic resin and the polyolefin wax may be mixed in advance (preliminary mixing) before being supplied to the injection molding machine, or the polyolefin wax is supplied to the resin supplied to the injection molding machine (for example, side feed). And may be mixed. In any of the above cases, a mixture of thermoplastic resin and polyolefin wax is formed at the time of injection. The premixing method is not particularly limited, and may be melt mixing or dry blending. In addition to the above-mentioned mixture, antioxidants, UV absorbers, light stabilizers, colorants, metal sarcophagus, plasticizers, foaming agents, fillers, anti-aging agents, flame retardants, antibacterial and antifungal agents Various additives can be mixed depending on the application.

 [0109] A mixture of thermoplastic rosin and polyolefin wax having LZL in the above range is obtained.

 0

Therefore, the polyolefin wax is usually contained in an amount of 0.5 to 15 parts by weight, preferably 1 to: LO parts by weight, more preferably 2 to 7 parts by weight with respect to 100 parts by weight of the thermoplastic resin. desirable. The mixture of thermoplastic resin and polyolefin wax thus obtained by premixing or side feed is injection molded into a desired shape.

 [0110] The injection molding can be performed under conventionally known conditions. Specifically, the molding temperature is

 Tr = 3/4 XTm + 100

 (In the formula, Tm indicates the melting temperature (° C) of thermoplastic resin, especially in the case of crystalline resin)

Usually determined by 180-400. C, preferably 200-300. C, in the range of more preferably 200 to 250 DEG ^o C, injection pressure force S typically 10 to 200, preferably ί or 20～150MPa, mold temperature usually 20 to 200 ° C, preferably 20 to 80 ° C, more preferably 20 to 60 ° C.

[0111] [Example]

 EXAMPLES Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the examples.

 [Comparative Example 1]

 The flow length of a propylene block copolymer (trade name: Prime Polypro J704WA, manufactured by Prime Polymer Co., Ltd., crystal melting temperature: 160 ° C.) was measured under the following conditions.

[0112] (Flow length measurement)

 An injection molding machine (manufactured by TOSHIBA MACHINE CO., LTD., 55ton injection) using a mold for measuring the flow length of resin (thickness lmm, width 10mm) under the conditions of a resin temperature of 220 ° C and a mold temperature of 40 ° C. Injection molding was performed with a molding machine (IS55EPN il. 5B)), and the flow length (spiral flow length) was measured.

 Next, the propylene block copolymer was injection molded under the following conditions to produce a molded product, and various physical properties were evaluated. The results are shown in Table 1.

 [Injection molding conditions]

 Injection molding machine: Toshiba Machine Co., Ltd., 55ton injection molding machine (IS55EPM1.5B) Molding temperature: 220 ° C

 Injection pressure: 105MPa

Mold temperature: 40 ° C Mold cooling time: 20 seconds

 〔Evaluation of the physical properties〕

 (Releasability)

 A flat plate (100mm x 100mm x 3mm thickness) was injection molded with the above injection molding machine under the above conditions (excluding mold cooling time) and cooled with the mold cooling time set to 10 seconds, and then the molded product in the mold was removed. Extrusion was performed with an ejector pin, and the releasability at this time was determined according to the following criteria.

 ◯: The molded product is released without resistance and does not deform.

 X: The molded product is deformed with a large release resistance due to sticking to the mold.

[0113] (Flow mark)

 A flat plate (100 mm x 100 mm x 3 mm thick) was injection molded under the above conditions using the above injection molding machine, and the flow mark was observed.

 Y: No flow mark

 X: With flow mark

 (Tensile yield stress)

 Using the above injection molding machine, a test piece was prepared under the above conditions, and the tensile yield stress was measured in accordance with JIS K7161.

[0114] (Bending elastic modulus, bending strength)

 Using the above injection molding machine, test specimens were prepared under the above conditions, and the flexural modulus and flexural strength were measured according to JIS K7171.

 (Heat-resistant)

 Test pieces were prepared using the above injection molding machine under the above conditions, and Vicat soft saddle points were measured in accordance with JIS K7206.

[0115] (Impact resistance)

 Using the above injection molding machine, test specimens were prepared under the above conditions, and Izod impact values were measured according to JIS K7110.

 [Example 2]

Propylene block copolymer (trade name: Prime Polypro J704WA, manufactured by Prime Polymer Co., Ltd., crystal melting temperature: 160 ° C) 1 part by weight or 3 parts by weight of a polyethylene wax (Etaselex (registered trademark) 30200BT, manufactured by Mitsui Chemicals, Inc., ethylene content 95 mol%, density: 913 kgZm ³ , average molecular weight (Mn) = 2000), Thorough mixing in a tumbler mixer produced a mixture of polypropylene and polyethylene wax. The flow length of this mixture was measured in the same manner as in Comparative Example 1. Further, this mixture was subjected to injection molding in the same manner as in Comparative Example 1, and various physical properties were evaluated. The results are shown in Table 1.

[0116] [Table 1]

 table 1

 [0117] A comparison of Examples 1 and 2 with Comparative Example 1 shows that the physical properties of the injection-molded product can be improved even if polyolefin wax (meta-waxene-based wax) is added to thermoplastic resin (polyolefin). No decrease was observed, indicating that the fluidity (flow length) has improved by 5%. For this reason, the mixture of thermoplastic resin and polyolefin wax improves the flow of the resin to the fine part of the mold and enables precision molding (molding with a shape faithful to the mold). Recognize. Furthermore, by adding polyolefin wax, the releasability from the mold can be improved, and sticking of the molded product to the mold can be prevented even in thin film molding or the like.

Claims

The scope of the claims

 [1] Using a spiral flow mold with a thickness of lmm and a width of 10mm, which contains thermoplastic resin and polyolefin wax, under the conditions of a resin temperature Tr and a mold temperature of 40 ° C, which is obtained by the following formula: The measured mixture of the flow length L when the polyolefin wax is included and the flow length L when the polyolefin wax is not included is LZL≥1.05.

 0 0

 A method for producing an injection-molded article, characterized by being molded by extrusion:

 Tr = 3/4 XTm + 100

 (In the formula, Tm indicates the melting temperature (° C) of thermoplastic resin.)

[2] The method for producing an injection-molded article according to claim 1, wherein 0.5 to 15 parts by weight of the polyolefin wax is contained with respect to 100 parts by weight of the thermoplastic resin.

[3] The method for producing an injection-molded article according to [1], wherein the polyolefin wax is polyethylene wax.

4. The method for producing an injection-molded article according to claim 1, wherein the thermoplastic resin is polypropylene or polyethylene.

[5] An injection-molded article obtained by the production method according to any one of claims 1 to 4.