JP4983408B2 - Polypropylene resin composition - Google Patents

Description

  The present invention relates to an olefin polymer composition in which an inorganic solid is uniformly finely dispersed.

  Polymers such as olefin polymers are used in a wide range of fields such as automobile parts, home appliances, miscellaneous goods, packaging materials, optical materials, and building materials. Depending on such various uses, it is required to provide higher functionality. For example, propylene polymer compositions containing various inorganic solids with respect to the propylene polymer are known.

  However, the surface energy of the inorganic solid is larger than that of the olefin polymer, and since the interaction between the inorganic solid and the olefin polymer is essentially small, the method of adding and containing the inorganic solid during plasticization and kneading of the polymer, The dispersion of the inorganic solid is not sufficient.

  Depending on the method, the effects expressed by finely dispersing the inorganic solid, such as vibration damping properties, do not appear sufficiently. An object of the present invention is to provide an olefin polymer composition having excellent performance (particularly excellent vibration damping properties) by finely dispersing an inorganic solid.

  The present invention is an olefin polymer composition containing an inorganic solid, wherein the inorganic solid has an aggregation degree θ of 0 <θ ≦ 10 (where θ is a value obtained by d ÷ D, where d Represents an inorganic solid dispersed particle diameter in the olefin polymer composition, and D represents an inorganic solid primary particle diameter used for inclusion in the olefin polymer). It relates to the polymer composition.

  According to the present invention, excellent performance (particularly vibration damping properties) is imparted to an olefin polymer composition without impairing transparency due to a uniformly uniformly finely dispersed inorganic solid.

Hereinafter, the present invention will be specifically described.
The olefin polymer composition of the present invention is an olefin polymer composition containing an inorganic solid and finely dispersed.
The inorganic solid may be a known inorganic material such as metal, ceramics, alloy, cermet, and amorphous alloy. More specific examples of the inorganic solid include Mg, V, Sr, Pb, Ag, Au, Al, Ga, Ti, W, Fe, Co, Ni, Zn, Cd, P, As, Sb, Bi, Pt, and rare earths. Simple metals such as metals; halides such as fluorides, chlorides, bromides and iodides of the metals; oxides of the metals; chalcogenides such as sulfides of the metals; nitrides of the metals; The metal phosphide; the metal arsenide; the metal carbide; the metal silicide; the metal boride; the metal hydroxide; the metal carbonate; the metal sulfate; the metal The metal silicate; the metal phosphate; the metal chlorite; the metal chlorate; and the metal perchlorate. Moreover, the compound containing 2 or more types of metal elements may be sufficient. Details are described in "4th Edition Experimental Chemistry Course 16 Inorganic Compounds" (1993 published by Maruzen Co., Ltd.).

Of these, a layered inorganic material is preferably used as the inorganic solid. Specific examples of the compound include simple substances such as graphite, black phosphorus, arsenic, antimony, and bismuth; halogens such as MgBr ₂ , CdI ₂ , AsI ₃ , VI ₃ , SrFCl, PbFI, and Ag ₂ F. Metal hydroxides; metal hydroxides such as Mg (OH) ₂ , Ca (OH) ₂ , Al (OH) ₃ , AlOOH, Mn (OH) ₂ , and Fe (OH) ₂ ; HfS ₂ , MoS ₂ , NITE _2, PTSE ₂ and transition metal chalcogenides, such as ZrS _2; GaS, GaSe, GaTe and, 13-16 compound such as _{InSe; PbO, Ge 2 Te 3} , SnO, SnS 2 and, SnSe 14-16 compound such as _{2; Mg 6 Al 2 (OH} ) 16 CO 3 · nH 2 O ( hydrotalcite), a layer such as _{Zn 6 Al 2 (OH) 16} CO 3 · nH 2 O Double hydroxide; layered silicate compound; high-temperature superconductor composed of copper oxide; organic conductor composed of charge transfer complex; organic superconductor; boron nitride (BN); layered titanate; and zirconium phosphate Examples of such metal phosphates are as follows. Of these, a layered metal oxide or a layered metal hydroxide is preferably used, and a layered metal hydroxide (especially aluminum hydroxide) is particularly preferably used in terms of improving vibration damping.

  The inorganic solid contained in the olefin polymer composition of the present invention is dispersed in a state where the degree of aggregation θ in the olefin polymer composition satisfies 0 <θ ≦ 10. In the above equation, θ is a value obtained by d ÷ D. Here, d represents the inorganic solid dispersed particle size in the olefin polymer composition, and D represents the primary particle size of the inorganic solid used for inclusion in the olefin polymer.

(ｉ＝１からｎまで；ｎ＝粒子数) The inorganic solid dispersed particle diameter d is a value calculated by the following method. An ultrathin section having a thickness of less than 1000 angstroms of the olefin polymer composition is photographed with a transmission electron microscope, and the area of the inorganic solid dispersed particles i in the two-dimensional image is detected by image analysis. The diameter of the circle giving the area is Ri, and Ri is substituted into the following equation, and the obtained value is the inorganic solid dispersed particle diameter d.

(i = 1 to n; n = number of particles)

Said D is the primary particle diameter of the inorganic solid used to obtain the olefin polymer composition of the present invention. The primary particle diameter referred to here is D determined by the following formula, assuming a BET specific surface area equivalent diameter calculated from the BET specific surface area.
D = 6 ÷ (specific gravity × BET specific surface area)
As the inorganic solid used to obtain the olefin polymer composition of the present invention, an inorganic solid having a primary particle size of 0.1 nm to 300 nm is preferable, and an inorganic solid having a primary particle size of 0.1 nm to 100 nm is more preferable. An inorganic solid having a primary particle size of 0.1 nm to 50 nm is more preferable.

  In the present invention, the degree of aggregation θ is preferably greater than 0 and 8 or less, more preferably greater than 0 and 6 or less.

  The content of the inorganic solid contained in the olefin polymer composition of the present invention is preferably 0.001 wt% or more and 50 wt% or less in order to develop the functionality of the inorganic solid. More preferably, it is 0.01 to 30 weight%, More preferably, it is 0.01 to 10 weight%.

  The inorganic solid is preferably contained in the olefin polymer composition with a smaller dispersed particle diameter, specifically, 70 wt% or more (more preferably 80 wt% or more, more preferably in the olefin polymer composition). The dispersion particle diameter d of the inorganic solid (85 wt% or more) is preferably 0.1 nm or more and 100 nm or less.

  If the inorganic solid is dispersed in the olefin polymer composition in such a fine state, the inorganic solid is dispersed with a particle size not larger than the length between the entanglement points of the polymer chains constituting the olefin polymer. However, in the process of deformation of the olefin polymer due to external stress, the inorganic solid is less likely to hinder the movement of the polymer chain constituting the olefin polymer, and it is considered that various physical properties of the polymer, such as impact strength, are not impaired. . In addition, the interfacial area between the inorganic solid and the olefin polymer increases, and the amount of heat energy dissipated due to friction at the interface increases accordingly. For example, it is considered that damping properties and the like are imparted to the olefin polymer.

（式中、ａは１〜２０の数を表し、Ｒ²は炭素原子数１〜２０の炭化水素基を表す。Ｘ²はハロゲン原子または炭素原子数１〜２０の炭化水素オキシ基を表し、全てのＸ²は同一であっても異なっていてもよい。）
以下、該製造方法について説明する。 Such an olefin polymer composition of the present invention comprises the following general formula [I] in the presence of an organosilicon compound (1) having a Si—O bond and an inorganic solid (5) having a primary particle diameter of 0.1 nm to 300 nm. A solid product obtained by reducing the titanium compound (2) represented by formula (1) with an organomagnesium compound (3), or an organosilicon compound (1) having an Si—O bond, an ester compound (4), and primary particles Solid product obtained by reducing titanium compound (2) represented by general formula [I] below with organic magnesium compound (3) in the presence of inorganic solid (5) having a diameter of 0.1 nm to 300 nm A solid catalyst component for olefin polymerization (A), an organoaluminum compound (B) obtained by contacting a halogenated compound (b) having halogenation ability and an electron donating compound (c), By using an olefin polymerization catalyst obtained by contacting an electron-donating compound (C), obtained by polymerizing olefins.

(In the formula, a represents a number of 1 to 20, R ² represents a hydrocarbon group having 1 to 20 carbon atoms, X ² represents a halogen atom or a hydrocarbon oxy group having 1 to 20 carbon atoms, All X ² may be the same or different.)
Hereinafter, the manufacturing method will be described.

（式中、ａは１〜２０の数を表し、Ｒ²は炭素原子数１〜２０の炭化水素基を表す。Ｘ²はハロゲン原子または炭素原子数１〜２０の炭化水素オキシ基を表し、全てのＸ²は同一であっても異なっていてもよい。） (A) Solid product The solid product (a) used for the preparation of the solid catalyst component for olefin polymerization is composed of an organic silicon compound (1) having a Si-O bond and an inorganic material having a primary particle size of 0.1 nm to 300 nm. In the presence of the solid (5), the titanium compound (2) represented by the following general formula [I] is reduced by the organomagnesium compound (3) or has a Si-O bond. In the presence of an organosilicon compound (1), an ester compound (4) and an inorganic solid (5) having a primary particle size of 0.1 nm to 300 nm, a titanium compound (2) represented by the following general formula [I] It is a solid product obtained by reduction with an organomagnesium compound (3).

(In the formula, a represents a number of 1 to 20, R ² represents a hydrocarbon group having 1 to 20 carbon atoms, X ² represents a halogen atom or a hydrocarbon oxy group having 1 to 20 carbon atoms, All X ² may be the same or different.)

  In particular, the inorganic solid contained in the solid product obtained by reduction is 100 times or less (more preferably 50 times or less, more preferably 10 times or less) of the primary particle diameter D of the inorganic solid (5) used. ) Is preferred. Examples of the inorganic solid (5) used for the preparation of the solid catalyst component for olefin polymerization include those already described.

Preferred examples of the organosilicon compound (1) having a Si—O bond include those represented by the following general formula.
Si (OR ¹⁰ ) _t R ¹¹ _4-t
R ¹² (R ¹³ ₂ SiO) _u SiR ¹⁴ ₃ or
(R ¹⁵ ₂ SiO) _v
R ¹⁰ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrocarbon group or hydrogen atom having 1 to 20 carbon atoms. Represents. t represents a number satisfying 0 <t ≦ 4, u represents an integer of 1 to 1000, and v represents an integer of 2 to 1000.

  Specific examples of such organosilicon compounds include tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, tetraisopropoxysilane, diisopropoxy-diisopropylsilane, tetrapropoxy. Silane, dipropoxydipropylsilane, tetrabutoxysilane, dibutoxydibutylsilane, dicyclopentoxydiethylsilane, diethoxydiphenylsilane, cyclohexyloxytrimethylsilane, phenoxytrimethylsilane, tetraphenoxysilane, triethoxyphenylsilane, hexamethyldi Siloxane, hexaethyldisilohexane, hexapropyldisiloxane, octaethyltrisiloxane, dimethylpolysiloxane Emissions, diphenyl polysiloxane, may be exemplified methylhydropolysiloxane, phenyl hydropolysiloxane like.

Among these organosilicon compounds, preferred are alkoxysilane compounds represented by the general formula Si (OR ¹⁰ ) _t R ¹¹ _4-t , in which case t is preferably a number satisfying 1 ≦ t ≦ 4, In particular, t = 4 tetraalkoxysilane is preferable, and tetraethoxysilane is most preferable.

（式中、ａは１〜２０の数を表し、Ｒ²は炭素原子数１〜２０の炭化水素基を表す。Ｘ²はハロゲン原子または炭素原子数１〜２０の炭化水素オキシ基を表し、全てのＸ²は同一であっても異なっていてもよい。） The titanium compound (2) is a titanium compound represented by the following general formula [I].

(In the formula, a represents a number of 1 to 20, R ² represents a hydrocarbon group having 1 to 20 carbon atoms, X ² represents a halogen atom or a hydrocarbon oxy group having 1 to 20 carbon atoms, All X ² may be the same or different.)

Specific examples of R ² include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, decyl, dodecyl and the like. And aryl groups such as phenyl group, cresyl group, xylyl group and naphthyl group, cycloalkyl groups such as cyclohexyl group and cyclopentyl group, allyl groups such as propenyl group, and aralkyl groups such as benzyl group.
Of these groups, an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms is preferable. A linear alkyl group having 2 to 18 carbon atoms is particularly preferable.

Examples of the halogen atom for X ² include a chlorine atom, a bromine atom, and an iodine atom. A chlorine atom is particularly preferable. The hydrocarbon oxy group having 1 to 20 carbon atoms in X ² is a hydrocarbon oxy group having a hydrocarbon group having 1 to 20 carbon atoms similar to R ² . X ² is particularly preferably an alkoxy group having a linear alkyl group having 2 to 18 carbon atoms.

  In the titanium compound represented by the general formula [I], a represents a number of 1 to 20, and is preferably a number satisfying 1 ≦ a ≦ 5.

  Specific examples of titanium compounds in which a is 2 or more include tetraisopropyl polytitanate (a mixture in the range of a = 2 to 10), tetra-n-butyl polytitanate (a mixture in the range of a = 2 to 10), Examples include tetra-n-hexyl polytitanate (a mixture in the range of a = 2 to 10) and tetra-n-octyl polytitanate (a mixture in the range of a = 2 to 10). Moreover, the condensate of the tetraalkoxy titanium obtained by making a small amount of water react with tetraalkoxy titanium can also be mentioned.

More preferably, the titanium compound (2) is represented by the general formula Ti (OR ² ) _q X ³ _4-q (wherein R ² represents a hydrocarbon group having 1 to 20 carbon atoms, X ³ represents a halogen atom, q Represents a number satisfying 0 <q ≦ 4).

The value of q of the titanium compound represented by the general formula Ti (OR ² ) _q X ³ _4-q is a number satisfying 0 <q ≦ 4, preferably a number satisfying 2 ≦ q ≦ 4, Particularly preferably, q = 4.

As a method for synthesizing the titanium compound represented by the general formula Ti (OR ² ) _q X ³ _4-q , a known method can be used. For example, a method of reacting Ti (OR ² ) ₄ and TiX ³ ₄ at a predetermined ratio, or a method of reacting a predetermined amount of TiX ³ ₄ with a corresponding alcohol (for example, R ² OH) can be used.
Specific examples of such titanium compounds include trihalogenated alkoxy titanium compounds such as methoxy titanium trichloride, ethoxy titanium trichloride, butoxy titanium trichloride, phenoxy titanium trichloride, ethoxy titanium tribromide, dimethoxy titanium dichloride, diethoxy titanium. Dihalogenated dialkoxy titanium such as dichloride, dibutoxy titanium dichloride, diphenoxy titanium dichloride, diethoxysilane dibromide, trimethoxy titanium chloride, triethoxy titanium chloride, tributoxy titanium chloride, triphenoxy titanium chloride, triethoxy titanium bromide, etc. Monohalogenated trialkoxytitanium compounds, tetramethoxy titanium, tetraethoxy titanium, tetrabut Shichitan and tetraalkoxy titanium compounds such as tetra-phenoxy titanium can be cited.

As the titanium compound (2), it is more preferable from the viewpoint of polymerization activity to use a titanium compound in which a in the titanium compound represented by the above general formula [I] is 2 or 4.
Tetra-n-butylpolytitanate is more preferable from the viewpoint of polymerization activity, and tetra-n-butyltitanium dimer or tetra-n-butyltitanium tetramer is particularly preferably used.

As the organomagnesium compound (3), any type of organomagnesium compound having a magnesium-carbon bond can be used. Particularly, a Grignard compound represented by the general formula R ¹⁶ MgX ⁵ (wherein Mg represents a magnesium atom, R ¹⁶ represents a hydrocarbon group having 1 to 20 carbon atoms, and X ⁵ represents a halogen atom) or a general formula R Dihydrocarbyl magnesium represented by ¹⁷ R ¹⁸ Mg (wherein Mg represents a magnesium atom and R ¹⁷ and R ¹⁸ each represent a hydrocarbon group having 1 to 20 carbon atoms) is preferably used. Here, R ¹⁷ and R ¹⁸ may be the same or different. Specific examples of R ^{16 to} R ¹⁸ are methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, isoamyl group, hexyl group, octyl group and 2-ethylhexyl group, respectively. , A phenyl group, a benzyl group and the like, an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and an alkenyl group. In particular, it is preferable from the viewpoint of catalyst performance to use a Grignard compound represented by R ¹⁶ MgX ⁵ in an ether solution.

  It is also possible to use a hydrocarbon-soluble complex of the above organic magnesium compound and an organic metal that solubilizes the organic magnesium compound in a hydrocarbon. Examples of organometallic compounds include Li, Be, B, Al or Zn compounds.

  As the ester compound (4), mono- or polyvalent carboxylic acid esters are used, and examples thereof include saturated aliphatic carboxylic acid esters, unsaturated aliphatic carboxylic acid esters, alicyclic carboxylic acid esters, and aromatic carboxylic acids. Mention may be made of esters. Specific examples include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, toluyl Methyl acid, ethyl toluate, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate , Methyl ethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-octyl phthalate, diphenyl phthalate, etc. it can.

  Among these ester compounds, unsaturated aliphatic carboxylic acid esters such as methacrylic acid esters and maleic acid esters or aromatic carboxylic acid esters such as phthalic acid esters are preferred, and dialkyl esters of phthalic acid are particularly preferred.

The titanium compound (2), organosilicon compound (1), inorganic solid (5) and ester compound (4) are preferably used after being dissolved, diluted or swollen in a suitable solvent.
Such solvents include aliphatic hydrocarbons such as hexane, heptane, octane and decane, aromatic hydrocarbons such as toluene and xylene, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decalin, diethyl ether, dibutyl ether, di- Examples include ether compounds such as isoamyl ether and tetrahydrofuran. Among these, it is preferable to use a solvent in which the inorganic solid (5) is uniformly dispersed. Particularly preferred is toluene.

The reduction reaction temperature is usually in the temperature range of −50 to 70 ° C., preferably −30 to 50 ° C., particularly preferably −25 to 35 ° C.
The reaction time is not particularly limited, but is usually about 30 minutes to 6 hours. Thereafter, a post reaction may be performed at a temperature of 20 to 120 ° C.

The amount of the organosilicon compound (1) used is the atomic ratio of silicon atoms to titanium atoms in the titanium compound (2), usually Si / Ti = 1 to 500, preferably 1 to 300, particularly preferably 3 to 100. Range.
The amount of the organic magnesium compound (3) used is usually (Ti + Si) /Mg=0.1-10, preferably 0.2-5.0, in terms of the atomic ratio of the sum of titanium atoms and silicon atoms and magnesium atoms. Especially preferably, it is the range of 0.5-2.0.
Titanium compound (2) and organosilicon compound (1) so that the molar ratio of Mg / Ti in the solid catalyst component (A) is in the range of 1 to 51, preferably 2 to 31, particularly preferably 4 to 26. The amount of the organomagnesium compound (3) used may be determined.
The amount of the inorganic solid (5) used is usually (inorganic solid (g)) / (titanium atom (mmol) in the titanium compound) = 0.05 as the weight with respect to the number of moles of titanium atoms in the titanium compound (2). It is -10000g / mmol, Preferably it is 0.1-5000g / mmol, More preferably, it is the range of 0.5-2000g / mmol.
Moreover, the usage-amount of the ester compound (4) of arbitrary components is a molar ratio of the ester compound with respect to the titanium atom of a titanium compound (2), and usually ester compound / Ti = 0.5-100, Preferably it is 1-60, Especially Preferably it is the range of 2-30.

  The solid product obtained by the reduction reaction is usually separated into solid and liquid and washed several times with an inert hydrocarbon solvent such as hexane and heptane or an inert aromatic hydrocarbon such as toluene.

  The solid product (a) is used for preparing a solid catalyst component for olefin polymerization in which an inorganic solid is finely dispersed in an olefin polymer. As such a solid catalyst component for olefin polymerization, a catalyst component for olefin polymerization obtained by contacting the solid product (a) with a halogen compound (b) having halogenation ability and an electron donating compound (c). Is mentioned.

(B) Halogen compound having a halogenating ability The halogen compound (b) having a halogenating ability is not particularly limited as long as it is a compound capable of halogenating the solid product (a), but is preferably an organic acid halide. (B1), Group 4 element halogen compound (b2), or Group 13 or Group 14 element halogen compound (b3).

  As the organic acid halide (b1), mono- or polyvalent carboxylic acid halides are preferably used, and examples thereof include aliphatic carboxylic acid halides, alicyclic carboxylic acid halides, and aromatic carboxylic acid halides. Specific examples include acetyl chloride, propionic acid chloride, butyric acid chloride, valeric acid chloride, acrylic acid chloride, methacrylic acid chloride, benzoic acid chloride, toluic acid chloride, anisic acid chloride, succinic acid chloride, malonic acid chloride, maleic acid chloride. Itaconic acid chloride, phthalic acid chloride and the like.

  Of these organic acid halides, aromatic carboxylic acid chlorides such as benzoic acid chloride, toluic acid chloride, and phthalic acid chloride are preferred, aromatic dicarboxylic acid dichlorides are more preferred, and phthalic acid chloride is particularly preferred.

The halogen compound (b2) of the Group 4 element is preferably a halogen compound of titanium, more preferably a general formula Ti (OR ⁹ ) _b X ⁴ _4-b (wherein R ⁹ has 1 to 20 carbon atoms) X ⁴ represents a halogen atom, and b represents a number satisfying 0 ≦ b <4.)

Specific examples of R ⁹ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, amyl group, isoamyl group, tert-amyl group, hexyl group, heptyl group, octyl group. And an alkyl group such as a decyl group and a dodecyl group, an aryl group such as a phenyl group, a cresyl group, a xylyl group and a naphthyl group, an allyl group such as a propenyl group, and an aralkyl group such as a benzyl group. Among these, an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms is preferable. A linear alkyl group having 2 to 18 carbon atoms is particularly preferable. It is also possible to use titanium compounds having two or more different OR ⁹ groups.
Examples of the halogen atom represented by X ⁴ include a chlorine atom, a bromine atom, and an iodine atom. Of these, a chlorine atom gives particularly favorable results.
In the titanium compound represented by the general formula Ti (OR ⁹ ) _b X ⁴ _4-b , b is a number satisfying 0 ≦ b <4, preferably a number satisfying 0 ≦ b ≦ 2, Preferably b = 0.

Specific examples of titanium compounds represented by the general formula Ti (OR ⁹ ) _b X _4-b include titanium tetrachlorides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide, and methoxy titanium trichloride. , Ethoxytitanium trichloride, butoxytitanium trichloride, phenoxytitanium trichloride, trihalogenated alkoxy titanium such as ethoxytitanium tribromide, dimethoxytitanium dichloride, diethoxytitanium dichloride, dibutoxytitanium dichloride, diphenoxytitanium dichloride, diethoxytitanium Dihalogenated dialkoxytitanium such as dibromide can be mentioned, and titanium tetrachloride is most preferred.

The group 13 or group 14 halogen compound (b3) is a compound having at least one group 13 element-halogen bond, or a compound having at least one group 14 element-halogen bond, and has the general formula MR ²⁷ _mn X ⁶ _n (wherein M represents a Group 13 or Group 14 atom, R ²⁷ represents a hydrocarbon group having 1 to 20 carbon atoms, X ⁶ represents a halogen atom, and m represents a valence of M). n is preferably a compound represented by the following formula: 0 <n ≦ m.
Examples of Group 13 atoms include B, Al, Ga, In, and Tl. B or Al is preferable, and Al is more preferable. Examples of the Group 14 atom include C, Si, Ge, Sn, and Pb, and Si, Ge, or Sn is preferable. M is particularly preferably a Group 14 atom, and most preferably Si.

m is the valence of M. For example, when M is Si, m = 4. n represents a number satisfying 0 <n ≦ m. When M is Si, n is preferably 3 or 4.
Examples of the halogen atom represented by X ⁶ include F, Cl, Br, and I, and Cl is preferred.

Specific examples of R ²⁷ include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group and the like. Examples thereof include aryl groups such as alkyl groups, phenyl groups, tolyl groups, cresyl groups, xylyl groups, and naphthyl groups, cycloalkyl groups such as cyclohexyl groups and cyclopentyl groups, allyl groups such as propenyl groups, and aralkyl groups such as benzyl groups. . Preferred R ²⁷ is an alkyl group or an aryl group, and particularly preferred R ²⁷ is a methyl group, an ethyl group, a normal propyl group, a phenyl group or a paratolyl group.

  Specific examples of Group 13 element halogen compounds include trichloroboron, methyldichloroboron, ethyldichloroboron, phenyldichloroboron, cyclohexyldichloroboron, dimethylchloroboron, methylethylchloroboron, trichloroaluminum, methyldichloroaluminum, ethyldichloro. Aluminum, phenyldichloroaluminum, cyclohexyldichloroaluminum, dimethylchloroaluminum, diethylchloroaluminum, methylethylchloroaluminum, ethylaluminum sesquichloride, gallium chloride, gallium dichloride, trichlorogallium, methyldichlorogallium, ethyldichlorogallium, phenyldichlorogallium, cyclohexyl Dichlorogallium, dimethylchlorogalli , Methyl ethyl chlorogallium, indium chloride, indium trichloride, methyl indium dichloride, phenyl indium dichloride, dimethyl indium chloride, thallium chloride, thallium trichloride, methyl thallium dichloride, phenyl thallium dichloride, dimethyl thallium chloride, etc. Also included are compounds in which chloro in the compound name is changed to fluoro, bromo, or iodo.

  Specific examples of Group 14 element halogen compounds include tetrachloromethane, trichloromethane, dichloromethane, monochloromethane, 1,1,1-trichloroethane, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2, 2-tetrachloroethane, tetrachlorosilane, trichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, normal propyltrichlorosilane, normal butyltrichlorosilane, phenyltrichlorosilane, benzyltrichlorosilane, paratolyltrichlorosilane, cyclohexyltrichlorosilane, dichlorosilane, methyl Dichlorosilane, ethyldichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, methylethyldichlorosilane, monochlorosilane, trimethylchloro Run, triphenylchlorosilane, tetrachlorogermane, trichlorogermane, methyltrichlorogermane, ethyltrichlorogermane, phenyltrichlorogermane, dichlorogermane, dimethyldichlorogermane, diethyldichlorogermane, diphenyldichlorogermane, monocrologermane, trimethylchlorogermane, triethylchlorogermane , Trinormalbutylchlorogermane, tetrachlorotin, methyltrichlorotin, normalbutyltrichlorotin, dimethyldichlorotin, dinormalbutyldichlorotin, diisobutyldichlorotin, diphenyldichlorotin, divinyldichlorotin, methyltrichlorotin, phenyltrichlorotin, Examples include dichlorolead, methylchlorolead, and phenylchlorolead. B, bromo or compound is changed to iodine, it is also included.

  As the group 13 or group 14 element halogen compound, tetrachlorosilane, phenyltrichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, normal propyltrichlorosilane, or paratolyltrichlorosilane is particularly preferable from the viewpoint of polymerization activity.

(C) Electron-donating compound As the electron-donating compound used for the preparation of the solid catalyst component, ethers (diethers), ketones, aldehydes, carboxylic acids, organic acid or inorganic acid esters, organic Examples thereof include oxygen-containing electron donating compounds such as acid amides and acid anhydrides of acids or inorganic acids, and nitrogen-containing electron donating compounds such as ammonia, amines, nitriles and isocyanates. Of these electron donating compounds, organic acid esters or ethers are preferred, carboxylic acid esters or diethers are more preferred, and carboxylic acid esters are more preferred.

  Examples of the carboxylic acid esters include mono- and polyvalent carboxylic acid esters, and examples thereof include saturated aliphatic carboxylic acid esters, unsaturated aliphatic carboxylic acid esters, alicyclic carboxylic acid esters, and aromatic carboxylic acid esters. There may be mentioned acid esters. Specific examples include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, methyl toluate, toluyl Ethyl acetate, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl phthalate Examples thereof include ethyl, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-octyl phthalate, and diphenyl phthalate.

  Of these carboxylic acid esters, unsaturated aliphatic carboxylic acid esters such as methacrylic acid esters and maleic acid esters or aromatic carboxylic acid esters such as benzoic acid esters and phthalic acid esters are preferably used. Particularly preferred are aromatic polycarboxylic esters, and most preferred are dialkyl phthalates.

（但し、Ｒ⁵ 〜Ｒ⁸ はそれぞれ独立に炭素原子数１〜２０の直鎖状、分岐状もしくは脂環式のアルキル基、アリール基またはアラルキル基であり、Ｒ⁶ およびＲ⁷ はそれぞれ独立に水素原子であってもよい。）で表されるジエーテル化合物を挙げることができる。 Preferred examples of diethers are preferably those of the general formula

(However, R ^{5 to} R ⁸ are each independently a linear, branched or alicyclic alkyl group, aryl group or aralkyl group having 1 to 20 carbon atoms, and R ⁶ and R ⁷ are each independently It may be a hydrogen atom.).

Specific examples include 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2-isopropyl-2-3,7-dimethyloctyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2 , 2-dicyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3- Dimethoxypropane, 2-isopropyl-2-cyclohexyl-1,3-dimethoxy Examples include propane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2-heptyl-2-pentyl-1,3-dimethoxypropane, and the like. it can.
Preferably, R ^{5 to} R ⁸ are each independently an alkyl group, more preferably R ⁶ and R ⁷ are each independently a branched or alicyclic alkyl group, and R ⁵ and R ⁸ are each independently Is a diether represented by the above general formula, which is a linear alkyl group.

(A) Solid catalyst component The solid catalyst component (A) for olefin polymerization is obtained by contacting the solid product (a) with a halogen compound (b) having a halogenation ability and an electron donating compound (c). Obtained.

  The contact treatment can be performed by any known method such as a slurry method or a mechanical pulverization means such as a ball mill that can contact each component. However, when mechanical pulverization is performed, a large amount of fine powder is generated in the solid catalyst component, The particle size distribution may be wide, which is not preferable from an industrial viewpoint. Therefore, it is preferable to contact both in the presence of a diluent.

  Moreover, although the next process can be performed as it is after the process, it is preferable to perform a cleaning operation with a cleaning agent in order to remove surplus. The cleaning operation with the cleaning agent is performed any number of times and is usually 2-3 times.

The cleaning agent is preferably inert to the component to be treated, such as aliphatic hydrocarbons such as pentane, hexane, heptane and octane, aromatic hydrocarbons such as benzene, toluene and xylene, cyclohexane and cyclopentane. Halogenated hydrocarbons such as alicyclic hydrocarbons, 1,2-dichloroethane, and monochlorobenzene can be used.
The amount of the cleaning agent used is usually 0.1 to 1000 ml per 1 g of the solid product (a) per one-step contact treatment. The amount is preferably 1 ml to 100 ml per 1 g.

The treatment and / or washing temperature is usually −50 to 150 ° C., preferably 0 to 140 ° C., more preferably 60 to 135 ° C.
Although there is no restriction | limiting in particular in processing time, Preferably it is 0.5 to 8 hours, More preferably, it is 1 to 6 hours. Although the washing time is not particularly limited, it is preferably 1 to 120 minutes, and more preferably 2 to 60 minutes.
A plurality of contact treatments may be repeated.

  The amount of the halogen compound (b) having a halogenating ability is usually 1 to 2000 mol, preferably 5 to 1000 mol, more preferably 10 to 800 mol, per mol of titanium atom in the solid product (a). .

  The amount of the electron donating compound (c) used is usually 0.1 to 50 mol, preferably 0.3 to 30 mol, more preferably 0.5 to 20 mol per mol of titanium atom in the solid product (a). It is.

  In the case where contact treatment is performed using each compound over a plurality of times, or when a plurality of types of compounds are used as each compound, each of the compounds (b) and (c) described above is used. The amount of use represents the amount of use for each type and for each type.

  The solid catalyst component obtained by the above-mentioned method is usually used for polymerization after solid-liquid separation and washing several times with an inert hydrocarbon solvent such as hexane and heptane. After solid-liquid separation, wash with a large amount of halogenated hydrocarbon solvent such as monochlorobenzene or aromatic hydrocarbon solvent such as toluene at least once at a temperature of 50 to 120 ° C. and then with an aliphatic hydrocarbon solvent such as hexane. After repeated washing, it is preferable to use for polymerization in view of catalytic activity and stereoregular polymerization ability.

  Using the obtained solid catalyst component, an olefin polymerization catalyst used for producing the olefin polymer composition of the present invention in which inorganic solids are uniformly finely dispersed is prepared. Such an olefin polymerization catalyst is an olefin polymerization catalyst obtained by contacting the solid catalyst component (A), the organoaluminum compound (B) and the electron donating compound (C).

(B) Organoaluminum compound The organoaluminum compound (B) used for the preparation of the catalyst has at least one Al-carbon bond in the molecule. A typical one is shown in the following general formula.
R ¹⁹ _w AlY _3-w
R ²⁰ R ²¹ Al—O—AlR ²² R ²³
(Wherein R ^{19 to} R ²³ represent a hydrocarbon group having 1 to 20 carbon atoms, Y represents a halogen atom, a hydrogen atom or an alkoxy group, and w is a number satisfying 2 ≦ w ≦ 3.)
Specific examples of such organoaluminum compounds include trialkylaluminum such as triethylaluminum, triisobutylaluminum, and trihexylaluminum, dialkylaluminum hydride such as diethylaluminum hydride and diisobutylaluminum hydride, dialkylaluminum halide such as diethylaluminum chloride, and triethylaluminum. Examples thereof include a mixture of a trialkylaluminum and a dialkylaluminum halide such as a mixture of benzene and diethylaluminum chloride, and an alkylalumoxane such as tetraethyldialumoxane and tetrabutyldialumoxane.

  Of these organoaluminum compounds, trialkylaluminum, a mixture of trialkylaluminum and dialkylaluminum halide, and alkylalumoxane are preferred, and in particular, triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride, and tetraethyldiammonium. Xane is preferred.

(C) Electron-donating compound As the electron-donating compound (C) used for the preparation of the catalyst, ethers (diethers), ketones, aldehydes, carboxylic acids, organic acid or inorganic acid esters, organic Examples thereof include oxygen-containing electron donating compounds such as acid amides and acid anhydrides of acids or inorganic acids, and nitrogen-containing electron donating compounds such as ammonia, amines, nitriles and isocyanates. Among these electron donating compounds, esters of inorganic acids or diethers are preferable, and more preferably a general formula R ³ _r Si (OR ⁴ ) _4-r (wherein R ³ represents 1 to 1 carbon atoms) 20 represents a hydrocarbon group or a hydrogen atom, R ⁴ represents a hydrocarbon group having 1 to 20 carbon atoms, and r represents a number satisfying 0 ≦ r <4 All R ³ and all R ⁴ May be the same or different. The alkoxysilicon compound represented by general formula R ²⁴ R ²⁵ Si (OR ²⁶ ) ₂ is particularly preferably used. . Here, in the formula, R ²⁴ is a hydrocarbon group having 3 to 20 carbon atoms in which the carbon atom adjacent to Si is secondary or tertiary, specifically, an isopropyl group, a sec-butyl group, a tert- Examples include branched alkyl groups such as butyl group and tert-amyl group, cycloalkyl groups such as cyclobutyl group, cyclopentyl group, and cyclohexyl group, cycloalkenyl groups such as cyclopentenyl group, and aryl groups such as phenyl group and tolyl group. It is done. In the formula, R ²⁵ is a hydrocarbon group having 1 to 20 carbon atoms, specifically, a linear alkyl group such as methyl group, ethyl group, propyl group, butyl group, pentyl group, isopropyl group, such as a branched alkyl group such as sec-butyl group, tert-butyl group, tert-amyl group, cycloalkyl group such as cyclopentyl group, cyclohexyl group, cycloalkenyl group such as cyclopentenyl group, phenyl group, tolyl group, etc. An aryl group etc. are mentioned. Further, in the formula, R ²⁶ is a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 5 carbon atoms.

Specific examples of the alkoxysilicon compound used as the electron donating compound (C) include diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxy. Silane, tert-butyl-n-propyldimethoxysilane, tert-butyl-n-butyldimethoxysilane, tert-amylmethyldimethoxysilane, tert-amylethyldimethoxysilane, tert-amyl-n-propyldimethoxysilane, tert-amyl- n-butyldimethoxysilane, isobutylisopropyldimethoxysilane, tert-butylisopropyldimethoxysilane, dicyclobutyldimethoxysilane, cyclobutyl Sopropyldimethoxysilane, cyclobutylisobutyldimethoxysilane, cyclobutyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclopentyl-tert-butyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane Cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, cyclohexyl-tert-butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethyl Xysilane, phenylisopropyldimethoxysilane, phenylisobutyldimethoxysilane, phenyl-tert-butyldimethoxysilane, phenylcyclopentyldimethoxysilane, diisopropyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldiethoxysilane, tert-butylmethyldiethoxy Silane, tert-butylethyldiethoxysilane, tert-butyl-n-propyldiethoxysilane, tert-butyl-n-butyldiethoxysilane, tert-amylmethyldiethoxysilane, tert-amylethyldiethoxysilane, tert- Amyl-n-propyldiethoxysilane, tert-amyl-n-butyldiethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyl Rudiethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldiethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, 2
-Norbornane methyldimethoxysilane etc. can be mentioned.

[Production of olefin polymer]
The olefin used for the production of the olefin polymer of the present invention is an olefin having 2 or more carbon atoms, and specific examples of such olefin include ethylene, propylene, butene-1, pentene-1, hexene-1, and heptene-1. , Linear monoolefins such as octene-1 and decene-1, branched monoolefins such as 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1, and vinylcyclohexane. It is done. One type of these olefins may be used, or two or more types may be used in combination. Among these olefins, it is preferable to perform homopolymerization using ethylene, propylene or butene-1, or to perform copolymerization using a mixed olefin containing ethylene, propylene or butene-1 as a main component. It is particularly preferable to carry out homopolymerization using styrene or to carry out copolymerization using a mixed olefin mainly composed of propylene. In the copolymerization in the present invention, two or more kinds of olefins selected from ethylene and the above α-olefin can be mixed and used. Furthermore, a compound having a polyunsaturated bond such as a conjugated diene or a non-conjugated diene can be used for the copolymerization. And heteroblock copolymerization which superposes | polymerizes in 2 steps or more can also be performed.

The catalyst is an olefin polymerization catalyst obtained by contacting the solid catalyst component (A), the organoaluminum (B), and the electron donating compound (C). The contact here may be any means as long as the catalyst components (A) to (C) are in contact with each other and a catalyst is formed. The components (A) to (D) may be diluted with a solvent in advance or not. A method of mixing and contacting (C), a method of separately supplying them to the polymerization tank and contacting them in the polymerization tank, and the like can be employed.
As a method for supplying each catalyst component or catalyst to the polymerization tank, it is preferable to supply the catalyst component or catalyst in an inert gas such as nitrogen or argon in the absence of moisture.

  Although the olefin polymerization is performed in the presence of the catalyst, the prepolymerization described below may be performed before such polymerization (main polymerization).

  The prepolymerization is usually carried out by supplying a small amount of olefin in the presence of the solid catalyst component (A) and the organoaluminum compound (B), and is preferably carried out in a slurry state. Examples of the solvent used for the slurry include inert hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, and toluene. Further, when slurrying, a liquid olefin can be used instead of a part or all of the inert hydrocarbon solvent.

  The amount of the organoaluminum compound used in the prepolymerization can be selected within a wide range, usually 0.5 to 700 mol, per mol of titanium atom in the solid catalyst component, preferably 0.8 to 500 mol. -200 mol is particularly preferred.

  The amount of olefin to be prepolymerized is usually 0.01 to 1000 g, preferably 0.05 to 500 g, particularly preferably 0.1 to 200 g, per 1 g of the solid catalyst component.

The slurry concentration during the prepolymerization is preferably 1 to 500 g-solid catalyst component / liter-solvent, and more preferably 3 to 300 g-solid catalyst component / liter-solvent. The prepolymerization temperature is preferably -20 to 100 ° C, particularly preferably 0 to 80 ° C. The partial pressure of the olefin in the gas phase portion in the prepolymerization is preferably 0.01~20kg / cm ^2, especially 0.1 to 10 / cm ² is preferred, the pressure in the prepolymerization, in liquid at a temperature This is not the case for certain olefins. Further, the prepolymerization time is not particularly limited, but usually 2 minutes to 15 hours is preferable.

  As a method of supplying the solid catalyst component (A), the organoaluminum compound (B), and the olefin when carrying out the prepolymerization, the olefin after the solid catalyst component (A) and the organoaluminum compound (B) are brought into contact with each other is used. Any method may be used, such as a method for supplying the organic aluminum compound (B) after the solid catalyst component (A) and the olefin are brought into contact with each other. In addition, as a method for supplying olefin, either a method of sequentially supplying olefin while maintaining the inside of the polymerization tank at a predetermined pressure, or a method of supplying all the predetermined amount of olefin first is used. good. It is also possible to add a chain transfer agent such as hydrogen in order to adjust the molecular weight of the resulting polymer.

  Further, when the solid catalyst component (A) is prepolymerized with a small amount of olefin in the presence of the organoaluminum compound (B), an electron donating compound (C) may coexist as necessary. The electron donating compound used is a part or all of the electron donating compound (C). The amount used is usually 0.01 to 400 mol, preferably 0.02 to 200 mol, particularly preferably 0.03 to 100 mol, per 1 mol of titanium atoms contained in the solid catalyst component (A). Yes, with respect to the organoaluminum compound (B), it is usually 0.003 to 5 mol, preferably 0.005 to 3 mol, and particularly preferably 0.01 to 2 mol.

  The method for supplying the electron donating compound (C) during the preliminary polymerization is not particularly limited, and may be supplied separately from the organoaluminum compound (A) or may be supplied in contact with the organic aluminum compound (A). Further, the olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization.

  Olefin obtained by contacting the aforementioned solid catalyst component (A), organoaluminum compound (B) and electron donating compound (C) after prepolymerization as described above or without prepolymerization The main polymerization of the olefin can be carried out in the presence of a polymerization catalyst.

  The amount of the organoaluminum compound used in the main polymerization can be selected in a wide range such as 1 to 1000 mol per 1 mol of the titanium atom in the solid catalyst component (A), but a range of 5 to 600 mol is particularly preferable. .

  The electron donating compound (C) used in the main polymerization is usually 0.1 to 2000 mol, preferably 0.3 to 1000 mol, per 1 mol of titanium atom contained in the solid catalyst component (A). Particularly preferably, the amount is from 0.5 to 800 mol, and is usually from 0.001 to 5 mol, preferably from 0.005 to 3 mol, particularly preferably from 0.01 to 1 mol, based on the organoaluminum compound.

Although this superposition | polymerization can be implemented over -30-300 degreeC normally, 20-180 degreeC is preferable. Although there is no restriction | limiting in particular about the superposition | polymerization pressure, Generally the pressure of a normal pressure-100 kg / cm < ² >, Preferably about 2-50 kg / cm < ² > is employ | adopted from the point of being industrial and economical. As the polymerization method, either batch type or continuous type is possible. Further, slurry polymerization or solution polymerization using an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane, and octane, and bulk polymerization or gas phase polymerization using a liquid olefin as a medium at the polymerization temperature are also possible.

  During the main polymerization, a chain transfer agent such as hydrogen can be added to adjust the molecular weight of the polymer.

  In the polymer composition of the present invention, additives such as an antioxidant, a pigment, an antistatic agent, a copper damage inhibitor, a foaming agent, a plasticizer, and a crosslinking agent can be blended in addition to the above basic components.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not specifically limited by the following examples. In Examples and Comparative Examples, evaluation methods for various physical properties of polymers are as follows.

(1) Intrinsic viscosity ([η]):
Tetralin was used as a solvent, and the temperature was measured at 135 ° C using an Ubbelohde viscometer.

(2) Haze (haze):
According to the method defined in JIS K7105. The test piece is a film having a thickness of 30 to 80 microns, produced by press-molding the polymer composition at 190 ° C.

(ｉ＝１からｎまで；ｎ＝粒子数)
＜比較例２の場合＞
混練により得られた成形片を−８０℃に冷却したミクロトームで切削して厚さ１０００オングストローム以下の超薄切片を作成し、成形片中の無機固体の分散状態を上記と同様に観察した。両場合とも、観察倍率は６０，０００倍である。 (3) Inorganic solid dispersed particle size in the polymer composition:
<In the case of Example 1>
The obtained powder particles were embedded in an epoxy polymer, and then this specimen was cut with a microtome cooled to −80 ° C. to prepare an ultrathin section having a thickness of 1000 Å or less. The dispersion state of the inorganic solid in the ultrathin slice was observed with a transmission electron microscope (H-8000 transmission electron microscope manufactured by Hitachi, Ltd.), and the two-dimensional image was obtained from the high-accuracy image analysis software “IP-” manufactured by Asahi Engineering. The image analysis process shown below was performed at 1000 "to determine the inorganic solid volume average dispersed particle size (inorganic solid dispersed particle size in the polymer composition).
The area of the inorganic solid dispersed particles i in the two-dimensional image was detected. The diameter of the circle giving the area is Ri, and Ri is substituted into the following equation.

(i = 1 to n; n = number of particles)
<In the case of Comparative Example 2>
The molded piece obtained by kneading was cut with a microtome cooled to −80 ° C. to prepare an ultrathin section having a thickness of 1000 angstroms or less, and the dispersion state of the inorganic solid in the molded piece was observed in the same manner as described above. In both cases, the observation magnification is 60,000 times.

(4) BET specific surface area:
Measured by nitrogen adsorption method. That is, molecules having a known adsorption occupation area were adsorbed on the surface of the sample powder, and the specific surface area of the sample was determined from the adsorption amount.

(5) Specific gravity:
Specific gravity with respect to water at 4 ° C. was measured using a Pycnometer PPY-6 manufactured by Cantachrome.

(6) Vibration suppression evaluation:
A press sheet having a thickness of 0.3 mm is prepared at 230 ° C. and cut into a size of 3 mm × 20 mm to obtain a test piece. Viscoelasticity was measured with Seiko Instruments Inc. EXSTER6000 at a measurement temperature of −150 to 150 ° C. and a frequency of 5 Hz. The larger the tan δ peak value, the better the damping performance.

[Example 1]
(1) Synthesis of solid product (a) After replacing a 200 ml flask equipped with a stirrer and a dropping funnel with nitrogen, 10 g of aluminum hydroxide previously slurried with 120 ml of hexane, of n-butylmagnesium chloride 25 ml of di-n-butyl ether solution (manufactured by Organic Synthesis Chemical Co., Ltd., n-butylmagnesium chloride concentration 2.1 mmol / ml) was mixed and stirred at room temperature for 1 hour. After the completion of stirring, solid-liquid separation was performed, and washing with 17 ml of hexane was repeated twice, followed by drying under reduced pressure to obtain pretreated aluminum hydroxide. The aluminum hydroxide used was obtained by hydrolyzing an aluminum alkoxide and drying the resulting product. The BET specific surface area was 153 m ² / g and the specific gravity was 3.00 g / c.
m ³ , primary particle diameter (BET specific surface area equivalent diameter) is 13 nm aluminum hydroxide.
Next, after replacing a 100 ml flask equipped with a stirrer and a dropping funnel with nitrogen, 7.5 g of pretreated aluminum hydroxide, 37.4 ml of hexane, 0.17 ml (0.5 mmol) of tetrabutoxy titanium, and 1.9 ml (8.5 mmol) of tetraethoxysilane was added to make a slurry liquid. Next, 4.3 ml of a di-n-butyl ether solution of n-butylmagnesium chloride (Organic Synthetic Chemical Co., Ltd., n-butylmagnesium chloride concentration 2.1 mmol / ml) was maintained while maintaining the temperature in the flask at 5 ° C. The solution was gradually dropped from the dropping funnel. After completion of dropping, the mixture was further stirred at 5 ° C. for 45 minutes, and then stirred at room temperature for another 45 minutes. Thereafter, solid-liquid separation was performed, and washing with 37.4 ml of hexane was repeated twice, and then 30.1 ml of toluene was added to obtain a solid product slurry.

(2) Synthesis of solid catalyst component After heating the solid product slurry obtained in (1) above to 95 ° C, 1.1 ml (4.1 mmol) of diisobutyl phthalate was added and contact treatment was performed for 1 hour. It was. Thereafter, solid-liquid separation was performed at the same temperature, and washing with 30.0 ml of toluene was performed twice at room temperature.
After washing, 30.0 ml of toluene was added, and a mixture of 0.9 ml (5.3 mmol) of di-n-butyl ether and 16.2 ml (147.7 mmol) of titanium tetrachloride was added, followed by contact treatment at 95 ° C. for 3 hours. Went. After the completion, solid-liquid separation was performed at the same temperature, followed by washing twice with 30.0 ml of toluene at the same temperature.
Subsequently, a mixture of 30.0 ml of toluene, 0.9 ml (5.3 mmol) of di-n-butyl ether and 16.2 ml (147.7 mmol) of titanium tetrachloride was added, and contact treatment was performed at 95 ° C. for 1 hour. . After the completion, solid-liquid separation was performed at the same temperature, followed by washing with 30.0 ml of toluene at the same temperature, followed by washing with 30.0 ml of hexane at room temperature three times, followed by drying under reduced pressure to obtain a solid catalyst. 10.1 g of component was obtained.

(3) Polymerization of propylene A 3 liter stirred stainless steel autoclave was replaced with argon and charged with 1000 ml of heptane, 2.6 mmol of triethylaluminum as component (B), and tert-butyl-n-propyl-dimethoxy as component (C) As the component (A), 0.26 mmol of silane and 1.495 g of the solid catalyst component synthesized in the above (2) were charged, and hydrogen corresponding to a partial pressure of 350 mmHg was added. Next, 94 g of liquefied propylene was charged, the temperature of the autoclave was raised to 60 ° C., and polymerization was carried out at 60 ° C. for 10 minutes. After the polymerization was completed, unreacted monomers were purged. The produced polymer was dried under reduced pressure at 70 ° C. for 2 hours to obtain 85 g of polypropylene powder.
Therefore, the yield of polypropylene per 1 g of the solid catalyst component was 57 g. The content of aluminum hydroxide in the obtained polymer is 14600 ppm by weight (calculated from the amount of aluminum hydroxide in the prepared catalyst and the weight ratio of the obtained polymer), and the dispersion state is observed with a transmission electron microscope. As a result, the dispersed particle diameter of aluminum hydroxide was 65.4 nm. θ was 5, and the dispersion particle diameter d of 88.9 wt% aluminum hydroxide in the polypropylene composition was 0.1 nm or more and 100 nm or less. The intrinsic viscosity of the polypropylene composition was [η] = 0.84 (dl / g), the tan δ peak intensity was 0.042, and the haze of the film of the composition was 74.7%.

[Comparative Example 1]
(1) Synthesis of solid product (a) After replacing a 500 ml flask equipped with a stirrer and a dropping funnel with nitrogen, 290 ml of hexane, 8.9 ml of tetrabutoxytitanium (8.9 g, 26.1 mmol), phthalate Diisobutyl acid 3.1 ml (3.3 g, 11.8 mmol) and tetraethoxysilane 87.4 ml (81.6 g, 392 mmol) were added to obtain a homogeneous solution. Next, 199 ml of a di-n-butyl ether solution of n-butylmagnesium chloride (Organic Synthetic Chemical Co., Ltd., n-butylmagnesium chloride concentration 2.1 mmol / ml) was added to the dropping funnel while maintaining the temperature in the flask at 6 ° C. It was dripped gradually from. After completion of the dropwise addition, the mixture was further stirred at 6 ° C. for 1 hour, and further stirred at room temperature for 1 hour. Thereafter, solid-liquid separation was performed, and washing was repeated three times with 260 ml of toluene, and then an appropriate amount of toluene was added to obtain a solid product slurry (0.4 g / ml).

(2) Synthesis of solid catalyst component 52 ml of the slurry containing the solid product obtained in the above (a) was added, 25.5 ml of the supernatant was taken out, 0.80 ml (6.45 mmol) of butyl ether and 16.4 titanium tetrachloride. A mixture of 0 ml (0.146 mol) was added, and then 1.6 ml of phthalic acid chloride (11.1 mmol: 0.20 ml / 1 g solid product) was added, and the mixture was heated to 115 ° C. and stirred for 3 hours. After completion of the reaction, the solid and liquid were separated at the same temperature, and then washed twice with 40 ml of toluene at the same temperature.
Then a mixture of 10.0 ml toluene, 0.45 ml (1.68 mmol) diisobutyl phthalate, 0.80 ml (6.45 mmol) butyl ether and 8.0 ml (0.073 mol) titanium tetrachloride was added and 115 The treatment was performed at 0 ° C. for 1 hour. After completion of the reaction, solid-liquid separation was performed at the same temperature, followed by washing with 40 ml of toluene three times at the same temperature, followed by washing with 40 ml of hexane three times and further drying under reduced pressure to obtain 7.36 g of a solid catalyst component.

(3) Polymerization of propylene A 3 liter stirred stainless steel autoclave was replaced with argon and charged with 1000 ml of heptane, 2.6 mmol of triethylaluminum as component (B), and tert-butyl-n-propyl-dimethoxy as component (C) 0.26 mmol of silane and 0.0273 g of the solid catalyst component synthesized in (2) above were charged as component (A), and hydrogen corresponding to a partial pressure of 1500 mmHg was added. Next, 80 g of liquefied propylene was charged, the temperature of the autoclave was raised to 70 ° C., and polymerization was performed at 70 ° C. for 60 minutes. After the polymerization was completed, unreacted monomers were purged. The produced polymer was dried under reduced pressure at 70 ° C. for 2 hours to obtain 138 g of polypropylene powder.
Therefore, the yield of polypropylene per 1 g of the solid catalyst component was 5062 g. The intrinsic viscosity of the obtained polypropylene was [η] = 0.86 (dl / g), and the tan δ peak intensity was 0.029. The haze of the polypropylene film was 74.3%.

[Comparative Example 2]
Using a roll kneader, aluminum hydroxide was added to the polypropylene of Comparative Example 1 so as to have a concentration of 14000 ppm by weight and kneaded. The aluminum hydroxide used is the same as in Example 1. The kneading temperature is 190 ° C., and the kneading time is 3 minutes. As a result of observing the dispersion state of aluminum hydroxide in the polymer composition with a transmission electron microscope, it was confirmed that the dispersion particle diameter of aluminum hydroxide was 1258 nm, and a large number of primary particles were aggregated. θ was 97, and the dispersion particle size d of 0.065 wt% aluminum hydroxide in the polypropylene composition was 0.1 nm or more and 100 nm or less. The intrinsic viscosity of the polypropylene composition was [η] = 0.86 (dl / g), the tan δ peak intensity was 0.029, and the haze of the film of the composition was 74.4%.

Claims (5)

In the presence of an organosilicon compound (1) having a Si—O bond and an inorganic solid (5) having a primary particle size of 0.1 nm to 300 nm, the titanium compound (2) is reduced with the organomagnesium compound (3). Solid catalyst component for olefin polymerization (A), organoaluminum compound (B), obtained by contacting the resulting solid product with a halogenated halogen compound (b) and an electron donating compound (c), and An olefin polymer composition produced using an olefin polymerization catalyst obtained by contacting the electron donating compound (C),
The inorganic solid is layered aluminum hydroxide , the electron donating compound (c) is an organic acid ester or ether, and the electron donating compound (C) is represented by the following general formula (I). The agglomeration degree θ of the inorganic solid is 0 <θ ≦ 10 (where θ is a value obtained by d ÷ D, where d is an inorganic content in the olefin polymer composition). Represents a solid dispersed particle diameter, and D represents a primary particle diameter of an inorganic solid used for inclusion in the olefin polymer.) In a state satisfying the condition, the inorganic solid is dispersed in the olefin polymer composition. The olefin polymer composition.

R ³ _r Si (OR ⁴ ) _4-r (I)

(Wherein R ³ represents a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, R ⁴ represents a hydrocarbon group having 1 to 20 carbon atoms, and r is a number satisfying 0 ≦ r <4. All R ³ and all R ⁴ may be the same or different.)   The olefin polymer composition according to claim 1, wherein the content of the inorganic solid contained in the olefin polymer composition is 0.001 wt% or more and 50 wt% or less.   The olefin polymer composition according to claim 1 or 2, wherein the primary particle diameter D is from 0.1 nm to 300 nm.   The olefin polymer composition according to any one of claims 1 to 3, wherein the dispersed particle diameter d of 70% or more of the inorganic solid in the olefin polymer composition is 0.1 nm to 100 nm.   The olefin polymer composition according to claim 1, wherein the olefin polymer is an ethylene or α-olefin polymer.