JP5116716B2 - Inorganic reinforcement compounding resin composition - Google Patents

Description

  The present invention relates to a resin composition for molding an inorganic reinforcing material. More specifically, the present invention relates to a resin composition for molding an inorganic reinforcing material that has excellent mechanical properties such as impact resistance, tensile properties, and bending properties.

  Thermoplastic resins or thermosetting resins such as polycarbonate resin, thermoplastic polyester resin, ABS resin, polyacetal resin, polyamide resin, polyphenylene oxide resin, polyimide resin, epoxy resin, thermosetting unsaturated polyester resin and phenol resin have a melting point Alternatively, since it has a high softening point and excellent mechanical properties, it is widely used in various industrial fields such as the automobile industry, the electric and electronic industries.

In order to increase the rigidity and heat resistance of these thermoplastic resins or thermosetting resins,
Inorganic reinforcing materials such as carbon fibers are blended.
However, when an inorganic reinforcing material is blended, there is a problem that high impact resistance of the thermoplastic resin or thermosetting resin is impaired.

  Therefore, in order to eliminate the problems caused by the blending of the inorganic reinforcing material, blending an olefin wax having a carboxyl group and / or a derivative group thereof (Patent Documents 1 and 2), and further adding a composite rubber graft copolymer Compounding (Patent Document 2) is performed. However, although these methods improve the impact resistance, there are problems in that poor appearance occurs and the elastic modulus decreases.

JP-A-8-188708 JP 7-238213 A

  An object of the present invention is to give excellent mechanical properties and impact resistance to a thermoplastic resin composition in which an inorganic reinforcing material is blended with a thermoplastic resin or a thermosetting resin.

  The present inventors have blended a silicone-modified olefin wax with a thermoplastic resin composition in which an inorganic reinforcing material is blended with a thermoplastic resin or a thermosetting resin, thereby providing mechanical properties such as tensile properties and bending properties, resistance to resistance. The inventors have found that excellent physical properties such as impact properties can be obtained, and have completed the present invention. That is, the resin composition for molding an inorganic reinforcing material according to the present invention includes the following (1) to (6).

(1) (A) 95 to 50 parts by weight of at least one resin selected from the group consisting of thermoplastic resins and thermosetting resins;
(B) 5 to 50 parts by weight of an inorganic reinforcing material;
(C) 0.01 to 10 parts by weight of a silicone-modified olefin wax (provided that the total of component (A) and component (B) is 100 parts by weight)
A resin composition for molding an inorganic reinforcing material, characterized in that

(2) The resin composition for molding an inorganic reinforcing material according to (1), which has 0.05 to 7 parts by weight of the (C) silicone-modified olefin wax.
(3) The thermoplastic resin (A) is a polycarbonate resin, a thermoplastic polyester resin, an ABS resin, a polyacetal resin, a polyamide resin, a polyphenylene oxide resin, or a polyimide resin, and the thermosetting resin is an epoxy resin or a thermosetting resin. (1) or (2), the inorganic reinforcing material-containing resin composition for molding, wherein the resin composition is at least one resin selected from the group consisting of unsaturated polyester resins and phenol resins.

  (4) The inorganic reinforcing material blend according to any one of (1) to (3), wherein the (B) inorganic reinforcing material is at least one filler selected from glass fibers and carbon fibers. Molding resin composition.

(5) The (C) silicone-modified olefin wax is an unmodified olefin wax (D) satisfying the following (i) to (vi) and a hydrogen silicone having one or more SiH bonds per molecule. The resin composition for molding an inorganic reinforcing material according to any one of (1) to (4), wherein the resin composition is obtained by addition reaction in the presence of a catalyst.
(I) a copolymer obtained by copolymerizing ethylene and at least one diene, or at least one olefin selected from ethylene and an α-olefin having 3 to 12 carbon atoms and at least one diene. Copolymer obtained by copolymerization (ii) 0.5 to 3.0 unsaturated group content per molecule (iii) Density is 870 to 980 kg / m ³
(Iv) Melting point is 70-130 ° C
(V) Number average molecular weight (Mn) of 400 to 5,000
(Vi) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 4.0 or less.

(6) The (C) silicone-modified olefin wax is an unmodified olefin wax (D) satisfying the following (vii) to (xii) and a hydrogen silicone having one or more SiH bonds per molecule. The resin composition for molding an inorganic reinforcing material according to any one of (1) to (4), wherein the resin composition is obtained by addition reaction in the presence of a catalyst.
(Vii) From a copolymer obtained by copolymerizing ethylene and vinyl norbornene (5-vinylbicyclo [2.2.1] hept-2-ene), or ethylene and an α-olefin having 3 to 12 carbon atoms Copolymer (viii) obtained by copolymerizing at least one selected olefin and vinyl norbornene 0.5 to 2.0 unsaturated groups per molecule (ix) Density 890 to 980 kg / M ³
(X) Melting point is 80-130 ° C
(Xi) Number average molecular weight (Mn) is 400 to 5,000.
(Xii) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 4.0 or less

  The resin composition for molding an inorganic reinforcing material according to the present invention has an effect of blending (B) an inorganic reinforcing material with at least one resin selected from the group consisting of (A) a thermoplastic resin and a thermosetting resin. It has excellent impact resistance and mechanical properties by blending (C) a silicone-modified olefin wax while maintaining excellent rigidity and heat resistance.

Hereinafter, the present invention will be specifically described.
The present invention comprises (A) at least one resin selected from the group consisting of a thermoplastic resin and a thermosetting resin, (B) an inorganic reinforcing material, and (C) an inorganic reinforcing material containing a silicone-modified olefin wax. This is a molding resin composition.

(A) Thermoplastic resin and thermosetting resin (A) The thermoplastic resin and thermosetting resin used in the present invention are thermoplastic resins such as polycarbonate resin, thermoplastic polyester resin, ABS resin, polyacetal resin, polyamide resin, Polyphenylene oxide resin and polyimide resin, and the thermosetting resin is at least one resin selected from the group consisting of an epoxy resin, a thermosetting unsaturated polyester resin, and a phenol resin. That is, these (A) thermoplastic resins and thermosetting resins can be used alone or in combination of two or more.

  The definition and production method of these (A) thermoplastic resins or thermosetting resins are well known. For example, “Practical Plastic Encyclopedia” (edited by the Practical Plastic Encyclopedia Editorial Committee, published by Sangyo Kaisha) It is described in the thing.

The following resins (1) to (7) are thermoplastic resins.
(1) Polycarbonate resin Typically, it is a resin obtained by reacting an aromatic diol (for example, bisphenol A) and phosgene. In the present invention, diethylene glycol diallyl carbonate is preferred.

Such a polycarbonate resin is commercially available, and examples thereof include trade names such as NOVAREX (Mitsubishi Chemical Corporation), Panlite (Teijin Chemicals Co., Ltd.), Lexan (Japan GE Plastics Co., Ltd.), It can be preferably used in the present invention.

(2) Thermoplastic polyester resin Typically a resin obtained by polycondensation of dicarboxylic acid and diol. In the present invention, polyethylene terephthalate, polybutylene terephthalate, polyethylene 2,6-naphthalenedicarboxylate Polycyclohexane terephthalate and the like are preferably used.

Such thermoplastic polyester resins are commercially available, and examples thereof include trade name Rynite (Dyupon Japan Limited) and the like, and can be preferably used in the present invention.

(3) ABS resin Typically, it is an impact resistant resin obtained by graft polymerization of acrylonitrile and styrene to polybutadiene. In the present invention, the polybutadiene component is 5 to 40% by weight, and the styrene component and Those having an acrylonitrile component weight ratio (styrene / acrylonitrile) of 70/30 to 80/20 are preferred.

Such ABS resins are commercially available, and examples thereof include trade names such as Stylac (Asahi Kasei Kogyo Co., Ltd.) and Psycolac (Ube Saikon Co., Ltd.), and can be preferably used in the present invention.

(4) Polyacetal resin Typically, a resin obtained by ring-opening polymerization of formalin or trioxane together with ethylene oxide as desired in the presence of a cationic catalyst, and having a polyoxymethylene chain as the main skeleton However, in the present invention, the copolymer type is preferable.

  Such polyacetal resins are commercially available, and examples thereof include the trade name Iupital (Mitsubishi Engineering Plastics Co., Ltd.) and can be preferably used in the present invention.

(5) Polyamide resin Typically, it is a resin obtained by polycondensation of diamine and dicarboxylic acid or ring-opening polymerization of caprolactam. In the present invention, aliphatic diamine and aliphatic or aromatic dicarboxylic acid The polycondensation reaction product of is preferable.

Such polyamide resins are commercially available, for example, the product name Leona (Asahi Kasei Corporation)
), Zytel (Deyupon Japan Limited) and the like, and can be preferably used in the present invention.

(6) Polyphenylene oxide resin Typically, it is a resin obtained by oxidative coupling of 2,6-dimethylphenol in the presence of a copper catalyst. However, this resin may be blended with other resins. Modified polyphenylene oxide resin can also be used in the present invention.

In the present invention, a blend modified product of a styrenic polymer is preferred.
Such polyphenylene oxide resins are commercially available, and examples thereof include trade names such as Zylon (Asahi Kasei Kogyo Co., Ltd.) and Iupiace (Mitsubishi Engineering Plastics Co., Ltd.), and can be preferably used in the present invention. .

(7) Polyimide resin Typically, it is a resin obtained by polycondensation of tetracarboxylic acid and diamine to form an imide bond in the main skeleton, but in the present invention, from pyromellitic anhydride and diaminodiphenyl ether What is formed is preferred.

Such a polyimide resin is commercially available, and examples thereof include trade name Vespel (Dyupon Japan Limited) and the like, and can be preferably used in the present invention.
Resin (8)-(10) demonstrated below is a thermosetting resin, and demonstrates the thing of the state before thermosetting.

(8) Epoxy resin Typically, it is a resin obtained by reacting an aromatic diol (for example, bisphenol A) and epichlorohydrin in the presence of an alkali. In the present invention, bisphenol having an epoxy equivalent of 170 to 5000 is used. A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin are preferable.

  Such epoxy resins are commercially available, for example, trade names such as Epomic (Mitsui Petrochemical Co., Ltd.), Epicron (Dainippon Ink Chemical Co., Ltd.), Sumi Epoxy (Sumitomo Chemical Co., Ltd.), etc. Can be preferably used in the present invention.

(9) Thermosetting unsaturated polyester resin Typically, it is a resin obtained by esterifying an aliphatic unsaturated dicarboxylic acid and an aliphatic diol. In the present invention, maleic acid or fumaric acid is used. A resin obtained by esterifying an unsaturated dicarboxylic acid such as ethylene glycol and a diol such as diethylene glycol is preferred.

  Such thermosetting unsaturated polyester resins are commercially available, and examples thereof include trade names such as Rigolac (Showa High Polymer Co., Ltd.), Sumicon (Sumitomo Bakelite Co., Ltd.), and the like, which are preferably used in the present invention. Can do.

(10) Phenolic resin In the present invention, both so-called novolak type and resol type are included, but a novolak type cured with hexamethylenetetramine and a solid resol mainly composed of dimethylene ether bonds are preferable.

  Such a phenol resin is commercially available, and examples thereof include trade name Sumiko PM (Sumitomo Bakelite Co., Ltd.), Nikkaline (Nippon Synthetic Chemical Industry Co., Ltd.) and the like, and can be preferably used in the present invention. .

  In the present invention, a combination of polycarbonate resin, polybutylene terephthalate, which is one of thermoplastic polyester resins, and a combination of polycarbonate resin and ABS resin is preferable.

  The content of at least one resin selected from the group consisting of (A) a thermoplastic resin and a thermosetting resin in the resin composition of the present invention comprises (A) a thermoplastic resin and a thermosetting resin. It is 95 to 50 parts by weight, preferably 94 to 55 parts by weight, more preferably 93 to 60 parts by weight per 100 parts by weight in total of at least one resin selected from the group and (B) inorganic reinforcement component. Part by weight, particularly preferably 92 to 75 parts by weight. Within the above range, a molding resin composition having an excellent balance between surface properties and mechanical properties can be obtained.

(B) Inorganic reinforcing material The (B) inorganic reinforcing material used by this invention says at least 1 sort (s) selected from glass fiber, carbon fiber, and fillers. These (B) inorganic reinforcing materials can be used alone or in combination of two or more.

  The type of glass fiber is not particularly limited, and roving glass, chopped strand glass, milled glass, and the like can be used. These may be used alone or in combination of two or more.

  The length of the glass fiber may be broken when it is mixed with the resin with an extruder or the like, and is not particularly limited, but is preferably 0.3 mm to 10 mm, and preferably 2 mm to 7 mm from the viewpoint of workability. The length of the glass fiber in the composition of the present invention is 2 mm to 5 mm. Although the thickness of the glass fiber is not particularly limited, the average fiber diameter is 1 to 25 μm, preferably 5 to 17 μm. Further, the aspect ratio (average fiber length / fiber diameter) is preferably 25 or less, but glass fibers having different aspect ratios can be mixed and used at an appropriate ratio. There is no particular limitation on the cross-sectional shape of the glass fiber, and a circular shape, an eyebrows shape, a gourd shape, an ellipse shape, a cylindrical shape and the like can be used.

  Moreover, the glass fiber may be surface-treated with a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, or the like. Examples of the silane coupling agent herein include vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ -Glycidoxypropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxy Examples include silane and γ-chloropropyltrimethoxysilane.

  In addition, the glass fiber may be subjected to a bundling treatment with an olefin resin, a styrene resin, an acrylic resin, a polyester resin, an epoxy resin, a urethane resin, or the like. In this case, the olefin resin or urethane resin used for the bundling treatment is used in a range that does not affect the physical properties of the entire composition.

  Further, the glass fiber may be coated with a metal such as nickel, copper, cobalt, silver, aluminum, iron, or an alloy thereof by a plating method or a vapor deposition method.

  There are no particular restrictions on the shape and type of the carbon fiber, and the shape may be a chopped strand, a roving strand, a milled fiber, or the like, and the type may be either pitch-based or polyacrylonitrile-based.

  In addition to those obtained by spinning or molding these raw material compositions and then carbonizing them, it is also possible to use carbon fibers obtained basically without passing through a spinning step as in the vapor phase growth method.

When such vapor grown carbon fibers are used, the fiber diameter is small and the L / D is large, so that it is possible to obtain a molded product having high rigidity and good appearance.
Further, the carbon fiber of the present invention can be used with a specific surface area increased by performing an activation treatment.

These carbon fibers are preferably those surface-treated with a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, or the like.
Examples of the sizing agent include epoxy resins, urethane resins, olefin resins, styrene resins, polyester resins, nylon resins, and the like. Epoxy resins and urethane resins are preferred.

The fiber diameter is generally in the range of 6 to 18 μm, but in the present invention, the diameter is preferably 0.5 to 15 μm, particularly preferably 1 to 10 μm.
The cut length of the chopped strand used in the present invention is preferably 1 to 15 mm, more preferably 2 to 10 mm, and most preferably 3 to 8 mm. In addition, the chopped strand is crushed during the molding.

  The aspect ratio (L / D), which is the ratio between the length L of the carbon fiber in the fiber axis direction and the fiber diameter D in the resin composition, is preferably in the range of 15 to 100, and more preferably in the range of 20 to 50.

  Fillers include calcium carbonate, silica, kaolin, clay, titanium oxide, barium sulfate, zinc oxide, amorphous fillers such as aluminum hydroxide, alumina, magnesium hydroxide, plate shapes such as talc, mica, or glass flakes. A filler, wollastonite, potassium titanate, basic magnesium sulfate, sepiolite, zonotlite, acicular filler such as aluminum borate, conductive filler such as metal powder, metal flake, and carbon black are used. Other glass beads, glass powder, etc. are used. These fillers may be used alone or in combination, or those having a surface coated with carbon or silane coupling may be used alone or in combination.

  In the present invention, among these inorganic reinforcing materials, glass fibers and carbon fibers are preferably used, and glass fibers are particularly preferable from the viewpoint of affinity with the silicone-modified olefin wax.

  The content of the (B) inorganic reinforcing material in the resin composition of the present invention is at least one resin selected from the group consisting of (A) a thermoplastic resin and a thermosetting resin, and (B) an inorganic reinforcing material. It is 5 to 50 parts by weight, preferably 6 to 45 parts by weight, and more preferably 7 to 40 parts by weight per 100 parts by weight in total with the components. When the amount is less than 5 parts by weight, the effect of improving the mechanical properties cannot be sufficiently obtained. When the amount is more than 50 parts by weight, the appearance at the time of molding is affected.

(C) Silicone-modified olefin wax (C) Silicone-modified olefin wax is obtained by producing (D) an unmodified olefin wax and modifying it.

<(D) Unmodified olefin wax>
The (D) unmodified olefin wax of the present invention can be obtained, for example, by copolymerizing an olefin and a diene using a metallocene catalyst as described later.

(Olefin)
Examples of the olefin used in the production of the (D) unmodified olefin wax of the present invention include ethylene and α-olefins having 3 to 12 carbon atoms.

  Examples of the α-olefin having 3 to 12 carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 3-methyl-1. -Pentene, 1-octene, 1-decene, 1-dodecene and the like. Among these, preferably an α-olefin having 3 to 10 carbon atoms, more preferably an α-olefin having 3 to 8 carbon atoms, particularly preferably propylene, 1-butene, 1-hexene, 4-methyl-1- Penten is preferred.

(Dien)
(D) Dienes used for the production of unmodified olefin waxes include butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene (5- Vinylbicyclo [2.2.1] hept-2-ene), dicyclopentadiene, 2-methyl-1,4-hexadiene, 2-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene, etc. It is. Among these, vinyl norbornene, ethylidene norbornene, dicyclopentadiene, 1,4-hexadiene, butadiene, isoprene, 2-methyl-1,4-hexadiene or 2-methyl-1,6-octadiene is preferable. Norbornene is particularly preferable because it has a bulky skeleton, so that the wax can be hardened even at a low density, and the wax product is hardly blocked.

  (D) Unmodified olefin wax is obtained by copolymerizing olefin and diene as described above, but is a copolymer of ethylene and diene, or ethylene and α-olefin having 3 to 12 carbon atoms. It is preferably a copolymer of at least one α-olefin and diene selected from: As the diene, vinyl norbornene (5-vinylbicyclo [2.2.1] hept-2-ene) is preferable.

  The (D) unmodified olefin wax used in the present invention contains a constituent unit derived from a diene in a proportion of 0.01 to 6.0 mol%, preferably 0.1 to 4.0 mol%. desirable. When (D) the unmodified olefin wax contains a structural unit derived from an α-olefin having 3 to 12 carbon atoms, the content is 0.01 to 15 mol%, preferably 0.1. -12 mol% is desirable.

When the (D) unmodified olefin wax used in the present invention contains a structural unit derived from a diene in a proportion within the above range, the polymerization activity is also moderately high.
Further, when a structural unit derived from an α-olefin having 3 to 12 carbon atoms is contained in a proportion within the above range, a molding resin composition having less surface tackiness and excellent mechanical properties and impact properties is obtained. Can do.

  The (D) unmodified olefin wax used in the present invention has an average of 0.5 to 3.0 / molecule, preferably 0.5 to 2.0 particles / molecule, more preferably 1.0 to 2.0. It is desirable to have an unsaturated group content in the range of individuals / molecules. (D) When the unsaturated group content in the unmodified olefin wax is within the above range, silicone is added to all the (D) unmodified olefin wax. A molding resin composition that effectively acts on the inorganic reinforcing material and has excellent mechanical properties and impact properties can be obtained.

In addition, (D) Unsaturated group content in an unmodified wax is measured as follows. ^The number M of unsaturated groups per 1,000 carbons can be obtained by comparing the peak area of the carbon of the unsaturated portion by ¹³ C-NMR with the peak area of the total carbon. The unsaturated group content per molecule can be calculated by Mn × M / 14,000 using the number average molecular weight Mn. In the present invention, the number M of unsaturated groups per 1,000 carbons is 1.4 to 105, preferably 1.4 to 70, and more preferably 2.8 to 70.

(D) used in the present invention unmodified olefin wax has a density measured by a density gradient tube method is 870 kg / m ³ or more, preferably 890 kg / m ³ or more, more preferably 910 kg / m ³ or more, and, 980 kg / M ³ or less, preferably 970 kg / m ³ or less, more preferably 960 kg / m ³ or less. (D) When the density of the unmodified olefinic wax is within the above range, a molding resin composition with less surface tackiness and excellent mechanical properties and impact properties can be obtained.

  The (D) unmodified olefin wax used in the present invention has a melting point measured by a differential scanning calorimeter (DSC) of 70 ° C. or higher, preferably 80 ° C. or higher, more preferably 90 ° C. or higher, particularly preferably 100 ° C. or higher. In addition, it is desirable that the temperature is 130 ° C. or lower, preferably 125 ° C. or lower, more preferably 120 ° C. or lower. (D) When the melting point of the unmodified olefin-based wax is within the above range, a molding resin composition with less surface tackiness and excellent mechanical properties and impact properties can be obtained.

  The (D) unmodified olefin wax used in the present invention has a number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of 400 to 5,000, preferably 400 to 4,000, more preferably 400 to 4,000. It is desirable that it is 3000, particularly preferably in the range of 1,500 to 2,500. (D) When the Mn of the unmodified olefin wax is within the above range, a molding resin composition with less surface tack is obtained, and the dispersibility of the silicone-modified olefin wax in the molding resin composition Excellent.

  The (D) unmodified olefin wax used in the present invention has a ratio (Mw / Mn) of weight average molecular weight to number average molecular weight measured by GPC of 4.0 or less, preferably 3.5 or less, more preferably It is desirable that it is 3.0 or less. Further, it is desirable that Mw / Mn is 1.1 or more, preferably 1.5 or more, more preferably 2.0 or more.

  In addition, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are polystyrene conversion values measured by gel permeation chromatography (GPC). Here, the measurement by GPC is performed under the conditions of temperature: 140 ° C. and solvent: orthodichlorobenzene.

  The (D) unmodified olefin wax used in the present invention has a penetration hardness of 15 dmm (dmm = 0.1 mm) or less, preferably 10 dmm or less, more preferably 3 dmm or less, and particularly preferably 1 dmm or less. . The penetration hardness can be measured according to JIS K2207. (D) When the penetration hardness of the unmodified olefin wax is within the above range, the mechanical properties of the molding resin composition are excellent.

The (D) unmodified olefin wax according to the present invention has (ii) an unsaturated group content of 0.5 to 3.0 / molecule, and (iii) a density of 870 to 980 kg / m ³ . (Iv) the melting point is 70 to 130 ° C., (v) the number average molecular weight (Mn) is 400 to 5,000, and (vi) Mw / Mn (Mw: weight average molecular weight) is 4.0 or less. It is desirable to be. It is also desirable that (vii) the penetration hardness is 15 dmm or less.

The (D) unmodified olefin wax according to the present invention is copolymerized using vinyl norbornene (5-vinylbicyclo [2.2.1] hept-2-ene) as a diene. In this case, (C) the silicone-modified olefin wax has (viii) an unsaturated group content of 0.5 to 2.0 / molecule, (ix) a density of 890 to 980 kg / m ³ , ( x) Melting point is 80 to 130 ° C., (xi) number average molecular weight (Mn) is 400 to 5,000, and (xii) Mw / Mn (Mw: weight average molecular weight) is 4.0 or less. Is desirable. It is also desirable that (xiii) penetration hardness is 15 dmm or less.

(D) The unmodified olefin wax has an intrinsic viscosity [η] measured in decalin at 135 ° C. of usually 0.04 to 0.47 dl · g ⁻¹ , preferably 0.04 to 0.30 dl · g ^−1. , more preferably 0.04~0.20dl · g ^-1, even more preferably it is preferably in the range of 0.05~0.18dl · g ^-1.

  The (D) unmodified olefin wax as described above is composed of, for example, a metallocene compound of a transition metal selected from Group 4 of the periodic table, an organoaluminum oxy compound, and / or an ionized ionic compound as follows. It can manufacture using a system catalyst.

<Metalocene catalyst>
(Metallocene compound)
The metallocene compound that forms the metallocene catalyst is a metallocene compound of a transition metal selected from Group 4 of the periodic table, and specific examples include compounds represented by the following formula (1).
M ¹ Lx (1)

Here, M ¹ is a transition metal selected from Group 4 of the periodic table, x is a valence of the transition metal M ¹ , and L is a ligand. Examples of the transition metal represented by M ¹ include zirconium, titanium, hafnium and the like. L is a ligand coordinated to the transition metal M ^1, and at least one of the ligands L is a ligand having a cyclopentadienyl skeleton. The ligand having a cyclopentadienyl skeleton may have a substituent. Examples of the ligand L having a cyclopentadienyl skeleton include a cyclopentadienyl group; a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an n- or i-propylcyclopentadienyl group, an n- Alkyl such as i-, sec- or t-butylcyclopentadienyl group, dimethylcyclopentadienyl group, methylpropylcyclopentadienyl group, methylbutylcyclopentadienyl group, methylbenzylcyclopentadienyl group, etc. A cycloalkyl-substituted cyclopentadienyl group; an indenyl group; a 4,5,6,7-tetrahydroindenyl group; a fluorenyl group, and the like. The hydrogen of the ligand L having a cyclopentadienyl skeleton may be substituted with a halogen atom or a trialkylsilyl group.

  When the metallocene compound has two or more ligands having a cyclopentadienyl skeleton as the ligand L, the ligands having two cyclopentadienyl skeletons are ethylene, propylene. Or a substituted alkylene group such as isopropylidene or diphenylmethylene; a substituted silylene group such as a silylene group or a dimethylsilylene group, a diphenylsilylene group, or a methylphenylsilylene group.

Examples of ligands other than ligands having a cyclopentadienyl skeleton (ligands having no cyclopentadienyl skeleton) L include hydrocarbon groups having 1 to 12 carbon atoms, alkoxy groups, aryloxy groups, sulfones. Examples include an acid-containing group (—SO ₃ R ¹ ), a halogen atom, or a hydrogen atom. Here, 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 metallocene compound)
When the metallocene compound represented by the above formula (1) has a transition metal valence of 4 (x = 4), for example, it is more specifically represented by the following formula (2).
R ² _k R ³ _l R ⁴ _m R ⁵ _n M ¹ (2)

Here, M ¹ is a transition metal selected from Group 4 of the periodic table, R ² is a group (ligand) having a cyclopentadienyl skeleton, and R ³ , R ⁴ and R ⁵ are each independently cyclopentadienyl. A group having a skeleton or a group having no skeleton (ligand). k is an integer of 1 or more, and k + l + m + n = 4.

In the above formula (2), as the metallocene compound in which M ¹ is zirconium and contains at least two ligands having a cyclopentadienyl skeleton, for example, bis (cyclopentadienyl) zirconium monochloride monohydride, Bis (cyclopentadienyl) zirconium dichloride, bis (1-methyl-3-butylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (1,3-dimethylcyclopentadienyl) zirconium dichloride It is done. In these compounds, compounds in which the 1,3-position substituted cyclopentadienyl group is replaced with a 1,2-position substituted cyclopentadienyl group can also be used.

Further, as the metallocene compound, in the above formula (2), at least two groups out of R ² , R ³ , R ⁴ and R ⁵ , for example, R ² and R ³ are groups having a cyclopentadienyl skeleton A bridge-type metallocene 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 cyclopentadienyl skeleton described above.

  Examples of such bridge-type metallocene compounds include ethylene bis (indenyl) dimethylzirconium, ethylenebis (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylene bis (indenyl) zirconium dichloride, methyl Examples include phenylsilylene bis (indenyl) zirconium dichloride.

(Example 2 of metallocene compound)
Examples of the metallocene compound include a metallocene compound described in JP-A-4-268307 represented by the following formula (3).

ここで、Ｍ¹は周期表第４族遷移金属であり、具体的にはチタニウム、ジルコニウム、ハフニウムが挙げられる。Ｒ¹¹およびＲ¹²はそれぞれ独立に、水素原子；炭素原子数１〜１０のアルキル基；炭素原子数１〜１０のアルコキシ基；炭素原子数６〜１０のアリール基；炭素原子数６〜１０のアリーロキシ基；炭素原子数２〜１０のアルケニル基；炭素原子数７〜４０のアリールアルキル基；炭素原子数７〜４０のアルキルアリール基；炭素原子数８〜４０のアリールアルケニル基；またはハロゲン原子である。Ｒ¹¹およびＲ¹²は、塩素原子であることが好ましい。

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 are each independently a hydrogen atom; an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; An aryloxy group; an alkenyl group having 2 to 10 carbon atoms; an arylalkyl group having 7 to 40 carbon atoms; an alkylaryl group having 7 to 40 carbon atoms; an arylalkenyl group having 8 to 40 carbon atoms; or a halogen atom is there. R ¹¹ and R ¹² are preferably chlorine atoms.

In the above formula (3), R ¹³ and R ¹⁴ are each independently a hydrogen atom, a halogen atom, an optionally halogenated alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, _{^{-N (R 20) 2, -SR}} 20, -OSi (R 20) 3, -Si (R 20) ₃ or -P (R ²⁰⁾ _2. R ²⁰ 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.

In the above formula (3), specific examples of R ¹⁵ and R ¹⁶ are defined as the same as R ¹³ and R ¹⁴ except for a hydrogen atom. R ¹⁵ and R ¹⁶ may be the same or different from each other, but are preferably the same. R ¹⁵ and R ¹⁶ are preferably alkyl groups having 1 to 4 carbon atoms which may be halogenated, specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, trifluoromethyl and the like. Particularly preferred is methyl.

In the above formula (3), as R ¹⁷ ,

＝ＢＲ²¹、＝ＡｌＲ²¹、−Ｇｅ−、−Ｓｎ−、−Ｏ−、−Ｓ−、＝ＳＯ、＝ＳＯ₂、＝
ＮＲ²¹、＝ＣＯ、＝ＰＲ²¹、＝Ｐ（Ｏ）Ｒ²¹などが挙げられる。

= BR ²¹ , = AlR ²¹ , -Ge-, -Sn-, -O-, -S-, = SO, = SO ₂ , =
NR ²¹ , ═CO, ═PR ²¹ , ═P (O) R ^{21 and the} like.

Here, M ² is silicon, germanium or tin, preferably silicon or germanium. R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, Fluoroaryl group having 6 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, aryl having 8 to 40 carbon atoms An alkenyl group or an alkylaryl group having 7 to 40 carbon atoms. “R ²¹ and R ²² ” or “R ²¹ and R ²³ ” may form a ring together with the atoms to which they are bonded. R ¹⁷ may be = CR ²¹ R ²² , = SiR ²¹ R ²² , = GeR ²¹ R ²² , -O-, -S-, = SO, = PR ²¹ or = P (O) R ^21. preferable. R ¹⁸ and R ¹⁹ are each independently the same as R ²¹ . m and n are each independently 0, 1 or 2, preferably 0 or 1, and m + n is 0, 1 or 2, preferably 0 or 1.

  Examples of the metallocene compound represented by the above formula (3) include, for example, rac-ethylene (2-methyl-1-indenyl) 2-zirconium dichloride, rac-dimethylsilylene (2-methyl-1-indenyl) 2. -Zirconium dichloride and the like. These metallocene compounds can be produced, for example, by the method described in JP-A-4-268307.

(Example 3 of metallocene compound)
As the metallocene compound, a metallocene compound represented by the following formula (4) can also be used.

式（４）中、Ｍ³は、周期表第４族の遷移金属原子を示し、具体的にはチタニウム、ジルコニウム、ハフニウムなどである。Ｒ²⁴およびＲ²⁵はそれぞれ独立に、水素原子、ハロゲン原子、炭素原子数１〜２０の炭化水素基、炭素原子数１〜２０のハロゲン化炭化水素基、ケイ素含有基、酸素含有基、イオウ含有基、窒素含有基またはリン含有基を示す。Ｒ²⁴は炭化水素基であることが好ましく、特にメチル、エチルまたはプロピルの炭素原子数１〜３のアルキル基であることが好ましい。Ｒ²⁵は水素原子または炭化水素基が好ましく、特に水素原子、またはメチル、エチルもしくはプロピルの炭素原子数１〜３のアルキル基であることが好ましい。Ｒ²⁶、Ｒ²⁷、Ｒ²⁸およびＲ²⁹はそれぞれ独立に、水素原子、ハロゲン原子、炭素原子数１〜２０の炭化水素基、炭素原子数１〜２０のハロゲン化炭化水素基を示す。これらの中で、水素原子、炭化水素基またはハロゲン化炭化水素基であることが好ましい。Ｒ²⁶とＲ²⁷、Ｒ²⁷とＲ²⁸、Ｒ²⁸とＲ²⁹のうち少なくとも１組は、それらが結合している炭素原子と一緒になって、単環の芳香族環を形成していてもよい。

In Formula (4), M ³ represents a transition metal atom of Group 4 of the periodic table, and specifically, titanium, zirconium, hafnium, and the like. R ²⁴ and R ²⁵ are each independently 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, an oxygen-containing group, or a sulfur-containing group. Group, nitrogen-containing group or phosphorus-containing group. R ²⁴ is preferably a hydrocarbon group, and 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 ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ each independently represent 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, a hydrogen atom, a hydrocarbon group, or a halogenated hydrocarbon group is preferable. At least one of R ²⁶ and R ²⁷ , R ²⁷ and R ²⁸ , and R ²⁸ and R ²⁹ may form a monocyclic aromatic ring together with the carbon atoms to which they are bonded. Good.

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 each independently represent 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 atom-containing group or a sulfur atom-containing group. Show. 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 -, - CO -, - S -, - SO -, - SO 2 -, - NR 30 -, - P (R 30) -, - P (O) (R 30) -, - BR ³⁰ — or —AlR ³⁰ — is shown. Here, in the formula (4), R ³⁰ 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, R ²⁶ and R ²⁷ , A ligand that includes a monocyclic aromatic ring formed by bonding at least one of R ²⁷ and R ²⁸ or R ²⁸ and R ²⁹ to each other and coordinates to M ³ is, for example, represented by the following formula: Can be mentioned.

（式中、Ｙは上記式（４）中のＹと同じもので定義される。）
（メタロセン化合物の例−４）
メタロセン化合物としては、また下記式（５）で表されるメタロセン化合物を用いることもできる。

(In the formula, Y is defined as the same as Y in the above formula (4).)
(Example 4 of metallocene compound)
As the metallocene compound, a metallocene compound represented by the following formula (5) can also be used.

式（５）中、Ｍ³、Ｒ²⁴、Ｒ²⁵、Ｒ²⁶、Ｒ²⁷、Ｒ²⁸およびＲ²⁹は、上記（４）と同じもので定義される。Ｒ²⁶、Ｒ²⁷、Ｒ²⁸およびＲ²⁹のうち、Ｒ²⁶を含む２個の基はアルキル基であることが好ましく、Ｒ²⁶とＲ²⁸、またはＲ²⁸とＲ²⁹がアルキル基であることが好ましい。このアルキル基は、２級または３級アルキル基であることが好ましく、ハロゲン原子、ケイ素含有基で置換されたものでもよい。ハロゲン原子、ケイ素含有基としては、Ｒ²⁴およびＲ²⁵で例示した置換基が挙げられる。Ｒ²⁶、Ｒ²⁷、Ｒ²⁸およびＲ²⁹のうち、アルキル基以外の基は、水素原子であることが好ましい。また、Ｒ²⁶、Ｒ²⁷、Ｒ²⁸およびＲ²⁹は、これらから選ばれる２種の基が互いに結合して芳香族環以外の単環あるいは多環を形成していてもよい。ハロゲン原子としては、上記Ｒ²⁴およびＲ²⁵と同様のものが挙げられる。Ｘ¹、Ｘ²およびＹは、前述のものと同様のものが挙げられる。

In the formula (5), M ³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ are defined as the same as the above (4). Of R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ , two groups including R ²⁶ are preferably alkyl groups, and R ²⁶ and R ²⁸ , or R ²⁸ and R ²⁹ are alkyl groups. preferable. The alkyl group is preferably a secondary or tertiary alkyl group, and may be substituted with a halogen atom or a silicon-containing group. Examples of the halogen atom and silicon-containing group include the substituents exemplified for R ²⁴ and R ²⁵ . Of R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ , the group other than the alkyl group is preferably a hydrogen atom. In addition, R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ may form a monocyclic or polycyclic ring other than an aromatic ring by bonding two groups selected from these together. Examples of the halogen atom are the same as those described above for R ²⁴ and R ²⁵ . Examples of X ¹ , X ² and Y are the same as those described above.

  Specific examples of the metallocene compound represented by the above formula (5) include rac-dimethylsilylene-bis (4,7-dimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,7 -Trimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,6-trimethyl-1-indenyl) zirconium dichloride, and the like.

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

(Example of metallocene compound-5)
As the metallocene compound, a metallocene compound represented by the following formula (6) can also be used.

式（６）中、Ｍ³、Ｒ²⁴、Ｘ¹、Ｘ²およびＹは、上記式（４）と同じもので定義される。Ｒ²⁴は炭化水素基であることが好ましく、特にメチル、エチル、プロピルまたはブチルの炭素原子数１〜４のアルキル基であることが好ましい。Ｒ²⁵は、炭素原子数６〜１６のアリール基を示す。Ｒ²⁵はフェニル、ナフチルであることが好ましい。アリール基は、ハロゲン原子、炭素原子数１〜２０の炭化水素基または炭素原子数１〜２０のハロゲン化炭化水素基で置換されたものでもよい。Ｘ¹およびＸ²としては、ハロゲン原子、炭素原子数１〜２０の炭化水素基であることが好ましい。

In the formula (6), M ³ , R ²⁴ , X ¹ , X ² and Y are defined as 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.

  Specific examples of the metallocene compound represented by the above formula (6) include rac-dimethylsilylene-bis (4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-phenyl). -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (α-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (β- Naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (1-anthryl) -1-indenyl) zirconium dichloride, and the like. In these compounds, transition metal compounds in which zirconium metal is replaced with titanium metal or hafnium metal can also be used.

(Example of metallocene compound-6)
As the metallocene compound, a metallocene compound represented by the following formula (7) can also be used.
LaM ⁴ X ³ ₂ (7)

Here, M ⁴ is a periodic table group 4 or lanthanide series metal. La is a derivative of a delocalized π bond group, and is a group that imparts a constraining geometry to the metal M ⁴ active site. X ³ is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 20 or less carbon atoms, a silyl group containing 20 or less silicon, or a germanyl group containing 20 or less germanium.
Among these compounds, a compound represented by the following formula (8) is preferable.

式（８）中、Ｍ⁴は、チタン、ジルコニウムまたはハフニウムである。Ｘ³は上記式（７）と同様のもので定義される。ＣｐはＭ⁴にπ結合しており、かつ置換基Ｚを有する置換シクロペンタジエニル基である。Ｚは酸素、イオウ、ホウ素または周期表第４族の元素（たとえばケイ素、ゲルマニウムまたは錫）である。Ｙは窒素、リン、酸素またはイオウを含む配位子であり、ＺとＹとで縮合環を形成していてもよい。このような式（８）で表されるメタロセン化合物の具体的な例として、（ジメチル（ｔ−ブチルアミド）（テトラメチル−η⁵−シクロペンタジエニル）シラン）チタンジクロリド、（（ｔ−ブチルアミド）（テトラメチル−η⁵−シクロペンタジエニル）−１，２−エタンジイル）チタンジクロリドなどが挙げられる。また、このメタロセン化合物において、チタンをジルコニウムまたはハフニウムに置き換えた化合物を挙げることもできる。

In the formula (8), M ⁴ is titanium, zirconium or hafnium. X ³ is defined as the same as the above formula (7). Cp is a substituted cyclopentadienyl group having a π bond to M ⁴ and having a substituent Z. Z is oxygen, sulfur, boron or an element belonging to Group 4 of the periodic table (for example, silicon, germanium or tin). Y is a ligand containing nitrogen, phosphorus, oxygen or sulfur, and Z and Y may form a condensed ring. Specific examples of the metallocene compound represented by the formula (8) include (dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane) titanium dichloride, ((t-butylamide) (Tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl) titanium dichloride and the like. In addition, in this metallocene compound, a compound in which titanium is replaced by zirconium or hafnium can be exemplified.

(Example 7 of metallocene compound)
As the metallocene compound, a metallocene compound represented by the following formula (9) can also be used.

式（９）中、Ｍ³は周期表第４族の遷移金属原子であり、具体的には、チタニウム、ジルコニウムまたはハフニウムであり、好ましくはジルコニウムである。複数のＲ³¹は互いに同一でも異なっていてもよく、そのうち少なくとも１個が炭素原子数１１〜２０のアリール基、炭素原子数１２〜４０のアリールアルキル基、炭素原子数１３〜４０のアリールアルケニル基、炭素原子数１２〜４０のアルキルアリール基またはケイ素含有基であるか、またはＲ³¹で示される基のうち隣接する少なくとも２個の基が、それらの結合する炭素原子とともに単数または複数の芳香族環または脂肪族環を形成している。この場合、Ｒ³¹により形成される環は、Ｒ³¹が結合する炭素原子を含んで全体として炭素原子数が４〜２０である。複数のＲ³¹のうち、アリール基、アリールアルキル基、アリールアルケニル基、アルキルアリール基および芳香族環、脂肪族環を形成しているＲ³¹以外のＲ³¹は、水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基またはケイ素含有基である。

In formula (9), M ³ is a transition metal atom of Group 4 of the periodic table, specifically titanium, zirconium or hafnium, preferably zirconium. A plurality of 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 arylalkyl group having 12 to 40 carbon atoms, or an arylalkenyl group having 13 to 40 carbon atoms , An alkylaryl group having 12 to 40 carbon atoms, a silicon-containing group, or at least two adjacent groups among the groups represented by R ³¹ , together with the carbon atom to which they are bonded, one or more aromatic groups A ring or an aliphatic ring is formed. In this case, the ring formed by R ^31, it is 4 to 20 carbon atoms in all including carbon atoms to which R ³¹ is bonded. Among the plurality of R ^31, aryl group, arylalkyl group, arylalkenyl group, an alkylaryl group and an aromatic ring, R ³¹ other than R ³¹ that forms an aliphatic ring is a hydrogen atom, a halogen atom, a carbon atom It is an alkyl group or silicon-containing group of formula 1-10.

R ³² each independently represents 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 10 carbon atoms, or 7 to 40 carbon atoms. An arylalkyl group, an arylalkenyl group having 8 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, or a phosphorus-containing group.

Further, at least two adjacent groups among 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, it is 4 to 20 carbon atoms in all including carbon atoms to which R ³² is bonded. Among the plurality of R ^32, an aromatic ring, R ³² other than R ³² that forms an aliphatic ring is a hydrogen atom, a halogen atom, an alkyl group or a silicon-containing group having 1 to 10 carbon atoms. In addition, the group in which the two groups represented by R ^{32 form} one or more aromatic rings or aliphatic rings includes groups in which the fluorenyl group forms a structure represented by the following formula.

Ｒ³²は、水素原子またはアルキル基であることが好ましく、特に水素原子またはメチル、エチル、プロピルの炭素原子数１〜３の炭化水素基であることが好ましい。Ｒ³²を有するフルオレニル基としては、２，７−ジアルキル−フルオレニル基が好適な例として挙げられ、この場合のアルキル基としては、炭素原子数１〜５のアルキル基が挙げられる。また、Ｒ³¹とＲ³²は互いに同一でも異なっていてもよい。Ｒ³³およびＲ³⁴はそれぞれ独立に、水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数２〜１０のアルケニル基、炭素原子数７〜４０のアリールアルキル基、炭素原子数８〜４０のアリールアルケニル基、炭素原子数７〜４０のアルキルアリール基、ケイ素含有基、酸素含有基、イオウ含有基、窒素含有基またはリン含有基である。これらのうち、Ｒ³³およびＲ³⁴は、少なくとも一方が炭素原子数１〜３のアルキル基であることが好ましい。

R ³² is preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl or propyl. A suitable example of the fluorenyl group having R ³² is a 2,7-dialkyl-fluorenyl group. In this case, the alkyl group includes an alkyl group having 1 to 5 carbon atoms. R ³¹ and R ³² may be the same as or different from each other. R ³³ and R ³⁴ are each independently 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 10 carbon atoms, or 7 carbon atoms. An arylalkyl group having ˜40, an arylalkenyl group having 8 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing 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 are each independently 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 sulfur-containing group or a nitrogen-containing group. Or a conjugated diene residue formed from X ¹ and X ² . The conjugated diene residue formed from X ¹ and X ² is preferably a residue of 1,3-butadiene, 2,4-hexadiene, 1-phenyl-1,3-pentadiene, or 1,4-diphenylbutadiene. 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 sulfur-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—, —CO—, —S—, —SO—, —SO ₂ —, —NR ³⁵ —, —P (R ³⁵ ) —, —P (O) (R ³⁵ ) —, — BR ³⁵ -or -AlR ³⁵ -is shown. Here, 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 portion of -Y- is composed of one or two atoms are preferable. R ³⁵ is preferably 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, more preferably a divalent silicon-containing group. Particularly preferred is silylene, alkylarylsilylene or arylsilylene.

(Example of metallocene compound-8)
As the metallocene compound, a metallocene compound represented by the following formula (10) can also be used.

式（１０）中、Ｍ³は周期表第４族の遷移金属原子であり、具体的にはチタニウム、ジルコニウムまたはハフニウムであり、好ましくはジルコニウムである。Ｒ³⁶はそれぞれ独立に、水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数６〜１０のアリール基、炭素原子数２〜１０のアルケニル基、ケイ素含有基、酸素含有基、イオウ含有基、窒素含有基またはリン含有基である。なお、上記アルキル基およびアルケニル基は、ハロゲン原子で置換されたものでもよい。Ｒ³⁶は、これらのうち、アルキル基、アリール基または水素原子であることが好ましく、特にメチル、エチル、ｎ−プロピル、ｉ−プロピルの炭素原子数１〜３の炭化水素基、フェニル、α−ナフチル、β−ナフチルなどのアリール基または水素原子であることが好ましい。Ｒ³⁷はそれぞれ独立に、水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数２〜１０のアルケニル基、炭素原子数７〜４０のアリールアルキル基、炭素原子数８〜４０のアリールアルケニル基、炭素原子数７〜４０のアルキルアリール基、ケイ素含有基、酸素含有基、イオウ含有基、窒素含有基またはリン含有基である。なお、上記アルキル基、アリール基、アルケニル基、アリールアルキル基、アリールアルケニル基およびアルキルアリール基は、ハロゲンで置換されたものでもよい。Ｒ³⁷はこれらのうち、水素原子またはアルキル基であることが好ましく、特に水素原子またはメチル、エチル、ｎ−プロピル、ｉ−プロピル、ｎ−ブチル、ｔｅｒｔ−ブチルの炭素原子数１〜４の炭化水素基であることが好ましい。

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 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a silicon-containing group, or an oxygen-containing group. A sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group. The alkyl group and alkenyl group may be substituted with a halogen atom. Among these, R ³⁶ is preferably an alkyl group, an aryl group or a hydrogen atom, particularly a methyl, ethyl, n-propyl, i-propyl hydrocarbon group having 1 to 3 carbon atoms, phenyl, α- An aryl group such as naphthyl and β-naphthyl or a hydrogen atom is preferable. R ³⁷ each independently represents 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 10 carbon atoms, or 7 to 40 carbon atoms. An arylalkyl group, an arylalkenyl group having 8 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, or a phosphorus-containing group. The alkyl group, aryl group, alkenyl group, arylalkyl group, arylalkenyl group and alkylaryl group may be substituted with halogen. Of these, R ³⁷ is preferably a hydrogen atom or an alkyl group, and particularly a hydrogen atom or a carbon atom having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, or tert-butyl. A hydrogen group is preferred.

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, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. A silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group.

Among these, it is preferable that any one of R ³⁸ and R ³⁹ is an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, propyl, and the other is a hydrogen atom. X ¹ and X ² are each independently 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 sulfur-containing group or a nitrogen-containing group. Or a conjugated diene residue formed from X ¹ and X ² . Among 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 -, - CO -, - S -, - SO -, - SO 2 -, - NR 40 -, - P (R 40) -, - P (O) (R 40) -, - BR ⁴⁰ -or -AlR ⁴⁰ -is shown. Here, R ⁴⁰ 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, Y is preferably a divalent hydrocarbon group having 1 to 5 carbon atoms, a divalent silicon-containing group, or a divalent germanium-containing group, and is preferably a divalent silicon-containing group. More preferred is alkylsilylene, alkylarylsilylene or arylsilylene.
The metallocene compounds described above are used alone or in combination of two or more. The metallocene compound may be diluted with a hydrocarbon or a halogenated hydrocarbon.

(Organic aluminum oxy compound)
The organoaluminum oxy compound may be a known aluminoxane or a benzene-insoluble organoaluminum oxy compound. Such a known aluminoxane is specifically represented by the following formula.

ここで、Ｒはメチル基、エチル基、プロピル基、ブチル基などの炭化水素基であり、好ましくはメチル基、エチル基、特に好ましくはメチル基であり、ｍは２以上、好ましくは５〜４０の整数である。

Here, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group or a butyl group, preferably a methyl group or an ethyl group, particularly preferably a methyl group, and m is 2 or more, preferably 5 to 40. Is an integer.

  The aluminoxane is formed by a mixed alkyloxyaluminum unit composed of an alkyloxyaluminum unit represented by the formula — (OAl (R ′)) — and an alkyloxyaluminum unit represented by the formula — (OAl (R ″)) —. Here, R ′ and R ″ can exemplify the same hydrocarbon group as R, and R ′ and R ″ represent different groups. A small amount of an organic compound component of a metal other than aluminum may be contained.

(Ionized ionic compounds)
Examples of ionized ionic compounds (sometimes referred to as ionic ionized compounds or ionic compounds) include Lewis acids, ionic compounds, borane compounds, and carborane compounds. As the Lewis acid, a compound represented by BR ₃ (R is a phenyl group which may have a substituent such as a fluorine, a methyl group or a trifluoromethyl group or fluorine) can be used. Specific examples of the Lewis acid include trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris ( Pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like.

  Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts. Examples of the trialkyl-substituted ammonium salt as the ionic compound include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, and tri (n-butyl) ammonium tetra (phenyl) boron. Examples of the dialkylammonium salt as the ionic compound include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

  Examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, and the like. .

  Examples of the borane compound include decaborane (9), bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] bis (dodecahydridododeca Examples thereof include salts of metal borane anions such as borate) nickelate (III).

  Examples of the carborane compound include 4-carbanonaborane (9), 1,3-dicarbanonaborane (8), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickel acid. Examples thereof include salts of metal carborane anions such as salt (IV).

Such ionized ionic compounds may be used alone or in combination of two or more.
Moreover, when forming a metallocene catalyst, the following organoaluminum compounds may be used together with the organoaluminum oxy compound and / or the ionized ionic compound.

(Organic aluminum compound)
As the organoaluminum compound used as necessary, a compound having at least one Al-carbon bond in the molecule can be used. Examples of such a compound include an organoaluminum compound represented by the following formula (11) and a complex alkylated product of a first group metal and aluminum represented by the following formula (12).
_{^{(R 6) m Al (OR}} 7) n H p X 4 q ··· (11)
(Wherein R ⁶ and R ⁷ are each independently a hydrocarbon group usually containing 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. X ⁴ is a halogen atom. M is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number satisfying 0 ≦ q <3, and m + n + p + q = 3.
(M ⁵ ) Al (R ⁶ ) (12)
(In the formula, M ⁵ is Li, Na or K, and R ⁶ is defined as the same as R ^{6 in the} general formula (11).)

(D) Method for Producing Unmodified Olefin Wax (D) The unmodified olefin wax used in the present invention is obtained by homopolymerizing ethylene and diene usually in a liquid phase in the presence of the metallocene catalyst. Alternatively, it is obtained by copolymerizing at least one α-olefin selected from ethylene and an α-olefin having 3 to 12 carbon atoms and at least one diene. At this time, a hydrocarbon solvent is generally used, but an α-olefin may be used as a solvent. The monomers used here are as described above.

  The polymerization method includes (D) suspension polymerization in which an unmodified olefin wax is present as particles in a solvent such as hexane, gas phase polymerization in which no solvent is used, and a polymerization temperature of 140 ° C. or higher. (D) Solution polymerization in which an unmodified olefin wax coexists with a solvent or is melted alone is possible, and among them, solution polymerization is preferable in terms of both economy and quality.

The polymerization reaction may be performed by either a batch method or a continuous method. When the polymerization is carried out by a batch method, the above catalyst components are used under the following concentration conditions.
The concentration of the metallocene compound in the polymerization system is usually 0.00005 to 0.1 mmol / liter (polymerization volume), preferably 0.0001 to 0.05 mmol / liter.

<(C) Silicone-modified olefin wax>
The (C) silicone-modified olefin wax used in the present invention can be obtained by hydrosilylating the above-mentioned (D) unmodified olefin wax with hydrogen silicone. It is known that it has excellent releasability and lubricity. Moreover, it has the feature that the thermal decomposition starting temperature measured in the atmospheric temperature atmosphere with the temperature rising temperature of 20 ° C./min is high. Furthermore, the surface tension at 180 ° C. by the Wilhelmy platinum plate method is low. By using these characteristics, it can be used alone or added to a compound composed of other thermoplastic resins, etc., so that good moldability, releasability, surface slipperiness, heat resistance, dispersibility of inorganic pigments such as fillers, etc. Can be given.

  As the silicone to be reacted, any hydrogen silicone known in the prior art may be used, but hydrogen silicone having one or more hydrosilyl groups (SiH bonds) per molecule is preferable. Further, those having a hydrosilyl group in the side chain of silicone are suitable, but those having a hydrosilyl group at both ends or one end can also be used. From the viewpoint of cost, those having a hydrosilyl group only on the side chain of the silicone are most advantageous. As is well known, the reaction between hydrogen silicone and olefinic wax is carried out using a platinum catalyst in the absence of a solvent or in a solvent. The reaction temperature is 30 ° C to 200 ° C, particularly preferably 120 ° C to 150 ° C. Since the melting point of the olefin wax is about 120 ° C., it is preferable to set the reaction temperature to 120 ° C. or more from the viewpoint of making the reaction system uniform. The reaction molar ratio between the hydrogen silicone and the olefinic wax is usually carried out under such conditions that the olefinic wax is in a small excess of about 1.05 to 1.2 times moles relative to the hydrogen silicone. However, the present invention is not limited to this. Specifically, the reaction can be carried out in a high boiling point solvent such as xylene, and the solvent can be distilled off under reduced pressure to obtain a silicone-modified olefin wax.

  Further, as the hydrogen silicone, a silane or siloxane compound having two or more hydrolyzable groups in one molecule may be used. In this case, examples of the hydrolyzable group include alkoxy groups such as methoxy group, ethoxy group and butoxy group; ketoxime groups such as dimethyl ketoxime group and methylethyl ketoxime group; acyloxy groups such as acetoxy group; isopropenyloxy group Alkenyloxy groups such as isobutenyloxy group; amino groups such as N-butylamino group and N, N-diethylamino group; amide groups such as N-methylacetamide group and the like. Of these, an alkoxy group, a ketoxime group, an alkenyloxy group, and an acyloxy group are preferable.

  The amount of the silicone-modified olefin wax is 100 parts by weight in total of a mixture comprising at least one resin selected from the group consisting of (A) a thermoplastic resin and a thermosetting resin and (B) an inorganic reinforcing material component. Is 0.01 to 10 parts by weight, preferably 0.05 to 7 parts by weight, and more preferably 0.1 to 5 parts by weight. If the amount is less than 0.01 parts by weight, sufficient mechanical properties and impact resistance cannot be obtained. If the amount is more than 10 parts by weight, bleeding out of the low molecular weight becomes remarkable, and the molding resin composition is blocked. Arise.

<Optional component>
The resin composition for molding with an inorganic reinforcing material of the present invention may contain any additive, for example, brominated bisphenol, brominated epoxy resin, brominated polystyrene, brominated polycarbonate, tricarbonate, as long as the object and effect of the present invention are not impaired. Flame retardants such as phenyl phosphate, phosphonic acid amide and red phosphorus, flame retardant aids such as antimony trioxide and sodium antimonate, heat stabilizers such as phosphate esters and phosphites, hindered phenols, etc. Such as antioxidants, heat-resistant agents, weathering agents, light stabilizers, mold release agents, flow modifiers, colorants, lubricants, antistatic agents, crystal nucleating agents, plasticizers and foaming agents as needed You may mix | blend the effective expression level.

  The (C) silicone-modified olefin wax of the present invention is excellent in mechanical properties such as tensile properties and bending properties and impact resistance, and the mechanism of the improvement is considered as follows. That is, the affinity between the silicone-modified olefin wax and the inorganic reinforcing material, or the effect of the silicone-modified olefin wax having a low surface tension to wet the surface of the inorganic reinforcing material, suppresses shearing on the reinforcing material such as glass fiber during molding. The reinforcing fiber length in the resin composition is kept long. Thereby, it is considered that excellent mechanical properties such as tensile properties and bending properties are exhibited. For improving impact resistance, the silicone-modified olefin wax covers the surface of the inorganic reinforcing material. When impact is applied, the thermoplastic resin or thermosetting resin and the silicone-modified olefin covering the inorganic reinforcing material are applied. It is considered that interfacial peeling occurs between the system waxes, uniform voids (voids) are generated, and the impact is absorbed.

<Method for producing resin composition for molding compounded with inorganic reinforcing material>
Any method can be used as a method for producing the resin composition for molding an inorganic reinforcing material of the present invention. For example, a thermoplastic resin or a thermosetting resin, an inorganic reinforcing material, a silicone-modified olefin wax, or other optional components simultaneously or in any order, tumbler, V-type blender, nauter mixer, Banbury mixer, kneading roll, uniaxial or A method of mixing with a twin screw extruder or the like is appropriately used.

  The resin composition thus obtained is molded by various known methods such as injection molding, extrusion molding and compression molding.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
(D) The properties of the unmodified olefin wax were measured by the following method and are shown in Table 1.

(1) Method for measuring the content of structural units derived from diene or α-olefin The content of structural units derived from diene or α-olefin in the unmodified wax is the carbon content of the unsaturated portion by ¹³ C-NMR. The number of unsaturated groups per 1,000 carbons is obtained by comparing the peak area of carbon and the peak area of all carbon, or the peak area of carbon of the α-olefin part and the peak area of all carbon by ¹³ C-NMR. Can do.

(2) Method for measuring the number of unsaturated groups per molecule The unsaturated group content per molecule is Mn x using the number average molecular weight Mn and the number of unsaturated groups M per 1,000 carbon determined above. It can be calculated by M / 14,000.

(3) Measuring method of density It measured with the density gradient tube method of JISK7112.

(4) Measuring method of melting | fusing point Melting | fusing point was measured by DSC-20 (made by Seiko Denshi Kogyo Co., Ltd.) according to the differential scanning calorimetry (DSC). About 10 mg of the sample was heated from −20 ° C. to 200 ° C. at 10 ° C./min, and the endothermic peak of the obtained curve was obtained as the melting point. Before this temperature rise measurement, the temperature of the resin is once raised to about 200 ° C., held for 5 minutes, and then lowered to room temperature (25 ° C.) at 20 ° C./min to unify the heat history of the resin. It is desirable.

(5) Measurement method of Mn and Mw The number average molecular weight Mn and the weight average molecular weight Mw were determined from GPC measurement. The measurement was performed under the following conditions. The number average molecular weight Mn and the weight average molecular weight Mw were determined based on the following conversion method by creating a calibration curve using a commercially available monodisperse standard polystyrene.
Apparatus: Gel permeation chromatograph Alliance GPC2000 (manufactured by Waters)
Solvent: o-dichlorobenzene column: TSKgel column (manufactured by Tosoh Corporation) x 4
Flow rate: 1.0 ml / min Sample: 0.15 mg / mL o-dichlorobenzene solution temperature: 140 ° C.
Molecular weight conversion: PE conversion / general-purpose calibration method The coefficient of the Mark-Houwink viscosity equation shown below was used for calculation of general-purpose calibration.
Coefficient of polystyrene (PS): KPS = 1.38 × 10 ⁻⁴ , aPS = 0.70
Coefficient of polyethylene (PE): KPE = 0.06 × 10 ⁻⁴ , aPE = 0.70

<Synthesis Example 1>
(Synthesis of olefin wax)
950 ml of hexane, 15 ml of propylene, and 35 ml of vinyl norbornene (5-vinylbicyclo [2.2.1] hept-2-ene) were charged into a stainless steel autoclave with an internal volume of 2 liters sufficiently purged with nitrogen, and hydrogen was added to a concentration of 0.1. It introduced until it became 25MPa (gauge pressure). Subsequently, after raising the temperature in the system to 150 ° C., 0.3 mmol of triisobutylaluminum, 0.004 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate, dimethyl (t-butylamide) (tetramethyl-η Polymerization was initiated by injecting 0.02 mmol of ⁵ -cyclopentadienyl) silane titanium dichloride (Sigma-Aldrich) with ethylene. Thereafter, only ethylene was continuously supplied to keep the total pressure at 2.9 MPa (gauge pressure), and polymerization was carried out at 150 ° C. for 20 minutes. After the polymerization was stopped by adding a small amount of ethanol into the system, unreacted ethylene and vinyl norbornene were purged. The resulting polymer solution was dried overnight at 100 ° C. under reduced pressure.

As described above, the number of unsaturated groups per 1,000 carbons is 8.6, the number of propylene per 1,000 carbons is 4.1, and the unsaturated group content (average) is 1.1 / molecule. An unsaturated group-containing polyethylene wax having a density of 945 kg / m ³ , a melting point of 112 ° C., Mn of 1,800, Mw of 4,800, and Mw / Mn of 2.6 Olefin wax (a-1)) was obtained.

<Synthesis Example 2>
(Synthesis of olefin wax)
A stainless steel autoclave with an internal volume of 2 liters, sufficiently purged with nitrogen, was charged with 905 ml of hexane, 35 ml of propylene, and 60 ml of vinylnorbornene (5-vinylbicyclo [2.2.1] hept-2-ene), and hydrogen was added to a concentration of 0. It introduced until it became 35 MPa (gauge pressure). Subsequently, after raising the temperature in the system to 150 ° C., 0.3 mmol of triisobutylaluminum, 0.004 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate, dimethyl (t-butylamide) (tetramethyl-η Polymerization was initiated by injecting 0.02 mmol of ⁵ -cyclopentadienyl) silane titanium dichloride (Sigma-Aldrich) with ethylene. Thereafter, only ethylene was continuously supplied to keep the total pressure at 2.9 MPa (gauge pressure), and polymerization was carried out at 150 ° C. for 20 minutes. After the polymerization was stopped by adding a small amount of ethanol into the system, unreacted ethylene and vinyl norbornene were purged. The resulting polymer solution was dried overnight at 100 ° C. under reduced pressure.

As described above, the number of unsaturated groups per 1,000 carbons is 14, the number of propylenes per 1,000 carbons is 35, the unsaturated group content (average) = 1.0 / molecule, and the density is 910 kg / m ³ , melting point 90 ° C., Mn 1,000, Mw 2,300, Mw / Mn 2.3 polyethylene-containing unsaturated wax (olefin wax ( a-2)) was obtained.

<Preparation Example 1>
180 hours of polyethylene wax (a-1) together with 240 g of one-end hydrogen silicone (1) represented by the following average structural formula, 2 L of xylene and 0.5 g of a 3% isopropanol solution of chloroplatinic acid under reflux of xylene for 5 hours Reacted. The solvent was distilled off under reduced pressure and heating to obtain a silicone-modified olefin wax (b-1).
One-end hydrogen silicone (1):
_{C 4 H 9 - ((CH} 3) 2 SiO) 30 - (CH 3) 2 SiH

<Preparation Example 2>
A silicone-modified olefin wax (b-2) is obtained in the same manner as in Preparation Example 1, except that the one-end hydrogen silicone (1) is changed to 35 g of hydrogen silicone (2) represented by the following average structural formula. It was.
Hydrogen silicone (2):
(CH ₃ ) ₃ SiO ((CH ₃ ) ₂ SiO) ₁₀ ((CH ₃ ) HSi) ₃ Si (CH ₃ ) ₃

<Preparation Example 3>
A silicone-modified olefin wax (b-3) was obtained in the same manner as in Preparation Example 1, except that polyethylene wax (a-2) was used instead of polyethylene wax (a-1).

<Preparation Example 4>
A silicone-modified olefin wax (b-4) was obtained in the same manner as in Preparation Example 2, except that polyethylene wax (a-2) was used instead of polyethylene wax (a-1).

<Example 1>
90 parts by weight of aromatic polycarbonate resin (Teijin Chemicals Ltd .: Panlite L-1225Y), 10 parts by weight of glass fiber for polycarbonate (Nittobo Co., Ltd .: chopped strand CS3PE455S), and silicone-modified olefin wax (b-1) An inorganic reinforcing material blended composition was obtained by extruding 0.5 parts by weight using a twin screw extruder (meshing biaxial opposite direction rotation type: manufactured by Hake Co., Ltd.) at a cylinder temperature of 300 ° C. and pelletized.

  The pellets were dried at 130 ° C. for 4 hours, and then an injection molding machine (EC-100N, manufactured by Toshiba Machine Co., Ltd.) was used. Cylinder temperature 290 ° C., screw rotation speed 100 rpm, injection primary pressure 100 MPa, secondary pressure 70 MPa, mold temperature Injection molding was performed at 80 ° C., and test pieces were prepared according to each JIS test. A tensile test, a bending test, and an impact test were performed by the following methods. Table 2 shows the composition of the inorganic reinforcing material-compounding resin composition and its physical properties.

Test Method (a) Tensile Strength A test piece was prepared using an injection molding machine, and the tensile strength and tensile elongation were measured based on JIS K-7162 under conditions of a load range of 500 kg and a test speed of 50 mm / min.

(B) Bending strength A test piece was prepared using an injection molding machine, and the bending strength and bending elastic modulus were measured under the conditions of a load range of 25 kg, a test speed of 2 mm / min, and a bending span of 64 mm based on JIS K-7171.

(C) Impact strength A test piece was prepared using an injection molding machine. Based on JIS K-7111, hammer weight 2J, hammer rotation moment 1.08 N · J, hammer lifting angle 50 °, impact speed 2.9 m / S, Charpy impact value was measured under the condition of a distance of 0.23 m from the rotation axis to the impact point.

<Example 2>
Except for using the silicone-modified olefin wax (b-2) instead of the silicone-modified olefin wax (b-1), pelletization was carried out in the same manner as in Example 1 to obtain a thermoplastic resin composition containing glass fiber reinforcement. In the same manner as in Example 1, injection molding was performed to prepare a test piece, and the same test was performed.

<Example 3>
Pelletization was performed in the same manner as in Example 1 except that the silicone-modified olefin wax (b-3) was used instead of the silicone-modified olefin wax (b-1) to obtain a glass fiber-reinforced material-containing thermoplastic resin composition. In the same manner as in Example 1, injection molding was performed to prepare a test piece, and the same test was performed.

<Example 4>
Except for using the silicone-modified olefin wax (b-4) instead of the silicone-modified olefin wax (b-1), pelletization was performed in the same manner as in Example 1 to obtain a thermoplastic resin composition containing glass fiber reinforcement. In the same manner as in Example 1, injection molding was performed to prepare a test piece, and the same test was performed.

<Example 5>
A thermoplastic resin composition containing a glass fiber reinforcement and pelletized in the same manner as in Example 1 except that 3 parts by weight of the silicone-modified olefin wax (b-3) was used instead of the silicone-modified olefin wax (b-1). A product was obtained and injection molded in the same manner as in Example 1 to prepare a test piece, and the same test was conducted.

<Example 6>
70 parts by weight of polybutylene terephthalate (Wintech Polymer Co., Ltd .: Duranex 2002), 30 parts by weight of glass fiber for polybutylene terephthalate (Nittobo Co., Ltd .: chopped strand CS3PE941S) and silicone-modified olefin wax (b-3) ) 0.5 parts by weight was extruded using a twin-screw extruder (same direction rotating HK-25D: manufactured by Parker Corporation) at a cylinder temperature of 260 ° C. to obtain an inorganic reinforcing material blended composition.

  After drying this pellet at 120 ° C. for 5 hours, using an injection molding machine (F85, manufactured by Crocker), cylinder temperature 250 ° C., screw rotation speed 100 rpm, injection primary pressure 60 MPa, secondary pressure 50 MPa, mold temperature 60 ° C. Injection molding was performed under the conditions, and test pieces were prepared according to each JIS test. A tensile test and a bending test were performed in the same manner as in Example 1. The impact test was performed in the same manner as in Example 1 except that the hammer weight in Example 1 was set to 1J. Table 2 shows the blending of the inorganic reinforcing material blending molding resin composition, molding conditions and physical properties thereof.

<Example 7>
A test piece was prepared by injection molding in the same manner as in Example 6 except that 3 parts by weight of the silicone-modified olefin wax (b-3) was used instead of 0.5 part by weight of the silicone-modified olefin wax (b-3). A similar test was made.

<Comparative Example 1>
For comparison, except that the silicone-modified olefin wax (b-1) is not added, pelletization is performed in the same manner as in Example 1 to obtain a thermoplastic resin composition containing glass fiber reinforcement, and injection molding is performed in the same manner as in Example 1. A test piece was prepared and a similar test was conducted.

<Comparative example 2>
A thermoplastic resin compounded with glass fiber reinforcement and pelletized in the same manner as in Example 1 except that maleic acid-modified high wax 1105A (Mitsui Chemicals, Inc.) is used instead of silicone-modified olefin wax (b-1). A composition was obtained, and injection molding was performed in the same manner as in Example 1 to prepare a test piece, and the same test was performed.

<Comparative Example 3>
Pelletized in the same manner as in Example 1 except that high-modified wax 110P (Mitsui Chemicals, Inc.), which is an unmodified wax, is used in place of the silicone-modified olefin wax (b-1), and the glass fiber reinforcement heat A plastic resin composition was obtained, and injection molding was performed in the same manner as in Example 1 to prepare a test piece, and the same test was performed.

<Comparative example 4>
Pelletization was attempted in the same manner as in Example 1 except that 15 parts by weight of the silicone-modified olefin wax (b-3) was used instead of the silicone-modified olefin wax (b-1), but kneading was insufficient. The strands were not stable and pellets could not be obtained.

<Comparative Example 5>
For comparison, except that the silicone-modified olefin wax (b-3) was not added, pelletized in the same manner as in Example 6 to obtain a thermoplastic resin composition containing glass fiber reinforcement, and injection molding as in Example 6. A test piece was prepared and a similar test was conducted.

<Comparative Example 6>
A test piece was prepared by performing injection molding in the same manner as in Example 6 except that maleic acid-modified high wax 1105A (Mitsui Chemicals, Inc.) was used instead of the silicone-modified olefin wax (b-3). The test was conducted.

<Comparative Example 7>
A test piece was prepared by injection molding in the same manner as in Example 6 except that 3 parts by weight of maleic acid-modified high wax 1105A (Mitsui Chemicals) was used in place of the silicone-modified olefin wax (b-3). The same test was conducted.

<Comparative Example 8>
A test piece was prepared by injection molding in the same manner as in Example 6 except that high wax 110P (Mitsui Chemicals, Inc.), which is an unmodified wax, was used instead of the silicone-modified olefin wax (b-3). A similar test was conducted.

  Tables 2 and 3 show the results of measuring physical properties of the test pieces obtained in Examples 1 to 7 and Comparative Examples 1 to 8 according to the following. In each example and comparative example, the content of each component was expressed with the total amount of component (A) and component (B) being 100 parts by weight.

Claims (6)

(A) 95-50 parts by weight of at least one resin selected from the group consisting of thermoplastic resins and thermosetting resins;
(B) 5 to 50 parts by weight of an inorganic reinforcing material;
(C) 0.01 to 10 parts by weight of a silicone-modified olefin wax (provided that the total of component (A) and component (B) is 100 parts by weight)
A resin composition for molding an inorganic reinforcing material, characterized in that   2. The resin composition for molding an inorganic reinforcing material according to claim 1, comprising 0.05 to 7 parts by weight of the (C) silicone-modified olefin wax.   The thermoplastic resin (A) is a polycarbonate resin, a thermoplastic polyester resin, an ABS resin, a polyacetal resin, a polyamide resin, a polyphenylene oxide resin, or a polyimide resin, and the thermosetting resin is an epoxy resin or a thermosetting unsaturated polyester. 3. The resin composition for molding an inorganic reinforcing material according to claim 1 or 2, wherein the resin composition is an at least one resin selected from the group consisting of a resin and a phenol resin.   The inorganic reinforcing material-compounding resin composition according to any one of claims 1 to 3, wherein the (B) inorganic reinforcing material is at least one filler selected from glass fibers and carbon fibers. . The (C) silicone-modified olefin wax is a catalyst comprising an unmodified olefin wax (D) satisfying the following (i) to (vi) and a hydrogen silicone having one or more SiH bonds per molecule: The resin composition for inorganic reinforcing material blending molding according to any one of claims 1 to 4, wherein the resin composition is obtained by addition reaction below.
(I) a copolymer obtained by copolymerizing ethylene and at least one diene, or at least one olefin selected from ethylene and an α-olefin having 3 to 12 carbon atoms and at least one diene. Copolymer obtained by copolymerization (ii) 0.5 to 3.0 unsaturated group content per molecule (iii) Density is 870 to 980 kg / m ³
(Iv) Melting point is 70-130 ° C
(V) Number average molecular weight (Mn) of 400 to 5,000
(Vi) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 4.0 or less. The (C) silicone-modified olefin wax is a catalyst comprising an unmodified olefin wax (D) satisfying the following (vii) to (xii) and a hydrogen silicone having one or more SiH bonds per molecule. The resin composition for inorganic reinforcing material blending molding according to any one of claims 1 to 4, wherein the resin composition is obtained by addition reaction below.
(Vii) From a copolymer obtained by copolymerizing ethylene and vinyl norbornene (5-vinylbicyclo [2.2.1] hept-2-ene), or ethylene and an α-olefin having 3 to 12 carbon atoms Copolymer (viii) obtained by copolymerizing at least one selected olefin and vinyl norbornene 0.5 to 2.0 unsaturated groups per molecule (ix) Density 890 to 980 kg / M ³
(X) Melting point is 80-130 ° C
(Xi) Number average molecular weight (Mn) is 400 to 5,000.
(Xii) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 4.0 or less