JP2807544B2 - Thermoplastic elastomer molded article with grain pattern and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a thermoplastic elastomer molded article having a grain pattern and a method for producing the same, and more particularly, to a mechanical pattern having a grain pattern having fine irregularities on the surface, particularly a deep grain pattern. The present invention relates to a thermoplastic elastomer molded article having excellent physical properties and a method for producing the same.

Technical Background of the Invention Conventionally, vinyl chloride resin (PVC) has been widely used for molded articles such as automobile dashboards and dolls. In particular, a dashboard having an embossed pattern, such as a dashboard for an automobile, is in high demand because of its high quality image.

By the way, as a method of manufacturing a molded article of a vinyl chloride resin having a grain pattern such as an automobile dashboard and a doll as described above, a vinyl chloride resin powder for a plastisol added with a plasticizer such as dioctyl phthalate is injected into a mold. Or immersing the mold in the powder, attaching the powder to the mold surface, heating and molding, so-called slush molding method, vinyl chloride resin sheet (PVC
A method for vacuum forming a sheet) is known.

However, the vinyl chloride resin has a problem that heat resistance, heat aging resistance, cold resistance and light resistance are inferior. Also, even if a molded article with a grain pattern is produced by performing slush molding or vacuum molding as described above using a vinyl chloride resin, the grain depth is about 90 μm, and therefore,
The appearance of a synthetic resin molded product having a deeper grain pattern has been desired.

The present inventors have conducted intensive studies to obtain a synthetic resin molded article having a deeper grain pattern instead of the above-described grain-patterned vinyl chloride resin article, and found that the crystalline olefin polymer portion and the amorphous olefin If rotational molding is performed using a finely powdered product of a polymer part and a crosslinked agent of a polymer particle, the production of a thermoplastic elastomer and the step of powdering the same can be omitted, resulting in a decrease in mechanical properties. It was found that a molded article having a small grain depth and excellent transferability of a grain pattern was obtained, and the present invention was completed.

Object of the Invention The present invention is intended to solve the problems associated with the prior art as described above, and instead of a grain-patterned vinyl chloride resin molded product, the grain depth is deeper, and the mechanical properties It is an object of the present invention to provide a thermoplastic elastomer molded article having a grain pattern without any decrease.

Another object of the present invention is to provide a method for producing a thermoplastic elastomer molded article having a grain pattern as described above, which can omit the step of producing the thermoplastic elastomer and the step of powdering the thermoplastic elastomer.

SUMMARY OF THE INVENTION The thermoplastic elastomer molded article with a grain pattern according to the present invention is obtained by subjecting a polymerized fine particle of a crystalline olefin polymer part and an amorphous olefin polymer part to a pulverization treatment in the presence of a crosslinking agent. In this case, a grain pattern is formed on the inner surface of the mold for transferring a grain pattern in a rotationally heated state by being closely adhered and melted in a fluidized plastic state.

In addition, the method for producing a thermoplastic elastomer molded article having a grain pattern according to the present invention comprises the steps of: forming a finely powdered polymer particle comprising a crystalline olefin polymer portion and an amorphous olefin polymer portion; In the presence, the mold is placed in a mold for transfer of a grain pattern, and the mold is sealed. Then, the mold is heated while rotating, so that the polymer particles are pulverized in a fluid plastic state in the mold. It is characterized in that it is brought into close contact with the surface and melted, and then the mold is cooled to obtain a thermoplastic elastomer molded product having a grain pattern on the surface.

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the thermoplastic elastomer molded article having a grain pattern according to the present invention and a method for producing the same will be specifically described.

First, the thermoplastic elastomer molded article having a grain pattern according to the present invention will be described.

In the present invention, a pulverized product of polymer particles comprising a crystalline olefin polymer part and an amorphous olefin polymer part is used.

The average particle size of the polymer particles before the pulverization treatment used in the present invention is usually 40 μm or more, preferably 40 to 5000 μm,
More preferably 100 ~ 4000μm, particularly preferably 300 ~
It is in the range of 3000 μm. The geometric standard deviation indicating the particle size distribution of the polymer particles used in the present invention is usually 1.
0-3.0, preferably 1.0-2.0, more preferably 1.0-1.
5, particularly preferably in the range from 1.0 to 1.3. In addition, the apparent bulk density of the polymer particles used in the present invention by natural fall is usually 0.2 g / ml or more, preferably 0.2 to 0.7 g / ml,
More preferably 0.3 to 0.7 g / ml, particularly preferably 0.35 to
It is in the range of 0.60 g / ml.

Further, in the polymer particles used in the present invention, particles passing through 150 mesh are preferably 30% by weight or less, more preferably 10% by weight or less, and particularly preferably 2% by weight or less. In addition, such polymer particles have a falling time of 5 to 25 seconds, preferably 5 to 20 seconds, particularly preferably 5 to 15 seconds, as defined below.

The average particle size, apparent bulk density, and falling seconds of the polymer particles as described above are measured as described below.

Average particle diameter: 300 g of polymer particles are 200 mm in diameter and 45 mm in depth made by Nippon Riken Kikai with stainless steel sieve (with openings of 7, 10,
After adding seven kinds of sieves of 14, 20, 42, 80, and 150 mesh in this order from top to bottom and further stacking a saucer at the bottom, cover the lid and then go to IIDA SIEVE SHAKER (Iida Seisakusho). Set and shake for 20 minutes. After shaking for 20 minutes, the polymer weight on each screen was weighed and the measurements were plotted on logarithmic established paper. The plots were connected by a curve, and the particle size (D ₅₀ ) at an integrated weight of 50% by weight was determined based on the curve, and this value was defined as the average particle size.

Meanwhile regard to geometric standard deviation, as well as that obtained from the value of the D ₅₀ small integrated from particle size 16% by weight of the particle diameter (D _16). (Geometric standard deviation = D ₅₀ / D ₁₆ ) Apparent bulk density: Measured in accordance with JIS K 6721-1977.
(However, the inner diameter of the inlet of the funnel used was 92.9 mmφ and the inner diameter of the outlet was 9.5 mmφ.) Falling seconds: Using the device for measuring the bulk density as it was, the sample was dropped into the receiver and raised from the receiver. The sample contained in a 100 ml container was transferred to the funnel with the damper again by scraping the sample with a glass rod, then the damper was pulled, and the time (second) required for the sample to completely drop from the bottom of the funnel was dropped. Number of seconds.

However, in measuring the number of seconds of falling, polymer particles obtained by removing particles having a mean particle size of 1.5 to 1.6 times or more by sieving were used.

When measuring the number of seconds dropped, set the receiver on the vibration table of a powder tester (Type PT-D manufactured by Hosokawa Micro, SER. No. 71190) and adjust the rheostat voltage so that the vibration width of the diaphragm becomes 1 mm. Then, the polymer particles were dropped while being vibrated.

The polymer particles used in the present invention are composed of a crystalline olefin polymer portion and an amorphous olefin polymer portion as described above, and have a so-called sea-island structure, but the amorphous olefin polymer portion is In addition, island portions are formed in the polymer particles. The average particle size of the island portion composed of the amorphous olefin polymer portion (including a part of the crystalline olefin polymer portion in some cases) is 0.5 μm or less, preferably 0.1 μm or less.
It is more preferable that the thickness be 0.00001 to 0.05 μm.

The average particle size of the island portion composed of the amorphous olefin polymer portion in the polymer particles is measured as described below.

Using an ultramicrotome, 500 to 100 polymer particles
Slice at 0 ° C at 0 ° C. Then, in the gas phase in about 1 sealed container containing 200 ml of 0.5% RuO ₄ aqueous solution,
The sliced sample is left for 30 minutes to stain the amorphous olefin polymer part in the sample. Next, the dyed sample is reinforced with carbon, and then observed with a transmission microscope. The particle size of the island is obtained for at least 50 particles, and the average value is defined as the average particle size of the island.

The polymer particles used in the present invention, it is preferable to use particles having the above properties, the method for producing particles having such properties is not particularly limited,
It is preferable to produce by adopting a method as described below, the polymer particles obtained by employing this method, the transition metal content in the ash content is usually 100 ppm or less, preferably 10 ppm or less, particularly preferably Is contained at a ratio of 5 ppm or less and a halogen content of usually 300 ppm or less, preferably 100 ppm or less, particularly preferably 50 ppm or less.

In the present invention, when a polymer is referred to, the polymer is used in a concept including both a homopolymer and a copolymer.

The polymer particles having the above properties can be obtained, for example, by polymerizing or copolymerizing an α-olefin having 2 to 20 carbon atoms.

Examples of such α-olefins include ethylene,
Propylene, butene-1, pentene-1, 2-methylbutene-1, 3-methylbutene-1, hexene-1, 3-
Methylpentene-1,4-methylpentene-1,3,3-
Dimethylbutene-1, heptene-1, methylhexene-
1, dimethylpentene-1, trimethylbutene-1, ethylpentene-1, octene-1, methylpentene
1, dimethylhexene-1, trimethylpentene-1,
Ethylhexene-1, methylethylpentene-1, diethylbutene-1, propylpentene-1, decene-1,
Examples thereof include α-olefins such as methylnonene-1, dimethyloctene-1, trimethylheptene-1, ethyloctene-1, methylethylheptene-1, diethylhexene-1, dodecene-1, and hexadodecene-1.

Among them, α-olefins having 2 to 8 carbon atoms are preferably used alone or in combination.

In the present invention, the repeating unit derived from the α-olefin is usually at least 50 mol%, preferably at least 80 mol%, more preferably at least 90 mol%, particularly preferably at least 90 mol%.
Polymer particles containing 100 mol% are used.

In the present invention, examples of other compounds that can be used in addition to the above-mentioned α-olefin include a chain polyene compound and a cyclic polyene compound. In the present invention, as the polyene compound, a polyene having two or more conjugated or non-conjugated olefinic double bonds is used. As such a chain polyene compound,
Specifically, 1,4-hexadiene, 1,5-hexadiene,
1,7-octadiene, 1,9-decadiene, 2,4,6-octatriene, 1,3,7-octatriene, 1,5,9-decatriene, divinylbenzene and the like are used. Specific examples of the cyclic polyene compound include 1,3-cyclopentadiene, 1,3-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, dicyclopentadiene, and dicyclopentadiene. Cyclohexadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, 5-isopropylidene-2-norbornene, methylhydroindene, 2,3
-Diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-
Propenyl-2,5-norbornadiene and the like are used.

In the present invention, a polyene compound obtained by condensing a cyclopentadiene such as cyclopentadiene with an α-olefin such as ethylene, propylene, and butene-1 using a Diels-Alder reaction can also be used. .

Furthermore, in the present invention, a cyclic monoene can be used. Specific examples of such a cyclic monoene include cyclopropene, cyclobutene, cyclopentene, cyclohexene, 3-methylcyclohexene, cycloheptene, cyclooctene, cyclodecene, Monochloroalkenes such as cyclododecene, tetracyclodecene, octacyclodecene, cycloeicosene, norbornene,
5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-
Dimethyl-2-norbornene, 5,5,6-trimethyl-2
-Bicycloalkenes such as norbornene and 2-bornene;
Tricycloalkenes such as 2,3,3a, 7a-tetrahydro-4,7-methano-1H-indene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene, 1,4,5 , 8-Dimethano-
1,2,3,4,4a, 5,8,8a-Octahydronaphthalene and these compounds, in addition to 2-methyl-1,4,5,8-dimethano-1,2,3,4, 4a, 5,8,8a-octahydronaphthalene, 2
-Ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-propyl-1,4,5,8-dimethano-1,2 , 3,4,4a, 5,8,8a-octahydronaphthalene,
2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a
-Octahydronaphthalene, 2-stearyl-1,4,5,8
-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-methyl-3-
Ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-chloro-1,4,5,8-dimethano-1,2, 3,4,4a, 5,8,8a-octahydronaphthalene, 2-
Bromo-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2, 3,4,4a, 5,8,8a-octahydronaphthalene, 2,3
-Dichloro-1,4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a-
Tetracycloalkenes such as octahydronaphthalene,
Hexacyclo [6,6,1,1 ^3,6, 1 ^10,13, 0 ^2,7, 0 ^9,14] heptadecene -4 pentacyclo [8,8,1 ^2,9, 1 ^4,7, 1 ^{11 , 18} , 0,0
^3,8, 0 ^12,17] henicosenoic -5, octacyclo [8,8,1
^2,9, 1 ^4,7, 1 ^{11, 18,} 1 ^{13, 16,} 0, 0 ^3,8, 0 ^12,17] docosenoic -5
And cyclic monoene compounds such as polycycloalkenes.

Furthermore, in the present invention, styrene and substituted styrene can also be used.

The polymer particles used in the present invention are obtained by polymerizing or copolymerizing at least the α-olefin as described above in the presence of a catalyst as described below. It can be carried out in the gas phase (gas phase method) or in the liquid phase (liquid phase method).

The polymerization reaction or copolymerization reaction by the liquid phase method is preferably performed in a suspension state so that the polymer particles to be produced are obtained in a solid state.

In the case of this polymerization reaction or copolymerization reaction, an inert hydrocarbon can be used. The raw material α-
An olefin may be used as a reaction solvent. The above polymerization or copolymerization may be performed by combining a liquid phase method and a gas phase method. In the production of the polymer particles used in the present invention, the polymerization or copolymerization is preferably carried out by a gas phase method, or a method of performing a reaction using an α-olefin as a solvent and then combining the gas phase method. .

In the present invention, when producing polymer particles used as a raw material, a method of simultaneously producing a crystalline olefin polymer portion and an amorphous olefin copolymer portion by supplying two or more types of monomers to a polymerization vessel, Alternatively, there is a method in which the synthesis of a crystalline olefin polymer part and the synthesis of an amorphous olefin polymer part can be performed separately and in series using at least two or more polymerization kettles. In this case, the latter method is preferred from the viewpoint that the molecular weight, composition, and amount of the amorphous olefin polymer portion can be freely changed.

The most preferred method is to synthesize a crystalline olefin polymer part by gas phase polymerization and then synthesize an amorphous olefin polymer part by gas phase polymerization, or a method of synthesizing a crystalline olefin polymer part using a monomer as a solvent. After the synthesis, a method of synthesizing an amorphous olefin polymerization portion by gas phase polymerization may be mentioned.

In the present invention, when performing the above-mentioned polymerization reaction or copolymerization reaction, usually, a catalyst component [A] containing a transition metal and an organometallic compound catalyst component [B] ] Is used.

As the catalyst component [A], the periodic table IV B
Group, a catalyst containing a transition metal atom of group VB,
Among these, a catalyst component containing at least one atom selected from the group consisting of titanium, zirconium, hafnium, and vanadium is more preferable.

Further, as another preferred catalyst component [A], a catalyst component containing a halogen atom and a magnesium atom in addition to the above-mentioned transition metal atom, a conjugated π electron to a transition metal atom belonging to Group IVB or VB of the periodic table. And a catalyst component containing a compound having a group coordinated thereto.

In the present invention, the catalyst component [A] is present in the reaction system in a solid state during the above-mentioned polymerization reaction or copolymerization reaction, or is present in a solid state by being supported on a carrier or the like. It is preferred to use a catalyst prepared so that

Hereinafter, a solid catalyst component [A] containing a transition metal atom, a halogen atom and a magnesium atom as described above.
This will be described in more detail with reference to an example.

The average particle size of the solid catalyst component [A] as described above is preferably 2 to 200 μm, more preferably 5 to 100 μm.
μm, particularly preferably in the range from 10 to 80 μm. The geometric standard deviation (δ _g ) as a scale for observing the particle size distribution of the solid catalyst [A] is preferably in the range of 1.0 to 3.0, more preferably 1.0 to 2.1, and particularly preferably 1.0 to 1.7.

Here, the average particle size and the particle size distribution of the catalyst component [A] can be measured by a light transmission method. Specifically, the dispersion prepared by adding the catalyst component [A] to the decalin solvent so as to have a concentration of 0.1% by weight is taken into a measuring cell, and the cell is irradiated with a fine light, and the particles are irradiated with the fine light. The particle size distribution is measured by continuously measuring the change in the intensity of light passing through.
The standard deviation (δ _g ) is determined from the lognormal distribution function based on the particle size distribution. More specifically, the standard deviation (δ _g ) is determined as the ratio (θ ₅₀ / θ ₁₆ ) between the average particle diameter (θ ₅₀ ) and the particle diameter (θ ₁₆ ) which becomes 16% by weight in view of the small particle diameter. Can be The average particle size of the catalyst is a weight average particle size.

The catalyst component [A] preferably has a shape such as a true sphere, an oval sphere, or a granule, and the particle has an aspect ratio of preferably 3 or less, more preferably 2 or less, and particularly preferably 1.5 or less. It is.

The aspect ratio can be determined by observing a group of catalyst particles with an optical microscope and measuring the major axis and the minor axis of 50 catalyst particles arbitrarily selected at that time.

When the catalyst component [A] has a magnesium atom, a titanium atom, a halogen atom, and an electron donor, the ratio of magnesium / titanium (atomic ratio) is preferably larger than 1, and this value is usually 2 to 50, preferably The halogen / titanium (atomic ratio) is usually in the range of 6 to 30.
-100, preferably 6-40, and the electron donor / titanium (molar ratio) is usually 0.1-10, preferably 0.2-2.
-6. The specific surface area of the catalyst component [A] is usually at least 3 m ² / g, preferably at least 40 m / ² g, more preferably in the range of 100 to 800 m ² / g.

Such a catalyst component [A] generally does not desorb the titanium compound in the catalyst component by a simple operation such as washing with hequinsan at room temperature.

In addition, the catalyst component [A] used in the present invention may contain other atoms and metals in addition to the above components, and further, a functional group or the like is introduced into the catalyst component [A]. May be further diluted with an organic or inorganic diluent.

The catalyst component [A] as described above includes, for example, an average particle diameter,
The particle size distribution is in the above-mentioned range, and furthermore, after forming the magnesium compound as described above, a method of preparing a catalyst, or contacting a liquid magnesium compound and a liquid titanium compound to form the particles as described above. It can be manufactured by employing a method such as a method of forming a solid catalyst so as to have properties.

Such a catalyst component [A] can be used as it is, or can be used after supporting a magnesium compound, a titanium compound and, if necessary, an electron donor on a carrier having a uniform shape. It is also possible to prepare a fine powder catalyst in advance, and then to granulate the fine powder catalyst into the above-mentioned preferable shape.

Such a catalyst component [A] is disclosed in JP-A-55-13.
Nos. 5102, 55-135103, 56-811 and 56-67311 and Japanese Patent Application Nos. 56-1811019 and 61-21109.

An example of a method for preparing the catalyst component [A] described in these publications or specifications will be described.

(1) A solid magnesium compound / electron donor complex having an average particle diameter of 1 to 200 μm and a geometric standard deviation (δ _g ) of particle size distribution of 3.0 or less is converted into an electron donor and / or an organoaluminum compound or halogen-containing silicon. It is reacted with a liquid titanium halide compound, preferably titanium tetrachloride, under the reaction conditions, with or without pretreatment with a reaction auxiliary such as a compound.

(2) reacting a liquid magnesium compound having no reducing ability with a liquid titanium compound, preferably in the presence of an electron donor, to have an average particle diameter of 1 to 200 μm;
Solid components having a geometric standard deviation (δ _g ) of particle size distribution of 3.0 or less are precipitated. Further, if necessary, the reaction is carried out with a liquid titanium compound, preferably titanium tetrachloride, or with a liquid titanium compound and an electron donor.

(3) By pre-contacting a liquid magnesium compound having a reducing ability and a reaction aid capable of eliminating the reducing ability of a magnesium compound such as a polysiloxane or a halogen-containing silicon compound, the average particle diameter is reduced. 1 to 200 μm, geometric standard deviation of particle size distribution (δ
_g ) After depositing a solid component having a value of 3.0 or less, the solid component is reacted with a liquid titanium compound, preferably titanium tetrachloride, or a titanium compound and an electron donor.

(4) After contacting a magnesium compound having a reducing ability with an inorganic carrier such as silica or an organic carrier, and then contacting the carrier with a halogen-containing compound or without contacting the same, a liquid titanium compound, preferably tetrachloride Contacting titanium or a titanium compound and an electron donor to react a magnesium compound supported on a carrier with a titanium compound or the like.

(5) In the method of (2) or (3), the Mg compound is supported on an inorganic carrier such as silica or alumina or an organic carrier such as polyethylene, polypropylene or polystyrene in the presence of these carriers.

Such a solid catalyst component [A] has a property that a polymer having high stereoregularity can be produced with high catalytic efficiency. For example, when propylene homopolymerization is carried out using this solid catalyst component [A], polypropylene having an isotacticity index (boiling n-heptane insoluble matter) of 92% or more, particularly 96% or more, is added to 1 mmol of titanium. The amount can be usually 3000 g or more, preferably 5000 g or more, and particularly preferably 10,000 g or more.

Examples of a magnesium compound, a halogen-containing silicon compound, a titanium compound, and an electron donor that can be used in the preparation of the catalyst component [A] as described above are shown below. The aluminum component used in the preparation of the catalyst component [A] is a compound exemplified in the later-described organometallic compound catalyst component [B].

Specific examples of the magnesium compound include inorganic magnesium compounds such as magnesium oxide, magnesium hydroxide, and hydrotalcite; carboxylate salts of magnesium, alkoxymagnesium, allyloxymagnesium, alkoxymagnesium halide, allyloxymagnesium halide, and magnesium dichloride. In addition to halides, organic magnesium compounds such as dialkyl magnesium, Grignard reagent, and diaryl magnesium are used.

As the titanium compound, specifically, titanium tetrachloride,
Titanium halides such as titanium trichloride, alkoxytitanium halide, allyloxytitanium halide, alkoxytitanium, allyloxytitanium and the like are used. Among these, titanium tetrahalide is preferred, and titanium tetrachloride is particularly preferred.

As the electron donor, specifically, oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides, acid anhydrides and alkoxysilanes; Nitrogen-containing electron donors such as ammonia, amines, nitriles and isocyanates are used.

Specific examples of the compound that can be used as such an electron donor include methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, and isopropyl alcohol. , Cumyl alcohol and isopropyl benzyl alcohol
18 alcohols; phenols having 6 to 20 carbon atoms such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol (these phenols may have a lower alkyl group) A ketone having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone; an aldehyde having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolylaldehyde and naphthaldehyde Methyl formate, methyl acetate, ethyl acetate, vinyl acetate,
Propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, benzoate Methyl acrylate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, anisic acid Methyl, n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadicate, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, Rusanji n- butyl phthalate, di n- pentyl, diisopentyl phthalate, di n
-Hexyl, diisohexyl phthalate, di-n-phthalate
Organic acid esters having 2 to 30 carbon atoms such as heptyl, diisoheptyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide and ethylene carbonate C2 to C15 acid halides such as acetyl chloride, benzoyl chloride, toluic acid chloride and anisic acid chloride; carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran and anisole and diphenyl ether 2-20 ethers, preferably diethers; acid amides such as acetic acid amide, benzoic acid amide and toluic acid amide; methylamine, ethylamine, diethylamine, tributylamine, Perijin, tribenzylamine, aniline, pyridine, amines such as picoline and tetramethylenediamine; acetonitrile, nitriles such as benzonitrile and tolunitrile; trimethyl phosphite, such as triethyl phosphite P-
Organic phosphorus compounds having an OC bond; Ethyl silicate and alkoxysilanes such as diphenyldimethoxysilane are used. These electron donors can be used alone or in combination.

Among such electron donors, preferred electron donors include esters of organic acids or inorganic acids, alkoxy (aryloxy) silane compounds, ethers, ketones, tertiary amines, acid halides, and active hydrogens such as acid anhydrides. These compounds are compounds having no organic acids, and particularly preferred are organic acid esters and alkoxy (aryloxy) silane compounds. Among them, esters of aromatic monocarboxylic acids and alcohols having 1 to 8 carbon atoms, malonic acid, substituted malonic acid, substituted succinic acid and maleic acid Particularly preferred are esters and diethers of acids, substituted maleic acids, dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid and phthalic acid with alcohols having 2 or more carbon atoms. Of course, these electron donors do not need to be added to the reaction system at the time of preparing the catalyst component [A]. For example, a compound which can be converted to these electron donors is added to the reaction system, and this compound is prepared in the catalyst preparation process. Can be converted to the above-mentioned electron donor.

The catalyst component [A] obtained as described above can be purified by sufficiently washing it with a liquid inert hydrocarbon compound after preparation. Specific examples of the hydrocarbon that can be used in this washing include n-pentane, isopentane, n-hexane, isohexane, and n-pentane.
-Aliphatic hydrocarbon compounds such as heptane, n-octane, isooctane, n-decane, n-dodecane, kerosene, and liquid paraffin; alicyclic hydrocarbon compounds such as cyclopentane, methylcyclopentane, cyclohexane and methylcyclohexane; benzene And aromatic hydrocarbon compounds such as toluene, xylene and cymene; and halogenated hydrocarbon compounds such as chlorobenzene and dichloroethane.

Such compounds can be used alone or in combination.

In the present invention, as the organometallic compound catalyst component [B], it is preferable to use an organoaluminum compound having at least one Al-carbon bond in the molecule.

Examples of such organoaluminum compounds include: (i) the formula R ¹ _m Al (OR ² ) _{n Hp} X _q (where R ¹ and R ² typically have 1 to 15 carbon atoms,
Preferably 1 to 4 hydrocarbon groups may be the same or different. X is a halogen atom, and m is 0
≦ m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, and q is 0 ≦
A number of q <3, moreover m + n + p + q = organic aluminum compound represented by 3 a is), and (ii) formula M ¹ AlR ¹ ₄ (wherein M ¹ is Li, Na, a K, R ¹ is A complex alkylated product of aluminum and a metal of Group I of the periodic table represented by the same meaning as described above.

Specific examples of the organoaluminum compound represented by the above formula (i) include the compounds described below.

A compound represented by the formula R ¹ _m Al (OR ² ) _3-m (where R ¹
And R ² have the same meaning as described above, and m is preferably 1.5
≦ m ≦ 3).

A compound represented by the formula R ¹ _m AlX _3-m (where R ¹ has the same meaning as described above, X is a halogen, and m is preferably 0 <
m <3).

A compound represented by the formula R ¹ _m AlH _3-m (where R ¹ has the same meaning as described above, and m is preferably 2 ≦ m <3).

A compound represented by the formula R ¹ _m Al (OR ² ) _n X _q (where R ¹
And R ² are the same as above. X is halogen, 0 <m ≦ 3, 0
≦ n <3, 0 ≦ q <3, and m + n + q = 3).

Specific examples of the organoaluminum compound represented by the above formula (i) include trialkylaluminums such as triethylaminium, tributylaluminum, and triisopropylaluminum; trialkenylaluminums such as triisoprenylaluminum; and diethylaluminumethoxy. Aluminum alkoxides such as dibutylaluminum butoxide and alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide, and a partial material having an average composition represented by the formula R ¹ _2.5 Al (OR ² ) _0.5 Alkyl aluminums, such as diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide, etc. Alkyl aluminum sesquihalides such as alkyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide, and alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, and butyl aluminum dibromide Halogenated alkylaluminums, Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride, Alkylaluminums such as ethylaluminum dihydride, propylaluminum dihydride, etc. , Ethyl aluminum ethoxycyclolide, butyl aluminum bute Shikurorido, partially alkoxylated and halogenated alkylaluminum such as such as ethyl aluminum ethoxy bromide is used.

The organoaluminum compound used in the present invention is a compound similar to the compound represented by the formula (i) such as an organoaluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. You may. Specific examples of such _{compounds, (CH 2 H 5) 2} AlOAl (C 2 H 5) 2, (CH 4 H 9) 2 AlOAl (C 4 H 9) 2, and And the like.

Specific examples of the organoaluminum compound represented by the formula (ii) include LiAl (C ₂ H ₅ ) ₄ and L
i Al (C ₇ H ₁₅ ) _{4 and the} like. Among these, it is particularly preferable to use a trialkylaluminum, a mixture of a trialkylaluminum and an alkylaluminum halide, and a mixture of a trialkylaluminum and an aluminum halide.

When performing the polymerization reaction, it is preferable to use an electron donor [C] in addition to the catalyst component [A] and the organometallic compound catalyst component [B].

As such an electron donor [C], specifically,
Amines, amides, ethers, ketones, nitriles, phosphines, stibines, arsines, phosphoamides, esters, thioethers, thioesters, acid anhydrides, acid halides, aldehydes, alcoholates , Alkoxy (aryloxy) silanes, organic acids, Table I of the Periodic Table, Groups II, III and IV
Examples include amides of metals belonging to the group, and acceptable salts thereof. The salts can also be formed in a reaction system by a reaction between an organic acid and an organometallic compound used as the catalyst component [B].

Specific examples of these electron donors include the compounds exemplified above as the catalyst component [A]. Among these electron donors, particularly preferred electron donors include organic acid esters, alkoxy (aryloxy) silane compounds, ethers, ketones, acid anhydrides and amides. In particular, when the electron donor in the catalyst component [A] is a monocarboxylic acid ester, the electron donor is preferably an alkyl ester of an aromatic carboxylic acid.

When the electron donor in the catalyst component [A] is an ester of a dicarboxylic acid and an alcohol having 2 or more carbon atoms, the electron donor [C] has the formula R _n Si (OR ¹ ) _4- It is preferable to use an alkoxy (aryloxy) silane compound represented by _n (where R and R ¹ each represent a hydrocarbon group and 0 ≦ n <4) or an amine having a large steric hindrance.

Specific examples of such an alkoxy (aryloxy) silane compound include trimethylmethoxysilane, trimethoxyethoxysilane, dimethyldimethoxysilane, dimethylethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, and t-butylmethyldisilane. Ethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane,
Bis-o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolylmethoxysilane,
Bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, n-propyltriethoxy Silane, decylmethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso- Butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane , Vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanedimethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyl Triallyloxy silane, vinyl tris (β-methoxyethoxy silane), dimethyltetraethoxydisiloxane and the like are used. Among them, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane,
Phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis-p-tolylmethoxysilane, p-
Preferred are tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, diphenyldiethoxysilane, ethyl silicate and the like.

As the amine having a large steric hindrance, 2,2,6,6
-Tetramethylpiperidine, 2,2,5,5-tetramethylpyrrolidine, or derivatives thereof, tetramethylmethylenediamine and the like are particularly preferred. Among these compounds, as an electron donor used as a catalyst component, an alkoxy (aryloxy) silane compound and a diether are particularly preferable.

Further, in the present invention, a catalyst component [i] containing a transition metal atom compound of Groups IVB and VB of the Periodic Table of the Elements having a group having a conjugated π electron as a ligand, and an organometallic compound catalyst component [ii] ] Can be preferably used.

Here, examples of the transition metals of Groups IVB and VB of the periodic table include metals such as zirconium, titanium, hafnium, chromium, and vanadium.

Examples of the ligand having a group having a conjugated π electron include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a t-butylcyclopentadienyl group, and a dimethylcyclopentadienyl group. Groups, alkyl-substituted cyclopentadienyl groups such as pentamethylcyclopentadienyl group, indenyl group, fluorenyl group and the like.

Further, at least two ligands having a cycloalkadienyl skeleton have a lower alkylene group or silicon,
Preferable examples include a group bonded through a group containing phosphorus, oxygen, and nitrogen.

Examples of such a group include groups such as an ethylenebisindenyl group and an isopropyl (cyclopentadienyl-1-fluorenyl) group.

One or more ligands having such a cycloalkadienyl skeleton coordinate with the transition metal, and
One is coordinated.

The ligand other than the ligand having a cycloalkadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen or hydrogen.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and the like. Specifically, examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. , An isopropyl group, a butyl group, and the like. Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. Examples of the aryl group include a phenyl group, a tolyl group, and the like. And a neofil group.

Examples of the alkoxy group include a methoxy group, an ethoxy group, and a butoxy group. Examples of the aryloxy group include a phenoxy group.

Examples of the halogen include fluorine, chlorine, bromine, and iodine.

Such a transition metal compound containing a ligand having a cycloalkadienyl skeleton used in the present invention, for example, when the valence of the transition metal is 4, more specifically, a compound represented by the formula R ² _k R ³ _l R ⁴ _m R ⁵ _n M (wherein, M is zirconium, titanium, hafnium, vanadium or the like, R ² is a group having a cycloalkadienyl skeleton, and R ³ , R ⁴ and R ⁵ are cycloalkaline A group having a dienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom or hydrogen, k is an integer of 1 or more, and k + l + m + n = 4) It is.

Particularly preferably, in the above formula, R ² and R ³ are groups having a cycloalkadienyl skeleton, and the two groups having a cycloalkadienyl skeleton are preferably a lower alkyl group or silicon, phosphorus, oxygen, nitrogen Is a compound bonded via a group containing

Hereinafter, specific examples of the transition metal compound containing a ligand having a cycloalkadienyl skeleton in which M is zirconium will be described.

Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium monobromide monohydride, bis (cyclopentadienyl) methylzirconium hydride, bis (cyclopentadienyl) ethylzirconium hydride, bis ( Cyclopentadienyl) phenyl zirconium hydride, bis (cyclopentadienyl) benzyl zirconium hydride, bis (cyclopentadienyl) neopentyl zirconium hydride, bis (methylcyclopentadienyl) zirconium monochloride hydride, bis (indenyl) zirconium Monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) ) Zirconium dibromide, bis (cyclopentadienyl) methyl zirconium monochloride, bis (cyclopentadienyl) ethyl zirconium monochloride, bis (cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium Monochloride, bis (cyclopentadienyl) benzylzirconium monochloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (t-butylcyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (indenyl) Zirconium dibromide, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diphenyl, bis (cyclope Tadienyl) zirconium dibenzyl, bis (cyclopentadienyl) zirconium methoxychloride, bis (cyclopentadienyl) zirconium ethoxychloride, bis (methylclopentadienyl) zirconium ethoxycyclolide, bis (cyclopentadienyl) zirconium phenoxycyclolide Bis (fluorenyl) zirconium dichloride, ethylenebis (indenyl) diethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium, ethylenebis (indenyl) ethylzirconium monochloride, ethylenebis (indenyl) zirconium dichloride, Isopropyl bisindenyl zirconium dichloride, isopropyl (cyclopentadienyl) 1-fluorenyl zirconium chloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis (indenyl) zirconium methoxymonochloride, ethylenebis (indenyl) zirconium ethoxymonochloride, ethylenebis (indenyl) zirconium phenoxymonochloride, ethylenebis ( Cyclopentadienyl) zirconium dichloride, propylene bis (cyclopentadienyl) zirconium dichloride, ethylenebis (t-butylcyclopentadienyl) zirconium dichloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) ) Dimethyl zirconium, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) methylzirconium monochloride, ethylenebis (4,5,6,7-tetrahydro-1-yne) Nil) zirconium dichloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dibromide, ethylenebis (4-methyl-1-indenyl) zirconium dichloride, ethylenebis (5-methyl-1-indenyl) ) Zirconium dichloride, ethylenebis (6-methyl-1-indenyl) zirconium dichloride, ethylenebis (7-methyl-1-indenyl) zirconium dichloride, ethylenebis (5-methoxy-1-indenyl) zirconium dichloride, ethylenebis (2 , 3-Dimethyl-1-indenyl) zirconium dichloride, ethylenebis (4,7-dimethyl-1-indenyl) zirconium dichloride, ethylenebis (4,7-dimethoxy-1-indenyl)
Zirconium dichloride.

In the above zirconium compound, a transition metal compound in which zirconium metal is replaced with titanium metal, hafnium metal, chromium metal, vanadium metal, or the like can also be used.

In this case, the organometallic compound catalyst component [ii]
For example, a conventionally known aluminoxane or organic aluminum oxy compound is used. The organoaluminum oxy compound is obtained, for example, by a reaction between an organoaluminum compound and water or a reaction between aluminoxane dissolved in a hydrocarbon solution and water or an active hydrogen-containing compound.

Such an organic aluminum oxy compound is insoluble or hardly soluble in benzene at 60 ° C.

In the present invention, the amount of the catalyst used varies depending on the type of the catalyst to be used and the like. For example, the catalyst component [A], the organometallic oxide catalyst component [B] and the electron donor [C] are used as described above. In the case or when the catalyst components (i) and (ii) are used, the catalyst component [A] or the catalyst component (ii) is usually used in an amount of 0.001 to 0.5 mmol, in terms of transition metal, per polymerization volume. Preferably 0.005-
The amount of the organometallic compound catalyst [B] used is 0.5 mmol, and the amount of the organometallic compound catalyst [B] used is 1 mole of the transition metal atom of the catalyst component [A] in the polymerization system.
Is usually used in an amount of 1 to 10,000 mol, preferably 5 to 500 mol. Further, when the electron donor [C] is used, the electron donor [C] is used in an amount of 100 mol or less, based on 1 mol of the transition metal atom of the catalyst component [A] in the polymerization system.
It is preferably used in an amount of 1 to 50 mol, particularly preferably 3 to 20 mol.

The polymerization temperature at the time of performing polymerization using the above-mentioned catalyst is usually 20 to 200 ° C., preferably 50 to 100 ° C., and the pressure is normal pressure to 100 kg / cm ² , preferably ^{2 to} 50 kg / cm ² It is.

In the present invention, it is preferable to carry out preliminary polymerization prior to main polymerization. When performing prepolymerization,
As the catalyst, at least the catalyst component [A] and the organometallic compound catalyst component [B] are used in combination, or the catalyst component (i) and the catalyst component (ii) are used in combination.

When titanium is used as the transition metal, the polymerization amount in the prepolymerization is usually 1 per 1 g of the titanium catalyst component.
~ 2000g, preferably 3 ~ 1000g, particularly preferably 10 ~ 50g
It is 0g.

The prepolymerization is preferably carried out using an inert hydrocarbon solvent. Examples of such an inert hydrocarbon solvent include propane, butane, n-pentane, i-pentane,
-Pentane, n-hexane, i-hexane, n-heptane, n-octane, i-octane, n-decane, n-dodecane, aliphatic hydrocarbons such as kerosene, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane Alicyclic hydrocarbons such as benzene, toluene,
Aromatic hydrocarbons such as xylene, methylene chloride,
Halogenated hydrocarbon compounds such as ethyl chloride, ethylene chloride and chlorobenzene are used. Among them, aliphatic hydrocarbons are preferred, and aliphatic hydrocarbons having 4 to 10 carbon atoms are particularly preferred. Further, a monomer used in the reaction can be used as a solvent.

As the α-olefin used for the prepolymerization,
Specifically, ethylene, propylene, 1-butene, 1-
Pentene, 4-methyl-1-pentene, 3-methyl-1
Α-olefins having 10 or less carbon atoms, such as -pentene, 1-heptene, 1-octene and 1-decene, are used, among which α-olefins having 3 to 6 carbon atoms are preferable, and propylene is particularly preferable. These α-olefins can be used alone or in combination of two or more as long as a crystalline polymer is produced.

In particular, polymer particles containing a large amount of the amorphous olefin polymer part and having good particle properties, for example, polymer particles containing the amorphous olefin polymer part in an amount of 30% by weight or more and having good particle properties. Is obtained by pre-polymerization, for example from 70 to
A method is proposed in which propylene and ethylene are copolymerized using a mixed gas consisting of 98 mol% of propylene and 30 to 2 mol% of ethylene.

The polymerization temperature in the prepolymerization differs depending on the α-olefin used and the use of the inert solvent and cannot be unconditionally specified, but is generally -40 to 80 ° C, preferably -20 to
It is 40 ° C, particularly preferably -10 to 30 ° C. For example, when propylene is used as the α-olefin, -40 to
70 ° C, -40 to 40 ° C when using 1-butene, 4
-Methyl-1-pentene and / or 3-methyl-1
-When pentene is used, it is in the range of -40 to 70 ° C. It should be noted that a hydrogen gas can also be allowed to coexist in the reaction system for this preliminary polymerization.

Producing polymer particles by conducting the polymerization reaction (main polymerization) by introducing the above-mentioned monomer into the reaction system after or without the preliminary polymerization as described above, and then performing the preliminary polymerization. Can be.

The monomer used in the main polymerization may be the same as or different from the monomer used in the prepolymerization.

The polymerization temperature of the main polymerization of such an olefin is usually
The temperature is from -50 to 200C, preferably from 0 to 150C. The polymerization pressure is usually atmospheric pressure to 100 kg / cm ^2, preferably atmospheric pressure to 50 kg / cm
² , and the polymerization reaction can be performed in any of a batch system, a semi-continuous system, and a continuous system.

The molecular weight of the obtained olefin polymer is hydrogen and / or
Or it can be adjusted by the polymerization temperature.

The polymer particles thus obtained contain a crystalline olefin polymer part and an amorphous olefin polymer part. And, in the present invention, the amorphous olefin polymer portion in the polymer particles is usually 20 to 80% by weight,
Preferably, it is contained in the range of 25 to 70% by weight, more preferably 30 to 60% by weight, particularly preferably 33 to 55% by weight. In the present invention, the content of such an amorphous olefin polymer can be determined by measuring the amount of a component soluble in n-decane at 23 ° C.

Further, the polymer particles used in the present invention, of the polymer constituting the polymer particles, the higher of the melting point of the crystalline olefin polymer portion or the glass transition point of the amorphous olefin polymer portion, whichever is higher. It is preferable that the polymer particles have not been substantially heated.

As described above, in the polymer particles which have not been substantially heated to a temperature equal to or higher than the higher of the melting point of the crystalline olefin polymer portion and the glass transition point of the amorphous olefin polymer portion, the amorphous The average particle size of the island portion composed of the functional olefin polymer portion is 0.5 μm or less, preferably 0.1 μm or less,
More preferably, it is 0.00001 to 0.05 μm.

The term “amorphous olefin polymer part” as used herein means a polymer that is soluble in n-decane at 23 ° C., and specifically refers to a polymer part separated by a solvent according to the following method.
That is, in the present specification, n with the addition of the polymer particles (3 g) is used.
After dissolving the decane (500 ml) solution at 140 to 145 ° C with stirring, stop stirring, cool to 80 ° C for 3 hours, cool to 23 ° C for 5 hours, and keep at 23 ° C for 5 hours. G-
A polymer obtained by filtering and separating using a 4-glass filter and removing n-decane from the obtained filtrate is referred to as “amorphous olefin polymer part”.

Examples of the crosslinking agent used in the present invention include organic peroxides, sulfur, phenolic vulcanizing agents, oximes, polyamines and the like. Peroxides and phenolic vulcanizing agents are preferred. Particularly, an organic peroxide is preferable.

Specific examples of the phenolic vulcanizing agent include an alkylphenol formaldehyde resin, a triazine-formaldehyde resin, and a melamine-formaldehyde resin.

As the organic peroxide, specifically, dicumyl peroxide, di-tert-butyl peroxide, 2,2
5-dimethyl-2,5-bis (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) Benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, dibenzoyl peroxide, tert-butylperoxybenzoate Are used. Of these, dibenzoyl peroxide and 1,3-bis (tert-butylperoxyisopropyl) benzene are preferred from the viewpoints of crosslinking reaction time, odor, and scorch stability.

In the present invention, the crosslinking agent is about 0.01 to 2 parts by weight, preferably 0.03 to 1.0 part by weight, more preferably 0.03 to 1.0 part by weight, based on 100 parts by weight of the finely powdered polymer particles as described above.
Used in amounts of 5 to 0.5 parts by weight.

Further, in order to realize the crosslinking reaction uniformly and moderately, it is preferable to add a crosslinking assistant. Specific examples of the crosslinking assistant include sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N, 4-dinitrosoaniline, nitrobenzene, diphenylguanidine, and trimethylolpropane. A peroxy crosslinking auxiliary such as -N, N'-m-phenylenedimaleimide or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, etc. And polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate. By using such a compound, a uniform and mild crosslinking reaction can be expected. In particular, divinylbenzene is easy to handle, has good compatibility with polymer particles, has an organic peroxide solubilizing effect, and also acts as a peroxide dispersing agent. This is most preferable because a molded article of a thermoplastic elastomer having a balance between properties and physical properties can be obtained.

In the present invention, such a crosslinking aid is used in an amount of 0.1 to 2 parts by weight, particularly 0.3 to 1 part by weight, based on 100 parts by weight of the finely powdered polymer particles, and is blended in this range. By doing so, a thermoplastic elastomer having excellent fluidity can be obtained, and a thermoplastic elastomer molded product having no change in physical properties due to heat history during processing and molding can be obtained.

In the present invention, when producing a thermoplastic elastomer molded product, in addition to finely powdered polymer particles, a crosslinking agent and a crosslinking aid, if necessary, polyisobutylene, a peroxide non-crosslinked type represented by butyl rubber, etc. The cross-linking reaction of the finely divided polymer particles can also be carried out in the presence of a hydrocarbon-based rubbery substance and / or a mineral oil-based softener.

Mineral oil-based softeners usually weaken the intermolecular force of rubber when rolling rubber to facilitate the processing, help disperse carbon black, white carbon, etc., or harden the vulcanized rubber. This is a high-boiling oil fraction used for the purpose of decreasing its hardness and increasing its flexibility or elasticity, and specifically, paraffinic, naphthenic or aromatic mineral oils are used.

Such a mineral oil-based softener, in order to further improve the flow properties of the thermoplastic elastomer, that is, moldability,
1 to 100 parts by weight, preferably 3 to 90 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the finely divided polymer particles.
It is blended in such an amount that it becomes 80 parts by weight.

In addition, the finely divided polymer particles used in the present invention,
Alternatively, a stabilizer containing fine particles of polymer particles and a crosslinking agent may be blended with a stabilizer. Specific examples of such a stabilizer include a phenol-based stabilizer, a phosphorus-based stabilizer, a sulfur-based stabilizer, a hindered amine-based stabilizer, and a higher fatty acid-based stabilizer.

Stabilizers such as those described above are pulverized products of polymer particles 10
0 to 10 parts by weight, preferably 0.01 to 10 parts by weight, preferably 0.05 to
Preferably, it is used in an amount of 5 parts by weight.

In addition, the finely divided polymer particles used in the present invention,
Alternatively, fillers such as calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, mica powder, asbestos, alumina, barium sulfate , Aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber,
Glass spheres, shirasu balloons, carbon fibers or colorants such as carbon black, titanium oxide, zinc white, red iron, ultramarine, navy blue, azo dyeing, nitroso dyes, lake pigments, phthalocyanine pigments and the like can also be blended.

The pulverized product of the polymer particles used in the present invention is 20
It is 400 to 400 mesh, preferably 42 to 200 mesh, and more preferably 65 to 150 mesh, and can be obtained by, for example, pulverizing the polymer particles.

In the present invention, the finely powdered polymer particles as described above are adhered in a fluidized plastic state to the inner surface of the crimp pattern transfer mold in a rotationally heated state in the presence of a crosslinking agent and melted. By crosslinking, a grain pattern is formed on the surface of the obtained thermoplastic elastomer molded product.

In the present invention, the phrase “the grain pattern transfer mold is in a rotationally heated state” refers to a state in which the grain pattern transfer mold is heated by, for example, a heater while being rotated. As described above, when the grain transfer mold is in a rotationally heated state, the finely powdered polymer particles in the sealed grain transfer mold are in a fluid plastic state, and the grain transfer is performed. A thermoplastic elastomer molded article having a grain pattern obtained by closely contacting the inner surface of the mold and melting to form a grain pattern on the surface is obtained.

In the present invention, the pulverized product of the polymer particles as described above penetrates deeply into the inside of the grain on the inner surface of the mold for transferring a grain pattern having fine irregularities, and adheres to the inner surface of the mold. As a result, a deep grain can be obtained as compared with a conventional molded article made of a vinyl chloride resin with a grain pattern. Incidentally, in the present invention, a thermoplastic elastomer molded article having a grain pattern having a grain depth of 150 μm or more is obtained, whereas a molded article having a grain depth of about 90 μm is obtained with a conventional vinyl chloride resin. It was a limit.

Next, an example of a method for producing a thermoplastic elastomer molded article having a grain pattern according to the present invention will be described with reference to the drawings.

FIG. 1 is a schematic cross-sectional view of a rotary molding apparatus used for producing a thermoplastic elastomer molded article having a grain pattern according to the present invention.

First, the finely powdered polymer particles are put into a grain transfer imprinting mold 1 in the presence of a crosslinking agent, and the mold 1 is sealed.

In the present invention, since such a finely powdered polymer particle is used, the shape of the mold 1 is not particularly limited, and dies having various shapes can be used. Can be manufactured.

Next, the grain-pattern transfer mold 1 is heated while rotating, so that the above-mentioned polymer particle pulverized product is brought into close contact with the mold inner surface in a fluid plastic state and melted.

When heating while rotating the mold 1, it is preferable to perform the heating in an atmosphere of an inert gas such as nitrogen or carbon dioxide.

 The heating temperature is usually 150 to 210 ° C.

In the present invention, since the grain pattern transfer mold 1 is heated while rotating using the mixture powder as described above, the polymer particles in the mold 1 are pulverized by fluid plasticization. And deeply penetrates into the inside of the grain provided on the inner surface of the mold 1 and closely adheres to the inner surface of the mold 1 to melt. Therefore, in the present invention, a thermoplastic elastomer molded article having a deep grain pattern can be obtained.

In the present invention, a crosslinking reaction is performed during the above-mentioned melting to produce a thermoplastic elastomer, and molding is performed simultaneously with the production.

Next, the grain transfer mold 1 is cooled to obtain a thermoplastic elastomer molded article having a grain pattern on the surface.

Examples of the cooling method include a method using air cooling and a method using water cooling.

The thermoplastic elastomer molded article having a grain pattern obtained by the production method according to the present invention is excellent in scratch resistance, appearance, and texture, but has already been filed by the applicant of the present invention and
By applying the surface treatment described in the specification of JP-A-62-331718 to the surface of the molded article, even better scratch resistance, appearance,
A thermoplastic elastomer molded article having a texture with a texture is obtained.

That is, as the surface treatment, first, a primer layer containing at least one compound selected from a saturated polyester and a chlorinated polyolefin is formed on the surface of the thermoplastic elastomer molded article having a grain pattern, and further, on this primer layer, To form a top coat layer containing at least one compound selected from a saturated polyester, an acrylate resin and an isocyanate resin. However, if the primer layer contains only a saturated polyester among at least one compound selected from a saturated polyester and a chlorinated polyolefin, the top coat layer must contain at least an acrylate resin. No.

In order to form a primer layer on the surface of a molded product, at least one compound selected from a saturated polyester and a chlorinated polyolefin is dissolved in an organic solvent, and the obtained coating liquid for forming a primer layer is molded according to a conventional method. It may be applied on the surface of the object.

Further, in order to form a top coat layer on the primer layer, at least one compound selected from a saturated polyester, an acrylate resin and an isocyanate resin is dissolved in an organic solvent, and the obtained top coat layer forming coating is applied. The solution may be applied on the primer layer according to a conventional method.

Effect of the Invention The grain-patterned thermoplastic elastomer molded product according to the present invention is obtained by pulverizing polymer particles comprising a crystalline olefin polymer part and an amorphous olefin polymer part in the presence of a crosslinking agent. In, the inner surface of the mold for transferring the grain pattern in the rotational heating state, in close contact with the fluid plastic state and melting,
Since a grain pattern is formed on the surface, not only a grain pattern having a small grain depth, but also a grain pattern having a greater grain depth can be formed as compared with a conventional PVC resin molded article with a grain pattern. This has the effect that there is no reduction in mechanical properties.

In addition, the thermoplastic elastomer molded article with a grain pattern according to the present invention has excellent elasticity and high strength even with a small rubber content, and has high strength, and is uniform, and has strength properties such as impact strength and tensile strength, toughness, and the like. There is an effect of being excellent in heat resistance, flexibility at low temperature, surface smoothness, paintability, and the like.

Further, according to the production method of the present invention, the thermoplastic elastomer production step and the powdering step thereof can be omitted, and a thermoplastic elastomer molded article having a grain pattern having the above-mentioned effects can be obtained. .

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

The thermoplastic elastomer molded products with a grain pattern obtained in Examples and Comparative Examples were evaluated for tensile properties, surface hardness, heat aging properties, grain depth, and gloss by the following methods. A sample for evaluation was punched out from the obtained molded product.

[Evaluation method] (1) Tensile properties According to the method of JIS K-6301.

(2) Surface hardness According to the method described in ASTM D 2240.

(3) Thermal aging characteristics After leaving the sample in an air oven at 120 ° C for 1000 hours, the sample was taken out and JI
It was measured by the tensile test method of SK-6301.

(4) Depression depth The distance from the peak to the valley of the emboss transferred to the surface of the molded product was measured.

(5) Gloss In accordance with JIS Z 8741 (a method for measuring specular gloss), the surface of the molded article subjected to graining was irradiated with light at an incident angle of 60 degrees, and the reflectance was expressed in%.

[Adjustment of the catalyst component [A]] Sufficiently use a high-speed stirrer (manufactured by Tokushu Kika Kogyo) with an internal volume of 2
After replacing with N ₂ , 700 ml of purified kerosene, 10 g of commercially available MgCl ₂ , 24.2 g of ethanol, and ₃ g of Emazol 320 (trade name, sorbitan distearate, manufactured by Kao Atlas Co., Ltd.) were added. The mixture was stirred at 800 rpm for 30 minutes. Under high-speed stirring, using a Teflon tube having an inner diameter of 5 mm, the solution was transferred to a glass flask 2 (with a stirrer) into which purified kerosene 1 previously cooled to -10 ° C was charged. The resulting solid was collected by filtration and washed sufficiently with hexane to obtain a carrier.

After suspending 7.5 g of the carrier in 150 ml of titanium tetrachloride at room temperature, 1.3 ml of diisobutyl phthalate was added and the system was treated with 120 ml of titanium tetrachloride.
The temperature was raised to ° C. After stirring and mixing at 120 ° C. for 2 hours, a solid portion was collected by filtration, suspended again in 150 ml of titanium tetrachloride, and again stirred and mixed at 130 ° C. for 2 hours. Further, a reaction solid was collected from the reaction product by filtration and washed with a sufficient amount of purified hexane to obtain a solid catalyst component (A). This component is composed of titanium 2.2% by weight, chlorine 63% by weight, magnesium 20% by weight, diisobutyl phthalate 5.5% in atomic conversion.
% By weight. A spherical catalyst having an average particle size of 64 μm and a geometric standard deviation (δ _g ) of the particle size distribution of 1.5 was obtained.

[Preliminary polymerization] The following preliminary polymerization was performed on the catalyst component [A].

After charging 200 ml of purified hexane into a 400 ml glass reactor purged with nitrogen, 20 mmol of triethylaluminum, 4 mmol of diphenyldimethoxysilane and 2 mmol of the Ti catalyst component [A] were charged in terms of titanium atoms, Propylene was supplied at a rate of 5.9 Nl / hour over 1 hour, and 2.8 g of propylene was polymerized per 1 g of the Ti catalyst component [A]. The temperature during the polymerization was kept at 20 ± 2 ° C. After the preliminary polymerization, the liquid part was removed by filtration, and the separated solid part was suspended again in decane.

[Polymerization] Production of copolymer (I) 2.0 kg of propylene and hydrogen
After adding 9N liter, the temperature was raised. At 50 ° C., 15 mmol of triethylaluminum, 1.5 mmol of cyclohexylmethyldimethoxysilane, and 0.05 mmol of a prepolymerized product of the catalyst component [A] in terms of titanium atom were added. Was kept at 70 ° C. Thirty minutes after the temperature reached 70 ° C., the vent valve was opened, and propylene was purged until the pressure inside the polymerization reactor reached normal pressure. After purging, copolymerization was subsequently carried out. That is, ethylene is 480 Nl / hour, propylene is 720 Nl / hour, and hydrogen is 12 Nl / hour.
It was fed to the polymerization vessel at the rate of the time. The pressure in the polymerization vessel is 10kg / c
The vent opening of the polymerization vessel was adjusted so as to obtain m ² · G. The temperature during the copolymerization was kept at 70 ° C. After a copolymerization time of 150 minutes had elapsed, the resulting polymer was depressurized and weighed 2.5 kg at 230 ° C.
MI under a load of 2 kg = 3.9 g / 10 min, ethylene content 28 mol%,
The apparent bulk specific gravity was 0.47. The amount of the n-decane soluble component at 23 ° C. was 28% by weight, and the ethylene content in the soluble component was
47 mol%.

The powder of the copolymer (I) has an average particle diameter of 2200 μm.
m, 0.1% by weight of the particles passing through the 150 mesh, and the falling time was 8.5 seconds. The geometric standard deviation of the polymer particles was 1.5.

Production of Copolymers (2) and (3) In the production of the copolymer (1), the copolymerization conditions were changed as follows, and the copolymerization conditions were changed as shown in Table 1. Copolymers (2) and (3) were produced in the same manner as in producing polymer (1).

The powder of the copolymer (2) has an average particle diameter of 2100 μm.
m, apparent density was 0.43 g / ml, particles passing through 150 mesh were 0.1% by weight, and fall time was 9.3 seconds. The geometric standard deviation of the polymer particles was 1.5.

Further, the powder of the above copolymer (3) has an average particle diameter.
2000 μm, apparent density 0.40 g / ml, particles passing through 150 mesh is 0.2% by weight, falling time is 1
0.3 seconds. The geometric standard deviation of the polymer particles is
1.6.

Table 1 shows the physical properties of the obtained copolymers (2) and (3).

[Preliminary polymerization] The following preliminary polymerization was performed on the catalyst component [A]. 400 ml of purified hexane was charged into one glass reactor purged with nitrogen, and 1.32 mmol of triethylaluminum, 0.27 mmol of cyclohexylmethyldimethoxysilane and
After charging 0.132 mmol of Ti catalyst component [A] in terms of titanium atom, propylene gas and ethylene gas were each added in 8.
The mixture was fed at a rate of 4 Nl / hr and 1.0 Nl / hr to the liquid phase of the polymerization vessel for 100 minutes while mixing. The temperature during prepolymerization is 20 ± 2.
C. After the preliminary polymerization, the liquid part was removed by filtration, and the separated solid part was suspended again in decane.

As a result of the analysis, in the prepolymerized solid catalyst, about 92 g of the polymer was present on 1 g of the used Ti catalyst component [A], while the separated filtrate contained the used Ti catalyst component [A]. Per 1g
There was 6.2 g of solvent soluble polymer.

Example 1 [Manufacture of molded article] First, the above copolymer was placed in a mold for transferring a grain pattern having a grain pattern with a grain depth of 150 μm on the inner surface, which was a mold for taking two dashboards for automobiles. 100 parts by weight of 42-80 mesh powder obtained by pulverizing (1) in an atmosphere of -60 ° C, 0.2 part by weight of 1,3-bis (tert-butylperoxyisopropyl) benzene, 0.3 part by weight of divinylbenzene and paraffin After a predetermined amount of a mixture powder obtained by mechanically mixing a solution dissolved and dispersed in 0.2 part by weight of the system process oil was added, the inside of the mold was placed under a nitrogen atmosphere.

Next, while rotating the mold, the mold was heated to 210 ° C. from the outside of the mold with a heater to flow-plasticize and melt the polymerized product of the polymer particles in the mold. During this time, 15
Heating was performed at 0 ° C. for 5 minutes and at 210 ° C. for 15 minutes.

Finally, the mold was cooled with water for 10 minutes to room temperature to obtain a thermoplastic elastomer molded article having a grain pattern.

With respect to the obtained thermoplastic elastomer molded article having a grain pattern, tensile properties, surface hardness, heat aging properties, grain depth, and gloss were evaluated by the methods described above.

 Table 2 shows the evaluation results.

Example 2 The procedure of Example 1 was repeated, except that the copolymer (2) was used instead of the copolymer (1), and the results shown in Table 2 were obtained.

Example 3 The procedure of Example 1 was repeated, except that the copolymer (3) was used in place of the copolymer (1), and that no paraffin-based process oil was used. I got

Example 4 In Example 3, 5 parts of paraffinic process oil were used.
Except for using parts by weight, the same procedure as in Example 3 was carried out, and the results in Table 2 were obtained.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of a rotary molding apparatus used for producing a thermoplastic elastomer molded article having a grain pattern according to the present invention. 1. Mold for transfer of grain pattern 2 .... Heater

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-281209 (JP, A) JP-A-59-221346 (JP, A) JP-A-2-57310 (JP, A) (58) Field (Int.Cl. ⁶ , DB name) B29C 41/00-41/52 C08J 3/24 C08L 23/00-33/26 B29K 23:00 B29L 31:52 B29L 31:58

Claims (4)

(57) [Claims] 1. A finely divided polymer particle comprising a crystalline olefin polymer part and an amorphous olefin polymer part,
In the presence of a cross-linking agent, a crimp pattern is formed on the inner surface of the crimp pattern transfer mold in a rotationally heated state by being closely adhered and melted in a fluidized plastic state, thereby forming a crimp pattern on the surface. Patterned thermoplastic elastomer molding. 2. The finely divided product of the polymer particles is 20 to 40.
2. The thermoplastic elastomer molded article with a grain pattern according to claim 1, wherein the molded article has a mesh of 0. 3. A pulverized product of polymer particles comprising a crystalline olefin polymer part and an amorphous olefin polymer part,
In the presence of a cross-linking agent, the mold is placed in a mold for transfer of a grain pattern, and the mold is sealed.Then, the mold is heated while being rotated so that the polymer particles are pulverized in a fluid plastic state. A method for producing a thermoplastic elastomer molded article having a grain pattern, wherein the thermoplastic elastomer molded article having a grain pattern on the surface is obtained by bringing the thermoplastic elastomer molded article into close contact with the inner surface of the mold and melting, and then cooling the mold. 4. A process for pulverizing the polymer particles, wherein
4. The method for producing a thermoplastic elastomer molded article having a grain pattern according to claim 3, wherein the molded article has a mesh of 0.