JPH03281209A - Thermoplastic elastomer molding with grain pattern and preparation thereof - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic elastomer molding with grain pattern with a deep grain depth and no decrease in mechanical properties by melt-adhering a finely powdered product of a polymer particle consisting of a crystalline olefin polymer part and an amorphous olefin polymer part on the inner surface of a mold for transferring a grain pattern in the presence of a crosslinking agent and forming thereby a grain pattern on the surface. CONSTITUTION:A thermoplastic elastomer molding with a grain pattern is prepd. by melt- adhering a finely powdered product of a polymer particle consisting of a crystalline olefin polymer part and an amorphous olefin polymer part on the inner surface of a mold for transferring a grain pattern in the presence of a crosslinking agent and forming thereby a grain pattern on the surface. A powder of a mixture contg. the finely powdered product of the polymer particle consisting of the crystalline olefin polymer part and the amorphous olefin polymer part and the crosslinking agent is sprayed on the inner surface of the heated mold 1 for transferring the grain pattern to melt-adhere the powder on the inner surface of the mold 1 and to crosslink it. The powder enters deeply into the inside of the grain treated on the inner surface of the mold 1 and melt-adheres thereon. The thermoplastic elastomer molding with the grain pattern on the surface thereof is obtd. by cooling the mold 1 for transferring the grain pattern.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a thermoplastic elastomer molded product with a textured pattern and a method for producing the same, and more particularly, to a mechanical molded product having a textured surface with a textured pattern consisting of fine irregularities, particularly a deep textured pattern. The present invention relates to a thermoplastic elastomer molded product with excellent physical properties and a method for producing the same.

Technical background of the invention and its problems Conventionally, vinyl chloride resin (PVC) has been widely used for molded products such as automobile dash boards and dolls. In particular, there is a high demand for embossed patterns, such as automobile dash boards, which have a strong image of luxury.

By the way, as a method for manufacturing vinyl chloride resin molded articles with grain patterns such as automobile dash boards and dolls as described above, a vinyl chloride resin powder for plastisol with a plasticizer such as dioctyl phthalate added thereto is injected into a mold. Alternatively, the so-called slush molding method, in which a mold is immersed in the powder, the powder is adhered to the mold surface, and molded by heating, is used to form a vinyl chloride resin sheet (PVC).
A method of vacuum forming a sheet (sheet) is known.

However, vinyl chloride resins have problems in that they are inferior in heat resistance, heat aging resistance, cold resistance, and light resistance. Also,
Even if a molded article with a grain pattern is produced by slush molding or vacuum forming using vinyl chloride resin as described above, the depth of the grain is about 90 μm. Therefore, the synthetic resin molding has a deeper grain pattern. The appearance of things was desired.

The present inventors conducted intensive research to obtain a synthetic resin molded product with a deeper grain pattern to replace the grained vinyl chloride resin molded product as described above, and found that the crystalline olefin polymer portion and the amorphous olefin By powder slush molding the finely powdered polymer particles consisting of the polymer moiety in the presence of a crosslinking agent, the production of thermoplastic elastomer and its powdering process can be omitted, and the mechanical properties can be improved. We have discovered that it is possible to obtain a molded product with no decrease in texture, deep grain depth, and excellent transferability of the grain pattern.
The present invention has now been completed.

Purpose of the Invention The present invention aims to solve the problems associated with the prior art as described above, and is an object of the present invention to provide a material with deeper grain depth and improved mechanical properties as an alternative to the grained vinyl chloride resin molded product. The object of the present invention is to provide a thermoplastic elastomer molded product with a grain pattern that does not deteriorate.

Another object of the present invention is to provide a method for producing a thermoplastic elastomer molded article with a textured pattern as described above, which can omit the thermoplastic elastomer production process and its powdering process.

Summary of the Invention The textured thermoplastic elastomer molded product according to the present invention is characterized in that finely powdered polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part are processed in the presence of a crosslinking agent. A textured pattern is formed on the surface by melting and adhering to the inner surface of a mold for transferring the textured pattern.

Further, the method for producing a thermoplastic elastomer molded product with a textured pattern according to the present invention includes the steps of: finely powdered polymer particles consisting of a crystalline olefin polymer portion and an amorphous olefin polymer portion; A thermoplastic elastomer molded product having a grain pattern on the surface is obtained by a powder slush molding method in which the mold is melted and adhered to the inner surface of a pre-heated grain pattern transfer mold in the presence of a mold, and then the mold is cooled. It is a feature.

DETAILED DESCRIPTION OF THE INVENTION The textured thermoplastic elastomer molded article and the method for producing the same according to the present invention will be specifically described below.

First, the textured thermoplastic elastomer molded article according to the present invention will be explained.

In the present invention, a finely powdered product of polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part is used.

The average particle diameter of the polymer particles used in the present invention before the pulverization treatment is usually 40 μm or more, preferably 40 to 5000 μm.
μm1 is more preferably in the range of 100 to 4000 μm1, particularly preferably 300 to 3000 μm. Also,
The geometric standard deviation indicating the particle size distribution of the polymer particles used in the present invention is usually 1.0 to 3.0, preferably 1.0.
~2.0, more preferably 1.0~. 1. ．． 5, particularly preferably from 1.0 to 3. Further, the apparent high density of the polymer particles used in the present invention due to natural fall is usually 0.2 g/m or more, preferably 0.2 to 2.
0,7 g/ml, more preferably 0.3
~0.7g/ml, particularly preferably 0.35-0.60
g/ml.

Further, the polymer particles used in the present invention are particles that pass through a 150 mesh, preferably 30 ffi% or less,
It is more preferably 10% by weight or less, particularly preferably 2% by weight or less. Further, such polymer particles have a fall time defined as below in seconds of 5 to 25 seconds, preferably 5 to 20 seconds, particularly preferably 5 to 15 seconds.

Note that the average particle diameter, apparent bulk density, and falling seconds of the polymer particles as described above are measured as follows.

Average particle size: 300 g of polymer particles were placed in a stainless steel sieve manufactured by Hhon Rikagaku Kikai with a diameter of 200 mm and a depth of 45 m + n (7 types of sieves with openings of 7.10, 14.20.42.80.150 mesh, in this order from top to bottom). Add it to the top two tiers (the trays are further stacked on the bottom tier) and put the lid on.
It was set in ER (Iida Seisakusho) and shaken for 2.20 minutes.

After shaking for 20 minutes, add to each sieve. Measure the weight of the polymer and compare the measurements. The numbers were plotted on established paper. the plot are connected by a curve, and the product is based on this curve. Particle size at 50% calculated weight (D5o) was determined, and this value was taken as the average particle diameter.

On the other hand, the geometric standard deviation was similarly determined from the particle diameter (D) of 16% by weight by integrating from the small particle diameter and the above-mentioned D5o value of 6. (Geometric standard deviation - D5o/D16) Apparent bulk density: Measured in accordance with Its K 6721-1977. (However, the inner diameter of the funnel used was 92.9 mmφ, and the inner diameter of the funnel 1 was 9.5 mmφ.) Using the device that measures falling seconds and bulk density as is, the sample was placed in the receiver. After dropping the sample into a 100 ml container, scrape the raised sample from the receiver with a glass rod, transfer the sample to the funnel with the damper inserted, and then pull the damper to allow the entire sample to fall from the bottom of the funnel. The time (seconds) required for this was defined as the number of falling seconds.

However, when measuring the number of seconds of falling, 1.5 to the average particle diameter of the sample By sieving particles that are 1.6 times larger The removed polymer particles were used.

When measuring the falling seconds, set the receiver on the vibration table of a powder tester (Type PT-D, SER, No. 71190 manufactured by Hosokawa Micro), and adjust the voltage of the rheostat so that the vibration 111 of the diaphragm becomes 1 m+n. The polymer particles were dropped while being adjusted and vibrated.

The polymer particles used in the present invention are composed of a crystalline olefin polymer part and an amorphous olefin polymer part, as shown in -1-, and have a so-called sea-island structure. The coalescing portion forms a local area in the polymer particle. 1. The local average particle diameter of this amorphous olefin polymer portion (including some crystalline olefin polymer portions as the case may be) is Q,5fzm or less, preferably 0.5fzm or less. 1μm or less, more preferably 0.00001
It is desirable that the thickness is 0.05 μm.

Note that the local average particle diameter of the amorphous olefin polymer portion in the polymer particles is measured as 17 as shown below.

Using an ultramicrotome, the polymer particles were
Slice into 1/1/1 0°C slices to a thickness of 1,000 people. then 0
．． 1 with 200 ml of an aqueous solution of 5% RuO4
The thinly sliced sample is placed in the gas phase in the airtight container of No. 1 for 30 minutes to dye the amorphous olefin polymer portion in the sample. Next, after reinforcing the dyed sample with carbon, it is observed using a transmission microscope, and the local particle size of at least 50 particles is determined, and the average value is taken as the local average particle size.

As the polymer particles used in the present invention, it is preferable to use particles having the above-mentioned characteristics, and there are no particular limitations on the method for producing particles having such characteristics, but the following methods may be used. The polymer particles obtained by this method have a transition metal content in the ash of usually 100 ppm or less, preferably 100 ppm or less, Oppm or less, particularly preferably 5 ppm or less, halogen content is usually a
o o ppm or less, preferably 1100 ppm or less,
It is particularly preferably contained in a proportion of 50 ppm or less.

In addition, when referring to a polymer in the present invention, the term "polymer" is used in a concept that includes both a homopolymer and a copolymer.

Polymer particles having the above characteristics can be obtained, for example, by polymerizing or copolymerizing α-olefins 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. -L3.3 dimethylbutene-1, heptene-1, methylhexene-11
Dimethylpentene-1, trimethylbutene-111 Ethylpentene-1, octene-1, methylpentene-1
, dimethylhexene-1, trimethylpentene-1, ethylhexene-1, published by methylethylpentene, diethylbutene-1, propylpentene-1, decene-1, methylnonene-1, dimethyloctene-1, trimethylhebutene-1, Mention may be made of α-olefins such as ethyl octene-11 methylethylhebutene-1, diethylhexene-1, dodecene-1 and hexadodecene-1.

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

In the present invention, polymer particles containing repeating units derived from the above α-olefin in an amount of usually 50 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, particularly preferably 100 mol% are used. used.

In the present invention, other compounds that can be used in addition to the above α-olefin include, for example, a chain polyene compound and a cyclic polyene compound 2. In the present invention, as the polyene compound, a polyene having two or more conjugated or non-conjugated olefinic double bonds is used, and as such a chain polyene compound, specifically, 1,4-hexadiene, 1.5-hexadiene, 1.7 octadiene, 1.9
-decadiene, 2,4.6-octatriene, l, 3
．． 7-octatriene, 1,5,9-decatriene, divinylbenzene, etc. are used. Further, specific examples of the cyclic polyene compound include 1.3-cyclopentadiene, 1.3-cyclohexadiene, 5ethyl-13-cyclohexadiene, 1.3-cyclohebutadiene, dicyclopentadiene, Dicyclohexadiene, 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, etc. are used.

In addition, in the present invention, cyclopentadiene such as cyclopentadiene 3 and ethylene, propylene,
A polyene compound obtained by condensing an α-olefin such as butene-1 using a Diels-Alder reaction can also be used.

Furthermore, in the present invention, cyclic monoenes can also be used, and specific examples of such cyclic monoenes include cyclopropene, cyclobutene, cyclopentene,
Monocycloalkenes such as cyclohexene, 3-methylcyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, teracyclodecene, octacyclodecene, cycloeicosene, norbornene,
5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5.6
-Simethyl-2-norbornene, 5.564limethyl-
Bicycloalkenes such as 2-norbornene and 2-bornene, 23.3 g, 7a-tetrahydro-47-methano-I
H-indene, 3a, 5.6.7a-tetrahuman O-
Tricycloalkenes such as 4,7-methano-IH-indene, I, 4,58-dimethano-1,2,3,4,4a
, 5.8.8a-octahydronaphthalene, onibi In addition to these compounds, 2-methyl 145.
8-dimethano-1,2,3,4,4a, 5.8.8a
-Octahydronaphthalene, 2 ethyl river, 4.5.8
- Dimethano 1234.4a 5.8.8a-Octahydronaphthalene, 2-Propyl, 4.5.8-Dimethano, 2.3.4.4a, 5.883-Octahydronaphthalene, 2-Hexyl-1 ,458-dimethano, 234.4a, 5.8.8a-octahydronaphthalene, 2-stearyl, 4.5.8-dimethano12,
3.4.4a, 5.8.8g-octahydronaphthalene, 23-dimethyl-1,4,5,8-dimethano,
2.3.4.4a, 588a-octahydronaphthalene, 2-methyl-3-ethyl, 4.5.8-dimethano-1,2,3,4,4a, 5.8.8a-octahydro macrophthalene , 2-chloro-1,4,5,8-dimethano-123,44a, 588a-octahydronaphthalene, 2-bromo, 4.5.8-dimethano, 2.
3.4.4a, 588a-octahydronaphthalene,
2-Fluoro-145,8-dimethano, 2.3.4
．． 4a, 5.8.8a-octahydronaphthalene, 2
．． 3-dichloro-1,4,5,8-dimethano 12344
a 5.8.8a-Tetracycloalkene with octahydronaphthalene, hexacyclo[6,65 3,610,13, o2.7.9.14], Futacha:, /,, 11 1 2.9 4 , 7 II, 18 pentacyclo[
8,8,I,1. 13.8 12.17 0.0. 0 ]] Henkokosen-5 Octashif 2.9 4.7 It, 18 13.16 3.
80 [8,8,I,1
,I,1. ．． 0.01
Examples include cyclic monoene compounds such as polycycloalkenes such as 2.17 0 ] tococene-5. Furthermore, styrene and substituted styrene can also be used in the present invention.

The polymer particles used in the present invention can be obtained by polymerizing or copolymerizing at least the above α-olefin in the presence of the following catalyst, but the above polymerization reaction or copolymerization reaction It can be carried out in the gas phase (vapor phase method) or in the liquid phase (liquid phase method).

The polymerization reaction or copolymerization reaction by the liquid phase method is preferably carried out in a suspended state so that the resulting polymer particles are obtained in a solid state.

An inert hydrocarbon can be used in this polymerization reaction or copolymerization reaction. Furthermore, the raw material α-olefin may be used as a reaction solvent.The above polymerization or copolymerization may be carried out in combination with a liquid phase method and a gas phase method. In the production of the polymer particles used in the present invention, the above polymerization or copolymerization is preferably carried out using a gas phase method, or a method in which a reaction is carried out using an α-olefin as a solvent followed by a 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 part and an amorphous olefin polymer part by supplying two or more types of monomers to a polymerization tank, or ,
One example is a method in which the synthesis of a crystalline olefin polymer portion and the synthesis of an amorphous olefin polymer portion can be carried out separately and in series using a polymerization kettle with at least two bases. 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 portion by gas phase polymerization and then synthesize an amorphous olefin polymer portion by gas phase polymerization, or to synthesize a crystalline olefin polymer portion using a monomer as a solvent. After synthesizing the polymer part, an amorphous olefin polymer part can be synthesized by gas phase polymerization.3 In the present invention, when carrying out the above polymerization reaction or copolymerization reaction,
Usually, a catalyst component [A] containing a transition metal and an organometallic compound catalyst component [A] of Groups 1, 2, and 2 of the Periodic Table of Elements
B] A catalyst consisting of the following is used.

The above catalyst component [A] is preferably a catalyst containing a transition metal atom of Group IVB or Group VB of the Periodic Table of Elements,
Among these, titanium, zirconia j1, hafnium,
More preferred is a catalyst component containing at least one type of atom selected from the group consisting of vanadium.

Other preferred catalyst components [A] 7 include catalyst components containing a halogen atom and a magnesium atom in addition to the above-mentioned transition metal atoms; A catalyst component containing a compound coordinated with a group having 7 is listed.

In the present invention, the catalyst component [A] is present in a solid state in the reaction system during the polymerization reaction or copolymerization reaction as described above, or is present in a solid state by being supported on a carrier or the like. It is preferable to use a catalyst prepared in such a way that

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

The average particle diameter of the solid catalyst component [A] as described above is:
Preferably 2 to 200 μm1, more preferably 5 to 10
0 μm1, particularly preferably within the range of 10 to 80 μm. Further, the geometric standard deviation (δ) as a measure of the particle size distribution of the solid catalyst [A] is preferably 1.0 to 3.0.
, more preferably 1.0 to 2.1, particularly preferably 1
．． It is within the range of 0 to 1.7.

Here, the average particle size and particle size distribution of the catalyst component [A] are:
It can be measured by a light transmission method.

9 Specifically, a dispersion prepared by adding the catalyst component [A] to a decalin solvent at a concentration of 0.61% by weight was placed in a measurement cell, and the cell was illuminated with a narrow light to ensure that the particles Particle size distribution is determined by continuously measuring changes in the intensity of light passing through it. Based on this particle size distribution, the standard deviation (δ) is determined from the number of lognormal distribution quantities. More specifically, the standard deviation (δ) is determined as the ratio (θ5o/θ16) between the average particle diameter (θ5o) and the particle diameter (θ16) which is 1-6% by weight considering the small particle size. Note that the average particle diameter of the catalyst is the weight average particle diameter.

Further, the catalyst component [A] preferably has a shape such as a true sphere, an elliptical sphere, or a granule, and the aspect ratio of the particles is preferably 3 or less, more preferably 2 or less, particularly preferably 1. 5 or less.

The aspect ratio is determined by observing the catalyst particle group with an optical microscope,
At that time, it is determined by measuring the long sleeve and short axis of 50 arbitrarily selected catalyst particles.

Further, when this catalyst component [A] has a magnesium atom, a titanium atom, a halogen atom, and an electron donor, the magnesium/titanium (atomic ratio) is preferably larger than 1, and this value is usually 2 to 50, preferably is 6
~30, halogen/titanium (atomic ratio) is usually in the range of 4 to 1-00, preferably 6 to 40, and electron donor/titanium (molar ratio) is usually in the range of 0 to 30. .1
~]0, preferably within the range of 0.2-6. Also, the specific surface area of this catalyst component [A] is usually 3 rr? /
g or more, preferably 40rd/g or more, more preferably 100 to 800rrr/g.

In such a catalyst component [A], the titanium compound in the catalyst component is generally not desorbed by simple operations such as washing with hexane at room temperature.

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

The catalyst component [A] as described above can be prepared, for example, by a method in which a catalyst is prepared after forming a magnesium compound having an average particle size and particle size distribution within the above-mentioned range and a shape as described above, or by a method in which a catalyst is prepared in a liquid form. It can be produced by employing a method such as a method of bringing a magnesium compound and a liquid titanium compound into contact to form a solid catalyst having the particle properties as described above.

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 uniformly shaped carrier. It is also possible to prepare a finely powdered catalyst in advance and then granulate this finely powdered catalyst into the preferred shape described above.

Regarding such catalyst component [A], Japanese Patent Application Laid-Open No. 55-1
No. 35102, No. 55-135!03, No. 56-81
No. 1, Publication No. 5G-67311 and Patent Application No. 1983-1
No. 81019 and No. 6121109.

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

2 (1) A solid magnesium compound/electron donor complex with an average particle diameter of 1 to 200/7 m and a geometric standard deviation (δ) of particle size distribution of 3.0 or less is used as an electron donor and /' or organoaluminum. With or without pretreatment with a reaction aid such as a compound or a halogen-containing silicon compound, it is reacted with a liquid titanium halide compound, preferably titanium tetrachloride, under reaction conditions.

(2) A magnesium compound that is liquid and does not have reducing ability and a liquid titanium compound are reacted, preferably in the presence of an electron donor, so that the average particle size is 1 to 200 p.
m, a solid component having a geometric standard deviation (δ) of particle size distribution of 3.0 or more is precipitated.

Further, if necessary, it is reacted with a liquid titanium compound, preferably butane tetrachloride, or with a liquid titanium compound and an electron donor.

(3) By bringing a magnesium compound which is liquid and has reducing ability into contact with a reaction aid capable of eliminating the reducing ability of the magnesium compound such as polysiloxane or a halogen-containing silicon compound, Average particle size is 1-200μm
After precipitating a solid component with a geometric standard deviation (δ) of particle size distribution of 3.0 or less, this solid component is reacted with a liquid titanium compound, preferably titanium tetrachloride, or a titanium compound and an electron Lj form. let

(4) After bringing a magnesium compound having reducing ability into contact with an inorganic or organic carrier such as silica, the carrier is then brought into contact with a halogen-containing compound or without contacting with a liquid titanium compound, preferably tetrachloride. Titanium or titanium compound and electronic Ij8
The magnesium compound supported on the carrier is brought into contact with the body to react with the titanium compound, etc.

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

Such a solid catalyst component [A] has the ability to produce a polymer having high stereoregularity with high catalytic efficiency. For example, when homopolymerizing propylene using this solid catalyst component [A], polypropylene with an isotoughness index (insoluble content in boiling n-hebutane) of 92% or more, especially 96% or more is produced. Usually 3000g per 1 mmol of titanium
more than 2, preferably 5000 g or more, particularly preferably 1
It is possible to produce more than 0,000 g.

Examples of magnesium compounds, halogen-containing silicon compounds, titanium compounds, and electron donors that can be used in the preparation of catalyst component [A] as described above are shown below. Also,
The aluminum 13 component used in the preparation of this catalyst component [A] is a compound exemplified in the organometallic compound catalyst component [B] described below.

Specific examples of the magnesium compound include inorganic magnesium compounds such as magnesium oxide, magnesium hydroxide, and hydrotalcite, carboxylates of magnesilla 1, alkoxymagnesium, 5-allyloxymagnesium, alkoxymagnesium halide, and allyloxymagnesium halide. In addition to magnesium cybaride, organic magnesium compounds such as dialkylmagnesium, Grignard reagent, and diarylmagnesium are used.

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

Examples of electron donors include oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic 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 compounds that can be used as such electron donors include methanol, ethanol, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, and phenylethyl alcohol. Alcohols having 1 to 18 carbon atoms such as alcohol, isopropyl alcohol, cumyl alcohol and isopropylbenzyl alcohol; Alcohols having 6 to 20 carbon atoms such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol. Phenols (these phenols may have a lower alkyl group); ketones having 3 to 15 carbon atoms, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone; acetaldehyde, propionaldehyde, octylaldehyde Aldehydes having 27 to 15 carbon atoms such as 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 dichloroacetate, ethyl dichloroacetate, methyl methacrylate,
Ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate,
Phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, n-butyl maleate,
Diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadic acid, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di-n-phthalate
Pentyl, diisopentyl phthalate, di-n-hexyl phthalate, diisohexyl phthalate, di-n-hebutyl phthalate, 8 diisoheptyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, di-2-ethylhexyl phthalate, γ- Organic acid esters having 2 to 30 carbon atoms such as butyrolactone, δ-valerolactone, coumarin, phthalide, and ethylene carbonate; acetyl chloride, penzoyl a
Acid halides having 2 to 15 carbon atoms such as toluyl chloride and anisyl chloride; ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran and anisole and diphenyl ether , preferably diethers; acid amides such as acetic acid amide, benzoic acid amide and toluic acid amide; amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline and tetramethylenediamine Nitriles such as acetonitrile, benzonitrile and tolnitrile; po such as trimethyl phosphite and triethyl phosphite
Organic phosphorus compounds having a -c bond; alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane are used.

These electron donors can be used alone or in combination.

Among such electron donors, preferable electron donors are:
Esters of organic or inorganic acids, alkoxy(aryloxy)silane compounds, ethers, ketones, tertiary amines,
Compounds without active hydrogen such as acid halides and acid anhydrides, and organic acid esters and alkoxy(aryloxy)silane compounds are particularly preferred, and among them, esters of aromatic monocarboxylic acids and alcohols having 1 to 8 carbon atoms,
malonic acid, substituted malonic acid, substituted succinic acid, maleic acid,
Particularly preferred are substituted maleic acid, 1,2-cyclohexanedicarboxylic acid, dicarboxylic acid such as phthalic acid, and esters and diethers of alcohols having 2 or more carbon atoms. Of course, these electron donors do not need to be added to the reaction system during the preparation of 0 catalyst components [AI, for example, they can be converted into one of these electron donors in the reaction system,
The compound to be obtained is blended, and the compound is converted into the electron donor in the catalyst preparation process. The catalyst component [AI obtained as described above] can be purified by washing thoroughly with a liquid inert hydrocarbon compound after preparation. Specifically, hydrocarbons that can be used in this cleaning include n-pentane, isopentane, n-hexane, isohexane, n-hebutane, ■-octane, isooctane, n-decane, and
- Aliphatic hydrocarbon compounds such as dodecane, kerosene, and liquid paraffin; Alicyclic hydrocarbon compounds such as cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane; Aromatic hydrocarbon compounds such as benzene, toluene, xylene, and cymene: Mention may be made of halogenated hydrocarbon compounds such as chlorobenzene and dichloroethane.

1 Such compounds can be used alone or in combination.

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

Examples of such organoaluminum compounds include (here, R and R2 are hydrocarbon groups having usually 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and may be the same or different from each other) .X is a halogen atom, m
is 0≦n1≦3, ■] is 0≦n<3, p is 0≦p<3,
q is a number such that 0≦q<3, and m + n0p
an organoaluminum compound represented by (10q = 3), and a metal of Group 1 of Periodic Table 2 represented by (where Ml is Li%Na%K and R1 has the same meaning as above); Examples include complex alkylated products with aluminum.

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

Formula R'oAI! (OR) Compound m compound (where R and R2 have the same meanings as above, m
is preferably a number of 1.5≦m≦3).

A compound represented by the formula R' mAn
m where R1 has the same meaning as above, X is halogen, and m preferably satisfies 0<m<3).

A compound represented by the formula R' m, l H3□ (where R1 has the same meaning as above, and m preferably satisfies 2≦m<
3).

Compound (where R1 and R2 are the same as above. X is halogen, Q<m≦3.0≦n<3.0≦q3, m+n
+q=3).

Specifically, the organoaluminated compounds represented by the above formula (i) include trialkylaluminiums such as triethylaluminum, tributylaluminium, and triisopropylaluminium, trialkenylaluminums such as triisoprenylaluminum, Dialkyl aluminum alkoxides such as diethylaluminum ethoxide and dibutyl aluminum butoxide; alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide;
Partially alkoxylated alkylaluminums having an average composition of Alkylaluminum sesquihalides such as sesquipromide, partially halogenated alkylaluminums such as alkylaluminum cybarides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide, diethylaluminum hydride, dibutylaluminum hydride dialkylaluminum hydrides such as ethylaluminum dihydride, alkylaluminum partially hydrogenated alkylaluminum halide such as probylaluminum dihydride, ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethyl Partially alkoxylated and halogenated alkylaluminums are used, such as aluminum ethoxypromide.

Furthermore, the organoaluminum compound used in the present invention is
For example, it may be a compound similar to the compound represented by formula (i), such as an organoaluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. Specific examples of such compounds include (CH) AnOAx (C,, R5), 52 (CH) Al0AI (C4H9)2, 92 and 6H5.

Further, specific examples of the organoaluminum compound represented by the above formula (i) include Li 2 Al(CH) and LiAl (C7H15)4 54 . Among these, it is particularly preferable to use trialkylaluminum, a mixture of trialkylaluminum and alkyl aluminum halide, and a mixture of trialkylaluminum and aluminum halide.

Further, when carrying out the polymerization reaction, it is preferable to use an electron donor [C] in addition to the catalyst component [Al and the organometallic compound catalyst component [B].

Specifically, such electron donors [C] include amines, amides, ethers, ketones, nitriles, phosphines, stibines, arsines, phosphoamides, esters, thioethers, thioesters,
Acid anhydrides, acid halides, aldehydes, alcoholates, alkoxy(aryloxy)silanes, organic acids, amides of metals belonging to Groups 1, 2, 2, and 2 of the periodic table. and their acceptable salts. Note that the salts are organic acids and catalyst components [B
] It can also be formed in the reaction system by reaction with an organometallic compound used as.

Specific examples of these electron donors include the compounds exemplified above for the catalyst component [Al. Among such electron donors, particularly preferred electron donors are:
These include organic acid esters, alkoxy(aryloxy)silane compounds, ethers, ketones, acid anhydrides, amides, and the like.

In particular, catalyst component 7 [When the electron donor in Al is a monocarboxylic acid ester, the electron donor is preferably an alkyl ester of an aromatic carboxylic acid.

In addition, when the electron donor in the catalyst component [Al is an ester of a dicarboxylic acid and an alcohol having 2 or more carbon atoms, the electron donor [C] is (However, in the above formula, R and R1 are It is preferable to use an alkoxy(aryloxy)silane compound representing a hydrocarbon group (0≦n<4) or a highly sterically hindered amine.

Specifically, such alkoxy(aryloxy)silane compounds include trimethylmethoxysilane, trimethoxyethoxysilane, dimethyldimethoxysilane,
Dimethylethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, 1-butylmethyljethoxysilane, l-amylmethyljethoxysilane, diphenyldimethoxysilane, phenylmethyldime8 toxysilane, diphenyljethoxysilane, bis-lotryl Dimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolylmethoxysilane, bis=p
- tolyljethoxysilane, bisethyl phenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyljethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane,
n-propyltriethoxysilane, decylmethoxysilane, decyltriethoxysilane, phenyltriethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, (
-butyltriethoxysilane, n-butyltriethoxysilane, i+o-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltriethoxysilane Methoxysilane, cyclohexyltrieth 9 Xysilane, 2-norbornanetrimethoxysilane, 2
-Norbornanetriethoxysilane, 2-norbornanedimethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxysilane, vinyltris(β-methoxyethoxysilane), dimethyltetraethoxydisiloxane, etc. is used.

Among these, especially ethyltriethoxysilane, lowpropyltriethoxysilane, t-butyltriethoxysilane,
Vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis-p-
Preferred are tolylmethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, dichlorohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, diphenyljethoxysilane, ethyl silicate, and the like.

Further, examples of the amine with large steric hindrance include 02,2.6.6-titramethylpiperidine, 2.25.
Particularly preferred are 5-tetramethylpyrrolidine, derivatives thereof, and tetramethylmethylenediamine.

Among these compounds, alkoxysilane compounds and diethers are particularly preferred as electron donors used as catalyst components.

In addition, in the present invention, a catalyst component [1] containing a transition metal atom compound of Groups IVB and VB of the Periodic Table of Elements having a group having conjugated π electrons as a ligand, and an organometallic compound catalyst component [ii] A catalyst consisting of can be preferably used.

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

Further, as a ligand a group having conjugated π electrons, for example, a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a t-butylcyclopentadienyl group, a dimethyl Schiff 10 pentadienyl group. , an alkyl-substituted cyclopentagenyl group such as a pentamethylcyclopentagenyl group, an indenyl group, a fluorenyl group, and the like.

Preferred examples include groups in which at least two of these cycloalkagenyl skeleton-containing ligands are bonded via a lower alkylene group or a group containing silicon, phosphorus, oxygen, or nitrogen.

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

One or more, preferably two, such ligands having a cycloalkagenyl skeleton are coordinated to the transition metal.

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

Examples of hydrocarbon groups having 1 to 12 carbon atoms include alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. Specifically, examples of alkyl groups include methyl groups, ethyl groups, Examples include propyl group, isopropyl group, butyl group, etc.; cycloalkyl group includes cyclopentyl group, cyclohexyl group, etc.; aryl group includes phenyl group, tolyl group, etc.; and aralkyl group includes benzyl group. group, neophyll group, etc.

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

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

For example, when the valence of the transition metal is 4, the transition metal compound containing a ligand having a cycloalkagenyl skeleton used in the present invention has the following formula: R2R3R4R5M kj! mn (wherein M is zirconium, titanium, hafnium, vanadium, etc., R2 is a group having a cycloalkagenyl skeleton, R, R and R5 are a group having a cycloalkagenyl skeleton, an alkyl group, a cyclo It is an alkyl 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+I +m+n=4).

Particularly preferably, R and R3 in the above formula are groups having a cycloalkagenyl group skeleton, and these two groups having a cycloalkagenyl skeleton include a lower alkyl group or silicon, phosphorus, oxygen, or nitrogen. It is a compound that is bonded through a group.

Hereinafter, specific examples of transition metal compounds containing a ligand having a cycloalkagenyl skeleton in which M is zirconium will be exemplified.

Bis(cyclopentadienyl)zirconium monohydride, bis(cyclopentadienyl)zirconium monopromide monohydride, bis(cyclopentadienyl)methylzirconium hydride, bis(cyclopentadienyl)ethylzirconium hydride , Bis(cyclopentagenyl)phenylzirconium hydride, Bis(cyclopentagenyl)benzylzirconium hydride, Bis(cyclopentagenyl)neopentylzirconium hydride, Bis(methylcyclopentagenyl)zirconium monochloride hydride, Bis( indenyl) zirconium monochloride monohydride, bis(cyclopentagenyl) zirconium dimethyl
Bis(cyclopentagenyl)zirconium di5-bromide, Bis(cyclopentagenyl)methylzirconium monochloride, Bis(cyclopentagenyl)ethylzirconium monochloride, Bis(cyclopentagenyl)cyclohexylzirconium monochloride , Bis(cyclopentagenyl)phenylzirconium monochloride, Bis(cyclopentagenyl)benzylzirconium monochloride, Bis(methylcyclopentagenyl)zirconium dichloride, Bis(i-butylcyclopentagenyl)zirconium dichloride bis( indenyl)zirconium dichloride, bis(indenyl)zirconium dichloride, bis(cyclopentagenyl)zirconium dimethyl, bis(cyclopentagenyl)zirconium di6 phenyl, bis(cyclopentagenyl)zirconium dibenzyl, bis(cyclopentagenyl)zirconium dibenzyl ) zirconium methoxy chloride, bis(cyclopentadienyl) zirconium ethoxy chloride, bis(methylcyclopentagenyl) zirconium ethoxychloride]
・Xychloride, bis(cyclopentajenyl)zirconium phenoxychloride, bis(fluorenyl)zirconium dichloride, dilene bis(indenyl)diethylzirconyl 15, ethyl nonbis(indenyl)diphenylzirconium, ethylenebis(indenyl)methylzirconium, ethylene Bis(indenyl)ethylzirconium monochloride, 7 ethylenebis(indenyl)zirconium dichloride, isopropylbisindenylzirconium dichloride, isopropyl(cyclopentagenyl)-1-fluorenylzirconium chloride, ethylenebis(indenyl)zirconium compound mid , Ethylene bis(indenyl) zirconium methoxy monochloride, Ethylene bis(indenyl) zirconium ethoxy monochloride, Ethylene bis(indenyl) zirconium phenoxy monochloride, Ethylene bis(cyclopentagenyl) zirconium dichloride, Propylene bis(cyclopentagenyl) Zirconium dichloride, ethylenebis(1-butylcyclopentadienyl)silconium dichloride, 8 ethylenebis(4,5,6,7-tetrahydro-1-indenyl)dimethylzirconiumuno 1, ethyl nonbis(4,5,6) ,7-tetrahydro-1-
indenyl) methylzirconium monochloride, ethylenebis(4,5,6,7-titrahydro-1-indenyl)zirconium dichloride, ethylenebis(4,5,6,7-tetrahydroindenyl)zirconium dichloride, ethyl〉bis(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-methoxyindenyl)zirconium, dichloride, ethylenebis(2,3-dimethyl-1-indenyl)zirconium dichloride, 9 ethylenebis(4,7-dimethylindenyl)zirconium dichloride, ethylenebis (4,7-simethoxy1-indenyl)
Zirconia dichloride.

In the above zirconium compounds, transition metal compounds in which zirconium metal is replaced with titanium metal, hafnium metal, chromium metal, vanadium metal, etc. can also be used.

Further, in this case, the organometallic compound catalyst component [ii
] and j, a conventionally known aluminoxane or organoaluminumoxy compound is used. This organoaluminumoxy compound is obtained, for example, by reaction of an organoaluminum compound with water, or by reaction of an aluminoxane dissolved in a hydrocarbon solution with water or an active hydrogen-containing compound.

Such organoaluminumoxy compounds are insoluble or poorly soluble in benzene at 60°C.

In the present invention, the amount of the catalyst used varies depending on the type of catalyst used, but for example, the catalyst component [A], the organometallic oxide catalyst component [B], and the electron donor [C] as described above are used. When used or when catalyst components (i) and (ii) are used, catalyst component [A] or catalyst component (11) is usually used in an amount of, for example, 0.001 in terms of transition metal per polymerization volume II. ~0.5 mmol,
It is preferably used in an amount of 0.005 to 0.5 mmol, and the amount of organometallic compound catalyst [B] used is based on 1 mole of transition metal atoms of catalyst component [A] in the polymerization system.
The metal atoms of the organometallic compound catalyst [B] are usually 1 to 100
00 mol, preferably 5 to 500 mol. Furthermore, when using the electron donor [C], the electron donor [C] is 100 mol or less, preferably 1 to 5 mol, per 1 mol of the transition metal atom of the catalyst component [A] in the polymerization system.
It is used in amounts of 0 mol, particularly preferably 3 to 20 mol.

The polymerization temperature when performing polymerization using the above catalyst is usually 20 to 200°C, preferably 50 to 100°C, and the pressure is normal pressure -100 kg/cnf, 1, preferably 2 to 50 kg/car. be.

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

(Left below) When titanium is used as the transition metal, the amount of polymerization in the prepolymerization is usually 1 to 2000 g, preferably 3 to 1000 g, particularly preferably 10 to 500 g, per 1 g of the titanium catalyst component. be.

Prepolymerization is preferably carried out using an inert hydrocarbon solvent, and such inert hydrocarbon solvents include:
Specifically, propane, butane, n-pentane, 1-pentane, n-hexane, i-hexane, n-hebutane,
Aliphatic hydrocarbons such as n-octane, 1-octane, n-decane, n-dodecane, kerosene, alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene, and xylene. Aromatic hydrocarbons such as methylene chloride, ethyl chloride, ethylene chloride, halogenated hydrocarbon compounds such as chlorobenzene are used. Among these, aliphatic hydrocarbons are preferred, and aliphatic hydrocarbons having 4 to 10 carbon atoms are particularly preferred. Furthermore, the monomer used in the reaction can also be used as a solvent.

Specifically, the α-olefin used in this prepolymerization includes 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, and among these, α-olefins having 3 to 6 carbon atoms are preferred, and propylene is particularly preferred. These α-olefins can be used alone, or two or more types can be used in combination as long as a crystalline polymer is produced.

In particular, polymer particles containing a large amount of amorphous olefin polymer moiety and having good particle properties, such as polymer particles containing 30% by weight or more of amorphous olefin polymer moiety and having good particle properties. To obtain a prepolymerization of e.g.
A method is proposed in which propylene and ethylene are copolymerized using a mixed gas consisting of ~98 mol% propylene and 30~2 mol% ethylene.

The polymerization temperature in prepolymerization also varies depending on the α-quaternary reflex used and the inert solvent used.
Although it cannot be generally specified, it is generally 140 to 80'C1 good J.
Niji < is -20 to 40°C1, particularly preferably -10 to 3
It is 0°C. For example, when propylene is used as the α-olefin, -40 to 70°C; when 1-butene is used, -40 to 40°C, 4-methyl-1-pentene and/or 3-methyl- When 1-pentene is used, the temperature is within the range of -40 to 70°C. Note that hydrogen gas can also be allowed to coexist in the reaction system for this prepolymerization.

After prepolymerizing as described above, or without prepolymerizing, the monomers described in 1. can be manufactured.

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

The polymerization temperature for the main polymerization of such olefins is usually -
The temperature is 50-200°C, preferably 0-1505°C. Polymerization pressure is usually normal pressure to 1.00 kg/c
nf, preferably normal pressure to 50 kg/cnf, and the polymerization reaction can be carried out in any of the batch, semi-continuous, and continuous methods.

The fraction 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 portion and an amorphous olefin polymer portion. In the present invention, the amorphous olefin polymer portion in the polymer particles is usually 20 to 80% by weight.
, preferably 25 to 70% by weight, more preferably 30% by weight
It is desirable that the content be within the range of 60% by weight, particularly preferably 33% to 55% by weight. In the present invention, the content of such amorphous olefin polymer is determined at 23°C.
It can be determined by measuring the amount of components soluble in n-decane.

Furthermore, the polymer particles used in the present invention have a melting point of the polymer constituting the polymer particles, a melting point of the crystalline olefin polymer portion, or a glass transition point of the amorphous olefin polymer portion, whichever is higher. Preferred are polymer particles that have never been substantially heated above the temperature of the polymer.

In this way, polymer particles that have never been substantially heated to a temperature higher than the melting point of the crystalline olefin polymer portion or the glass transition point of the amorphous olefin polymer portion, whichever is higher, are amorphous. The average particle diameter of the high part consisting of the olefin polymer part is 0.5 μrn or less, preferably 0.1 μm.
The following, more preferably 0, 00001 to 0,
It is 0571m.

Here, [amorphous olefin polymer part-1 is 23'
It refers to a polymer that dissolves in n-decane at a temperature of 0.degree. C., and specifically refers to a polymer portion that has been solvent-fractionated by the following method. In other words, in this specification, a solution of n-decane (500 ml) to which polymer particles (3 g) were added was added with stirring for 1 hour.
After performing the dissolution reaction at 40-145°C, stop stirring,
Cooled to 80℃ for 3 hours, 23℃ for 5 hours, and further cooled to 23℃.
The polymer obtained by filtration and separation using a -4 glass filter and removing n-decane from the obtained filtrate after being kept at 7°C for 5 hours is referred to as the "amorphous olefin polymer portion".

In the present invention, the finely powdered polymer particles as described above are melted and adhered to the inner surface of a previously heated grain pattern transfer mold in the presence of a crosslinking agent, and then the mold is cooled. A thermoplastic elastomer molded product having a grain pattern on the surface is obtained by a powder slush molding method, and a thermoplastic elastomer is produced by a crosslinking reaction during the melting, and molding is performed simultaneously with the production.

Organic peroxides, sulfur, phenolic vulcanizing agents, oximes, polyamines, etc. are used as the above-mentioned crosslinking agents. A sulfurizing agent is preferred.

Particularly preferred are organic peroxides.

As the phenolic vulcanizing agent, specifically, an alkylphenol formaldehyde resin, a tria-8 dine-formaldehyde resin, and a melamine-formaldehyde resin are used.

In addition, specific examples of organic peroxides include dicumyl peroxide, di(e'(-butyl peroxide),
2,5-dimethyl-2,5-bis(je-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(je-butylperoxy)hexane,
ter l-butylperoxy)hexyne-3,1
, 3-bis(l e t t-butylperoxyisopropyl)benzene, 1,1-bis(le+1-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-44-bis(leN-butylperoxy) Valerate, dibenzoyl peroxide, le-butyl peroxybenzoate, etc. are used. Among these, dibenzoyl peroxide and 1,3-bis(te+l-butylperoxyisopropyl)benzene are preferred from the viewpoint of crosslinking reaction time, odor, and scorch stability.

Further, in order to achieve a uniform and moderate crosslinking reaction, it is preferable to include a crosslinking aid. Specific examples of crosslinking aids include sulfur, p-quinonedioxime, p,p'-dibenzoylquinonedioxime, N-methyl9N,4-dinitrosoaniline, nitrobenzene, diphenylguanidine, and trimethylolpropane. N, N'-
Peroxy crosslinking aids such as m-phenylene dimaleimide, or polyfunctional agents such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethyl glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate. methacrylate monomers, polyfunctional vinyl monomers such as vinyl butyrald or vinyl stearate, and the like. By using such a compound, a uniform and mild crosslinking reaction can be expected. In particular, divinylbenzene
It is easy to handle, has good compatibility with polymer particles, has an organic peroxide solubilizing effect, and also works as a peroxide dispersion aid, so the crosslinking reaction is homogeneous and improves fluidity and physical properties. This is most preferable because a thermoplastic elastomer molded product with well-balanced properties can be obtained.

In the present invention, such a crosslinking auxiliary agent is used in an amount of 0.1 to 100 parts by weight per 100 parts by weight of the pulverized product of the zero-polymerized particles.
It is used in an amount of 2 parts by weight, especially 0.3 to 1 part by weight, and by blending within this range, a thermoplastic elastomer with excellent fluidity can be obtained, and the change in physical properties due to thermal history during processing and molding can be avoided. A molded article of thermoplastic elastomer is obtained.

In the present invention, when producing a thermoplastic elastomer molded article, in addition to the finely powdered polymer particles, a crosslinking agent, and a crosslinking auxiliary agent, a non-crosslinked peroxide typified by polyisobutylene, butyl rubber, etc. The crosslinking reaction of the pulverized product of 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 forces of rubber during roll processing, making processing easier.
A high boiling point petroleum distillate that is used to help disperse carbon black, white carbon, etc., or to reduce the hardness of vulcanized rubber and increase its flexibility or elasticity. Paraffinic, naphthenic, or aromatic mineral oils are used.

Such a mineral oil-based softener is used in an amount of 1 to 10 parts by weight per 100 parts by weight of the finely powdered polymer particles, in order to further improve the flow characteristics, that is, the moldability of the thermoplastic elastomer.
It is blended in an amount such that the amount is 0 parts by weight, preferably 3 to 90 parts by weight, and more preferably 5 to 80 parts by weight.

Further, a stabilizer may be added to the finely powdered polymer particles used in the present invention or the mixture containing the finely treated polymer particles and a crosslinking agent. Specifically, such stabilizers include phenolic stabilizers,
Phosphorus stabilizers, sulfur stabilizers, hindered amine stabilizers, higher fatty acid stabilizers, etc. are used.

The above-mentioned stabilizer is a finely powdered product of polymer particles 10
It is desirable to use it in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight.

In addition, fillers such as calcium carbonate, calcium silicate 13, clay, etc. , kaolin, talc, silica,
Diatomaceous earth, mica powder, asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass bulbs, shirasu balloons, carbon fiber or coloring agents such as carbon fiber, titanium oxide,
Zinc 413, pen color, ultramarine blue, navy blue, azo dye, nitroso dye, raw pigment, phthalocyanine pigment, etc. can also be blended.

The finely powdered polymer particles used in the present invention are
~400 meshes, preferably 42-200 meshes,
More preferably, the mesh size is 65 to 150, and can be obtained by, for example, pulverizing the above polymer particles.

In the present invention, the finely powdered polymer particles as described above are melted and adhered to the inner surface of a grain pattern transfer mold in the presence of a crosslinking agent and crosslinked, thereby obtaining thermoplasticity. A grain pattern is formed on the surface of the elastomer molded product.

In the present invention, the finely powdered polymer particles as described above penetrate deeply into the grains on the inner surface of the grain pattern transfer mold, which has fine irregularities, and melt onto the inner surface of the mold. Because of the adhesion, deeper grains can be obtained compared to conventional molded products made of vinyl chloride resin with grain patterns. By the way,
In the present invention, a thermoplastic elastomer molded article with a grain pattern having a grain depth of 150 μm or more can be obtained, whereas with conventional vinyl chloride resin, the grain depth is 9 Q p m.
The limit was to obtain a molded product of a certain degree.

Next, a method for manufacturing a textured thermoplastic elastomer molded article according to the present invention will be described.

The method for producing a thermoplastic elastomer molded product with a textured pattern according to the present invention includes molding the pulverized product of the above-mentioned polymer particles into a molded product having a textured pattern on the surface by powder slush molding in the presence of a crosslinking agent. This is a method of manufacturing.

The above powder slush molding method and (7) For example, there is a molding method as shown in F below.

(1) A powder of a mixture of a finely powdered polymer particle and a crosslinking agent is sprayed onto the inner surface of a preheated mold to melt and adhere to the inner surface of the mold, and then the mold is cooled. Molding method to obtain molded products.

(2) Spray the pulverized polymer particles and crosslinking agent separately onto the inner surface of the pre-heated mold to melt and adhere to the inner surface of the mold, and then remove the mold. A molding method that obtains a molded product by cooling.

(3) A powder mixture containing a finely divided polymer particle and a crosslinking agent is put into a preheated mold, and after collecting the excess unmelted powder, the mold is removed. A skin molding method in which the molten material is fixed by cooling and removed from the mold as a product ([Automotive Technology J Vo 1.43. No.
, 5.1989. p74-80).

In the present invention, powder slush molding is performed using a mold for transferring a textured pattern whose inner surface has fine irregularities.

Here, the powder slush molding method for the ligand (1) will be explained with reference to the drawings.

5. Figure 1 shows that a crystalline olefin polymer portion and an amorphous olefin polymer are formed on the inner surface of a textured pattern transfer mold used when producing a textured thermoplastic elastomer molded product according to the present invention. FIG. 2 is a schematic diagram showing a state in which a powder of a mixture containing a finely powdered polymer particle consisting of 1,000 ml of polymer particles, a crosslinking agent, and, if necessary, a crosslinking auxiliary agent, is sprayed.

In the present invention, the grain pattern transfer mold 1 is first heated.

The temperature of this heating is usually 150 to 210°C.

Next, the powder of the above-mentioned mixture is sprayed onto the inner surface of the grain pattern transfer mold 1 that has been heated in advance, so that the powder is melted and adhered to the inner surface of the mold 1, thereby causing crosslinking.

The above-mentioned spraying method may be a conventionally known method, such as a method using a spray gun.

In the powder slush molding method (1) above, the powder of the molecule mixture is sprayed onto the inner surface of the grain pattern transfer mold 1. It bites deeply into the interior and melts and adheres to the inner surface of the mold 1 by receiving the heat of the mold 1 which has been heated in advance. Therefore, in this molding method, a thermoplastic elastomer molded article with a deep grain pattern can be obtained. The same can be said of the powder slush molding method (2) above.

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

Examples of the cooling method include air cooling, water cooling, and the like.

The textured thermoplastic elastomer molded product obtained by the production method according to the present invention has excellent scratch resistance, appearance, and texture.
By applying the surface treatment described in 2-331718 to the surface of the molded product, even better scratch resistance,
A thermoplastic elastomer molded article with a textured appearance and texture is obtained.

7 That is, as the surface treatment, first, saturated polyester,
A top coat comprising a primer layer containing at least one compound selected from chlorinated polyolefins, and further comprising at least one compound selected from saturated polyesters, acrylic ester resins, and isocyanate resins on the primer layer. form a layer. However, if the primer layer contains only saturated polyester out of at least one compound selected from saturated polyester and chlorinated polyolefin, the top coat layer must not contain at least an acrylic ester resin. It won't happen.

To form a primer layer on the surface of the molded product, at least one compound selected from saturated polyester and chlorinated polyolefin is dissolved in an organic solvent, and the resulting coating solution for forming the primer layer is molded according to a conventional method. Just apply it on the surface of the object.

In addition, in order to form a top coat layer on the primer layer, at least one compound selected from saturated polyester, acrylic acid ester resin, and isocyanate resin is dissolved in an organic solvent, and the resulting top coat layer is formed. The coating solution may be applied onto the primer layer according to a conventional method.

Effects of the Invention In the textured thermoplastic elastomer molded article of the present invention, a finely powdered product of polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part can be used as a textured pattern transfer metal. By melting and adhering to the inner surface of the mold and crosslinking,
Since a grain pattern is formed on the surface of the obtained thermoplastic elastomer molded product, it not only has a shallow grain pattern, but also has a deeper grain pattern compared to conventional grained vinyl chloride resin molded products. This has the effect that a deeper grain pattern can be formed, and also has the effect that mechanical properties do not deteriorate.

Further, according to the manufacturing method of the present invention, the manufacturing process of the thermoplastic elastomer and the process of powdering the thermoplastic elastomer can be omitted, and a molded article of the thermoplastic elastomer 9 with a textured pattern having the above-mentioned effects can be obtained. It will be done.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Regarding the textured thermoplastic elastomer molded products obtained in the Examples and Comparative Examples, the tensile properties, surface hardness,
Heat aging characteristics, grain depth and gloss were evaluated by the following methods. Samples for evaluation were taken by punching out the obtained molded product.

[Evaluation method] (1) Tensile properties Its K-630177) Method Niyor.

(2) Surface hardness According to the method described in ASTM 0224G.

(3) Heat aging properties After the sample was left in an air oven at 120° C. for 100 hours, the sample was taken out and measured using the tensile test method of Monthly SK-6301.

(4) Grain depth The distance from the top of the emboss transferred to the surface of the molded article to the bottom of the valley was measured.

(5) Gloss Moon 328741 (Specular gloss measurement method)
Accordingly, the surface of the textured molded article was irradiated with 0 light at an incident angle of 60 degrees, and the reflectance was expressed in %.

[Adjustment of catalyst component [A]] A high-speed stirring device (manufactured by Tokushu Kikasa Gyo) with an internal volume of 21 was heated to sufficient N.
After 2 substitutions, 700 ml of refined kerosene, commercially available MgC
C12Lo, ethanol 24. ．． 2 g and 3 g of Emazol 320 (trade name, Kao Atlas (stock system, Sorbitan Distear-t)) were added, and the system was warmed to y/y while stirring.1.
The mixture was stirred at 20° C. and 800 tpm for 30 minutes. Refined kerosene 17 was pre-cooled to -10°C using a Teflon duplex with an inner diameter of 5 mm under high-speed stirring. Transfer the liquid to a 21 glass flask (with a stirrer) filled with
Ta. The produced solid was collected by filtration and thoroughly washed with hexane to obtain a carrier.

After suspending 7.5 g of the carrier in 50 ml of titanium tetrachloride at room temperature, 1.3 ml of diisobutyl phthalate was added and the system was heated to 120°C. After stirring and mixing at 1200C for 2 hours, the solid part was collected by filtration and 1,++
The mixture was suspended in 1-50 ml of titanium tetrachloride, and stirred and mixed again at 130°C for 2 hours. Furthermore, 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 contained 2.2% by weight of titanium and 63% of chlorine in terms of atoms). % by weight, 20% by weight of magnesium, and 5.5% by weight of diisobutyl phthalate.A truly spherical catalyst with an average particle size of 64 It m and a geometric standard deviation (δ) of particle size distribution of 1.5 was obtained.

[Preliminary polymerization] The catalyst component [A] was subjected to the following preliminary polymerization.

After charging 200 ml of purified hexane into a 400 ml glass reactor purged with nitrogen, 4 mmol of triethylaluminum 209 silane and 2 mmol of the Ti catalyst component [A] in terms of titanium atoms were charged. , 5. Propylene was fed at a rate of 9 Nl/h over 1 hour, and the Ti catalyst component [Al1. 2.8 g of propylene was polymerized per g. The temperature during polymerization was kept at 20±2°C. After the prepolymerization,
Two liquid parts were removed by filtration, and the separated solid part was resuspended in decane.

[Polymerization] Production of copolymer (1) 2.0 kg of propylene and hydrogen 1. After adding 9 N liters, the temperature was raised to 50°.
At step C, 15 mmol of triethylaluminum, 1.5 mmol of cyclohexylmethyldimethoxysilane, and 0.05 mmol of the prepolymerized product of catalyst component [A] in terms of titanium atoms were added, and the temperature inside the polymerization vessel was maintained at 70°C. 70
30 minutes after reaching the temperature, the vent valve was opened and propylene was purged until the inside of the polymerization vessel reached normal pressure. After purging, copolymerization was carried out subsequently. That is, ethylene is 48ONl/
At 1/' hour, propylene was supplied to the polymerization vessel at a rate of 720 N (1/' hour, and hydrogen was supplied to the polymerization vessel at a rate of 12 Nl/hour. Ben 1, the opening degree was adjusted.The temperature during copolymerization was kept at 70°C. After 150 minutes of polymerization time, the pressure was released and the obtained polymer weighed 2.5 kg. MI-3.9g/IQ, ethylene content 28 mol%, and apparent bulk specific gravity 0.47.

Further, the amount of the 23° Cn-decane soluble component was 28% by weight, and the ethylene content in the soluble component was 47 mol%.

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

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

The powder of the above copolymer (2) has an average particle size of 2 1
0 0 tt m, and the apparent density is 0.43 g/m
1, the number of particles passing through the 150 mesh was 0.1% by weight, and the falling time was 9.3 seconds. Moreover, the geometric standard deviation of this polymer particle was 1.5.

Further, the powder of the above copolymer (3) has an average particle diameter of 2
000 μm, the apparent density was 0.40 g/ml, the particles passing through the 150 mesh were 0.2% by weight, and the falling time was 10.3 seconds. Moreover, the geometric standard deviation of this polymer particle was 1.6.

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

[Prepolymerization] Catalyst component [A] was subjected to the following prepolymerization. 400 ml of purified hexane in a nitrogen-purged glass reactor II
After charging, 1.32 mmol of triethylaluminum,
0.27 mmol of cyclohexylmethyldimethoxysilane and the above Ti catalyst component [A] in terms of titanium atoms.
．． After charging 131 mmol, propylene gas and ethylene gas were fed into the liquid phase of the polymerization reactor for 100 minutes while mixing at a rate of 8.4 Nl/hr and 1.011/hr, respectively. Moreover, the humidity was maintained at 20±2° C. during the prepolymerization.

After the preliminary polymerization, the liquid portion was removed by filtration, and the separated solid portion was suspended again in decane.

As a result of the analysis, the prepolymerized solid catalyst contained the Ti catalyst component [Al1. About 92 g of polymer was present on g, while in the separated filtrate the used Ti catalyst component [A
There was an equivalent of 6.2 g of solvent-soluble polymer per 11 g.

/ Table Example 1 [Manufacture of molded product] First, a mold for transferring a grain pattern, which is a mold for an automobile dash board and has a grain pattern with a grain depth of 150 μm on the inner surface, was heated to 210° C. in advance. Next, under a nitrogen seal, the above copolymer was heated to -60°C on the inner surface of this mold.
100 parts by weight of 42 to 80 mesh powder obtained by crushing in an atmosphere, 0.2 parts by weight of 13-bis((e"lebutylperoxyisopropyl)benzene), 0.3 parts by weight of divinylbenzene and a paraffin process. oil 0
．． A powder of a mixture obtained by mechanically mixing 2 parts by weight of a solution dissolved and dispersed was sprayed to melt and adhere.

Finally, this mold was cooled to obtain a textured thermoplastic elastomer molded product.

The size of the obtained thermoplastic elastomer molded article with a textured pattern was 1200 mm in length, 500 mm in width, and 1.0 mm in thickness.
Met.

The tensile properties, surface hardness, heat aging properties, grain depth, and gloss of the obtained thermoplastic elastomer molded product with grain patterns were evaluated by the above-mentioned methods.

The evaluation results are shown in Table 2.

Example 2 The same procedure as in Example 1 was carried out except that copolymer (2) was used instead of copolymer (1) in Example 1, and Table 2
The results were obtained.

Example 3 In Example 1, co-rTc was used instead of copolymer (1).
Table 2
The results were obtained.

Example 4 In Example 3, the paraffinic process oil was
The same procedure as in Example 3 was carried out except that parts by weight were used, and the results shown in Table 2 were obtained.

Example 5 In Example 1, instead of spraying the powder of the mixture obtained by mechanical mixing onto a mold that had been preheated to 210°C and melting it into tight contact, the powder was poured into the mold. The same procedure as in Example 1 was carried out, except that the method of melting and adhering the powder and recovering the excess unmelted powder was carried out, and the results shown in Table 2 were obtained.

Example 1 In Example 1, 10 pulverized powders of copolymer (1)
and a solution in which 0.2 parts by weight of 1,3-bis(left-butylperoxyisopropyl)benzene is dissolved and dispersed in 0.3 parts by weight of divinylbenzene and 0.2 parts by weight of paraffinic process oil. The results shown in Table 2 were obtained by carrying out the same procedure as in Example 1 except that they were sprayed separately without mixing.

[Brief explanation of drawings]

FIG. 1 shows that a finely powdered product of polymer particles and a crosslinking agent are applied to the inner surface of a mold for transferring a grain pattern used when producing a thermo-FiJ plastic elastomer molding with a grain pattern according to the present invention. FIG. 3 is a schematic diagram showing a state in which powder of a mixture containing the powder is sprayed. 1...Mold for grain pattern transfer

Claims (1)

[Scope of Claims] 1) Finely powdered polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part are processed into a mold for transferring a grain pattern in the presence of a crosslinking agent. A thermoplastic elastomer molded article with a textured pattern, characterized in that a textured pattern is formed on the surface by melting and adhering to the inner surface. 2) The textured thermoplastic elastomer molded product according to claim 1, wherein the finely pulverized product of the polymer particles has a mesh size of 20 to 400 mesh. 3) Finely powdered polymer particles consisting of a crystalline olefin polymer part and an amorphous olefin polymer part are applied to the inner surface of a preheated grain pattern transfer mold in the presence of a crosslinking agent. 1. A method for producing a thermoplastic elastomer molded article with a textured pattern, the method comprising obtaining a thermoplastic elastomer molded article having a textured surface on the surface by a powder slush molding method in which the mold is cooled after being melted and adhered. 4) The method for producing a textured thermoplastic elastomer molded article according to claim 3, wherein the finely divided polymer particles have a mesh size of 20 to 400 mesh.