JPH1036580A - Thermoplastic elastomer resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic elastomer resin composition, hardly causing the stickiness, excellent in flexibility and gloss and useful for automotive parts, etc., by including a specific resin component and an ethylene-α-olefin copolymer rubber in a specific proportion therein. SOLUTION: This thermoplastic elastomer resin composition is obtained by formulating 100 pts.wt. resin component comprising (A) 30-70 pts.wt. ethylene (co)polymer, prepared by homopolymerizing ethylene or copolymerizing the ethylene with an α-olefin in the presence of a catalyst containing an organic cyclic compound having a conjugated double band and a compound of a group IV transition metal of the periodic table, having (i) 0.86-0.96g/cm<3> density (d), (ii) 0.01-100g/10min melt flow rate (MFR), (iii) 1.5-4.5 molecular weight distribution, (iv) 1.08-2.00 compositional distribution parameter Cb , satisfying (a) X<2.0 when the content X (wt.%) of a fraction soluble in o- dichlorobenzene, density (d) and MFR are represented by formula d-0.008×log MFR>=0.93 and (d) the formula when the X, (d) and MFR are represented by the formula d-0.008×log MFR<0.93 and further satisfying (vi) the plural peaks in a curve of an elution temperature-elution amount according to a continuous temperature raising elution fractionation method (YREF) and (B) 70-30 pts.wt. propylene-based polymer with (C) 70-200 pts.wt. ethylene-α-olefin copolymer rubber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic elastomer composition which is excellent in flexibility, excellent in fluidity, tensile properties, impact strength, heat resistance, oil resistance and gloss, and can withstand repeated fatigue. More specifically, it relates to a thermoplastic elastomer composition containing an ethylene / α-olefin copolymer rubber, a specific ethylene (co) polymer, and a propylene-based polymer.

[0002]

2. Description of the Related Art Polyolefin-based thermoplastic elastomers include ethylene-propylene copolymer rubber (EPR) and ethylene-propylene-non-conjugated diene copolymer rubber (E).
Blends using an amorphous copolymer rubber such as PDM) as a soft segment and a crystalline polyolefin such as polyethylene or polypropylene as a hard segment, or a composition obtained by partially cross-linking these blends are known. I have. Also, a method for producing these by direct multistage polymerization is known. By changing the ratio of each of these segments, various grades of products are manufactured from those having high flexibility to those having high rigidity. Flexible grades have received a great deal of attention as rubber-like materials because they can be widely used in applications such as automobile parts, home appliances, civil engineering, and daily necessities. When producing such a flexible grade, in order to maintain rubber-like flexibility, the proportion of soft segments (such as EPR and EPDM) is increased, and the proportion of hard segments (such as polyethylene and polypropylene) is reduced. There is a need to. However, since soft segments such as EPR and EPDM have low tensile strength and poor heat resistance, oil resistance, fluidity, and the like, a flexible thermoplastic elastomer containing many such soft segments still has the above-mentioned properties. Due to such disadvantages, it cannot be used for various purposes. Increasing the percentage of hard segments to remedy these problems results in loss of flexibility and loss of the characteristics of a flexible thermoplastic elastomer. When polypropylene is used for the hard segment, a thermoplastic elastomer having excellent heat resistance can be obtained, but flexibility and gloss are deteriorated. When polyethylene is used as the hard segment, gloss is excellent, but heat resistance is deteriorated. In order to solve these problems, ultra-low-density linear polyethylene and polypropylene using a Ziegler catalyst have been mixed into the hard segment (for example, JP-A-63-39942).
issue). However, ultra-low-density linear polyethylene has many high-branching low-molecular-weight components, so that it elutes into the contents more frequently, and it still cannot provide sufficient stickiness, durability against repeated deformation, mechanical properties, and gloss. These compositions have not always been sufficiently improved.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to satisfy these requirements. In particular, it is excellent in flexibility, excellent in fluidity, tensile properties, impact strength, heat resistance, oil resistance, gloss, and stickiness. Another object of the present invention is to provide a thermoplastic elastomer composition which has a low heat resistance and good durability against repeated deformation.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in accordance with the above-mentioned object, and as a result, have found that ethylene-α-olefin copolymer rubber (C) has a narrow molecular weight distribution despite its narrow molecular weight distribution. The above object is achieved by using a novel ethylene (co) polymer (A) having a relatively wide composition distribution and a low content of a low molecular weight component and an amorphous portion, and further using a propylene polymer (B). It has been achieved.

That is, the first aspect of the present invention is to provide (A) ethylene homopolymerization or ethylene and α in the presence of a catalyst containing at least an organic cyclic compound having a conjugated double bond and a transition metal compound of Group IV of the periodic table. -Obtained by copolymerizing an olefin, the following (a) to
30 to 70 parts by weight of ethylene (co) polymer satisfying (f), (a) density 0.86 to 0.96 g / cm ³ (b) melt flow rate (MFR) 0.01 to 100 g / 10 min (c ) Molecular weight distribution (Mw / Mn) 1.5 to 4.5 (d) Composition distribution parameter Cb 1.08 to 2.00 (e) Amount of orthodichlorobenzene (ODCB) soluble at 25 ° C. X (% by weight) And the density d and MFR satisfy the following relationship: a) When d-0.008 × logMFR ≧ 0.93, X <2.0 b) When d-0.008 × logMFR <0.93, X <9.8 × 10 ³ × (0.9300−d (+ 0.008 × log MFR) ² +2.0 (Equation 1) (f) There are a plurality of peaks in the elution temperature-elution amount curve by the continuous heating elution fractionation method (TREF). (B) Ethylene / α-olefin copolymer rubber 70 to 2 parts per 100 parts by weight of resin component consisting of 70 to 30 parts by weight of propylene polymer
A thermoplastic elastomer resin composition comprising 100 parts by weight. The second aspect of the present invention is the first aspect of the present invention.
(C) Ethylene / α-olefin copolymer with respect to 100 parts by weight of a resin component consisting of (A) 30 to 70 parts by weight of an ethylene (co) polymer and (B) 70 to 30 parts by weight of a propylene polymer. A thermoplastic elastomer resin composition obtained by partially crosslinking a composition comprising 70 to 200 parts by weight of rubber.

Hereinafter, the present invention will be described in more detail. The (A) ethylene (co) polymer of the present invention includes an ethylene homopolymer or a copolymer of ethylene and one or more selected from α-olefins having 3 to 20 carbon atoms. The α-olefin having 3 to 20 carbon atoms is preferably 3 to 12 and specifically includes propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, -Decene, 1-dodecene, and the like. The content of these α-olefins is usually 30 mol% or less in total, preferably 20 mol%.
It is desirable to select within the following range.

The density (a) of the ethylene (co) polymer (A) of the present invention varies depending on the required properties of its application.
It is in the range of 86 to 0.96 g / cm ³ . For example, in applications requiring rigidity, those having a density of 0.92 g / cm ³ or more are preferably used. In applications where flexibility and impact resistance are particularly required, those having 0.92 g / cm ³ or less are preferably used. In addition, generally, it is preferably 0.1.
87 to 0.93 g / cm ³ , more preferably 0.87 to 0.93 g / cm ³
It is in the range of 0.91 g / cm ³ . 0.86g /
If it is less than ³ cm ³ , rigidity and heat resistance are inferior, and the surface of the composition becomes sticky to cause a problem. If it exceeds 0.96 g / cm ³ , the mechanical strength such as flexibility, impact resistance and tensile strength of the composition is undesirably reduced.

The M of the ethylene (co) polymer (A) of the present invention
FR (b) is in the range of 0.01 to 100 g / 10 min, preferably 0.1 to 50 g / 10 min.
If the MFR is less than 0.01 g / 10 min, the MF of the composition
R is too low, the fluidity is poor, and the moldability is poor. If it exceeds 100 g / 10 min, the impact resistance of the composition,
Mechanical strength such as tensile strength decreases.

In the present invention, the molecular weight distribution Mw / Mn (c) of the ethylene (co) polymer (A) is calculated by gel permeation chromatography (GPC) using a weight average molecular weight (Mw) and a number average molecular weight (Mw). Mn) and the ratio Mw / Mn. Ethylene α of the present invention
The Mw / Mn of the -olefin copolymer is from 1.5 to 4.5, preferably from 1.5 to 3.5, more preferably from 2.
It is desirably in the range of 0 to 3.0, more preferably 2.2 to 2.9. If Mw / Mn is less than 1.5, the molding processability of the composition will be poor, and if it exceeds 4.5, the impact resistance of the composition will be poor or stickiness will occur.

The composition distribution parameter Cb (d) of the ethylene (co) polymer (A) of the present invention is in the range of 1.08 to 2.00, preferably 1.10 to 1.80, and more preferably 1.12. It is in the range of 1.70. Cb value of 2.00
If the ratio exceeds the above, the impact resistance, tensile properties, durability against repeated deformation, environmental stress deterioration resistance of the composition may deteriorate, and the stickiness of the molded product may increase. If the Cb value of the copolymer is less than 1.08, the heat resistance may decrease.

The method for measuring the composition distribution parameter Cb (d) of the ethylene (co) polymer of the present invention is as follows.

A heat stabilizer is added to the sample, and the sample is heated and dissolved at 135 ° C. in ODCB so that the sample concentration becomes 0.2% by weight. The heated solution is transferred to a column filled with diatomaceous earth (Celite 545), filled and cooled to 25 ° C. at a rate of 0.1 ° C./min, and the sample is deposited on the celite surface. next,
While flowing ODCB through the column at a constant flow rate, the temperature of the column is increased stepwise to 120 ° C. in steps of 5 ° C., and a solution in which a sample is dissolved is collected at each temperature.
After cooling the solution, the sample is reprecipitated with methanol, filtered and dried to obtain samples at each elution temperature. The weight fraction and the degree of branching (the number of branches per 1000 carbon atoms) of the separated sample are measured. 13C-NMR measurement of degree of branching
Ask by

For each fraction collected at 30 ° C. to 90 ° C. by such a method, the following correction of the degree of branching is performed. That is, the degree of branching measured against the elution temperature is plotted, and the correlation is approximated to a straight line by the least square method,
Create a calibration curve. The correlation coefficient of this approximation is large enough.
The value obtained from this calibration curve is defined as the degree of branching of each fraction. Note that, for a fraction collected at an elution temperature of 95 ° C. or higher, this correction is not performed because a linear relationship is not always established between the elution temperature and the degree of branching.

Next, the weight fraction w of each fraction
The _i, the amount of change in the degree of branching b _i per the elution temperature 5 ° C. (b _i
Obtaining the relative concentration c _i divided by chromatography b _i-1), by plotting the relative concentration against the branching degree to obtain a composition distribution curve. This composition distribution curve is divided by a certain width, and the composition distribution parameter Cb is calculated from the following equation.

(Equation 1) Here, c _j and b _j are the relative density and branching degree of the j-th section, respectively. The composition distribution parameter Cb is 1.0 when the composition of the sample is uniform, and the value increases as the composition distribution spreads.

Many proposals have been made for a method of describing the composition distribution of an ethylene (co) polymer. For example, in Japanese Patent Application Laid-Open No. 60-88016, numerical processing is performed on the assumption that the cumulative weight fraction has a specific distribution (log normal distribution) with respect to the number of branches of each separated sample obtained by solvent separation of the sample. The ratio between the weight average branching degree (Cw) and the number average branching degree (Cn) is determined. The accuracy of this approximation calculation decreases when the number of branches of the sample and the cumulative weight fraction deviate from the log-normal distribution.
When measurements are made on LDPE, the correlation coefficient R2 is quite low and the accuracy of the values is not sufficient. This Cw / Cn and Cb of the present invention have different definitions and measurement methods.

The (A) ethylene (co) polymer of the present invention comprises:
The ODCB-soluble component amount X (e) at 25 ° C. indicates the ratio of the high branching degree component and the low molecular weight component contained in the ethylene (co) polymer, and causes the reduction in heat resistance and the stickiness of the molded product surface. Therefore, it is desirable that the number is small. O
The amount of DCB solubles is affected by the α-olefin content and average molecular weight of the entire copolymer, ie, density and MFR. Therefore, the amount X (% by weight) of the ODCB-soluble component
Is less than 2% by weight, preferably less than 1% by weight when the relationship between density d and MFR satisfies d-0.008 × log MFR ≧ 0.93;
More preferably, the content is less than 0.5% by weight. The relationship between d and the MFR is d-0.008 × log MFR <0.
When satisfying 93, X <9.8 × 10 ³ × (0.9300-d + 0.
008 × log MFR) ² +2.0, preferably X
<7.4 × 10 ³ × (0.9300-d + 0.008 × log MFR) ² +
1.0, more preferably X <5.6 × 10 ³ × (0.9300-d
+ 0.008 × log MFR) ² +0.5 is desirable. The fact that the density, the MFR and the amount of the ODCB-soluble component satisfy the above relationship indicates that the α-olefin contained in the entire copolymer is not ubiquitous.

The amount X of ODCB-soluble matter at 25 ° C. is measured by the following method. That is, 0.5 g of a sample is added to 20 ml of ODCB, heated at 135 ° C. for 2 hours to completely dissolve the sample, and then cooled to 25 ° C.
After leaving this solution at 25 ° C. overnight, the filtrate is collected by filtering through a Teflon filter. The filtrate, which is the sample solution, was subjected to infrared spectroscopy to measure the asymmetric stretching vibration wave number of methylene 2925.
The absorption peak intensity around cm ^-1 is measured, and the concentration of the sample in the filtrate is calculated from a calibration curve created in advance. From this value, the ODCB-soluble matter at 25 ° C. is determined.

The ethylene (co) polymer of the present invention must have a plurality of peaks (f) in an elution temperature-elution amount curve obtained by a continuous heating elution fractionation method (TREF),
It is particularly preferable that the peak on the high temperature side exists between 85 ° C and 100 ° C. The presence of this peak increases the melting point and the crystallinity, thereby improving the heat resistance and rigidity of the molded article. FIG. 1 shows an elution temperature-elution amount curve of the copolymer of the present invention. FIG. 2 shows an elution temperature-elution amount curve of a copolymer with a so-called commercially available metallocene catalyst, which are remarkably different.

The method for measuring TREF according to the present invention is as follows. A heat-resistant stabilizer is added to the sample, and the sample is heated and dissolved at 135 ° C. in ODCB so that the sample concentration becomes 0.05% by weight. After injecting 5 ml of this heated solution into a column filled with glass beads, the solution was cooled at a cooling rate of 0.1 ° C./min.
Cool down to ° C. and deposit the sample on the surface of the glass beads. Next, the column temperature is raised at a constant rate of 50 ° C./hr while flowing ODCB through the column at a constant flow rate, and samples that can be dissolved in the solution at each temperature are sequentially eluted. On this occasion,
The sample concentration in the solvent is the wave number 2 of the asymmetric stretching vibration of methylene.
Absorption at 925 cm ^-1 is continuously detected with an infrared detector. From this concentration, an elution temperature-elution amount curve can be obtained. In the TREF analysis, a change in the elution rate with respect to a temperature change can be continuously analyzed with a very small amount of sample, so that relatively fine peaks that cannot be detected by the fractionation method can be detected.

Preparation of (A) Ethylene (co) polymer of the present invention
The structure is at least an organic cyclic compound having at least a conjugated double bond.
Of catalysts containing transition metal compounds of Group IV and Periodic Table
Below, ethylene alone or ethylene and carbon number 3-20
By (co) polymerizing α-olefins
Will be The above catalyst has the following (1) Group IV transition of the periodic table
Organic cyclic compound having a metal compound and (3) conjugated double bond
Contact the following catalyst components (2) and (4)
(Co) polymerization with the catalyst obtained by
desirable. That is, (1): general formula Me¹R¹ _pR^Two
_q(OR^Three)_rX¹ _4-pqrGroup IV of the periodic table represented by
Transition metal compound (wherein Me¹Is zirconium, titanium,
Hafnium, R¹And R^ThreeAre individually carbon number 1 to
24 hydrocarbon or trialkylsilyl groups, R^TwoIs
2,4-pentanedionato ligand or a derivative thereof
Dibenzoylmethanato ligand, benzoylacetona
X representing a derivative such as a ligand¹Indicates a halogen atom
And p, q and r are respectively 0 ≦ p ≦ 4, 0 ≦ q ≦
4, an integer satisfying the range of 0 ≦ r ≦ 4, 0 ≦ p + q + r ≦ 4
(2): General formula Me^TwoR^Four _m(OR^Five)_n
X^Two _zmnA compound represented by the formula: ^TwoIs the periodic table
Group I-III elements, R^FourAnd R^FiveEach have 1 to 24 carbon atoms
A hydrocarbon group of X^TwoIs a halogen atom or a hydrogen atom (
But X^TwoIs Me when hydrogen is a hydrogen atom^TwoIs the Periodic Table III
Group element), and z is Me^TwoShows the valence of
And m and n are each 0 ≦ m ≦ z, 0 ≦ n ≦ z, and 0
≦ m + n ≦ z), (3):
An organic cyclic compound having a double bond, and (4): Al
A modified organoaluminum compound containing -O-Al bond and
And / or boron compounds that come into contact with each other
Medium.

The general formula Me ¹ R ¹ _{p of the} catalyst component (1)
Wherein Me ¹ of _{^{R 2 q (OR 3) rX}} 1 compound represented by the _4-pqr represents zirconium, titanium, hafnium. The type of these transition metals is not limited, and a plurality of transition metals can be used. However, it is particularly preferable that zirconium having excellent weather resistance of the copolymer is contained. R ¹ and R ³ are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms,
Specifically, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group; alkenyl groups such as vinyl group and allyl group; phenyl group, tolyl group, xylyl group, mesityl group, indenyl group and naphthyl group And an aralkyl group such as a benzyl group, a trityl group, a phenethyl group, a styryl group, a benzhydryl group, a phenylbutyl group, and a neofuyl group. These may have branches. R ² is a 2,4-pentanedionato ligand or a derivative thereof (CH ₃ COCHCOC)
H ₃ ) or a derivative such as a dibenzoylmethanato ligand or a benzoylacetonato ligand. X ¹ represents a halogen atom such as fluorine, iodine, chlorine and bromine, and p, q and r are respectively 0 ≦ p ≦ 4, 0 ≦ q ≦
4, 0 ≦ r ≦ 4, 0 ≦ p + q + r ≦ 4.

The catalyst component (1) Examples of the compounds represented by the general formula include tetramethyl zirconium, tetraethyl zirconium, tetrabenzyl zirconium, tetrapropoxy zirconium, tripropoxy monochlorodisilconium, dipropoxy dichloro zirconium, tetrabutoxy zirconium, tributoxy zirconium and tributy zirconium. Butoxymonochlorodisilconium, dibutoxydichlorozirconium, tetrabutoxytitanium, tetrabutoxyhafnium and the like. Specific examples of the 2,4-pentanedionato ligand or derivatives thereof include tetra (2,4- (Pentanedionato) zirconium, tri (2,4-pentanedionato) chloride zirconium, di (2,4-pentanedionato) diethoxide zirconium, di (2,4
-Pentanedionato) di-n-propoxide zirconium, di (2,4-pentanedionato) di-n-butoxide zirconium, di (2,4-pentanedionato)
Dibenzyl zirconium, di (2,4-pentanedionato) dineofyl zirconium, tetra (dibenzoyl methanate) zirconium, di (dibenzoyl methanate) diethoxide zirconium, di (dibenzoyl methanate) di-n Zirconium propoxide, zirconium di (benzoylacetonate) diethoxide, zirconium di (dibenzoylacetonate) and the like, and zirconium di-n-propoxide may be used in combination of two or more. .

The general formula Me ² R ⁴ _{m of the} catalyst component (2)
(OR ⁵ ) _n X ² Me ^{2 in} the formula of the compound represented by _zmn
Represents an element of Groups I to III of the periodic table, such as lithium, sodium, potassium, magnesium, calcium, zinc, boron, and aluminum. R ⁴ and R ⁵ are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 1 carbon atoms.
2, more preferably 1 to 8 hydrocarbon groups, specifically, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group; alkenyl groups such as vinyl group and allyl group; phenyl group And aryl groups such as a tolyl group, a xylyl group, a mesityl group, an indenyl group and a naphthyl group; and aralkyl groups such as a benzyl group, a trityl group, a phenethyl group, a styryl group, a benzhydryl group, a phenylbutyl group and a neofuyl group. These may have branches. X ² represents a halogen atom or a hydrogen atom such as fluorine, iodine, chlorine and bromine. However, when X ² is a hydrogen atom, Me ² is limited to a group III element of the periodic table exemplified by boron, aluminum and the like. Z represents the valence of Me ² , m and n are integers satisfying 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively, and 0 ≦ m + n ≦ z.

Examples of the compounds represented by the general formula of the catalyst component (2) include organic lithium compounds such as methyllithium and ethyllithium; and organic magnesium compounds such as dimethylmagnesium, diethylmagnesium, methylmagnesium chloride and ethylmagnesium chloride. Organic zinc compounds such as dimethyl zinc and diethyl zinc; organic boron compounds such as trimethyl boron and triethyl boron; trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trihexyl aluminum, tridecyl aluminum, diethyl aluminum chloride, and diethyl aluminum chloride Aluminum dichloride, ethyl aluminum sesquichloride, diethyl aluminum ethoxide, diethyl aluminum An organoaluminum compound such as hydride, and the like.

As the organic cyclic compound having a conjugated double bond of the catalyst component (3), two or more, preferably two to four, more preferably two to two cyclic conjugated double bonds are used.
One or more rings having three rings and a total carbon number of 4
To 24, preferably 4 to 12; a cyclic hydrocarbon compound in which the cyclic hydrocarbon compound is partially 1 to 6 hydrocarbon residues (typically, an alkyl group or an aralkyl group having 1 to 12 carbon atoms). A) substituted cyclic hydrocarbon compound;
2 or more, preferably 2 to 4 conjugated double bonds,
More preferably, an organosilicon compound having one or more rings having 2 to 3 rings and having a cyclic hydrocarbon group having a total carbon number of 4 to 24, preferably 4 to 12; Organosilicon compounds substituted with 1 to 6 hydrocarbon residues or alkali metal salts (sodium or lithium salts). Particularly preferably, those having a cyclopentadiene structure in any of the molecules are desirable.

Examples of the preferred compounds include cyclopentadiene, indene, azulene and their alkyl, aryl, aralkyl, alkoxy or aryloxy derivatives. Further, a compound obtained by bonding (crosslinking) these compounds via an alkylene group (the number of carbon atoms of which is usually 2 to 8, preferably 2 to 3) is also preferably used.

The organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula. A _L SiR _4-L wherein A represents the above-mentioned cyclic hydrogen group exemplified by a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group, and R represents a methyl group, an ethyl group, a propyl group. Alkyl groups such as methoxy, ethoxy, propoxy and butoxy groups; aryl groups such as phenyl groups; aryloxy groups such as phenoxy groups; aralkyl groups such as benzyl groups. And represents a hydrocarbon residue having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms or hydrogen, and L represents 1
≦ L ≦ 4, preferably 1 ≦ L ≦ 3.

Specific examples of the organic cyclic hydrocarbon compound of the component (3) include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, 1,3-dimethylcyclopentadiene, indene, and 4-methyl-1.
C5-C24 cyclopolyene or substituted cyclopolyene such as -indene, 4,7-dimethylindene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, azulene, fluorene, methylfluorene, monocyclopentadienyl Examples include silane, biscyclopentadienyl silane, triscyclopentadienyl silane, monoindenyl silane, bisindenyl silane, and trisindenyl silane.

The modified organoaluminum compound containing an Al—O—Al bond of the catalyst component (4) is preferably a modified organoaluminum usually called aluminoxane, which is obtained by reacting an alkylaluminum compound with water. Usually 1 to 100, preferably 1 to
It contains 50 Al-O-Al bonds. The modified organoaluminum compound may be linear or cyclic.

The reaction between the organoaluminum and water is usually carried out in an inert hydrocarbon. As the inert hydrocarbon,
Aliphatic, alicyclic or aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, benzene, toluene and xylene are preferred. The reaction ratio between water and the organic aluminum compound (water / Al molar ratio) is usually 0.25 / 1 to
It is desirable that the ratio be 1.2 / 1, preferably 0.5 / 1 to 1/1.

Specific examples of the boron compound include triethylammonium tetra (pentafluorophenyl) borate (triethylammonium tetra (pentafluorophenyl) borate) and dimethylanilinium tetra (pentafluorophenyl) borate (dimethylanilinium) Tetra (pentafluorophenyl) borate), butylammonium tetra (pentafluorophenyl) borate, N, N-dimethylaniliniumtetra (pentafluorophenyl) borate, N, N-dimethylaniliniumtetra (3,5-difluorophenyl) Borate and the like.

In the present invention, the catalyst component (1)
A catalyst obtained by bringing (4) into contact with each other,
It can be used for a polymerization reaction by being supported on an inorganic carrier and / or a particulate polymer carrier (5). Ingredient (5)
In the inorganic carrier, in the stage of preparing the catalyst of the present invention, as long as the original shape is maintained, powder, granule, flake, foil, fiber, etc. Regardless of the shape, a maximum length in a range of usually 5 to 200 μm, preferably 10 to 100 μm is suitable. Further, the inorganic carrier is preferably porous, and usually has a surface area of 50 to 1000 m ^2.
/ G, pore volume is in the range of 0.05-3 cm ³ / g. As the inorganic carrier of the present invention, a carbonaceous material, a metal, a metal oxide, a metal chloride, a metal carbonate or a mixture thereof can be used, and these are usually in the air at 200 to 900 ° C. or in nitrogen or argon. It is used by firing in an inert gas.

Suitable inorganic carriers that can be used
Metals include iron, aluminum, nickel, etc.
Can be In addition, as the metal oxide, Periodic Tables I to VII
Specific examples include single oxides or complex oxides of Group I.
Has SiO_Two, Al_TwoO_Three, MgO, CaO, B
_TwoO_Three, TiO_Two, ZrO_Two, Fe_TwoO_Three, SiO_Twoー
Al _TwoO_Three, Al_TwoO_Three-MgO, Al_TwoO_Three-Ca
O, Al_TwoO_Three-MgO-CaO, Al_TwoO_Three-MgO
-SiO_Two, Al_TwoO_Three-CuO, Al_TwoO_Three-Fe_Two
O_Three, Al_TwoO_Three-NiO, SiO_Two-MgO etc.
I can do it. Note that the above formula expressed as an oxide is a molecular formula
But only the composition. In other words, the present invention
The structure and component ratio of the double oxide used in
It is not limited. Also used in the present invention
Metal oxides can absorb a small amount of moisture.
And may contain a small amount of impurities.

As the metal chloride, for example, alkali metal and alkaline earth metal chlorides are preferable, and specifically, MgCl ₂ , CaCl _{2 and the} like are particularly preferable. As the metal carbonate, a carbonate of an alkali metal or an alkaline earth metal is preferable, and specific examples include magnesium carbonate, calcium carbonate, barium carbonate and the like. Examples of the carbonaceous substance include carbon black and activated carbon. Although any of the above inorganic carriers can be suitably used in the present invention, use of metal oxides such as silica and alumina is particularly preferable.

On the other hand, as the particulate polymer carrier, any of a thermoplastic resin and a thermosetting resin can be used as long as they maintain a solid state without melting or the like at the time of catalyst preparation and polymerization reaction. The particle size is usually 5-2000μ
m, preferably in the range of 10 to 100 μm. The molecular weight of these polymer carriers is not particularly limited as long as the polymer can exist as a solid substance at the time of catalyst preparation and polymerization reaction.
It can be used arbitrarily from low molecular weight to ultra high molecular weight. Specifically, various types of polyolefins (preferably having 2 to 12 carbon atoms) represented by particulate ethylene polymer, ethylene / α-olefin copolymer, propylene polymer or copolymer, poly 1-butene, polyester , Polyamide, polyvinyl chloride, polymethyl (meth) acrylate, polystyrene, polynorbornene, various natural polymers, and mixtures thereof.

The above-mentioned inorganic carrier and / or particulate polymer carrier can be used as they are, but preferably, as a pretreatment, these carriers are converted to an organic aluminum compound or a modified organic aluminum compound containing an Al—O—Al bond. After the contact treatment, it can be used as the component (5).

The (A) ethylene (co) polymer of the present invention comprises:
It is produced by a gas phase method, a slurry method, a solution method or the like, and is not particularly limited, such as a one-stage polymerization method or a multi-stage polymerization method. By using the ethylene (co) polymer (A) polymerized by the above method and satisfying the above (a) to (f), flexibility,
A composition having a good balance between mechanical strength and heat resistance, and having excellent gloss and durability against repeated use.

The (B) propylene polymer of the present invention is
A propylene homopolymer, a block copolymer of propylene and α-olefin, a random copolymer of propylene and α-olefin, and the like. A preferred copolymer is propylene and α having 2 to 8 carbon atoms (excluding 3 carbon atoms). -Copolymers with one or more olefins, such as ethylene, 1-butene, 4-methyl-1-pentene,
-Hexene, 1-octene and the like are preferred. These copolymer components in the copolymer are preferably at most 30 mol%.
The propylene polymer is polymerized by a known technique using a Ziegler-Natta type catalyst. Particularly in applications requiring heat resistance, propylene homopolymers are preferably used, but block polymers and random polymers have excellent permanent elongation, and can be used depending on their properties.

The (B) propylene polymer having a melt flow rate (MFR) of 0.1 to 100 g / 10 min, more preferably 0.5 to 70 g / 10 min is used. If the MFR is less than 0.1 g / 10 min, the flowability of the composition is poor and molding is difficult. On the other hand, if it exceeds 70 g / 10 min, the tensile strength and impact strength become weak, which is not preferable. These MFRs may be prepared by thermally decomposing a polymerized polymer together with an organic peroxide.

The (C) ethylene / α-olefin copolymer rubber of the present invention is an ethylene / α-olefin copolymer rubber or an ethylene / α-olefin / non-conjugated diene copolymer rubber. It is a crystalline copolymer. Examples of the α-olefin in the ethylene / α-olefin copolymer rubber component include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene. Particularly preferred is propylene. Non-conjugated dienes include 1,4-hexadiene,
Examples thereof include 1,6-octadiene, dicyclopentadiene, vinyl norbornene, and ethylidene norbornene. Preferably, they are 1,4-hexadiene and ethylidene norbornene.

The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the ethylene / α-olefin copolymer rubber (C) is 10
Those having about 95 are preferred. If the Mooney viscosity of the ethylene / α-olefin copolymer rubber is less than 10, the tensile strength of the composition is lowered and the surface becomes sticky, which is not preferable. If the Mooney viscosity exceeds 95, the fluidity of the composition becomes poor, which is not preferable.

The ethylene (co) polymer (A) (hereinafter referred to as component (A)), the propylene-based polymer (B) (hereinafter referred to as component (B)), and ethylene-α occupy in the thermoplastic elastomer composition of the present invention. The composition ratio of the olefin copolymer rubber (C) (hereinafter referred to as component (C)) is such that component (A) is 30 to 70 parts by weight, preferably 40 to 60 parts by weight, and component (B) is 70 to 30 parts by weight. , Preferably 60 to
Component (C) is 70 to 200 parts by weight, preferably 100 to 150 parts by weight, based on 100 parts by weight of component (A) + component (B). Component (A) is 7
If the amount exceeds 0 parts by weight, heat resistance and fluidity decrease, and if it is less than 30 parts by weight, flexibility and gloss are insufficient, which is not desirable. When the amount of the component (B) exceeds 70 parts by weight, the heat resistance is good, but the flexibility and gloss are insufficient. When the amount is less than 30 parts by weight, the heat resistance deteriorates. If component (C) is less than 70 parts by weight per 100 parts by weight of component (A) + component (B), the flexibility is insufficient, and if it exceeds 200 parts by weight, heat resistance and strength are reduced.

The thermoplastic elastomer of the present invention is used in a partially crosslinked state particularly for applications requiring heat resistance and oil resistance. The partial cross-linking is to cross-link a part of the composition and to partially cross-link using a cross-linking agent while maintaining fluidity. When performing partial cross-linking, the components (A), (B) and (C) may be blended so as to have a predetermined composition ratio, and then partially cross-linked. In order to obtain the properties and gloss, it is preferred that the component (B) and the component (C) are blended, and the component (A) is blended after the partial crosslinking, although the tensile strength and the heat resistance are slightly lowered.
As a method for producing a partially crosslinked product, any known technique can be used. A typical example is a method in which a crosslinking agent is added to the composition to perform mechanical melt-kneading, and a single-screw and twin-screw extruder, a Banbury mixer, various kneaders, various cross-linkers using a roll, or the like can be used. it can. The temperature of the melt-kneading is generally 300 ° C. or less, preferably a temperature at which the half-life of the crosslinking agent used is 1 minute or less, and usually 100 to 100 ° C.
300 ° C. Further, after mixing a crosslinking agent by impregnation or the like, partial crosslinking may be performed by heat or radiation.

As the crosslinking agent, an organic peroxide is usually used. Specifically, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butyl peroxide, di (t-butylperoxy) diisopropylbenzene, di (t-butylperoxy) diisobutyl Benzene, dicumyl peroxide, t-butylcumyl peroxide, t-butylperoxybenzoate, 1,
Examples include 1-bis (t-butylperoxy) -3,3,5-trimethyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide and the like. Also,
A crosslinking aid may be used. Specifically, liquid polybutadiene, divinylbenzene, ethylene dimethacrylate,
Diallyl phthalate and the like can be mentioned. The amount of the crosslinking agent to be used is 0.005 to 3% by weight, preferably 0.05 to 1% by weight, based on the resin composition. The amount of the cross-linking agent used is determined by the performance required for the cross-linked composition, and is not necessarily limited to these figures. Also,
Several kinds of crosslinking agents and crosslinking aids may be used in combination depending on the purpose. The boiling xylene-insoluble fraction (gel fraction) measured by extracting the thermoplastic elastomer composition of the present invention obtained by partially crosslinking in this way with boiling xylene for 5 hours is as follows:
It is 0.5 to 60% by weight, preferably 2 to 50% by weight. When the gel fraction is less than 0.5% by weight, oil resistance and the like are reduced, and when the gel fraction exceeds 60% by weight, tensile strength and elongation are undesirably reduced.

In the present invention, various fillers such as carbon black, calcium carbonate, silica, metal fibers, carbon fibers and the like, an antioxidant, a hardening agent, etc. may be used as long as the properties intended in the present invention are not substantially impaired. Known additives such as flame retardants, lubricants, antistatic agents, anti-fogging agents, pigments, ultraviolet absorbers, dispersants, etc., and paraffins, naphthenes or aromatics for the purpose of helping the dispersion of fillers and increasing flexibility and elasticity System-based vegetable oil may be blended if necessary. When partial crosslinking is performed, the above additives may be added before and after crosslinking or during crosslinking (particularly during melt-kneading), if necessary. Further, within a range that does not essentially impair the properties intended in the present invention, crystalline polyolefins such as high-density polyethylene, low-density polyethylene, linear low-density polyethylene, natural rubber, various synthetic rubbers, styrene-based thermoplastic compositions, and the like The various resins and rubbers described above may be blended as necessary.

The thermoplastic elastomer composition of the present invention can be prepared by injection molding, extrusion molding, hollow molding, inflation molding,
Molded by T-die molding, etc. For example, used as bumpers, mudguards, interior skin materials for automobile parts, hoses and packings for home appliances, and used for building gaskets, sound insulation materials, stationery, household goods, etc. Can be

[0047]

Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. The test method used in this example is as follows. (Physical Property Test Method) MFR: Based on JIS K6758. Tensile test: Based on JIS K6301. Specimens were prepared using No. 3 dumbbells and measured at a pulling speed of 50 mm / min. Permanent elongation: Based on JIS K6301. A test piece was prepared using a No. 3 dumbbell. The test piece was held at 100% elongation for 10 minutes, suddenly contracted, and determined from the elongation rate after leaving for 10 minutes. Vicat softening point: A sample having a thickness of 3 mm was prepared by pressing (210 ° C.) and used for measurement. The heat transfer medium was heated at a rate of 50 ° C./60 minutes while applying a load of 250 g through a needle indenter vertically placed on the test piece in the heating solution, and the heat transfer medium when the needle indenter penetrated 1 mm was applied. Was taken as the Vicat softening point. Hardness: A test piece was prepared according to JIS K6301 and measured using an A-type testing machine. Oil resistance: A test piece was prepared according to JIS K6301, and the volume change at 70 ° C. for 22 hours was determined using JIS No. 3 oil. Gel fraction: Using a hot press (190 ° C., 5 minutes), prepare a sheet having a thickness of 200 μm, cut out three sheets of 40 mm × 20 mm, and put them in a wire mesh bag of 120 mesh each. Extract with boiling xylene for 5 hours using a double tube soxhlet extractor. The boiling xylene-insoluble matter is taken out, dried under vacuum (80 ° C, 7 hours), and the boiling xylene-insoluble matter is determined as a gel fraction. Surface gloss: A flat plate having a size of 11 cm × 15 cm and a thickness of 2 mm is formed by injection molding at a cylinder temperature of 200 ° C. using a mirror-finished mold, and this flat plate is used to form a Nippon Denshoku Co., Ltd. in accordance with JIS Z8741. Gs (60 °) was determined using a digital variable gloss meter VGS-1D manufactured by Kogyo Co., Ltd.

(Polymerization of Ethylene / α-Olefin Copolymer) Preparation of Solid Catalyst Purified toluene was added to a catalyst preparation device (No. 1) with an electromagnetic induction stirrer under nitrogen, and then dipropoxydichlorozirconium (Zr (OPr)) 28 g of ₂ Cl ₂ ) and 48 g of methylcyclopentadiene were added, and 45 g of tridecylaluminum was added dropwise while maintaining the system at 0 ° C. After completion of the dropwise addition, the reaction system was maintained at 50 ° C. and stirred for 16 hours. This solution is designated as solution A. Next, purified toluene was added to another catalyst preparation device with a stirrer (No. 2) under nitrogen, and the above-mentioned solution A and then a toluene solution of 6.4 mol of methylaluminoxane were added and reacted. This is designated as solution B. Next, purified toluene was added to a stirrer-equipped preparation device (No. 1) under nitrogen, and then 1,400 g of silica (Fuji Devison, grade # 952, surface area 300 m ² / g) previously calcined at 400 ° C. for a predetermined time was added. After the addition, the entire amount of the B solution was added, and the mixture was stirred at room temperature. Then, the solvent was removed by nitrogen blowing to obtain a solid catalyst powder having good fluidity. This is designated as catalyst C.

Polymerization of Samples A1 and A2 Using a continuous fluidized bed gas phase polymerization apparatus, a polymerization temperature of 70
A copolymerization of ethylene and 1-butene was performed at a temperature of 20 ° C. and a total pressure of 20 kgf / cm ² G. The polymerization was carried out by continuously supplying the catalyst C, and the polymerization was carried out while continuously supplying each gas in order to keep the gas composition in the system constant. When the sample amount was insufficient, these operations were repeated to obtain a required amount.
The physical properties of the produced copolymer are as follows. A1 A2 MFR (g / 10 min): 0.9 1.0 Density (g / cm ³ ): 0.900 0.920 Molecular weight distribution (Mw / Mn): 2.8 2.7 ODCB soluble matter (W%) ): 5.9 1.0 X (value of formula 1) (W%): 10.6 2.98 Cb: 1.3 1.25 TREF peak: plural plural

Sample B1 was a propylene-ethylene random copolymer having an MFR of 7 g / 10 min (ethylene content: 5.9).
mol%) and B2 is a propylene-ethylene block copolymer having an MFR of 8 g / 10 min (ethylene content: 5.3 mol).
1%), B3 is a propylene homopolymer having an MFR of 1 g / 10 min.

Polymerization of Samples C1 and C2 C1 is an ethylene-propylene copolymer rubber copolymerized using a vanadyl ethyl trichloroaluminum sesquichloride catalyst. Mooney viscosity of copolymer rubber (ML
_{1 + 4} , 100 ° C.) is 73 and the propylene content is 2
The content was 6% by weight and the density was 0.862 g / cm ³ . C2
Is a copolymer rubber obtained by copolymerizing ethylene, propylene and ethylidene norbornene (ENB) using a vanadyl ethyl trichloride-based aluminum sesquichloride catalyst. Mooney viscosity of copolymer rubber (ML _{1 + 4} , 100 ℃)
Was 90, the propylene content was 27% by weight, the density was 0.863 g / cm ³ , and the ENB content in the copolymer rubber was 16 in terms of iodine value.

(Examples 1 to 9) The effects of the present invention were examined. Among the components shown in Table 1, component (B) was a propylene-based polymer, and component (C) was ethylene.
0.5% by weight of di (t-butylperoxy) dipropylbenzene as a crosslinking agent in an α-olefin copolymer rubber,
After dry-blending 0.1% by weight of Irganox 1010 (trade name, manufactured by Ciba Geigy) as an antioxidant and 0.15% by weight of calcium stearate (all weights are based on 100 parts by weight of the total polymer) as a lubricant,
Put into a Banbury mixer preheated to 200 ° C.
Kneading was performed for a minute. Subsequently, the component (A) ethylene (co) polymer was charged and kneaded again at 200 ° C. for 10 minutes to obtain a thermoplastic elastomer composition. Various tests were performed by the above-described methods. The results are shown in Table 1. (Example 10) A composition similar to that of Example 1 was used, and no partial crosslinking was performed. Table 1 shows the results.

Comparative Example 1 Instead of the ethylene / 1-butene copolymer of Example 1, ethylene and 1-butene were copolymerized with a conventional Ziegler catalyst to give an MFR of 0.9 g / 10
min, density: 0.900 g / cm ³ , except that linear low density polyethylene A3 was used. Table 1 shows the results. The strength is weak and the elongation is large. (Comparative Example 2) Instead of the ethylene / 1-butene copolymer of Example 2, ethylene and 1-butene were copolymerized with an ordinary Ziegler catalyst to obtain an MFR of 0.9 g / 10 min and a density of:
The procedure was performed in the same manner as in Example 2 except that linear low-density polyethylene A3 of 0.900 g / cm ³ was used. Table 1 shows the results. Permanent elongation is somewhat large and gloss is somewhat poor. (Comparative Example 3) Instead of the ethylene / 1-butene copolymer of Example 2, ethylene and 1-butene were copolymerized with a usual Ziegler catalyst to give an MFR of 1.0 g / 10 min and a density of:
The same procedure as in Example 2 was carried out except that a linear low-density polyethylene A4 of 0.920 g / cm ³ was used. Table 1 shows the results. Large permanent elongation. The gloss is somewhat poor. (Comparative Example 4) The same operation as in Example 2 was carried out except that the component A-1 was changed to 20 parts by weight and the component B-1 was changed to 80 parts by weight. Table 1 shows the results. No flexibility and large permanent elongation. In addition, the gloss is poor. (Comparative Example 5) Component A of Example 2
Example 2 was repeated except that the amount of Component-1 was 80 parts by weight and the amount of Component B-1 was 20 parts by weight. Table 1 shows the results. Poor heat resistance and insufficient strength. (Comparative Example 6) The same operation as in Example 2 was carried out except that the component C-2 in Example 2 was used in an amount of 300 parts by weight. Table 1 shows the results.
Low strength and poor gloss. In addition, heat resistance is poor. (Comparative Example 7) A composition similar to that of Comparative Example 1 was used without partial crosslinking. Table 1 shows the results. Low strength and large permanent elongation.

[0054]

[Table 1]

[0055]

According to the present invention, flexibility can be obtained by blending a specific ethylene (co) polymer or propylene polymer having a narrow molecular weight distribution and a moderate composition distribution with an ethylene / α-olefin copolymer rubber. It is possible to provide a thermoplastic elastomer composition that is rich, has excellent fluidity, tensile properties, impact strength, heat resistance, oil resistance, gloss, is less sticky, and can withstand repeated fatigue. Further, by partially crosslinking these compositions, a thermoplastic elastomer composition having further improved heat resistance and oil resistance can be provided.
Since the thermoplastic elastomer composition of the present invention has the above excellent properties, it can be used for automobile parts such as bumpers, mudguards, interior skin materials, home appliances, various packings, building gaskets, and civil engineering materials such as sound insulation materials. It can be widely used for daily necessities such as architecture and stationery.

[Brief description of the drawings]

FIG. 1 is a TREF curve of a copolymer used in the present invention.

FIG. 2 is a TREF curve of a metallocene copolymer.

Claims (2)

[Claims] (1) Either homopolymerization of ethylene or copolymerization of ethylene and an α-olefin in the presence of a catalyst containing (A) an organic cyclic compound having at least a conjugated double bond and a transition metal compound of Group IV of the periodic table. And the ethylene (co) polymer 30 satisfying the following (a) to (f):
(A) Density 0.86 to 0.96 g / cm ³ (b) Melt flow rate (MFR) 0.01 to 100 g / 10 min (c) Molecular weight distribution (Mw / Mn) 1.5 to 4 0.5 (d) Composition distribution parameter Cb 1.08 to 2.00 (e) Amount of orthodichlorobenzene (ODCB) soluble matter at 25 ° C. X (% by weight) and density d and MFR a) d-0.008 × logMFR X ≥ 0.93 X <2.0 b) d-0.008 x log MFR <0.93 X <9.8 x 10 ³ x (0.9300-d + 0.008 x log MFR) ² + 2.0 (Equation 1) (f) Continuous rise The peak of the elution temperature-elution amount curve by the thermal elution fractionation method (TREF) has a plurality of peaks. (B) 100 parts by weight of the resin component composed of 70 to 30 parts by weight of the propylene polymer and (C) ethylene / α-olefin Polymer rubber 70-2
A thermoplastic elastomer resin composition comprising 100 parts by weight. 2. A resin component consisting of 30 to 70 parts by weight of (A) an ethylene (co) polymer and (B) 70 to 30 parts by weight of a propylene polymer according to claim 1, C) Ethylene / α-olefin copolymer rubber 7
A thermoplastic elastomer resin composition obtained by partially crosslinking a composition comprising 0 to 200 parts by weight.