JP2000026697A - Propylene resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a propylene resin composition, which is excellent in processability and weld appearance, by compounding a propylene/ethylene block copolymer, an ethylene/α-olefin/diene copolymerized rubber, talc and high-density polyethylene. SOLUTION: The resin composition comprises 100 parts by weight of a propylene-ethylene block copolymer, 1 to 50 parts by weight of an ethylene/α- olefin or ethylene/α-olefin/diene copolymerized rubber having an MFR value (at 230 deg.C under a load of 2.16 kg) of 0.05 to 1.2 g/10 minutes, 5 to 60 parts by weight of talc having an average particle size of 1.5 to 15 μm, and 0 to 10 parts by weight of high-density polyethylene having an MFR value (at 190 deg.C under a load of 2.16 kg) of 11 g/10 minutes. The propylene/ethylene block copolymer contains 60 to 95 wt.% of a crystalline polypropylene moiety and 5 to 40 wt.% of a propylene/ethylene random copolymer moiety having an ethylene content of 30 wt.% or more, and has a swell index of 1.4 or below.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an excellent injection molding (injection compression molding) processability and physical property balance (high rigidity, impact strength and surface hardness) of a molded product, as well as excellent low gloss and weld appearance. The present invention relates to a novel propylene-based resin composition that can be commercialized by painting, and relates to a propylene-based resin composition suitable as a material for various industrial parts, automobile parts, particularly automobile interior parts.

[0002]

2. Description of the Related Art Conventionally, various molded articles in the field of industrial parts, such as automobile parts such as bumpers, instrument panels, fan shrouds and glove boxes, and parts of household electric appliances such as televisions, VTRs and washing machines, etc. Many of the resin compositions have been put to practical use by utilizing their excellent moldability, mechanical strength and economical characteristics. However, in recent years, each of the above uses has been increasingly advanced in function and product size, and accordingly, in the field of automotive interior parts, for example, in the field of automobile interior parts, high moldability and high physical property balance ( High rigidity, impact strength and surface hardness of molded products), and in addition to the cost-effective advancement of non-coating, the appearance of a high degree of appearance, specifically low gloss, which gives a calm texture, and product value There is a demand for a further improvement in the weld appearance (in which the linear pattern of the flow butting portion of the resin is less conspicuous) that further enhances the weld appearance.

[0003] With respect to lowering the gloss and improving the weld appearance of a propylene-based resin composition, a composition in which a propylene polymer is filled with a partially crosslinked elastomer or an ethylene-propylene-conjugated diene-terpolymer (JP-A-7-157)
607), a composition in which an inorganic filler is blended with a specific propylene-based polymer-containing composition (JP-A-9-7169).
No. 1), a composition in which a specific propylene resin is blended with an α-olefin copolymer having 4 to 18 carbon atoms and talc (Japanese Patent Application Laid-Open No. 9-263665), A composition comprising an ethylene / α-olefin copolymer obtained by polymerization under a specific catalyst, a specific high-density polyethylene and talc (JP-A-10-78)
No. 51) is disclosed. Although these compositions have achieved low gloss and improved weld appearance to some extent, they are still insufficient, and also in terms of molding processability and physical properties balance, as moldings become larger and thinner, they are still in need. Insufficient.

[0004]

Under such circumstances, the present invention is excellent in injection molding (injection compression molding) workability (fluidity) and has a high balance of physical properties (high rigidity, impact strength and surface hardness). By providing a propylene-based resin composition that is also excellent in low gloss and weld appearance,
It is an object of the present invention to provide high-performance industrial parts and automobile parts, especially automobile interior parts, which do not require painting and therefore can reduce costs.

[0005]

Means for Solving the Problems The present inventors have conducted various studies to solve the above-mentioned problems, and as a result, have found that a specific propylene / ethylene-block copolymer has a specific ethylene / α-olefin. Copolymer rubber or ethylene / α
-Propylene resin composition obtained by blending olefin / diene copolymer rubber, specific talc and, in some cases, specific high-density polyethylene in a specific ratio has excellent injection molding (injection compression molding) processability. The present invention was found to be excellent in balance of physical properties (high rigidity, impact strength and surface strength), low gloss and excellent weld appearance, and capable of being commercialized without painting, and completed the present invention. It is. That is, the present invention provides the following components (a) to
(D) a propylene-based resin composition. (A) Homopolymer part of crystalline polypropylene (A unit part)
60 to 95% by weight, an ethylene content of 30% by weight or more, and a weight average molecular weight (Mw) of 200,000 to
1,000,000 ethylene-propylene-random copolymerized portion (B unit portion) of 5 to 40% by weight, and a melt flow rate (MF) of the entire component (a).
R: 230 ° C, 2.16 kg) is 10 to 200 g / 10
Propylene / ethylene-block copolymer having a swell index value (S value: 190 ° C.) of 1.4 or less: 100 parts by weight (b) α-olefin having 3 to 8 carbon atoms in 20 to 50 parts by weight Ethylene / α-olefin copolymer rubber or ethylene / α-olefin / diene copolymer rubber having a MFR (230 ° C., 2.16 kg) of 0.05 to 1.2 g / 10 min. 50 parts by weight (c) Talc having an average particle size of 1.5 to 15 μm: 5 to 60
Parts by weight (d) MFR (190 ° C., 2.16 kg) is 11 g / 1
0 minutes or more, high density polyethylene: 0 to 10 parts by weight

[0006]

DETAILED DESCRIPTION OF THE INVENTION [I] Propylene resin composition Constituents The propylene-based resin composition of the present invention comprises the following component (a):
It consists of component (b), component (c) and optionally component (d). (1): Propylene-ethylene-block copolymer [component (a)] (i) Structure The propylene-ethylene-block copolymer of the component (a) used in the present invention is a crystal obtained by homopolymerization of propylene. Polypropylene homopolymer portion (A
Unit) is 60 to 95% by weight, preferably 65 to 92% by weight.
%, Particularly preferably 70 to 85% by weight. Further, the ethylene content is 30% by weight or more, preferably 35% by weight or more, particularly preferably 40% by weight or more, and the weight average molecular weight (Mw) is 200,000 to 1,000,000.
00, preferably 250,000 to 900,000, particularly preferably 300,000 to 800,000 ethylene-propylene-random copolymerized moiety (B unit)
From 5 to 40% by weight, preferably from 8 to 35% by weight, particularly preferably from 15 to 30% by weight. Further, the MFR of the whole component (a) is 10 to 200 g / 10
Min, preferably 15 to 100 g / 10 min, particularly preferably 20 to 80 g / 10 min, and the swell index value (S
Value) is at most 1.4, preferably at most 1.2, particularly preferably at most 1.1. Further, the density of the A unit is 0.9071 g / cm ³ or more, particularly 0.9
It is preferably at least 081 g / cm ³ .

When the content of the crystalline propylene homopolymerized portion (A unit) is less than the above range, the rigidity and the surface hardness of the molded article are insufficient, while when it exceeds the above range, the impact strength and the low gloss are insufficient. When the content ratio of the ethylene / propylene-random copolymerized portion (B unit portion) is less than the above range, impact strength and low glossiness are insufficient.
Insufficient rigidity and surface hardness of molded products. If the ethylene content of the B unit is less than the above range, the surface hardness and low gloss of the molded product are insufficient, and the weld appearance is deteriorated. In addition, the B
If the Mw of the unit exceeds the above range, the weld appearance is significantly impaired or the impact strength is reduced.
The surface hardness of the molded article decreases. Further, the propylene
If the MFR of the whole ethylene-block copolymer is less than the above range, the moldability and weld appearance are poor, while if it exceeds the above range, the impact strength is insufficient, and if the S value exceeds the above, the weld appearance is reduced. The propylene / ethylene-block copolymer may be used alone or in combination of two or more as long as the above physical properties are satisfied.

(Ii) Production The propylene / ethylene-block copolymer is produced by slurry polymerization, gas phase polymerization or liquid phase bulk polymerization using a highly stereoregular catalyst. Either type of continuous polymerization can be employed. In producing the propylene / ethylene-block copolymer, first, a crystalline polypropylene portion (A unit portion) is formed by homopolymerization of propylene,
Next, an ethylene-propylene-random copolymerized portion (B unit portion) formed by random copolymerization of ethylene and propylene is preferable from the viewpoint of quality. For example, homopolymerization of propylene is performed on a solid component formed by contacting titanium tetrachloride, an organic acid halide and an organosilicon compound with magnesium chloride using a catalyst in which an organoaluminum compound component is combined, and then ethylene and propylene are mixed. It can be produced by performing random copolymerization. The propylene / ethylene-block copolymer is a terpolymer or a copolymer containing an unsaturated compound, for example, an α-olefin such as 1-butene and a vinyl ester such as vinyl acetate, within a range not impairing the effects of the present invention. It may be a combination or a mixture thereof. The propylene / ethylene-
The block copolymer may be in the form of a pellet or a powder.

Further, the MFR and S value of the propylene / ethylene-block copolymer may be adjusted under polymerization conditions or arbitrarily controlled with a peroxide after polymerization. If anything, the latter is preferable in terms of weld appearance and low gloss, and it is a preferable method to use the peroxide-treated propylene / ethylene-block copolymer for the whole or a part of the component (a). By the way, when the peroxide treatment is performed, the MFR is generally large, the S value is small, and the molecular weight distribution can be controlled to be narrow.

The peroxide which can be used for controlling the MFR and the S value of the propylene / ethylene-block copolymer is not particularly limited. For example, ketone peroxides such as methyl ethyl ketone peroxide and methyl isobutyl ketone peroxide; Peroxyketals such as n-butyl-4,4-bis (t-butylperoxide) valerate; hydroperoxides such as cumene hydroperoxide and diisopropylbenzene hydroperoxide; 1,3-bis (t-butylperoxy-)
Diisopropyl peroxide such as isopropyl) benzene and dicumyl peroxide; diacyl peroxide such as benzoyl peroxide; percarbonate such as bis- (4-t-butylcyclohexyl) peroxydicarbonate; t-butylperoxy acetate and the like Peroxyester and the like can be mentioned. Among them, it is preferable that the 10-hour half-life temperature is 100 ° C. or more, and the 1-minute half-life temperature is not less than the melting point of the propylene / ethylene-block copolymer, and such a peroxide is, for example, cumene hydroperoxide. Diisopropylbenzene hydroperoxide; 1,3-bis (t-butylperoxy-isopropyl) benzene; 2,5-dimethyl-2,
5-di (t-butylperoxy) hexane; dicumyl peroxide and the like. These may be used alone or in combination of two or more.

[0011] The content of the B unit in the propylene / ethylene-block copolymer is measured by immersing 1 g of a sample in 300 ml of boiling xylene for 30 minutes to dissolve it, cooling it to room temperature, and filtering it with a glass filter. It is a value calculated back from the solid phase weight obtained by filtration and drying. The ethylene content is measured by an infrared spectrum analysis method or the like. The Mw of the B unit is measured by separately concentrating and drying the dissolved substance that has been filtered (passed) through the above glass filter, and then subjecting it to gel permeation chromatography (GPC). MFR is JIS-K7210 (2
(30 ° C., 2.16 kg). The S value is measured using a melt indexer (MFR measuring device ... J
ISK7210), extrusion temperature 190 ° C., nozzle inner diameter 1.0 mm, nozzle length 8 mm, extrusion speed 0.1 g /
The sample is extruded into a graduated cylinder (in ethyl alcohol) under the conditions of minutes, and the diameter of the solidified sample is
Measure with laser light meter or micrometer,
It is calculated by the following formula. S value = solidified extrusion sample diameter / nozzle inner diameter The S value can be approximated and replaced by a die swell value (190 ° C., extrusion nozzle diameter 1.0 mm, shear rate = 24 sec ⁻¹ ) determined by a capillary rheometer.
If anything, it is often 0.05 to 0.10.

(2): Ethylene / α-olefin copolymer rubber or ethylene / α-olefin / diene copolymer rubber [Component (b)] The ethylene / α-component of component (b) used in the present invention.
The olefin copolymer rubber or ethylene / α-olefin / diene copolymer rubber contains 20 to 50% by weight, preferably 20 to 45% by weight, particularly preferably 20 to 40% by weight of α-olefin having 3 to 8 carbon atoms. In the case of a terpolymer rubber with diene, it contains 1 to 10% by weight, preferably 2 to 8% by weight, particularly preferably 3 to 6% by weight of diene, and has an MFR (230 ° C., 2.16 kg). ) Is 0.05
To 1.2 g / 10 min, preferably 0.1 to 0.8 g / 1
0 minutes, particularly preferably 0.1 to 0.5 g / 10 minutes. Here, the density is 0.85 to 0.89 g / c.
m ³ , a glass transition point of preferably −40 ° C. or less,
Those having a density of 0.85 to 0.88 g / cm ³ and a glass transition point of -45 ° C or less are particularly preferred. MFR is 0.0
If it is less than 5 g / 10 minutes, the impact strength will be insufficient, while
When it exceeds 1.2 g / 10 minutes, low gloss is insufficient, so that it is not suitable.

As the α-olefin to be contained, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene and the like can be mentioned. Among them, propylene, 1-butene, 1-hexene and 1-octene are preferred, and propylene, 1-butene and 1-octene are particularly preferred. In the case of a terpolymer with a diene, examples of the diene to be copolymerized include ethylidene norbornene, dicyclopentadiene, and 1,4-hexadiene.
Particularly, ethylidene norbornene is preferable. When the content of the α-olefin is less than the above range, the impact strength of the propylene-based resin composition of the present invention is inferior, and when it exceeds the above range, the rigidity and surface hardness of the propylene-based resin composition decrease, Each is unsuitable.

These copolymer rubbers may be used alone or in combination of two or more. Ethylene / α-olefin copolymer rubber and ethylene / α-olefin / diene copolymer rubber may be used, but rather, from the viewpoint of weld appearance, low gloss, balance of impact strength, etc. Ethylene / α-olefin / diene copolymer rubber is preferred, and ethylene / propylene / diene copolymer rubber is particularly preferred.

[0015] The production method is not particularly limited, but may be a vanadium compound or WO-91 / 04257.
And those produced using a vanadium compound-based catalyst from the viewpoints of weld appearance, low gloss, balance of impact strength, and the like.

The content of α-olefin is determined by a conventional method such as infrared spectroscopy or ¹³ C-NMR (in general, the value obtained by infrared spectroscopy is smaller at lower densities as compared with ¹³ C-NMR). (Which tends to be about 10-50%). MFR is JIS-K721
0 (230 ° C., 2.16 kg). The density is a value measured according to JIS-K7112. The glass transition point is measured by a differential calorimeter (DS
C, for example, RDC-220 manufactured by Seiko Denshi Kogyo Co., Ltd.) (20 ° C./min).

(3); Talc [Component (c)] The talc of the component (c) used in the present invention has an average particle size of 1.5 to 15 μm, preferably 1.5 to 15 μm.
10 μm, particularly preferably 2 to 8 μm.
The talc is effective for improving low gloss and rigidity, dimensional stability and adjustment of a molded product, and the like. Further, the talc preferably has an average aspect ratio of 4 or more, particularly preferably 5 or more.
When the average particle size of talc is less than 1.5 μm, low gloss is insufficient. On the other hand, when it exceeds 15 μm, impact strength and rigidity are insufficient. The talc is first manufactured by, for example, crushing raw talc with an impact mill or a micron mill type pulverizer, or finely pulverizing with a jet mill or the like, and then adjusting the classification using a cyclone or a micron separator. To manufacture. Here, the gemstone is preferably made in China because of its low metal impurity content. The talc may be surface-treated with various metal salts or the like, and may be so-called compressed talc having an apparent specific volume of 2.50 ml / g or less. The average particle size of talc is a value measured using a laser diffraction / scattering type particle size distribution analyzer. As a measuring device, for example, LA-920 manufactured by Horiba, Ltd. is preferable because of excellent measurement accuracy. The measurement of the diameter, length and aspect ratio of talc can be obtained from values measured with a microscope or the like.

(4): High-density polyethylene [Component (d)] The high-density polyethylene of the component (d) optionally used in the present invention has an MFR (190 ° C., 2.16 kg).
Is at least 11 g / 10 min, preferably 11 to 50 g / 10
Min, particularly preferably 15 to 30 g / 10 min, and a density of 0.94 to 0.98 g / cm ³ , preferably 0.94
To 0.97 g / cm ³ , particularly preferably 0.95 to 0.5 g / cm ³ .
97 g / cm ³ . Those having an MFR or density outside the above range are unsuitable because of low glossiness, poor weld appearance and poor scratch resistance. The MFR is JIS-K7210 (190
C., 2.16 kg).
The density is measured according to JIS-K7112.

(5): Other components (optional components)
[Component (e)] In the propylene-based resin composition of the present invention, the components (a), (b) and (b) are used in a range that does not significantly impair the effects of the present invention or in order to further improve the performance. In addition to c) and (d), any of the following additives and ingredients can be blended. Specifically, pigments for coloring, antioxidants, antistatic agents, light stabilizers, ultraviolet absorbers, nucleating agents, flame retardants, dispersants, polystyrenes other than the above components (a) to (d), etc. Various resins, EPR, EPDM, E
Examples of the material include various rubbers such as BR, EOR, SEBS, SEP, and SEPS, and various fillers such as calcium carbonate, barium sulfate, and mica. Above all, M
FR (230 ° C., 2.16 kg) exceeding 1.2 g / 10 min, ethylene / α-olefin having 3 to 8 carbon atoms (·
Diene) copolymer rubber and / or calcium carbonate,
Various fillers such as barium sulfate, wollastonite, and glasses are effective for injection molding (injection compression molding) workability, weld appearance, low gloss, and improvement of the balance of physical properties.

Further, an antistatic agent such as a nonionic or cationic antistatic agent is extremely effective for imparting or improving the antistatic property of the composition or molded article of the present invention. Specific examples include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, glycerin fatty acid ester, alkyl diethanolamine, alkyl diethanol amide, and alkyl diethanol amine ester.

Further, light stabilizers and ultraviolet absorbers such as hindered amine compounds, benzoate compounds, benzotriazoles, benzophenones and formamidines are useful for imparting and improving the weather resistance of the compositions and molded articles of the present invention. Extremely effective. Specific examples include a condensate of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine as a hindered amine compound; poly [[6- (1,
(1,3,3-tetramethylbutyl) imino-1,3,5
-Triazine-2,4-diyl] [(2,2,6,6-
Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]]; tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1 , 2,3,4-butanetetracarboxylate; tetrakis (1,2,2,6,6
-Pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate; poly [2-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl)
Hexamethylenediamine-4- (N-morpholino) simtriazine]; bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate; bis-2,2,6
6-tetramethyl-4-piperidyl sebacate; and benzoate-based compounds such as 2,4-di-t
-Butylphenyl-3 ', 5'-di-t-butyl-4'
-Hydroxybenzoate; n-hexadecyl-3,5
-Di-t-butyl-4-hydroxybenzoate and the like, and as the benzotriazole type, 2- (2'-
Hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole and the like, and benzophenones include 2-hydroxy-4-n-octoxybenzophenone.

Further, a nucleating agent, for example, an inorganic nucleating agent such as talc or an organic nucleating agent such as a metal salt of an aromatic carboxylic acid, a metal salt of an sorbitol or a metal salt of an aromatic phosphate may be used as a molded article of the composition of the present invention. It is extremely effective for imparting and improving the rigidity, heat resistance and hardness of the steel. Specific examples include talc, metal salts of aromatic carboxylic acids such as aluminum-mono-hydroxy-di-pt-butylbenzoate, sodium benzoate, and the like. 3,2,4-dibenzylidene-sorbitol; 1,3,2,4-di- (p-methyl-benzylidene) sorbitol; 1,3,2,4-di- (p-ethyl-benzylidene) sorbitol; 1 , 3,2,4-di-
(2 ′, 4′-di-methyl-benzylidene) sorbitol; 1,3-p-chloro-benzylidene-2,4-p-
Methyl-benzylidene-sorbitol; 1,3,2,4
-Di- (p-propyl-benzylidene) sorbitol, and the like, and examples of aromatic metal phosphates include:
Sodium bis (4-t-butylphenyl) phosphate; sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate; lithium-
2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate and the like.

Further, various metal salts as a dispersant enhance the dispersibility of the talc and the coloring content, and are extremely effective in improving the rigidity, heat resistance, hardness, weld appearance and texture of the molded article of the composition of the present invention. It is valid. Specific examples include calcium stearate, magnesium stearate, calcium behenate, magnesium behenate, zinc behenate, zinc montanate, calcium montanate, magnesium montanate, calcium melisinate, magnesium melisinate, zinc melisinate, cerotic acid. Examples thereof include calcium, magnesium serotinate, zinc serotinate, calcium lignocerate, magnesium lignocerate, and zinc lignocerate.

2. Blending Ratio The components (b), (c) and (d) to be blended in the propylene-based resin composition of the present invention are blended based on 100 parts by weight of the component (a). Ethylene / α-olefin copolymer rubber or ethylene / α of component (b) blended in the propylene resin composition of the present invention.
-The compounding ratio of the olefin / diene copolymer rubber is 1 to 50 parts by weight, preferably 2 to 30 parts by weight, particularly preferably 3 to 25 parts by weight based on 100 parts by weight of the component (a). If the compounding ratio is less than 1 part by weight, low gloss, poor weld appearance and impact strength are insufficient, and if it exceeds 50 parts by weight, hardness, rigidity and injection molding processability are inferior and each is unsuitable.

The proportion of talc in the component (c) to be mixed in the propylene resin composition of the present invention is as follows.
5 to 60 parts by weight, preferably 10 to 100 parts by weight
It is preferably from 50 to 50 parts by weight, particularly preferably from 20 to 40 parts by weight. If the compounding ratio is less than 5 parts by weight, low gloss, rigidity and heat resistance are insufficient, and if it exceeds 60 parts by weight, weld appearance, impact strength and molding workability are deteriorated, and each is unsuitable.

The proportion of the high-density polyethylene of the component (d) optionally blended in the propylene resin composition of the present invention is based on 100 parts by weight of the component (a).
It is 0 to 10 parts by weight, preferably 1 to 8 parts by weight, particularly preferably 2 to 6 parts by weight. If the compounding ratio exceeds the above range, low glossiness, weld appearance, rigidity and heat resistance are deteriorated, which is not suitable.

3. Production of propylene-based resin composition (1) Kneading and granulation The propylene-based resin composition of the present invention comprises the component (a)
Component (b), component (c), and optionally component (d) and component (e) are blended at the above-mentioned blending ratio, and a single screw extruder, a twin screw extruder, a Banbury mixer, a roll mixer, a Brabender-Plastograph, It is obtained by kneading and granulating using a usual kneader such as a kneader. In this case, it is desirable to select a kneading / granulating method capable of improving the dispersion of each component, and usually kneading / granulating using a twin screw extruder.
Granulation is performed. During the kneading and granulation, the above components (a), (b) and (c), and optionally, a mixture of the components (d) and (e) may be simultaneously kneaded,
In order to improve the performance, it is also possible to divide each component, for example, first knead some or all of component (a) and component (b), and then knead and granulate the remaining components. At this time, the above-mentioned peroxide can be blended together with the components (a) to (e) and kneaded and granulated. This method can be applied to the MFR and SFR of the propylene-based resin composition of the present invention. Value control, fluidity (moldability), low gloss,
Effective and preferable kneading for further improvement of weld appearance, etc.
It is a granulation method.

(2) Molding of propylene-based resin composition The propylene-based resin composition thus obtained is molded by injection molding (including gas injection molding) or injection compression molding (press injection). Various molded products can be obtained.

[II] Physical Properties of Propylene Resin Composition The propylene resin composition of the present invention produced by the above method has an MFR (230 ° C., 2.16 kg) of preferably 10 g / 10 min or more, particularly preferably 20g /
It is controlled to 10 minutes or more, and has good injection moldability and injection compression moldability, and preferably has a flexural modulus of preferably 1
800 Mpa or more, particularly preferably 2000 Mpa
As described above, the notched Izod impact strength (23 ° C.) is preferably 10 KJ / m ² or more, and particularly preferably ²⁰ KJ / m ^2.
m ² or more, the Rockwell hardness of the surface of the molded product, preferably 60 or more, especially with preferably excellent in controlled and balanced properties in more than 65, good low gloss, preferably 2.0% or less is embossed gloss value And particularly preferably low gloss having a grain gloss value of 1.6% or less.
The value is preferably 1.1 or less, particularly preferably 1.
05 or less, showing a good weld appearance, and in addition, each performance of a high appearance in which flow marks are hardly generated can be exhibited.

[III] Applications Since the propylene-based resin composition of the present invention can exhibit the above-mentioned performance, the propylene-based resin composition exhibits practical performance as a molding material for various industrial products such as products for various living materials, automobile parts and home electric appliances. Particularly, it is suitable as a molding material for interior and exterior parts for automobiles, especially for interior parts such as instrument panels, consoles, trims, pillars, and door trims.

[0031]

EXAMPLES In order to describe the propylene-based resin composition of the present invention in more detail, the present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples. [I] Raw materials The raw materials here are as follows. (1) Component (a): Each contains an antioxidant, and the powdery product is dry-blended. a-1: 8 units of A unit having a density of 0.9091 g / cm ³
9% by weight, ethylene content 51% by weight, weight average molecular weight 7
A propylene / ethylene block produced by gas phase polymerization containing 30,000 B units in an amount of 11% by weight and having an MFR of 62 g / 10 min and an S value of 1.17 for the entire component (a). Polymer (pellet). a-2: 7 units of A unit having a density of 0.9092 g / cm ³
5% by weight, ethylene content 42% by weight, weight average molecular weight 3
A propylene / ethylene-block copolymer produced by gas phase polymerization containing 80,000 B unit parts in an amount of 25% by weight and having an overall polymerization MFR of 30 g / 10 min and an S value of 1.02 for component (a). Polymer (powder). a-3: 8 units of A unit having a density of 0.9092 g / cm ³
4% by weight, ethylene content 60% by weight, weight average molecular weight 5
A propylene / ethylene-block copolymer produced by gas phase polymerization, containing 16% by weight of each of 60,000 B unit parts, and comprising 1,3-bis (t-butylperoxy- Isopropyl) benzene to give a polymerization MFR of the whole component (a) of 31 g / 1.
A propylene / ethylene-block copolymer (pellet) in which the S value is controlled to 0.98 for 0 minute. a-4: 8 units of A unit having a density of 0.9092 g / cm ³
0% by weight, ethylene content 49% by weight, weight average molecular weight 4
A propylene / ethylene-block copolymer produced by gas phase polymerization, containing 20% by weight of each of 40,000 B unit parts, and comprising 1,3-bis (t-butylperoxy- (Isopropyl) benzene, and the polymerization MFR of the entire component (a) was reduced to 35 g / 1.
A propylene / ethylene-block copolymer (pellet) in which the S value is controlled to 1.00 for 0 minutes. a-5: 7 units of A unit having a density of 0.9092 g / cm ³
3% by weight, ethylene content 57% by weight, weight average molecular weight 3
A propylene / ethylene block produced by gas phase polymerization containing 30,000 B unit parts in an amount of 27% by weight and having an MFR of 33 g / 10 min and an S value of 1.09 for the whole component (a). Polymer (powder). a-6: 8 units of A unit having a density of 0.9091 g / cm ³
5% by weight, ethylene content 51% by weight, weight average molecular weight 3
A propylene / ethylene-block copolymer produced by gas phase polymerization containing 80,000 B unit parts at 15% by weight and having a total MFR of 8 g / 10 min and an S value of 1.22 for component (a). Polymer (pellet). a-7: 9 units of A unit having a density of 0.9091 g / cm ³
2 weight%, ethylene content 39 weight%, weight average molecular weight 1,050,000 each containing 8 weight% of B unit part,
And the polymerization MFR of the whole component (a) is 60 g / 10 min.
A propylene / ethylene-block copolymer (pellet) produced by slurry polymerization having a value of 1.56. a-8: 9 units of A unit having a density of 0.9091 g / cm ³
3% by weight, ethylene content 20% by weight, weight average molecular weight 8
A propylene / ethylene-block copolymer produced by slurry polymerization containing 7% by weight of each of 20,000 B unit parts and having a total MFR of 48 g / 10 min and an S value of 1.52 for the whole component (a) Coalescing (pellet).

(2) Component (b): All in the form of pellets b-1: 14.5% by weight of octene (infrared method)
And the MFR is 1.1 g / 10 min and the density is 0.870 g /
An ethylene / 1-octene copolymer rubber having a cm ³ and a glass transition point of −57.5 ° C. produced by a solution polymerization method using a metallocene catalyst. b-2: contains 26.2% by weight of propylene (infrared method)
And the MFR is 0.6 g / 10 min and the density is 0.860 g /
An ethylene-propylene copolymer rubber having a cm ³ and a glass transition point of −54.3 ° C. produced by a solution polymerization method using a vanadium-based catalyst. b-3: contains 27.9% by weight of propylene (infrared method)
And the MFR is 0.2 g / 10 min and the density is 0.863 g /
An ethylene / propylene / ethylidene norbornene copolymer rubber having a cm ³ and a glass transition point of −48.9 ° C. produced by a solution polymerization method using a vanadium-based catalyst. b-4: Contains 24.1% by weight of 1-octene (infrared method)
And the MFR is 12.0 g / 10 min and the density is 0.871 g
/ Cm ³ , having a glass transition point of −58.4 ° C., prepared by a solution polymerization method using a metallocene-based catalyst.
Octene copolymer rubber. b-5: containing 12.7% by weight of 1-butene (infrared method)
And the MFR is 2.1 g / 10 min and the density is 0.863 g /
An ethylene / 1-butene copolymer rubber having a cm ³ and a glass transition point of −60.8 ° C. produced by a solution polymerization method using a metallocene catalyst. The MFR here is 230 ° C.
2.16 kg condition measurement.

(3) Component (c) c-1: Talc having an average particle size of 5.2 μm and an average aspect ratio of 6. c-2: average particle size of 23.5 μm, average aspect ratio of 4
Talc.

(4) Component (d) d-1: MFR (190 ° C., 2.16 kg) is 20 g /
High density polyethylene with a density of 0.958 g / cm ³ for 10 minutes.

[II] Evaluation method Evaluation was performed by the following method. (1) MFR: 230 according to JIS-K7210
It measured at 2.degree. (2) S value: melt indexer (MFR measuring device ... J
ISK7210), extrusion temperature 190 ° C., nozzle inner diameter 1.0 mm, nozzle length 8 mm, extrusion speed 0.1 g /
The sample is extruded into a graduated cylinder (in ethyl alcohol) under the conditions of minutes, and the diameter of the solidified sample is
It was measured with a laser light meter and calculated by the following equation. S value = solidified extrusion sample diameter / nozzle inner diameter

(3) Flexural modulus: Measured at a temperature of 23 ° C. according to JIS-K7203. This value is also a measure of heat resistance. (4) Izod impact strength: Measured with a notch at a temperature of 23 ° C. in accordance with JIS-K7110. (5) Rockwell hardness: Measured on an R scale at a temperature of 23 ° C. in accordance with JIS-K7202. (6) Grain gloss: 360 × 100 × 3 mmt. The gloss of the measurement plane of an injection-molded sheet in which a C-type grain having a depth of 100 μm was applied to the measurement plane was measured according to JIS-K7.
The measurement was performed under the condition of an incident angle of 60 ° in accordance with No. 105.

(7) Weld appearance: A resin is injection-molded from the gates at both ends in the longitudinal direction using a sheet metal mold for measuring gloss and gloss, and a butt-shaped weld line (linear pattern) is formed substantially at the center of the sheet. This part was visually observed and judged as follows. A: Weld line is not recognized at all or hardly noticeable. B: Very slight weld line is observed. C: Weld line is observed. D: The weld line is clearly conspicuous. In this case, A and B are practically usable levels as unpainted molded products.

(8) Flow mark: 360 × 100 × 2
mmt. With a depth of 100 μm
The resin is injection-molded from one gate in the longitudinal direction using an injection-molded sheet die provided with the C-shaped grain of the above, and the flow mark (wave-shaped flow pattern) generated on the measurement plane is visually observed to determine the following. It was judged as follows. A: A flow mark is not recognized at all on the plane, or a very small amount is recognized at the tip. B: A flow mark is observed, but its generation is inconspicuous at 250 mm or more from the gate. C: Flow mark was recognized, and the occurrence was 2
Less than 50mm. In this case, A and B are at a practically usable level as unpainted medium / large molded products.

Examples 1 to 6 and Comparative Examples 1 to 6 The above components (a), (b), (c) and (d) were combined with 0.3 parts by weight of calcium behenate (component (a) ~ Per 100 parts by weight of the component (d)), mixed at a ratio shown in Table 1 and thoroughly mixed with a tumbler mixer. A high speed twin screw extruder (KC manufactured by Kobe Steel Ltd.)
M) and kneaded and granulated. However, in Example 6, 1,3-bis (t-butylperoxy-isopropyl) benzene was further blended in addition to the above components. Thereafter, the obtained pellets were supplied to an injection molding machine, and a test piece for evaluation was molded and evaluated. In addition, grain gloss, weld appearance,
For the flow mark appearance, 1.5 parts by weight of a black-gray-colored master batch was dry-blended during injection molding so that the surface state could be easily observed. Table 2 shows the evaluation results.

As shown in Table 2, each of the resin compositions having the compositions shown in Examples 1 to 6 has good fluidity (injection molding workability, injection compression molding workability) and good physical properties (rigidity, rigidity, In addition to showing a balance of impact strength and hardness), the molded article had an extremely low grain gloss, a good weld appearance, was suppressed from generating flow marks, and had a practically sufficient molded appearance as an unpainted molded article. On the other hand, those shown in Comparative Examples 1 to 6
Their performance balance was poor. Example 5
11.5 mm × 420 mm × 305 m
mx 3.5 mmt. The vehicle instrument panel of (approximate dimensions) was manufactured using J4000EV (molding temperature 220 ° C., mold temperature 40 ° C., injection pressure 800 kg) manufactured by Japan Steel Works, Ltd.
/ Cm ² ), good moldability, good mechanical strength balance, sufficient practicality without painting, good appearance were exhibited, and scratch resistance and durability were also good.

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

The propylene resin composition of the present invention has excellent injection (injection compression) molding processability, physical properties balance (high rigidity, impact strength and surface hardness), low gloss and good weld appearance. In addition to having practically sufficient appearance performance as an unpainted molded product, it also has good scratch resistance and durability, so it is suitable for various household products, industrial parts, etc., especially automotive parts, especially instrument panels, It is an important material for molding interior parts such as trims and pillars.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 23:04) (72) Inventor Akira Amano 1 Tohocho, Yokkaichi, Mie Japan Yokkaichi Technology, Japan Inside the center (72) Inventor Masahide Hamaura 1 Toho-cho, Yokkaichi-shi, Mie Japan Polychem Corporation Yokkaichi Technical Center (72) Inventor Takashi Niimi 1-Toho-cho, Yokkaichi-shi, Mie Yokkaichi Technical Center Japan F-term (reference) 4J002 BB033 BB152 BP021 DJ046 GN00

Claims (9)

[Claims] 1. A propylene-based resin composition comprising the following components (a) to (d). (A) Homopolymer part of crystalline polypropylene (A unit part)
60 to 95% by weight, an ethylene content of 30% by weight or more, and a weight average molecular weight (Mw) of 200,000 to
1,000,000 ethylene-propylene-random copolymerized portion (B unit portion) of 5 to 40% by weight, and a melt flow rate (MF) of the entire component (a).
R: 230 ° C, 2.16 kg) is 10 to 200 g / 10
Propylene / ethylene-block copolymer having a swell index value (S value: 190 ° C.) of 1.4 or less: 100 parts by weight (b) α-olefin having 3 to 8 carbon atoms in 20 to 50 parts by weight Ethylene / α-olefin copolymer rubber or ethylene / α-olefin / diene copolymer rubber having a MFR (230 ° C., 2.16 kg) of 0.05 to 1.2 g / 10 min. 50 parts by weight (c) Talc having an average particle size of 1.5 to 15 μm: 5 to 60
Parts by weight (d) MFR (190 ° C., 2.16 kg) is 11 g / 1
0 minutes or more, high density polyethylene: 0 to 10 parts by weight 2. A propylene / ethylene-block copolymer containing at least a part of the component (a) in an amount of 15 to 30% by weight of an ethylene / propylene / random copolymer part (B unit). The propylene-based resin composition according to item 1. 3. An ethylene / propylene-random copolymer part (B unit) of the component (a) has an ethylene content of 45.
% By weight or more and a weight average molecular weight (Mw) of 300,
The propylene-based resin composition according to claim 1, wherein the propylene-based resin composition has a molecular weight of 000 to 800,000. 4. The propylene-based resin composition according to claim 1, wherein at least a part of the component (a) is a propylene / ethylene-block copolymer which has been subjected to a peroxide treatment after polymerization. 5. Component (b) containing 0.1 to 0.5 g of MFR
The propylene-based resin composition according to any one of claims 1 to 4, wherein the propylene-based resin composition is an ethylene / propylene / diene copolymer rubber. 6. The propylene resin composition according to claim 1, wherein the component (b) is an ethylene / propylene / diene copolymer rubber polymerized using a vanadium catalyst. 7. A composition produced by a method of simultaneously adding and treating a peroxide when kneading and granulating components (a) to (d) and optionally other components (e). 1-6
The propylene-based resin composition according to item 1. 8. An MFR (230 ° C., 2.16 kg) of 1
0 g / 10 or more, flexural modulus of 1800 Mpa or more, I
zod impact strength (23 ° C.) is least 10 KJ / m ² or more, a Rockwell hardness of 60 or more, according to claims 1-7 embossed gloss values of 2.0% or less and the S value has a 1.1 following performance Propylene resin composition. 9. An automobile part formed by injection molding or injection compression molding using the propylene-based resin composition according to claim 1.