JP3366373B2 - Propylene resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a high mechanical strength variation.
Molding, with good molded product appearance and moldability.
The present invention relates to a propylene-based resin composition. [0002] 2. Description of the Related Art Conventionally, various moldings in the field of industrial parts.
Goods such as bumpers, instrument panels, fan shrouds,
Automotive parts such as robe boxes, TV cases, VTRs
Materials for various parts of home appliances such as cases and washing machine covers
And fillers such as talc and various whiskers, and various rubbers
Polypropylene resin composition reinforced by compounding components
But with its excellent mechanical strength, moldability and economy
It has been put to practical use in large quantities by taking advantage of its characteristics. This
Especially high mechanical strength
When balance, good molded product appearance and moldability are required
In the past, the conventional method was to make the filler finer, ethylene propylene
The blending of the ren copolymer rubber component and the separation of metal salts and wax
Improvements have been attempted by adding powders. [0003] SUMMARY OF THE INVENTION
-Finer particles reduce the strength and appearance due to secondary agglomeration.
The addition of the rubber component not only increases the cost but also reduces the rigidity,
In addition, the addition of the existing dispersant reduces mold contamination, etc.
I have a problem. In other words, rigidity (heat resistance)
If the mechanical strength balance of impact strength is low,
For example, in the case of injection molding, the flow mark (waveform flow pattern)
Occurs), the mold is contaminated, and
Due to the low level of formability (fluidity),
Often hinders design freedom and productivity
Was. [0004] [Means for Solving the Problems] [Summary of the Invention] The present inventors have set out to solve the above problems.
In addition, as a result of repeated research, specific propylene
Ren block copolymer, specific styrene / ethylene / butyl
Tylene / styrene block copolymer and specific treatment
Propylene-based resin composition comprising
Semi-mechanical strength balance, good molded product appearance and moldability
To complete the present invention.
Was. That is, the propylene resin composition of the present invention
The product comprises the following components (a) to (d):
Things.  Component (a): crystalline polypropylene portion (component A) and ethylene / propylene run Propylene / ethylene block copolymer containing dam copolymer part (component B) Wherein the component A accounts for 60 to 95% by weight of the entire block copolymer, MFR is 5 to 300 g / 10 min, and the same density is 0.9070 g / cm^ThreeAbove The B component accounts for 5 to 40% by weight of the entire block copolymer, and its ethylene content is And the MFR of the entire block copolymer is 3 to 80% by weight. ２００200 g / 10 min, and the weight average molecular weight / number average molecular weight (Mw / Mn) is 5 To 15 block copolymer: 100 parts by weight  Component (b): bound styrene content 10-25%, number average molecular weight (Mn) 10,000 ５０50,000, MFR (230 ° C., 2.16 kg) 50-250 g / 10 min Styrene / ethylene / butylene / styrene block copolymer:                                                       3 to 100 parts by weight [0006]  Component (c): at least one compound represented by the following general formula [I], [II] or [III] The surface-treated product is used in an amount ratio of 0.01 to 8 parts by weight per 100 parts by weight of the filler. The total length measured by a laser light scattering type particle size distribution analyzer is 15 talc having an average particle diameter of 1 to 6 μm or less and an average aspect ratio of 5 or more And an inorganic whisker having an average diameter of 2 μm or less and an average aspect ratio of 5 or more At least one filler selected from: 3 to 100 parts by weight General formula [I] (R¹COO) nM (Where R¹Is a monovalent hydrocarbon having a molecular weight of 250 to 500
Having a molecular weight of 250 to 500 containing an amino group or a hydroxy group
Represents a monovalent hydrocarbon, M is lithium, calcium,
Represents a strontium or barium atom, and n is an element of M
Represents the same number as the child price. ) General formula [II] [0007] Embedded image (Where R^TwoIs a hydrocarbon having 4 to 29 carbon atoms
Having 4 to 29 carbon atoms containing a hydroxyl group or a hydroxyl group
Groups which are the same or different from each other;^ThreeIs the carbon number
1 to 8 hydrocarbon groups, hydrogen atoms, hydroxyl groups, R^Two
Represents the same or different groups selected from COO-
You. ) General formula [III] [0009] Embedded image (Wherein R^FourIs a hydrocarbon having 1 to 8 carbon atoms
Group, hydrogen atom, hydroxyl group, R^TwoChoose from COO-
At least one of the same or different groups
One is R^TwoIncluding COO- and including hydroxyl groups
At least one compound. )  Component (d): Mooney viscosity ML_{1 + 4}(100 ° C) 10-100, ethylene content Is 40 to 85% by weight of ethylene rubber: 0 to 20 parts by weight [Specific description of the invention] [I] Propylene resin composition (1) Constituent components (a) Propylene / ethylene block copolymer ((a)
Minutes) The above (a) component constituting the propylene-based resin composition of the present invention.
Propylene-ethylene block copolymer
Crystalline polypropylene (A component) and ethylene pro
Block containing pyrene random copolymerized moiety (component B)
A copolymer, wherein the component A is a block copolymer
60-95%, preferably 70-95% by weight of the body
Occupies 5 to 300 g / 10 min of MFR, preferably
10-250 g / 10 minutes, and the density is 0.9070 g /
cm^ThreeAbove, preferably 0.9075 g / cm^Threethat's all,
Particularly preferably 0.9080 g / cm^ThreeAbove
And the component B is 5 to 4 parts of the whole block copolymer.
0% by weight, preferably 5 to 30% by weight.
Len content of 20 to 80% by weight, preferably 25 to 75 weight
% Of propylene / ethylene
MFR of the entire block copolymer is 3 to 200 g / 10
Min, preferably 5 to 150 g / 10 min, particularly preferably
10 to 100 g / 10 min, and weight average molecular weight / number flat
Average molecular weight (Mw / Mn) of 5 to 15, preferably 6 to 1
Five. Here, the value of ethylene content is the infrared spec.
Can be measured by a torque analysis method or the like.
Is the value of JIS-K7210 (230 ° C, 2.16 kg)
Can be measured in accordance with Also contains B component
The value of the quantity is 2 g of the sample in 300 g of boiling xylene.
After immersion for a minute, cool to room temperature,
The solid phase that has been deposited
It can be obtained by back calculation from the obtained solid weight.
Wear. Furthermore, weight average molecular weight / number average molecular weight (Mw / M
The value of n) is determined by gel permeation chromatography.
(GPC). [0012] Such a propylene-ethylene component (a)
Block copolymers are produced using highly stereoregular polymerization catalysts.
By slurry polymerization, gas phase polymerization or liquid phase bulk polymerization
It is manufactured. The propylene / ethylene block
Batch polymerization, continuous polymerization
Either type of continuous polymerization can be employed. Also this propyle
When manufacturing ethylene-ethylene block copolymers,
Either part may be polymerized first, but
Polymerizes the reactive polypropylene portion and then
Copolymerization of ren-random copolymer is preferable for quality.
No. As the highly stereoregular polymerization catalyst, conventionally, trichloride
Organic in combination with titanium composition and organoaluminum compound
Catalyst systems to which acid esters are added are known.
High MFR block copolymer by using the above catalyst system
Since a large amount of solvent-soluble by-products is produced during the production of
Propylene / ethylene block copolymer of component (a) above
Is difficult to manufacture. Therefore, the results
Fruit, magnesium chloride, titanium tetrachloride, organic acid halide
Of solid catalyst formed by contacting organic and organosilicon compounds
Combination catalyst of organic and aluminum compounds
187707 and JP-A-62-246906
To solve the above problem, and (a)
Component propylene / ethylene block copolymer
Can be obtained using these combined catalysts.
Is preferred. The component (a) propylene / ethylene bromide
MFR of the block copolymer is 3 g / 10 min or more
Is essential, and if the MFR is less than the above range, the molded product
Is inferior in appearance and poor in moldability. other
On the other hand, those exceeding the above range were inferior in the impact resistance of the molded product
It is unsuitable. Further, the block copolymer
The MFR values of the above ranges were obtained only by changing the polymerization conditions.
It is preferable that the polymer is adjusted to
After producing a lower MFR block copolymer,
Decomposed with peroxides such as dialkyl peroxide
To achieve a high MFR, or to switch between a low MFR product and a high MFR product.
It can be blended and adjusted to a desired MFR. Ma
In addition, the ratio of the component B of the block copolymer falls within the above range.
If it is less, the impact resistance of the molded product is poor.
On the other hand, those exceeding the above range,
The density of component A of the block copolymer is less than the above range
Is inadequate due to insufficient rigidity (heat resistance) of the molded product
is there. Further, the weight average molecular weight / number of this block copolymer
If the average molecular weight (Mw / Mn) is out of the above range,
The appearance of the molded product is poor and unsuitable. This block copolymer significantly demonstrates the effects of the present invention.
Other unsaturated monomers (for example, butane)
Vinyl ethers such as α-olefins and vinyl acetate
Unsaturation such as stell, or acrylic acid and maleic anhydride
Terpolymer containing organic acid or derivative thereof)
It may be. (B) Styrene / ethylene / butylene / styrene
Len block copolymer (component (b)) The component (b) constituting the propylene-based resin composition of the present invention.
Styrene / ethylene / butylene / styrene block
As the copolymer, an amount of bound styrene of 10 to 25% is preferable.
13 to 25%, particularly preferably 15 to 22%,
Average molecular weight 10,000-50,000, preferably 1
5,000 to 40,000, particularly preferably 20,000
0-35,000, MFR (230 ° C, 2.16 kg)
50 to 250 g / 10 min, preferably 60 to 200 g /
10 minutes, particularly preferably 90 to 180 g / 10 minutes
It is a len-based elastomer. Where the amount of bound styrene
If the number average molecular weight / MFR value is out of the above range,
The performance of the shaped article, especially the impact strength, is inferior. Furthermore,
Vinyl content of the elastomer (of hydrogenated polybutadiene part)
1,2-bond amount) is 25 to 60%, particularly 30 to 50%,
It is desirable that The weight average of the elastomer
Average molecular weight / number average molecular weight (Mw / Mn) is in the range of 1-3
Preferably in the range of 1.3 to 2.5.
No. The amount of bound styrene, number average molecular weight, and weight
Average molecular weight / number average molecular weight / vinyl content (hydrogenated polybutadi
1,2-bond amount of the ene portion)
Method, gel permeation chromatography (GP
It is a value measured by a conventional method such as C) or NMR. The styrene-ethylene-butylene of the present invention
Similar to styrene block copolymer, for example
For example, styrene-butadiene-styrene block copolymer
Body, styrene / isoprene / styrene block copolymer
And styrene-ethylene-propylene block copolymer
And various other styrene elastomers.
However, since the effects of the present invention cannot be obtained with these materials,
Improper. Styrene / ethylene / butylene of the present invention
-As a method for producing styrene block copolymer,
Generally, but not exclusively, styrene-butadiene
Of hydrogenated styrene copolymer by partial hydrogenation
Can be. (C) Filler (component (c)) The component (c) constituting the propylene-based resin composition of the present invention.
The fillers of general formulas [I], [II] and
Is at least one of the specific compounds represented by [III]
Light scattering, surface treated with different surface treatment agents
Substantially the whole length measured by a particle size distribution analyzer is 1
5 μm or less, average particle size of 1 to 6 μm and average
Talc with a pect ratio of 5 or more and an average diameter of 2 μm or less
And from inorganic whiskers with an average aspect ratio of 5 or more
At least one filler selected. General formula [I] (R¹COO) nM (Where R¹Is a monovalent hydrocarbon having a molecular weight of 250 to 500
Having a molecular weight of 250 to 500 containing an amino group or a hydroxy group
Represents a monovalent hydrocarbon, M is lithium, calcium,
Represents a strontium or barium atom, and n is an element of M
Represents the same number as the child price. ) General formula [II] [0018] Embedded image (Wherein R^TwoIs a hydrocarbon having 4 to 29 carbon atoms
Having 4 to 29 carbon atoms containing a hydroxyl group or a hydroxyl group
Groups which are the same or different from each other;^ThreeIs the carbon number
1 to 8 hydrocarbon groups, hydrogen atoms, hydroxyl groups, R^Two
Represents the same or different groups selected from COO-
You. ) General formula [III] [0020] Embedded image (Where R^FourIs a hydrocarbon having 1 to 8 carbon atoms
Group, hydrogen atom, hydroxyl group, R^TwoChoose from COO-
At least one of the same or different groups
One is R^TwoIncluding COO- and including hydroxyl groups
At least one compound. ) [0022] Filler As the filler of the component (c), talc or inorganic material
It is a whisker.talc For talc subjected to surface treatment, it has a substantial overall length
Having a mean particle size of 1 to 6 μm and a flat
The average aspect ratio is 5 or more. Such a tall
For example, talc is used to crush rough talc with an impact mill or micron mill.
Pulverized with a micropulverizer, then a micron mill, jet-type powder
After pulverizing with a crusher, cyclone or micron separator
It is manufactured by classifying and adjusting it. Here talc
Gemstones are preferred from China because of their low metal impurity content.
The term "substantially" means that the length of the talc is almost talc.
Particles that fall within this range. Average particle size of talc
The measurement was performed using a laser light scattering particle size distribution analyzer.
Values, such as those manufactured by Horiba
Desirable because the measurement accuracy of LA-500 manufactured by Sakusho is excellent
New The length and aspect ratio are measured with a microscope.
Value. Furthermore, length and average aspect ratio are out of the above range
If talc with an average particle size exceeding the above range is used,
The mechanical strength balance and appearance of the molded product are inferior.
Disperses talc when the average particle size is smaller than the above range
It is difficult to balance the mechanical strength and appearance of the molded product.
It is not preferable because it worsens. [0023]Mineral whiskers The average particle size used for surface treatment is 2 μm or less and the average
As an inorganic whisker with a spec ratio of 5 or more,
Typically, aluminum borate whiskers, potassium titanate
Um whisker, magnesium sulfate whisker, carbon fiber
Wei, calcium carbonate whisker, titanium oxide whisker
And the like. Among them, the average particle size is 1
μm or less and an average aspect ratio of 10 or more
Luminium whiskers, potassium titanate whiskers,
Magnesium sulfate whisker, carbon fiber, calcium carbonate
Mwhiskers are preferred. The average length is limited.
Not determined. [0024]Filler surface treatment Filler selected from these talc and inorganic whiskers
Is used after surface treatment by the following method.
The surface-treated filler balances the mechanical strength of the molded product.
It is effective for improving the appearance of molded products. Surface treatmentProcessing conditions The filler is represented by the following general formula [I], [II] or [III].
100 parts by weight of at least one compound to be filled
0.01 to 8 parts by weight, preferably 0.1 to 8 parts by weight
Parts by weight, particularly preferably 0.3 to 8 parts by weight.
Surface-treated. The surface treatment is with filler and after
Mix the surface treatment agent using a high-speed mixer or tumbler.
It can be done by combining. Surface treatment conditions
Is generally 10 to 80 ° C, preferably 20 to 50 ° C.
At a temperature of 100C to 1000rpm, preferably
Stir and mix at 200-600 rpm
This is done. The surface treatment is performed using the components (a) to (c).
Kneading of each component using single screw extruder, twin screw extruder, etc.
During the process of producing a propylene-based resin composition
And simultaneously mix untreated filler and surface treatment agent
Simultaneous kneading and surface treatment of components (a) to (c)
However, the filler can be surface-treated in advance.
It is preferable to keep it. [0026]Surface treatment agent Surface treatment used to treat the surface of the filler
The physical agent is represented by the following general formula [I], [II] or [III].
At least one compound. General formula [I] (R¹COO) nM (Where R¹Is a monovalent hydrocarbon having a molecular weight of 250 to 500
Having a molecular weight of 250 to 500 containing an amino group or a hydroxy group
Represents a monovalent hydrocarbon, M is lithium, calcium,
Represents a strontium or barium atom, and n is an element of M
Represents the same number as the child price. ) General formula [II] [0027] Embedded image (Where R^TwoIs a hydrocarbon having 4 to 29 carbon atoms
Having 4 to 29 carbon atoms containing a hydroxyl group or a hydroxyl group
Groups which are the same or different from each other;^ThreeIs the carbon number
1 to 8 hydrocarbon groups, hydrogen atoms, hydroxyl groups, R^Two
Represents the same or different groups selected from COO-
You. ) General formula [III] [0029] Embedded image Where R^FourIs a hydrocarbon having 1 to 8 carbon atoms
Group, hydrogen atom, hydroxyl group, R^TwoChoose from COO-
At least one of the same or different groups
Is R^TwoContains COO- and does not contain hydroxyl groups
At least one compound. ) Such a general formula [I]
The compounds mentioned are arachiic acid, behenic acid, cello
Formic acid, montanic acid, melicic acid, abietic acid,
Organic acids such as stropimaric acid and hydroxystearic acid
Metal salts can be mentioned. Specifically, behenic acid
Titanium, lithium montanate, hydroxystearic acid
Lithium, calcium behenate, calcium calcium montanate
, Calcium hydroxystearate, behenate strike
Rontium, barium beherate, hydroxystearyl
Barium phosphate, barium montanate, etc.
Wear. Of these, calcium salts and ba
Lium salts are preferred, with calcium salts being particularly preferred.
You. Other than the above metal salts, the effect of suppressing mold contamination and high level
Demonstrate mechanical strength balance and good moldability
Can not. In the general formulas [II] and [III],
As the compound represented, trimethylolpropant
Reester, trimethylolpropane diester, pen
Taerythritol tetraester, pentaerythritol
Lutriester, pentaerythritol diester,
Lyserine triester, glycerin diester, propyl
Len glycol diester, propylene glycol mono
Esters and the like. Specifically, trimethylolpropane
Centric plate, trimethylolpropane trilaure
, Trimethylolpropane trimiristate, bird
Methylol propane tripalmitate, trimethylol
Propane tristearate, trimethylolpropant
Libehenate, trimethylolpropane trimontane
G, trimethylolpropane trioleate, trimethyl
Roll propane zika plate, trimethylol propane
Dilaurate, trimethylolpropane dimyristate
G, trimethylolpropane divalmitate, trimethyl
Roll propane distearate, trimethylol propa
Nzibeherate, trimethylolpropane dimontane
Pentaerythritol tetrahebutate, pentae
Risuritol tetracarbyl, pentaerythritol
Tetralaurate, pentaerythritol tetramyris
Tate, pentaerythritol tetrapalmitate, pea
Antaerythritol tetrastearate, pentaerythr
Litol tetrabeherate, pentaerythritol tet
Lamontanate, pentaerythritol tetraoleate
Pentaerythritol trica plate, pentaerythritol
Thritol trilaurate, pentaerythritol tri
Myristate, pentaerythritol tripalmitate
G, pentaerythritol tristearate, pentae
Risuritol tribehenate, pentaerythritol
Limontanate, pentaerythritol zika plate,
Pentaerythritol dilaurate, pentaerythritol
Luge myristate, pentaerythritol dipalmite
Pentaerythritol distearate, pentae
Risulitol dibehenate, pentaerythritol dimo
Tantanate, glycerin trilaurate, glycerin
Rimyristate, glycerin tripalmitate, glyce
Lintristearate, glycerin trimiristate,
Glycerin tripalmitate, glycerin tristeale
Glycerin tribehenate, glycerin trimone
Thanate, glycerin dilaurate, glycerin dimilli
State, glycerin dipalmitate, glycerin disis
Tearate, glycerin dibehenate, glycerin dimo
Tantanate, propylene glycol dilaurate, professional
Pyrene glycol dimyristate, propylene glycol
Luge palmitate, propylene glycol disteary
G, propylene glycol dibehenate, propylene glycol
Recall dimontanate, propylene glycol monola
Urate, propylene glycol monomyristate,
Propylene glycol monopalmitate, propylene glycol
Coal monostearate, propylene glycol monobe
Henate, propylene glycol monomontanate, etc.
Can be mentioned. The preferred compound among these is trimethyl
Roll propane tristearate, trimethylol pro
Pantribehenate, pentaerythritol tetraheb
Tate, pentaerythritol tetraca plate, pen
Taerythritol tetralaurate, pentaerythritol
Tetramyristate, pentaerythritol tetra
Palmitate, pentaerythritol tetrastearate
G, pentaerythritol tetrabehenate, pentae
Lithritol tetramontanate, pentaerythritol
Letetraoleate, pentaerythritol tristea
Rate, pentaerythritol tribehenate, penta
Erythritol trimontanate, pentaerythritol
Lustearate, pentaerythritol dibehene
G, glycerin trilaurate, glycerin trimiris
Tate, glycerin tripalmitate, glycerin tri
Stearate, glycerin tribehenate, glycerin
Trimontanate, glycerin distearate, glycer
Lindi behenate, propylene glycol monostearate
And propylene glycol monobehenate.
More preferably, pentaerythritol tetrahebute
Pentaerythritol tetracaprate, pentae
Risuritol tetralaurate, pentaerythritol
Tetramyristate, pentaerythritol tetrapal
Mitate, pentaerythritol tetrastearate,
Pentaerythritol tetrabehenate, pentaerythr
Litol tetramontanate, pentaerythritol te
Traoleate, glycerin trilaurate, glycerin
Triglyceride, glycerin tripalmitate,
Lyserine tristearate, glycerin tribehene
And glycerin trimontanate. Above compound
For other compounds, the effect of suppressing mold contamination and the high level of mechanical
Strength balance and good moldability can be exhibited
Absent. Component (d): Ethylene rubber component (component (d)
Minutes) Before used in the propylene-based resin composition of the present invention
The ethylene rubber component of component (d) has Mooney viscosity ML
_{1 + 4}(100 ° C.) is 10 to 100, preferably 20 to 9
5, particularly preferably 30 to 95, ethylene content of 40 to
85% by weight, preferably 50-85% by weight, particularly preferred
Or 60 to 80% by weight of an ethylene rubber. concrete
For example, amorphous ethylene-propylene binary copolymer
Body (EPM), amorphous ethylene propylene diene
Copolymer (EPDM), amorphous ethylene / butene binary
Copolymer (EBM), amorphous ethylene propylene
Ten terpolymer (EPBM) and the like. The etch
The len-based rubber component may be a mixture of the above various rubbers.
The shape is bale, pellet, flake
Shape, crumb shape, etc. Mooney viscosity ML_{1 + 4}
(100 ° C) less than 10 have a balance of mechanical strength
Inferior, more than 100, the appearance of molded products is inferior
Is not practical. Component (e): Other components The propylene-based resin composition of the present invention comprises the above (a) to (d).
In addition to the essential components, pigments are usually blended for coloring
In order to further improve the performance,
Antioxidants, antistatic agents, flame retardants, dispersants, etc.
Can be performed, and furthermore, the effect of the present invention is not significantly impaired.
Various resins other than the essential components (a) to (d) in the range,
Various kinds of elastomers and various fillers can be compounded.
You. (2) Quantity ratio In the propylene-based resin composition of the present invention,
The quantitative ratio is important, and among the above essential components (a) to (d),
The propylene / ethylene block copolymer of the component (a)
100 parts by weight are used as a blending standard. The component (b)
Tylene / ethylene / butylene / styrene block copolymer
As for the amount of the body, the propylene
3 to 100 weight per 100 parts by weight of the len block copolymer
Parts by weight, preferably 5 to 60 parts by weight, particularly preferably 7 to
It is blended in an amount ratio of 40 parts by weight. Stille of component (b)
Of ethylene-butylene-styrene block copolymer
If the amount is less than the above range, the impact strength is poor, and
If it exceeds the range, the heat resistance rigidity and the appearance of the molded product become inferior.
It is inappropriate. The amount of the filler of the component (c) and
The propylene / ethylene block of component (a)
3 to 100 parts by weight, preferably 100 parts by weight of the copolymer
8 to 80 parts by weight, particularly preferably 15 to 60 parts by weight
It is. The amount of the filler of the component (c) is out of the above range.
At full, the rigidity (heat resistance) and dimensional stability of the molded product are inferior.
Exceeding the above range will result in inferior impact resistance and molded product appearance.
Therefore it is inappropriate. The ethylene rubber of the component (d)
The amount of the propylene / ethylene component (a)
0 to 20 parts by weight per 100 parts by weight of the block copolymer,
Preferably 3 to 20 parts by weight, particularly preferably 5 to 18 parts by weight
Parts. In view of the compounding amount of the ethylene rubber of the component (d)
Beyond this range, heat resistance and rigidity will deteriorate,
Appropriate. [II] Production of propylene resin composition The components (a) to (d) are blended according to the above-mentioned quantitative ratios.
With this, a propylene-based resin composition can be produced.
Wear. These components are generally mixed in a single-screw extruder,
Extruder, Banbury mixer, roll, Brabender pump
Kneading and kneading using ordinary kneading machines such as last graph and kneader
It is generally obtained by granulation. In this case,
It is preferable to select a kneading granulation method to improve the dispersion.
Usually, kneading and granulation are performed using a twin screw extruder. On this occasion,
The above components (a) to (d) may be simultaneously kneaded,
Each component is divided in order to improve the performance, for example, first (a)
And part or all of component (b)
Can be kneaded and granulated. Mixing is generally 1
At a temperature of 90 to 250 ° C, preferably 200 to 240 ° C
It is done in. Also, as described above, such (a)
When kneading each component of the components (d) to (d), a surface treatment agent is used.
After mixing, kneading of components (a) to (d) and surface treatment are the same.
Sometimes it can be done. [III] Molding of propylene resin composition
Use (1) Molding The propylene-based resin composition thus obtained can be used in various
Molding method, ie injection molding, compression molding, extrusion molding
(Sheet molding, blow molding)
Products are obtained, but among these molding methods,
Injection molding, injection compression molding (press injection)
It is preferred to do so. (2) Use The propylene-based resin composition of the present invention has a high level of molding quality.
Good mechanical strength balance and good appearance and moldability (flowability)
In addition to having coating, mold contamination is also suppressed, and more excellent coating
Properties and dimensional stability can be expressed.
Various moldings in the industrial parts field, especially with high functionality and large size
Goods, such as bumpers, fenders, spoilers, in
Automotive interior and exterior parts such as panels, trims, glove boxes, etc.
Goods, TV case, VTR case, washing machine cover, cleaning
Parts for home appliances such as machine cases, stereo cases, etc.
Practical enough as a material for various parts for audio product parts
Performance. [0038] EXAMPLES The present invention will be more specifically described with reference to the following experimental examples.
explain. The evaluation method performed here is as follows.
is there. <Moldability>Liquidity Spy having a cross-sectional shape of 14 mm in width and 2.3 mm in thickness
Molding (flow) length (average value) of Lal test piece (two-row type)
Was measured. In addition, molding was performed using Toshiba Machine's IS-170
Using an extrusion molding machine, molding conditions are 220 ° C and 600 kg / c.
m^TwoI went in.Appearance and flow mark observation The spiral test piece was injection molded and its appearance (flow
-Mark) was visually observed.Judgment ◎: Good appearance with almost no recognition. ：: Slightly recognized, but practically acceptable. X: Clearly recognized and practically difficult.Mold contamination The above injection molding machine has a length and width of 100 mm each and a thickness of 3
mm sheet at 220 ° C and 600 kg / cm^TwoCondition
It is continuously molded with about 50% filling of
Mold contamination (cloudy pattern) begins to appear at the end of the loaded resin
The number of shots before turning was observed. The larger this number is,
This shows that the effect of suppressing mold contamination is exhibited. <Evaluation of mechanical strength>Flexural modulus It measured based on JIS-K7203. Measurement temperature is 2
3 ° C. This measured value is also a measure of heat resistance.IZOD impact strength Measured according to JIS-K7110 (cutting rich)
Was. The measurement temperature is 23 ° C. Examples 1-4 and Comparative Examples 1-4 The following components (a), (b), (c) and (d) are shown.
1 and mixed with tetrakis [methylene-3
-(3 ', 5'-di-t-butyl-4'-hydroxyf
Enyl) propionate] methane is combined with the components (a) to (d).
0.08 parts by weight, di-steer for 100 parts by weight
0.07 parts by weight of ril-thio-di-propionate
And mix them thoroughly with a high-speed mixer (c-
1 except). After that, Kobe Steel Ltd. high-speed twin shaft
Using an extruder, knead and granulated at a temperature of 220 ° C.
(Except for c-1 only from the latter half of the kneading extruder)
Loaded. ) Supply the obtained pellets to the above injection molding machine
The test piece for measuring physical properties and the spiral test piece were
It was molded under temperature conditions and evaluated. The evaluation result
It is shown in Table 1. (A) Component a-1: MFR 90 g / 10 min, density 0.9091
g / cm^ThreeCrystalline polypropylene part (component A) 89
Wt%, ethylene propylene with an ethylene content of 40 wt%
14% by weight of a random copolymerized component (component B)
Having an overall polymerization MFR of 37 g / 10 min, Mw / Mn
Propylene-ethylene block copolymer having a value of 8.2 a-2: MFR: 75 g / 10 min, density: 0.9089
g / cm^ThreeCrystalline polypropylene part (component A) 85
Wt%, ethylene propylene with an ethylene content of 45 wt%
Each containing 16% by weight of a random copolymerized component (component B)
Having an overall polymerization MFR of 32 g / 10 min, Mw / Mn
Propylene-ethylene block copolymer having 8.7 a-3: MFR of 45 g / 10 min, density of 0.9062
g / cm^ThreeCrystalline polypropylene part (component A) 91
Wt%, ethylene propylene with an ethylene content of 70 wt%
Contains 7% by weight of renrandom copolymer (B component)
And the overall polymerization MFR is 21 g / 10 min, and Mw / Mn is
4.5 propylene / ethylene block copolymer (B) Component b-1: bound styrene content 20%, number average molecular weight 33.0
00, MFR 90g / 10min styrene ethylene
Tylene / styrene block copolymer b-2: bound styrene content 18%, number average molecular weight 28.0
00, MFR 160g / 10min styrene ethylene
Butylene / styrene block copolymer b-3: bound styrene content 40%, number average molecular weight 90,0
00, MFR 1g / 10min styrene / ethylene / butyl
Len-styrene block copolymer (C) Component c-1: The average diameter is 0.7 μm and the average aspect ratio is 3
0 magnesium sulfate whiskers, whiskers 10
5 parts by weight of pentaerythritol tetra per 0 parts by weight
Surface treatment with stearate (at a temperature of 30 ° C with a mixer)
Blended). c-2: substantially the entire length is 13 μm or less,
The portion having a length of less than 10 μm is 99.5% and the average particle size is 3.
0 μm talc having an average aspect ratio of 6
2.5 parts by weight of pentaerythritol per 100 parts by weight
Surface treatment with tetrastearate (30 with high-speed mixer)
Blend at a temperature of ℃. c-3: The same untreated talc as above was added to the talc 100 times
Expressed as 2 parts by weight of glycerin tristearate per part by weight
Surface treatment (blending at a temperature of 25 ° C with a high-speed mixer)
What was given. c-4: The same untreated talc as above was added to the talc 100 times
Surface treatment with 1 part by weight of calcium behenate per part by weight
(Blend at a temperature of 30 ° C. with a high-speed mixer).
thing. c-5: 11% over 15 μm length, 10 μm length
Untreated talc with less than 72%, average particle size of 8.9 μm c-6: The same untreated talc as c-2 was added to the talc 100.
Expressed as 2 parts by weight of magnesium stearate per part by weight
Surface treatment (blend at a temperature of 30 ° C with a high-speed mixer)
What was given. c-7: The same untreated talc as c-2 was added to the talc 100.
5 parts by weight of pentaerythritol monocap per part by weight
Surface treatment at a rate (break at 25 ° C with a high-speed mixer)
Render). Component (d) d-1: Mooney viscosity ML_{1 + 4}(100 ° C) is 88,
Ethylene rubber with a titanium content of 68% by weight d-2: Mooney viscosity ML_{1 + 4}(100 ° C) 70, d
Ethylene rubber with 73% by weight of titanium d-3: Mooney viscosity ML_{1 + 4}(100 ° C.) is 110,
Ethylene rubber with an ethylene content of 38% by weight [0045] [Table 1]As shown in Table 1, the compositions shown in Examples 1 to 4
Resin compositions with good mechanical strength
Mold, product appearance and moldability, and mold contamination
Was suppressed. On the other hand, those shown in Comparative Examples 1 to 4
Also mechanical strength balance, molded product appearance and moldability, mold contamination
Was partially or entirely inadequate. [0047] The propylene resin composition of the present invention is
Propylene / ethylene block copolymer specific to the composition of
Body, specific styrenic elastomer and specific treatment
Talc whiskers are used for conventional molding
Unlike polypropylene resin composition, mold contamination is suppressed
Good moldability and molded product appearance with high flowability
With a high level of mechanical strength balance
, Bumper, huender, instrument panel, fan shroud
Interior and exterior parts such as
Case, VTR case, washing machine cover, vacuum cleaner case, etc.
Molding resin composition for various parts such as home appliances
And has excellent applicability.

Continuation of the front page (72) Inventor Masayuki Matsuoka 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Yuka Co., Ltd. Yokkaichi Research Laboratory (56) References JP-A-1-256557 (JP, A) JP-A-4 −300 935 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 53/00 C08L 53/02 C08K 9/04

Claims (1)

(57) [Claims] (1) A propylene-based resin composition comprising the following components (a) to (d). Component (a): a propylene / ethylene block copolymer containing a crystalline polypropylene portion (component A) and an ethylene / propylene random copolymer portion (component B), wherein the component A is a component of the entire block copolymer. Occupies 60 to 95% by weight, its MFR is 5 to 300 g / 10 min, its density is 0.9070 g / cm ³ or more, and the B component accounts for 5 to 40% by weight of the whole block copolymer; When the ethylene content is 20 to 80% by weight, the MFR of the entire block copolymer is 3 to 200 g / 10 min, and the weight average molecular weight / number average molecular weight (Mw / Mn) is 5 to 15 Block copolymer: 100 parts by weight (b) Component: Bound styrene amount: 10 to 25%, number average molecular weight (Mn): 10,000 to 50,000, MFR (230 ° C., 2.16 kg) 50 to 2 0 g / 10 min styrene / ethylene / butylene / styrene block copolymer: 3 to 100 parts by weight (c) Component: At least one compound represented by the following general formula [I], [II] or [III] Substantially the entire length measured by a laser light scattering type particle size distribution meter, which is surface-treated using an amount ratio of 0.01 to 8 parts by weight per 100 parts by weight of the filler, is 15 μm or less and the average At least one filler selected from talc having a particle size of 1 to 6 μm and an average aspect ratio of 5 or more and inorganic whiskers having an average diameter of 2 μm or less and an average aspect ratio of 5 or more: 3 to 100 parts by weight: General formula [I (R ¹ COO) nM (wherein, R ¹ represents a monovalent hydrocarbon group having a molecular weight of 250 to 500 or a monovalent hydrocarbon having a molecular weight of 250 to 500 containing a hydroxy group, and M represents lithium or calcium. ,
Represents a strontium or barium atom, and n represents the same number as the valence of M. ) General formula [II] (Wherein, R ² is a hydrocarbon group having 4 to 29 carbon atoms or a hydrocarbon group having 4 to 29 carbon atoms including a hydroxyl group, and represents the same or different groups, and R ³ is a hydrocarbon group having 1 to 8 carbon atoms.) Represents the same or different groups selected from a hydrogen group, a hydrogen atom, a hydroxyl group, and R ² COO—.) General formula [III] (Wherein R ⁴ represents a hydrocarbon group having 1 to 8 carbon atoms, a hydrogen atom,
A hydroxyl group and a group identical or different from each other selected from R ² COO—, at least one of which is R ² COO;
-And one hydroxyl group in the compound even if it contains a hydroxyl group. Component (d): Ethylene rubber having Mooney viscosity ML _{1 + 4} (100 ° C.) of 10 to 100 and ethylene content of 40 to 85% by weight: 0 to 20 parts by weight