JP3525531B2 - Polypropylene resin composite composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polypropylene resin composite composition, and more specifically, it contains a highly crystalline polypropylene resin as a main component, and particularly has low injection moldability, rigidity, impact resistance, and brittleness temperature. It has an excellent balance of physical properties,
The present invention relates to a polypropylene resin composite composition that can be favorably used for large-sized molded articles such as home electric appliance parts, building materials, and industrial parts.

[0002]

2. Description of the Related Art Polypropylene resin composite compositions are widely used as materials for home electric appliances, building materials, industrial parts, etc., from the viewpoints of design freedom, weight reduction, recyclability and the like. In pursuit of functionality and economic efficiency of various products, products are becoming larger and thinner, and there is a demand for highly fluid polypropylene resin composite compositions with excellent injection molding processability, rigidity, and impact resistance. There is.

As a method for improving the impact resistance of polypropylene resin, many proposals have been made of polypropylene resin compositions in which polypropylene resin is blended with a thermoplastic elastomer such as an amorphous ethylene / propylene copolymer or a hydrogenated block copolymer. ing. For example, such techniques include Japanese Patent Laid-Open Nos. 58-17139 and 58-2.
06644, JP-A-61-34048, JP-A-1-
No. 268739 is cited. However, when the content of the elastomer is small, these proposed compositions have an insufficient balance of physical properties of rigidity and impact resistance, have low tensile elongation, and are inferior in high-speed impact resistance. Alternatively, an elastomer composition containing a large amount of a hydrogenated block copolymer or a softening agent has low rigidity and is not suitable for a large-sized molded product.

JP-A-57-73034 and JP-A-61-
No. 276840 discloses a composition in which an ethylene polymer and a rubber-like component are blended with a crystalline propylene polymer, or a rubber-like component with an ethylene / polypropylene copolymer,
A composition having a good balance of physical properties and moldability is shown by a composition containing a filler and optionally an ethylene polymer.

The amorphous ethylene-propylene copolymer used as the rubber-like component has a relatively large blending amount, and has a problem in large-sized thin-wall molding due to a decrease in rigidity or a decrease in fluidity. Further, JP-A-63-156842 discloses a highly crystalline polypropylene homopolymer, a styrene-ethylene / butylene-styrene block copolymer or a styrene-ethylene / propylene block copolymer, and an ethylene / propylene-based copolymer. Although a composition containing a copolymer rubber or polyethylene is shown, it does not always satisfy the balance between rigidity and impact resistance. The present situation is that a composition capable of performing large-sized thin-wall molding with a low embrittlement temperature, which has improved impact resistance while maintaining excellent rigidity of polypropylene resin, has not yet been obtained.

[0006]

The present inventors have previously found that the dispersed state of the elastomer largely depends on the improvement of the balance between rigidity and impact resistance, and filed a patent application (Japanese Patent Application No. 5-148273). Further, an intensive study was conducted on the elastomer component having a small decrease in the rigidity of polypropylene resin and having a high impact resistance improving effect and its dispersibility as a problem to be solved.
As a result, high crystalline polypropylene resin to the hydrogenated block copolymer and high density polyethylene down the elastomer component at a specific blending ratio, elastomeric cohesive phase dispersed in the continuous phase of the propylene homopolymer component of the high crystalline polypropylene resin form a fine dispersed state in particulate, higher density polyethylene in to the inside, by forming a two-phase structure comprising a hydrogenated block copolymer outside, rigidity, impact resistance remarkably improved and embrittlement The inventors have found that the temperature decreases and have completed the present invention.

[0007]

That is, the present invention is
[A] Melt flow rate is 10 to 150 g / 10 minutes,
50 to 90 parts by weight of a highly crystalline polypropylene homopolymer having a 1,2,4-trichlorobenzene insoluble content at 120 ° C. of 50% or more or an ethylene-propylene block copolymer having an ethylene content of less than 4% by weight. ,
[B] in (a) and (b) formed know configured to elastomer, (a) component, the unsaturated polymer block A and a conjugated diene compound portion consisting mainly of at least one vinyl aromatic compound is 20% A polymer block B mainly composed of at least one olefin compound hydrogenated to an extent not exceeding 10% and a vinyl aromatic compound content of 10% or more and less than 30%, and a melt flow rate is used.
The hydrogenated block copolymer of 0.3 to 0.6 times the component (a), the component (b) has a density of 0.96 g / cm ³ or more,
The melt flow rate of the component (a) used is 0.5 to
0.8 times the high-density polyethylene, these (a) and (b)
The compounding ratio of 5 to 25 parts by weight of an elastomer component in the range of 40/60 to 80/20% by weight and 5 to 25 parts by weight of [c] a granular or plate-like inorganic filler. The elastomer coagulated dispersed phase dispersed in the continuous phase of the polypropylene single component of (1) is polyethylene or a mixture of polyethylene and an ethylene / polypropylene copolymer on the inside, and the hydrogenated block copolymer which is the component (a) on the outside. To form a two-phase structure
Polypropylene resin composite composition and symptoms, and its elastomeric cohesive disperse phase, 0.1 average particle size in the form of particles
Polypropylene resin composite finely dispersed to 1 μm, and the ratio (film thickness ratio) of the average particle diameter to the thickness of the outer hydrogenated block copolymer forming a two-phase structure is 10 to 30%. A composition is provided.

The highly crystalline polypropylene resin used in the present invention is obtained by multi-stage polymerization in the presence of a highly stereoregular catalyst, and has a melt flow rate (hereinafter referred to as MFR in the present invention) of 10 to 150 g / 10 minutes, 120
Highly crystalline polypropylene homopolymer having a weight ratio of 1,2,4-trichlorobenzene (hereinafter referred to as TCB in the present invention) insoluble matter at 50 ° C of 50% or more, or an ethylene-propylene block having an ethylene content of less than 4% by weight. It is a copolymer. Such highly crystalline polypropylene resin,
For example, it can be manufactured by the method disclosed in JP-A-5-65321.

When the ethylene content exceeds 4% by weight,
Since the elastomer-aggregated dispersed phase is not dispersed in fine particles, the rigidity and the surface hardness of the molded product are significantly reduced, and the effects of the present invention cannot be obtained. When the MFR is less than 10 g / 10 minutes, the fluidity is poor and the flow distance during injection molding is short,
The appearance of the molded product is poor and the injection molding processability is poor, making thin wall molding difficult. If the MFR exceeds 150 g / 10 minutes, the impact strength decreases, which is not preferable. The most preferred MFR is
It is in the range of 20 to 100 g / 10 minutes. Further, when fractionation is performed by TCB, it is necessary that the weight ratio of the TCB-soluble component at 30 ° C. is 10% or less and the TCB-insoluble component at 120 ° C. is 50% or more.

Here, the classification by TCB used in the present invention is as follows. Wild et al. Poimer Preprin
ts Am. Chem. Soc., 18, 182 (197
In 7), it was carried out according to the temperature rising elution fractionation method used for fractionation of linear low density polyethylene. That is, a predetermined amount of polypropylene resin and antioxidant were dissolved in TCB by heating, and the solution was filled in a stainless steel column filled with sea sand and kept at a temperature of 160 ° C., and then the temperature of the column was lowered to room temperature. , Crystallize polypropylene resin. After the temperature of this column was raised to 30 ° C. again, TCB warmed to 30 ° C. was flowed in through a pipe connected to the column to take out a soluble component.

Methyl alcohol is added to the TCB solution to dissolve the soluble matter, and the soluble matter is reprecipitated, fractionated and dried to obtain the soluble matter at 30 ° C. Further, the TCB-insoluble matter at 120 ° C. is the same as at 30 ° C., after the TCB-soluble matter at 120 ° C. was taken out, the column temperature was changed to 160 ° C.
The temperature can be raised to, and the same can be obtained thereafter. 30 ° C
TCB soluble content in 10% is substantially amorphous.
If it exceeds, the rigidity is poor, and it is preferably 7% or less. The TCB insoluble content at 120 ° C. is a particularly highly crystalline portion, and when it is 50% or less, rigidity and heat distortion resistance are poor,
It is preferably 55% or more.

In order to further improve the rigidity and heat resistance of the polypropylene resin composite composition of the present invention, it is preferable that the propylene homopolymer in the component (a) has a high isotactic pentad fraction. .950 or higher is recommended. The isotactic pentad fraction means A. Za
Macrobelle et al., Macromolecule
s, 6 , 925 (1973), that is, an isotactic chain of pentad units in a crystalline polypropylene molecular chain measured using 13 C-NMR, that is, five consecutive propylene monomer units. Is the fraction of propylene monomer units at the center of the meso-bonded chains. However, regarding attribution of NMR absorption peaks, Macromolecules, 8 , 687
(1975).

The hydrogenated block copolymer used in the present invention has a polymer block A containing at least one vinyl aromatic compound as a main component and a conjugated diene compound moiety having an unsaturation of 2 or less.
At least 1 hydrogenated to a degree not exceeding 0%
Composed of a polymer block B mainly composed of individual olefin compounds and having a vinyl aromatic compound content of 10% or more 30
%, The MFR at 230 ° C. is 0.3 to 0.6 times that of the highly crystalline polypropylene resin used.

When the MFR is higher than that of the highly crystalline polypropylene resin used, it does not disperse into particles when dispersed in the polypropylene component, and the hydrogenated block copolymer alone tends to be in a layered dispersed state, and Lower than the above range
If not, the viscosity difference during melting is large and the effect of the present invention cannot be obtained.

The polymer block A mainly composed of a vinyl aromatic compound has a weight ratio of the vinyl aromatic compound to the conjugated diene compound of 100/0 to 51/49, preferably 100.
A polymer block having a composition range of / 0 to 70/30, and when a vinyl aromatic compound and a conjugated diene compound are copolymerized, the distribution of the conjugated diene compound in this block is random or tapered (monomers along the molecular chain). The composition may be increased or decreased), partially block-shaped, or any combination thereof.

The vinyl aromatic compound provided here is one or more of alkyl styrenes such as styrene, α-methyl styrene, p-methyl styrene and p-tert-butyl styrene, p-methoxy styrene and vinyl naphthalene. Among two or more selected, styrene and p-methylstyrene are particularly preferable. Further, as the conjugated diene compound, butadiene, isoprene, piperylene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3
Of these, one or more selected from octadiene and the like, butadiene and / or isoprene are particularly preferable.

The content of the vinyl aromatic compound is required to be 10% or more and less than 30%. If it is less than 10%, the rigidity is lowered, and if it exceeds 30%, a coarse dispersion state is formed and the impact is generated. Strength is reduced.

As the method for producing the block copolymer, for example, Japanese Patent Publication No. 36-19286 and Japanese Patent Publication No. 43-1.
Methods described in Japanese Patent Publication No. 4979, Japanese Patent Publication No. 49-36957 and the like can be mentioned. Further, it is necessary to hydrogenate the above block copolymer by a known method, for example, a method described in JP-B-42-8704, JP-B-63-4841, or JP-B-1-37970. When the hydrogenation rate is low, the compatibility with the polypropylene resin is insufficient and the impact resistance is poor, and it is not preferable because it is easily deteriorated by heat during mixing and molding. The hydrogenation rate is measured by the nuclear magnetic resonance apparatus (NM
It can be analyzed by instrumental analysis using R).

The high-density polyethylene used in the present invention has a density of 0.96 g / cm ³ or more and is 0.5 to 0.8 times as fluid as the highly crystalline polypropylene resin used in MFR. When the density is 0.96 g / cm ³ or less,
It is not preferable because the rigidity decreases. In addition the MFR is <br/> than the above range, when dispersed in the polypropylene component, the effect of the present invention become dispersed state of the large particles became Kuku to obtain
And becomes brittle and the impact resistance deteriorates, which is not preferable.

[0020] It should be noted that, in the present invention, ethylene, if necessary
Butene-1 copolymer may be used. The copolymer is
A copolymer obtained by polymerizing ethylene and butene-1 using a normal catalyst, a so-called Ziegler-Natta catalyst, wherein the butene-1 content in the copolymer is 15 to 25 as measured by infrared spectroscopy. % By weight, preferably 17-22
weight%. The MFR at 230 ° C. is equal to or lower than that of the highly crystalline polypropylene resin used and equal to or higher than 1/20. When the MFR is higher than that of the highly crystalline polypropylene resin used, when it is dispersed in the polypropylene component, it does not disperse in the form of particles, and tends to be in a layered dispersed state by itself. Since the difference is large and it is difficult to disperse finely, the effect of the present invention cannot be obtained. When the butene-1 content in the copolymer is less than 15% by weight, the effect of improving impact strength is low, and when it exceeds 25% by weight, the rigidity and hardness are lowered, and the balance between rigidity and impact strength is deteriorated.

Specific examples of the granular or plate-like inorganic filler used in the present invention include talc, mica, clay, wollastonite, calcium carbonate, barium sulfate, diatomaceous earth, basic magnesium sulfate, and the like. These 1 or more types can be used suitably. Further, the inorganic filler may be surface-treated with various treatment agents. Examples of the surface treatment include various treatments such as a silane coupling agent type, a higher fatty acid salt type, and an organic titanate type.

A preferable inorganic filler is fine talc having an average particle size of 0.3 to 5 μm. Most preferably, the average particle size is 0.5 to 2 μm. When the average particle size is 0.3 μm or less, talc secondary aggregation occurs and the dispersibility deteriorates, and when it exceeds 5 μm, rigidity and impact strength decrease. Here, the average particle size is a particle size value at a point of 50% in a cumulative distribution curve of particle size measured by a particle size distribution measuring device by a liquid phase sedimentation light transmission method. This inorganic filler is mixed in 5 to 25 parts by weight. Preferably 7-20
If the amount exceeds 25 parts by weight, the impact strength is lowered and the balance between rigidity and impact strength is deteriorated, which is not preferable.

A major feature of the present invention is that, as an elastomer component to be blended with a specific highly crystalline polypropylene resin,
The hydrogenated block copolymer and high density polyethylene emissions in combination with a specific blending ratio, it is an further limiting the MFR. That is, there hydrogenated block copolymer and high density polyethylene <br/> ethylene in to the mixing ratio range of 40 / 60-80 / 20, by further appropriately limited to one another these MFR, high crystallinity That is, the elastomer aggregate dispersion phase dispersed in the polypropylene single phase of the polypropylene resin forms a two-phase structure and is finely dispersed in the form of particles having an average particle diameter of 1 μm or less.

While the hydrogenated block copolymer has a high impact resistance improving effect, it has a large decrease in rigidity and hardness which are characteristics of polypropylene resin. On the other hand, high density polyethylene
In contrast, the impact resistance improving effect is low, but the rigidity and hardness are high. In order to bring out each of these characteristics, a two-phase structure was formed and finely dispersed.

[0025] In the mixing ratio of the hydrogenated block copolymer and high density polyethylene emissions of the elastomer component is 40/60 or less, the thickness of the hydrogenated block copolymer phase surrounding the polyethylene emission phase <br/> in the elastomeric cohesive disperse phase Becomes thin,
The effect of improving the impact resistance is low, and at 80/20 or more, the hydrogenated block copolymer phase becomes thick and the rigidity is lowered, and the hydrogenated block copolymer of the present invention and the high density polyethylene are obtained. The combined effect of The preferred blending ratio is
It is 50/50 to 70/30.

Furthermore, the mixing ratio of the hydrogenated block copolymer and high density <br/> polyethylene emissions, the thickness of the hydrogenated block copolymer portion of the outer forming a two-phase structure changes, elastomeric cohesive dispersion A range having a thickness of 10 to 30% of the average particle diameter of the phase is effective for improving impact resistance. Most preferably, it is 12 to 25%. This elastomer component is blended in an amount of 5 to 25 parts by weight. It is preferably from 7 to 22 parts by weight, and when it is less than 5 parts by weight, the effect of improving the impact strength is small, and when it exceeds 25 parts by weight, the rigidity is largely lowered, and the balance between the rigidity and the impact strength is unfavorable.

The average particle diameter of the elastomer aggregate dispersed phase (domain) in the present invention is determined by taking a transmission electron microscope photograph (magnification ratio × 10000) of the resin by the ultrathin section method. Since the dispersed particles shown in the electron micrograph are not perfectly circular, an image processing apparatus (Asahi Kasei: IP-100
0) was used to determine the equivalent circle diameter of the aggregation-dispersed phase subjected to the prescribed treatment, and the average value was used as the average particle diameter.

The elastomer aggregate dispersed phase dispersed in the continuous phase (matrix) of the polypropylene single component of the highly crystalline polypropylene resin is particulate and has an average particle size of 0.1.
By finely dispersing in the range of up to 1 μm, the balance between rigidity and impact strength is excellent. When the average particle size is 0.1 μm or less and 1 μm or more, the physical property balance is poor. Preferably, the average particle size is 0.2 to 0.8 μm.

Furthermore, the thickness of the hydrogenated block copolymer portion of the elastomeric cohesive dispersed phase forming a two-phase structure, an average particle diameter of the inner polyethylene down phase by the method described above, elastomeric cohesive required previously The difference between the average particle size of the dispersed phase and the average particle size is taken and multiplied by 1/2. The film thickness ratio of the present invention is the average particle size of the elastomer aggregate dispersed phase and 2
It is the ratio with the film thickness of the hydrogenated block copolymer portion outside the elastomer aggregate dispersion phase forming the phase structure.

The polypropylene resin composite composition of the present invention can be manufactured by a method of pelletizing using a mechanical kneader in a melt kneading method. For example, it is preferable that each component constituting the resin composition of the present invention is premixed with a Henschel mixer, a blender or the like, and then melt-kneaded with a high-speed twin-screw extruder at a temperature of 180 to 250 ° C. Further, the hydrogenated block copolymer and the high strength polyethylene <br/> ethylene emission that consists of an elastomer component prior to premixing, may be used in advance melt kneading.

If necessary, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, lubricants, pigments, antistatic agents, metal deterioration inhibitors, crystal nucleating agents, higher fatty acid salts, flame retardants, etc. Various additives can be appropriately added. The polypropylene resin composite composition thus obtained is used for various large molded articles by an injection molding method.

[0032]

EXAMPLES The polypropylene resin composite composition of the present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. The test methods used in Examples and Comparative Examples were as follows.

Melt Flow Rate (MFR) According to ASTM D1238. Temperature: 230 ℃, load:
2.16 kgf Flexural Modulus Complies with ASTM D790. Izod impact value Complies with ASTM D256. Brittleness temperature According to ASTM D746.

Measurement of high-speed surface impact strength Using an injection-molded flat plate with a thickness of 3 mm, the total absorbed energy at the time of impact destruction was measured by a falling weight graphic impact tester B type manufactured by Toyo Seiki Co., Ltd. Impact speed: 5 m / sec, Striker diameter: 1 inch Evaluation of injection molding workability A mold for spiral flow test with a cross section of width 10 mm and thickness 1 mm was attached to an injection molding machine, and the resin temperature, mold temperature, The resin flowability is compared under the same ejection pressure, ejection velocity, and ejection molding time, and when the flow distance is large and thin-walled molded products can be easily molded, it is rated as bad, and when bad, it is evaluated as defective.

Measurement of Dispersion State of Emulsion Coagulation Dispersed Phase, Average Particle Size and Film Thickness A part of the central portion of an injection-molded flat plate having a thickness of 3 mm was cut out,
After staining with ruthenium tetroxide, an ultrathin section was cut out using an ultramicrotome, and a transmission electron microscope (manufactured by Hitachi) was used to observe an electron microscopic image of the microstructure of the average coagulated dispersed phase. Then, the image was taken at a magnification of 10,000 times to prepare a photograph having a field of view of 220 mm in length and 180 mm in width.

In the photograph, the inorganic filler (for example, talc) and the elastomer component dyed with ruthenium tetraoxide are shown as a black cohesive dispersed phase. It is observed that talc is elongated and scale-like, and the elastomer component is almost uniformly dispersed in particles or layers. Furthermore,
Elastomeric cohesive dispersed phase, inner polyethylene emission phase is dyed crystal lamellae or darken, the hydrogenated block copolymer outside as surrounding packaging it is most black stained 2 phase structure is observed. Since the dispersed particles shown in the electron micrograph are not perfectly circular, an image processing device (made by Asahi Kasei: IP
-1000) and the minimum removal area of the aggregated dispersed phase is set to 0.
Image processing was performed with a diameter of 005 μm ² , and the average value of the equivalent circle diameters was determined and used as the average particle diameter of the aggregated dispersed phase.

Next, the thickness of the outer hydrogenated block copolymer portion of the elastomeric cohesive dispersed phase forming a two-phase structure, the average particle diameter of the inner polyethylene emission phase determined by the above method, obtained previously The difference between the average particle diameter and the average particle diameter of the elastomer-aggregated dispersed phase is multiplied by 1/2.
Further, the ratio of the film thickness of the hydrogenated block copolymer portion to the average particle size of the elastomer aggregate dispersed phase was defined as the film thickness ratio.

Comprehensive Evaluation The relationship between the blending amount of the inorganic filler and the flexural modulus, the relationship between the blending amount of the elastomer component and the Izod value, and the balance of the molding processability were compared. evaluated.

Examples 1 to 5 and Comparative Examples 1 to 11 Highly crystalline polypropylene resins, hydrogenated block copolymers, high density polyethylene / or ethylene butene-1 copolymers and inorganic additives are shown in Tables 3 and 4. In addition to the content of each component described in 1., pentaerythrityl-
Tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.3PHR, tris (2,4-di-t-butylphenyl) phosphite.
2 PHR, 0.2 PHR of magnesium stearate, 0.2 PHR of 2,2'methylenebis (4,6-di-t-butylphenyl) sodium phosphate were added, and premixed for 1 minute with a Henschel mixer to prepare a mixture. Was extruded at a kneading temperature of 180 ° C. to 200 ° C. using a high-speed biaxial kneader to obtain a pellet-shaped resin composition. The obtained pellets were molded into test pieces for physical properties by injection molding, various physical properties were measured, and the results are summarized in Tables 3 and 4.
The following raw materials are used as the raw materials shown in Tables 3 and 4, and the mixing ratios are parts by weight.

Polypropylene resin A-1 shown in Table 1 by applying the high stereoregular highly active catalyst and polymerization conditions described in JP-A-5-65321.
The highly crystalline polypropylene resins of ~ A-6 were polymerized and used.

[0041]

[Table 1]

Hydrogenated block copolymer n-butyllithium was used as a polymerization catalyst, and tetrahydrofuran was used as a vinyl content modifier in cyclohexane solution.
The block copolymers shown in Table 2 were synthesized by anion block copolymerizing styrene and butadiene. The polymer structure was controlled by charging a monomer, and the molecular weight was controlled by changing the catalyst amount. The styrene content was measured with an ultraviolet spectrophotometer, and the vinyl content was measured with a nuclear magnetic resonance apparatus.

Next, each block copolymer was treated with di-p-tolylbis (1-cyclopentadiene) titanium and n-butyllithium as a hydrogenation catalyst to obtain a hydrogen pressure of 5 kg / cm ³ ,
Hydrogenation was carried out at a temperature of 50 ° C. for 2 hours. 90% or more of the double bonds in the butadiene block portion were hydrogenated, and the benzene ring in the styrene block portion remained almost unhydrogenated. The hydrogenation rate was measured using a nuclear magnetic resonance apparatus.

[0044]

[Table 2]

High-density polyethylene C-1: Density = 0.96 g / cm ³ , MFR = 2 g /
10 minutes C-2: density = 0.97 g / cm ³ , MFR = 20 g /
10 minutes C-3: density = 0.97 g / cm ³ , MFR = 55 g /
10 minutes C-4: Density = 0.94 g / cm ³ , MFR = 15 g /
10 minutes Ethylene / butene-1 copolymer E-1: butene-1 content = 20%, MFR = 7 g / 1
0 minutes E-2: butene-1 content = 17%, MFR = 35 g / 1
0 minutes Inorganic filler D-1: Asada Milling (manufactured) MMR, talc having an average particle size of 1 μm.

Comparative Example 1 When a polypropylene resin having a composition of 7% and an ethylene content of 7% is used, the aggregated and dispersed phase becomes large, and the rigidity and impact resistance are low.

Comparative Example 2 When a polypropylene resin having a high MFR was used in the composition of Example 4 and the hydrogenated block copolymer and the high-density polyethylene were changed to have high fluidity, the moldability was excellent but the embrittlement was caused. The temperature is high and the impact resistance is poor.

Comparative Example 3 When a polypropylene resin having a low MFR was used in the composition of Example 4 and the hydrogenated block copolymer and high-density polyethylene were changed to have low fluidity, the physical properties of rigidity and impact resistance were improved. However, it is not suitable for large-scale thin-wall molding because it has poor workability for extrusion molding and requires high extrusion molding temperature and pressure.

Comparative Example 4 With the composition of Example 4, when the styrene content of the hydrogenated block copolymer was 40%, the coagulated dispersed phase became large and it was difficult to form a two-phase structure, resulting in poor physical property balance.

Comparative Example 5 MFR of hydrogenated block copolymer having the composition of Example 4
However, when a resin having a higher value than that of polypropylene resin is used, the coagulation-dispersed phase becomes layered, resulting in poor physical property balance.

Comparative Example 6 In the composition of Example 4, when the MFR ratio of the hydrogenated block copolymer and the polypropylene resin was large, the coagulated dispersed phase was 2
It does not have a phase structure and has poor physical property balance.

Comparative Example 7 In the composition of Example 4, when the blending ratio of the hydrogenated block copolymer and the high density polyethylene was about 28/72, the hydrogenated block copolymer was thin and the embrittlement temperature was high. , Inferior in impact resistance.

Comparative Example 8 In the composition of Example 4, when the blending ratio of the hydrogenated block copolymer and the high density polyethylene was about 89/11, the film thickness of the hydrogenated block copolymer was large and the rigidity was poor.

Comparative Example 9 With the composition of Example 4, when the MFR of the high-density polyethylene is lower than that of the polypropylene resin, the average particle size of the coagulation-dispersed phase becomes large and the balance of physical properties is poor.

Comparative Example 10 With the composition of Example 4, when the density of the high-density polyethylene is low, the rigidity is poor.

Comparative Example 11 M of ethylene / butene-1 copolymer having the composition shown in Table 4 was used.
When the FR having a higher FR than that of the polypropylene resin was used, the coagulation-dispersed phase was layered and the physical property balance was poor.

[0057]

[Table 3]

[0058]

[Table 4]

[0059]

According to the present invention, high fluidity of the high crystalline polypropylene in a specific hydrogenated block copolymer having a MFR of high-density polyethylene down the specific combination blended at a ratio elastomeric component and an inorganic filler By blending, the elastomer aggregate dispersion phase dispersed in the continuous phase of the polypropylene single component of the polypropylene resin can form a two-phase structure, and can be finely dispersed in the form of particles, achieving a high physical property balance, Suitable for large-sized thin-walled molded products.

[Brief description of drawings]

FIG. 1 is an electron micrograph of a particle structure showing a dispersed state of an elastomer of a resin composite composition of Example 4.

2 is a partially enlarged photograph of a structure of dispersed particles of the elastomer of FIG.

Continuation of front page (51) Int.Cl. ⁷ identification code FI C08L 23:04) (56) Reference JP-A-57-73034 (JP, A) JP-A-2-51551 (JP, A) JP-A-SHO 61-152752 (JP, A) JP-A-6-172593 (JP, A) JP-A-7-48485 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 23/00 -23/36 C08L 53/00-53/02

Claims (2)

(57) [Claims] 1. A melt flow rate of 10 to 15
A highly crystalline polypropylene homopolymer having a weight ratio of 1,2,4-trichlorobenzene insoluble matter at 0 ° C / 10 minutes and 120 ° C of 50% or more or an ethylene-propylene block copolymer having an ethylene content of less than 4% by weight. Fifty
90 parts by weight, with [B] (a) and (b) formed know configured elastomer, (a) component, the polymer block A and a conjugated diene compound portion consisting mainly of at least one vinyl aromatic compound A polymer block B mainly composed of at least one olefin compound hydrogenated to such an extent that the unsaturation of the vinyl aromatic compound does not exceed 20%, and the content of the vinyl aromatic compound is 10% or more and less than 30%. Rate is 0.3 to 0.6 times the hydrogenated block copolymer of the component (a), and the component (b) has a density of 0.96 g.
/ Cm ³ or more, melt flow rate used [a]
Min 0.5-0.8 times the high-density polyethylene, these <br/> (a) and the scope of the elastomeric ratio of 40 / 60-80 / 20% by weight of (b) 5 to 25 Parts by weight, 5 to 25 parts by weight of [c] granular or plate-like inorganic filler, and dispersed in the continuous phase of the polypropylene single component of the highly crystalline polypropylene resin, the elastomer-aggregated dispersed phase has polyethylene or polyethylene inside. and in admixture state of an ethylene-polypropylene copolymer, the outer side to the (a) that the polypropylene resin composite composition characterized to form a two-phase structure comprising a hydrogenated block copolymer as the component. 2. The elastomer coagulated dispersed phase is finely dispersed in the form of particles having an average particle size of 0.1 to 1 μm, and further the thickness of the outer hydrogenated block copolymer forming a two-phase structure with the average particle size. The polypropylene resin composite composition according to claim 1, wherein the ratio (film thickness ratio) is 10 to 30%.