JP2020114897A - Foamable thermoplastic resin composition and molding including the same - Google Patents

Abstract

To provide a foamable thermoplastic resin composition that can form an excellent foaming structure even when containing a large amount of inorganic substance powder and provide a lightweight molding and a molding including the same.SOLUTION: A foamable thermoplastic resin composition contains at least a thermoplastic resin, inorganic substance powder and a chemical foaming agent. The thermoplastic resin contains a polypropylene that does not include a long-chain branch (B) and a polypropylene that includes a long-chain branched structure (A) in a mass ratio of 80:20-98:2. A foam molding obtained thereby has an excellent foaming structure and is light in weight, and has excellent surface properties and physical properties such as strength.SELECTED DRAWING: None

Description

The present invention relates to a thermoplastic foam resin composition and a molded article using the same.

Conventionally, thermoplastic resins have been widely used with paper materials derived from forest resources as materials for various industrial and household molded products, food packaging and molded packaging for general products, etc. Now that it has become an international problem, in parallel with the viewpoint of making them non-toxic, recyclable, and incinerable, reduction of the consumption of thermoplastic resins and paper materials is also largely studied.

From such a point, an inorganic substance powder-blended thermoplastic resin composition obtained by highly filling an inorganic substance powder in a thermoplastic resin has been proposed and put into practical use.

For example, U.S. Pat. No. 6,096,086 discloses a composition comprising about 43% to about 18% by weight polyethylene, 56% to 80% by weight inorganic mineral powder, and about 1% to about 2% by weight additive. Polyethylene type with high content of inorganic mineral powder by mixing, extruding, pelletizing, forming parison, forming into a sheet by blow molding, and at the same time stretching with a pulling roller and stretching in biaxial direction Synthetic paper has been proposed.

Further, in Patent Document 2, the inorganic substance powder to be blended has a predetermined average particle size range and does not contain coarse particles, and high shear stress is exerted by using an extruder with a twin screw for kneading the composition. Kneading and kneading, extruding into a sheet by a T-die method, and adjusting the stretching ratio in the longitudinal and transverse directions to within a specified value to adjust the stretched sheet to a desired apparent specific gravity. Therefore, it has been proposed to provide a resin sheet containing a high amount of an inorganic filler, which suppresses the inclusion of foreign matters, has a uniform thickness, has an apparent specific gravity similar to paper, and is excellent in commercial properties.

In Patent Document 3, in the processing resin sheet in which such an inorganic filler is highly blended, by adjusting the degree of stretching, the specific gravity is within a predetermined range, and the water absorption is within a predetermined range. It has been proposed to provide a processing resin sheet in which a processing material can be efficiently applied or vapor-deposited on the surface of the resin sheet at low cost and the laminated layers are firmly adhered.

Further, in Patent Document 4, as a composite material for offset printing, a thermoplastic resin as a base material that supports an ink coating layer formed on the surface thereof, an inorganic filler or an organic filler that serves as a core for forming pores, and the like. The resin composition obtained by mixing and is formed into a sheet by a known method, and the obtained sheet is uniaxially or biaxially stretched to form a large number of fine pores inside, whitening the support, and the degree of stretching. It is shown that the specific gravity is adjusted to be within a predetermined range by adjusting.

Further, in Patent Document 5, a main component is a thermoplastic resin composition containing 1 to 900 parts by weight of a filler with respect to 100 parts by weight of a thermoplastic resin having a long chain branching index of 0.35 to 0.70, or The mixing ratio of polypropylene and low-density polyethylene was 95:5 to 70:30 by weight, the melt tension (melt tension) was 0.1 to 3.0 g, and the melt flow rate (230°C) was 10 to 50 g/10. It is shown that the surface of a substrate is coated with a thermoplastic resin composition containing 1 to 900 parts by weight of a filler with respect to 100 parts by weight of a thermoplastic resin as a component.

As described above, the inorganic substance powder-blended thermoplastic resin composition obtained by highly filling the inorganic substance powder in the thermoplastic resin is not only excellent in terms of environment and economy, but also excellent in various physical properties, In addition to the above-described aspects such as extrusion-molded products and coating on the surface of a base material, application to injection-molded products and the like is expected. However, because it is highly filled with inorganic substance powder, it has a higher specific gravity than general-purpose resin molded products such as polypropylene (specific gravity about 0.9), and it is lightweight for more general commercial use. Was needed.

JP 2001-71378 A JP, 2013-10931, A International Publication No. WO2014/109267 International Publication No. WO2017/057739 JP, 10-219042, A

As a means for reducing the weight of a molded article formed from a composition in which a powder of an inorganic substance is highly filled in a thermoplastic resin, a foaming technique is more effective than a stretching technique as shown in the prior art. Among them, chemical foaming is considered to be promising as a method capable of high-magnification foaming (=low specific gravity). However, the thermoplastic resin composition containing a large amount of the inorganic substance powder, compared with a general-purpose thermoplastic resin composition containing no inorganic substance powder or only a very small amount, the fluidity of the resin composition is hindered and uniform. However, the desired foamed state was not obtained, and the foamed state was greatly varied.
In addition, due to such a variation in the foaming state, there is a problem in that the surface condition of the molded product becomes uneven and the mechanical properties also vary greatly.
Thus, in obtaining a foamed molded product from a thermoplastic resin composition containing a large amount of an inorganic substance powder, the moldability is not excellent simply by adding a chemical foaming agent, the deterioration of the surface quality due to the foam breaking, and the foam structure. And the deterioration of mechanical properties occur.

The present invention has been made in view of the above circumstances, and a thermoplastic foamed resin composition capable of forming a good foamed structure and providing a lightweight molded article even if it contains a large amount of inorganic substance powder. , And a molded article using the same. The present invention also contains a large amount of inorganic substance powder, has good drawdown characteristics at the time of heating and melting, good resin spreadability, and can maintain a desired foaming state uniformly during foaming. Another object is to provide a thermoplastic foamed resin composition that can be molded into a molded product excellent in physical properties such as mechanical properties, and a molded product using the same. Another object of the present invention is to provide a thermoplastic foamed resin composition having excellent heat resistance and flame retardancy, and a molded article using the same.

The present inventors have conducted extensive studies in order to solve the above problems, in obtaining a foamed molded article from a thermoplastic resin composition containing a thermoplastic resin, an inorganic substance powder and a chemical foaming agent, during molding In order to obtain a molded product which has a uniform desired foamed state and does not have a variation in the foamed state without impairing the fluidity of the resin composition, and therefore the surface condition and the mechanical properties are highly uniform. From the viewpoint that the foam structure and the shape of the resin product can be maintained if the fluidity of the polymer can be suppressed even in the temperature range above the melting point of the polymer, especially during foam molding, without deteriorating the moldability and processability. Recalling that polypropylene (B) having no long chain branching is blended with polypropylene (A) having a long chain branching structure in order to suppress such fluidity and enable good foam formation, It has been found that a molded product having a good foaming structure can be obtained even if a large amount of inorganic substance powder is contained, if the compounding ratio is set to a specific ratio. Further, in such a thermoplastic foamed resin composition, even if it contains a large amount of inorganic substance powder, it has good drawdown characteristics and resin spreadability during heating and melting, and can be molded into various forms with good characteristics. Further, the present invention has been achieved by finding that the obtained molded article has excellent heat resistance and flame retardancy.

That is, the present invention for solving the above-mentioned problems is a thermoplastic foaming resin composition comprising at least a thermoplastic resin, an inorganic substance powder and a chemical foaming agent, wherein the thermoplastic resin has long chain branching. The thermoplastic foamed resin composition contains polypropylene (B) and polypropylene (A) having a long-chain branched structure in a mass ratio of 80:20 to 98:2.

In one aspect of the thermoplastic foamed resin composition according to the present invention, a thermoplastic foamed resin composition containing the thermoplastic resin and the inorganic substance powder in a mass ratio of 50:50 to 10:90 is shown. ..

In another aspect of the thermoplastic foamed resin composition according to the present invention, the polypropylene (A) having the long chain branched structure has an isotactic triad fraction (mm) measured by ¹³ C-NMR of 90%. A thermoplastic foamed resin composition which is polypropylene having a long-chain branched structure as described above is shown.

In another aspect of the thermoplastic foamed resin composition according to the present invention, the polypropylene (A) having the long-chain branched structure has a melt flow rate (230° C.) of 1.0 to 10.0 g/10 minutes. , A thermoplastic foamed resin composition which is polypropylene having a long-chain branched structure having a melt tension (230° C.) of 3.5 to 30.0 g.

In another aspect of the thermoplastic foamed resin composition according to the present invention, the polypropylene (B) having no long chain branching structure has a melt flow rate (230°C) of 0.3 to 50.0 g/10 minutes. The thermoplastic foamed resin composition is polypropylene.

In still another aspect of the thermoplastic foamed resin composition according to the present invention, there is shown a thermoplastic foamed resin composition in which the inorganic substance powder has an average particle diameter of 0.1 μm or more and 50.0 μm or less.

In still another embodiment of the thermoplastic foamed resin composition according to the present invention, a thermoplastic foamed resin composition in which the inorganic substance powder is calcium carbonate is further shown.

In one aspect of the thermoplastic foaming resin composition according to the present invention, there is shown a thermoplastic foaming resin composition in which the inorganic substance powder is heavy calcium carbonate.

In one aspect of the thermoplastic foaming resin composition according to the present invention, the chemical foaming agent is a group consisting of hydrogen carbonate, carbonate, nitrite, water or crystal water-containing inorganic substance, water azo compound and nitroso compound. A thermoplastic foam resin composition that is at least one selected is shown.

In a preferable embodiment of the thermoplastic foaming resin composition according to the present invention, there is shown a thermoplastic foaming resin composition in which the chemical foaming agent is sodium hydrogen carbonate.

In a further preferred aspect of the thermoplastic foamed resin composition according to the present invention, the thermoplastic foamed resin composition contains the sodium hydrogen carbonate in an amount of 1.00 to 10.00 mass% with respect to the total mass of the composition. Things are shown.

The present invention which solves the above-mentioned problems is a molded product comprising the above thermoplastic foamed resin composition.

In one aspect of the molded product according to the present invention, a molded product having an apparent density of 1.3 to 0.8 g/cm ³ is shown.

According to the present invention, it is possible to provide a thermoplastic foaming resin composition capable of forming a good foaming structure even if it contains a large amount of inorganic substance powder, and a molded article such as a sheet using the same. .. ADVANTAGE OF THE INVENTION According to this invention, even if it contains many inorganic substance powders, the thermoplastic foamed resin composition which has good drawdown characteristics at the time of heat melting, resin spreadability, and can be shape|molded in various forms with favorable characteristics. , And a molded product using the same. The present invention can further provide a thermoplastic foamed resin composition having excellent heat resistance and flame retardancy, and a molded article using the same.

It is drawing which shows the shape of the molded product shape|molded in the Example.

Hereinafter, the present invention will be described in detail based on embodiments.

<Thermoplastic foamed resin composition>
The thermoplastic foamed resin composition of the present invention contains at least a thermoplastic resin, an inorganic substance powder and a chemical foaming agent. As the thermoplastic resin, a propylene-based polymer (B having no long chain branching structure) is used. ) And a propylene-based polymer (A) having a long-chain branched structure at a specific ratio described below. Hereinafter, each component constituting the thermoplastic foamed resin composition according to the present invention will be described in detail.

<<Propylene Polymer Having Long Chain Branched Structure>>
The thermoplastic foamed resin composition according to the present invention contains a propylene-based polymer (A) having a long chain branched structure as one component constituting the thermoplastic resin.
In the present specification, the “propylene polymer having a long chain branch structure” or “polypropylene having a long chain branch structure” means a propylene polymer or polypropylene having a structure having a polypropylene chain branched from a polypropylene main chain skeleton. Say That is, the "long chain branch" means that a branch is formed in the polymer main chain by polymerizing the monomer, and a short chain derived from a monomer forming the main chain such as a methyl group in a propylene polymer. It does not include chain branching. In the present specification, more specifically, “long-chain branch” refers to a propylene-based polymer residue having 5 or more carbon atoms branched from the main chain of the propylene-based polymer. A branch having 5 or more carbon atoms and a branch having 4 or less carbon atoms can be distinguished by the difference in the peak position of the branched carbon (Macromol. chem. physs. 2003, Vol. 204, page 1738). In addition, the related description part in this document is taken in this specification by the said relationship.
On the other hand, the polypropylene main chain skeleton is a linear polypropylene that may have a short chain branch.

Having a long chain branch in polypropylene is a method based on a rheological property of a resin, for example, a method for calculating a branching index g′ using a relationship between a molecular weight and a viscosity by a general analysis method such as intrinsic viscosity, ¹³ C -It can be confirmed by a method using NMR.

(Branching index g')
The branching index g'is known as a direct index for long chain branching. The detailed description is given in “Development in Polymer Characterization-4” (JV Dawkins ed. Applied Science Publishers, 1983), and the definition of the branching index g′ is as follows.

Branch index g′=[η] _br /[η] _lin
[Η] _br : Intrinsic viscosity of polymer (br) having long-chain branched structure [η] _lin : Intrinsic viscosity of linear polymer having the same molecular weight as polymer (br)

As is clear from the above definition, when the branching index g′ takes a value smaller than 1, it is determined that a long-chain branched structure exists, and the value of the branching index g′ becomes smaller as the long-chain branched structure increases. ..

The branching index g'can be obtained as a function of absolute molecular weight Mabs by using gel permeation chromatography (GPC) with a light scatterometer and a viscometer in the detector. The method for measuring the branching index g'is described in detail in JP-A-2005-40213, but it can be measured, for example, according to the following.

[Measuring method]
GPC: Alliance GPCV2000 (Waters)
Detector: Described in order of connection Multi-angle laser light scattering detector (MALLS): DAWN-E (Wyatt Technology)
Differential refractometer (RI): GPC attached Viscometer (Viscometer): GPC attached Mobile phase solvent: 1,2,4-trichlorobenzene (added at a concentration of 0.5 mg/mL)
Mobile phase flow rate: 1 mL/min Column: Tosoh GMHHR-H(S) Two HTs connected Sample injection part temperature: 140°C
Column temperature: 140℃
Detector temperature: All 140 ℃
Sample concentration: 1 mg/mL
Injection volume (sample loop volume): 0.2175 mL

[analysis method]
In order to obtain the absolute molecular weight (Mabs), the root mean square radius of gyration (Rg), and the intrinsic viscosity ([η]) obtained from Viscometer obtained from the multi-angle laser light scattering detector (MALLS), the data processing attached to MALLS was processed. The calculation is performed using software ASTRA (version 4.73.04) with reference to the following documents.

Reference: "Developments in Polymer Characterization-4" (JV Dawkins ed. Applied Science Publishers, 1983. Chapter 1).
Polymer, 45, 6495-6505 (2004).
Macromolecules, 33, 2424-2436 (2000).
Macromolecules, 33, 6945-6952 (2000).
(Descriptions of relevant parts of these documents are incorporated herein by their association.)

The propylene-based polymer having a long-chain branched structure used in the present invention has a branching index g′ of 0.30 or more and less than 1.00 when the absolute molecular weight Mabs determined by light scattering is 1,000,000. It is more preferably 0.55 or more and 0.98 or less, still more preferably 0.75 or more and 0.96 or less, and most preferably 0.78 or more and 0.95 or less.

The propylene-based polymer (A) having a long-chain branch is considered to have a comb-shaped chain as a molecular structure, and when g′ is less than 0.30, the number of main chains is small and the ratio of side chains is extremely large. As a result, the melt tension may not be sufficient. On the other hand, when g'is 1.00, this means that there is no branching, and even if it is blended with the propylene-based polymer (B) which does not have a long chain branching structure described later, it is a draw. This is because down characteristics and resin spreadability cannot be improved. When the branching index g'is in the range of 0.55 or more and 0.98 or less, more preferably 0.75 or more and 0.96 or less, and particularly 0.78 or more and 0.95 or less, sufficient melt tension is exhibited. On the other hand, since a problem such as gelation does not occur, it reduces the moldability and processability of the thermoplastic foamed resin composition when blended with a propylene polymer (B) having no long-chain branch described below at a predetermined ratio. Improves the drawdown characteristics and resin spreadability better. Therefore, when performing foam molding using the foamed resin composition, it is possible to effectively suppress the occurrence of a phenomenon in which bubbles grow too much and are connected to an adjacent cell, and a molded article having a good foam structure. Can be obtained. Further, since a good foamed structure can be formed, excellent surface quality and mechanical characteristics are exhibited without deterioration of surface quality such as swirl marks and deterioration of mechanical characteristics caused by cell breakage.

( ¹³ C-NMR)
Furthermore, ¹³ C-NMR can distinguish the short-chain branched structure and the long-chain branched structure, as described above. Macromol. Chem. Phys. 2003, vol. A detailed description is given in 204 and 1738, but it is as follows.
The propylene-based polymer (A) having a long chain branched structure has, for example, a specific branched structure represented by the following structural formula (1). In Structural Formula (1), C _a , C _b , and C _c represent a methylene carbon adjacent to the branched carbon, C _br represents a methine carbon at the base of the branched chain, and P ¹ , P ² , and P ³ represent , A propylene polymer residue is shown. In addition, P ¹ , P ² , and P ³ may themselves contain a branched carbon (C _br ) different from the C _br described in the structural formula (1).

Such a branched structure is identified by ¹³ C-NMR analysis. The attribution of each peak is described in Macromolecules, Vol. 35, No. 10. 2002, pages 3839-3842 can be referred to. That is, one at each of 43.9 to 44.1 ppm, 44.5 to 44.7 ppm, and 44.7 to 44.9 ppm, a total of three methylene carbons (C _a , C _b , and C _c ), were observed, Methine carbon (C _br ) is observed at 31.5-31.7 ppm. Hereinafter, the methine carbon observed at 31.5 to 31.7 ppm may be abbreviated as branched methine carbon (C _br ).
Three methylene carbons close to the branched methyne carbon C _br has it is a feature observed is divided into three non-equivalent to the diastereotopic.

Such a branched chain assigned by ¹³ C-NMR indicates a propylene-based polymer residue having 5 or more carbon atoms branched from the main chain of the propylene-based polymer, and the branch having 4 or less carbon atoms is branched. Since it can be distinguished by the difference in the peak position of carbon, the presence or absence of the long-chain branched structure can be determined by confirming the peak of this branched methine carbon.
The ¹³ C-NMR measuring method in this specification is as follows.

[ ¹³ C-NMR measurement method]
An NMR sample having an inner diameter of 10 mm was prepared by adding 200 mg of a sample to 2.4 ml of o-dichlorobenzene/benzene deuterated bromide (C ₆ D ₅ Br)=4/1 (volume ratio) and hexamethyldisiloxane which is a chemical shift reference substance. Put in a tube to dissolve and perform ¹³ C-NMR measurement.
^{The 13} C-NMR measurement is performed using an AV400M type NMR apparatus manufactured by Bruker BioSpin Co., Ltd. equipped with a cryoprobe having a diameter of 10 mm.
The measurement is performed at a sample temperature of 120° C. by the complete proton decoupling method. Other conditions are as follows.
Pulse angle: 90°
Pulse interval: 4 seconds Accumulation number: 20000 Chemical shift was set with the peak of methyl carbon of hexamethyldisiloxane as 1.98 ppm, and chemical shifts of peaks due to other carbons were based on this.
The amount of long chain branching can be calculated using the peak near 44 ppm.

The polypropylene polymer having a long chain branch preferably has a long chain branch amount of 0.01/1000 total propylene or more, which is quantified from a peak at around 44 ppm in a ¹³ C-NMR spectrum, and more preferably 0. 0.03/1000 total propylene or more, more preferably 0.05/1000 total propylene or more. It is preferably 1.00 pieces/1000 total propylene or less, more preferably 0.50 pieces/1000 total propylene or less, and further preferably 0.30 pieces/1000 total propylene or less. Within this range, a sufficient melt tension is exhibited, but the problem of gelation does not occur. Therefore, when blended with a propylene polymer (B) having no long-chain branch described below in a predetermined ratio, the thermoplasticity is improved. The drawdown characteristics and the resin spreadability can be better improved without lowering the moldability and processability of the foamed resin composition, and a good foamed structure can be formed during foam molding such as injection molding.

Furthermore, as the propylene unit of the propylene-based polymer (A) having the long-chain branched structure, from the viewpoint of improving the mechanical properties such as heat resistance and viscoelasticity of the thermoplastic composition according to the present invention, It is preferable to have a structure with high stereoregularity. Specifically, the isotactic triad fraction (mm) obtained by ¹³ C-NMR measurement (that is, the mm fraction of three consecutive propylene units) is a sufficiently high value, specifically 90.0%. It is preferable to have the above high stereoregularity.

Here, the mm fraction refers to three consecutive propylene units in which the direction of the methyl branch in each one unit is the same direction when considering any three consecutive propylene units constituting the polypropylene chain as one unit. It is a ratio and is a value indicating to what degree the three-dimensional structure of the methyl group in the molecular chain is isotactically controlled.

The three continuous propylene units can be roughly classified into three types represented by the formulas (3a) to (3c) described later, and the mm fraction is {the number of units of the following formula (3a)}/{the following formula ( 3a) the number of units+the number of units of the following formula (3b)+the number of units of the following formula (3c)}×100, and this value is defined as the propylene polymer (A) having a long chain branch and From the viewpoint of mechanical properties such as heat resistance and viscoelasticity of the composition containing the same, 90.0% or more, more preferably 91.0% or more, further preferably 93.0% or more, further preferably 95.0% or more. Particularly preferred. Further, the upper limit is 100.0%, but usually, from the viewpoint of the difficulty in product manufacturing management and the resulting cost, 99.8% or less, more preferably 99.5% or less, and further preferably 99.0%. The following is even more preferable.

The mm fraction of three consecutive propylene units can be calculated using, for example, the result of ¹³ C-NMR measurement under the same conditions as in the case of the analysis of the branched structure in ¹³ C-NMR described above. In this case, the preparation condition of the sample and the measurement condition of ¹³ C-NMR are not particularly limited as long as the propylene unit can be suitably quantified. For example, 390 mg of the sample is used as an o-dichlorobenzene/deuterated odor. Benzene (C ₆ D ₅ Br)=4/1 (volume ratio) 2.6 ml and hexamethyldisiloxane, which is a reference substance for chemical shift, were put into an NMR sample tube having an inner diameter of 10 mm and dissolved, and a known spectrometer was used Then, ¹³ C-NMR measurement is performed.
Pulse angle: 90°
Pulse interval: 15 seconds Resonance frequency: 100 MHz or more Accumulation frequency: 128 times or more Observation area: -20 ppm to 179 ppm

The attribution of each peak is as described in Macromolecules, Vol. 35, No. 10. 2002, pages 3839-3842 can be referred to.

Three types of three consecutive propylene units constituting the propylene-based polymer molecule are represented by the following formulas (3a) to (3c). The following formula (3a) represents the mm structure, the following formula (3b) represents the mr structure, and the following formula (3c) represents the rr structure.

The ¹³ C-NMR measurement result used in the mm fraction of three consecutive propylene units is specifically the methyl of central propylene in the three consecutive propylene units represented by the following formulas (3a) to (3c). It is the result of having quantified the amount of methyl groups using the peak of carbon originating in a group.
The chemical shifts of the three types of methyl groups are as follows.
mm: around 24.3 ppm to 21.1 ppm mr: around 21.2 ppm to 20.5 ppm rr: around 20.5 ppm to 19.8 ppm

The chemical shift ranges of the three types of methyl groups of interest are approximately the above chemical shift ranges. Although it may change slightly depending on the molecular weight and the like, it is easy to identify the signal derived from the methyl group of interest.

Furthermore, the propylene-based polymer (A) having the long-chain branched structure has a melt flow rate measured at a temperature of 230° C. and a load of 2.16 Kg according to JIS K7210-1:2014 (ISO 1133-1:2011). The (MFR) is preferably 1.0 to 10.0 g/10 minutes. It is preferably 1.0 to 3.0 g/10 minutes, more preferably 1.0 to 2.5 g/10 minutes.

When the MFR of the propylene-based polymer (A) having a long chain branch is within the above range, the thermoplastic foamed resin composition containing the same may cause a significant decrease in the fluidity and a decrease in the processability. On the other hand, by adding a predetermined amount to the propylene-based polymer (B) having no long-chain branch described below, it is possible to improve the heat resistance and stretch resistance of the obtained foamed molded product in a predetermined temperature range. ..

Further, the propylene-based polymer (A) having the long-chain branched structure has a melt tension at a temperature of 230° C. of 5 to 30 g, more preferably 10 to 30 g, and further preferably 14 to 30 g.
When the melt tension of the propylene-based polymer (A) having a long chain branch is within the above range, it is possible to maintain a good closed cell structure during foam molding using a thermoplastic foaming resin composition containing the same. As a result, it is possible to obtain a molded product having excellent foamed structure, surface quality, mechanical properties and the like.

The melt tension in the present invention is a value measured under the following conditions.

[Measurement condition]
Measuring device: Toyo Seiki Seisakusho Co., Ltd. Capillograph 1B
Capillary: diameter 2.0 mm, length 40 mm
Cylinder diameter: 9.55 mm
Cylinder extrusion rate: 20 mm/min Take-up speed: 4.0 m/min (However, when the melt tension is too high and the resin breaks, lower the take-up speed and measure at the highest take-off speed.)
Temperature: 230 ℃

Further, the propylene-based polymer (A) having the long-chain branched structure preferably has a melt tension value and the melt flow rate (MFR) value that satisfy the following conditions.
log(melt tension)≧−0.9×log(MFR)+0.7, or 30≧melt tension≧15
When the melt tension satisfies this condition, the propylene-based polymer (B) having no long-chain branched structure described below is blended with the propylene-based polymer (A) having the long-chain branched structure to obtain a resin composition. It is possible to further improve the heat resistance when the molded product as described above passes through a device having a heat setting step, while maintaining good workability such as spreadability.
In addition, the following conditions:
log(melt tension)≧−0.9×log(MFR)+0.9, or 30≧melt tension≧15
More preferably, the following conditions are satisfied:
log(melt tension)≧−0.9×log(MFR)+1.1, or 30≧melt tension≧15
It is more preferable to satisfy.

Generally, the propylene-based polymer (A) having a long-chain branched structure is produced by a method of introducing a branched structure by modification using radiation or peroxide, a method of two-step polymerization, or a method of adding a small amount of diene. , A metallocene catalyst is used to produce a propylene macromer having a vinyl structure at the end by a specific complex and specific polymerization conditions in the first polymerization step (macromer synthesis step), and then the second polymerization step (macromer synthesis step). In the copolymerization step), a method of performing a macromer copolymerization method of forming a long-chain branched structure by copolymerizing with propylene under a specific catalyst and specific polymerization conditions is known. The metallocene catalyst used in the macromer copolymerization method is different from the simple non-bridged metallocene catalyst used in the synthesis of linear polypropylene, and is not particularly limited to bridged metallocenes and half metallocenes. The metallocene complex of is used as a highly selective catalyst.

The method for producing the propylene-based polymer (A) having a long-chain branched structure used in the present invention is particularly limited as long as the propylene-based polymer (A) having a long-chain branched structure has the above-mentioned predetermined properties. However, the manufacturing method may be any one. However, since it is desirable to have a structure having higher stereoregularity as described above, those synthesized by the macromer copolymerization method using a metallocene catalyst can be preferably exemplified. A synthetic method in which polymerization is carried out using such a specific metallocene catalyst is described in detail in, for example, JP-A-2009-299025.

As an example of a preferable method for producing a propylene-based polymer having a long-chain branched structure, a method for producing a propylene-based polymer using the following catalyst components (K), (L) and (M) as a propylene polymerization catalyst can be mentioned. ..
(K): at least one component [K-1] which is a compound represented by the following general formula (k1) and at least one component [K-2] which is a compound represented by the following general formula (k2). One type, two or more types of transition metal compounds of Group 4 of the periodic table;
(L): ion-exchange layered silicate; and (M): organoaluminum compound.

Hereinafter, the catalyst components (K), (L) and (M) will be described in detail.

・Catalyst component (K)
(I) Component [K-1]: compound represented by the following general formula (k1)

[In the general formula (k1), R ¹ and R ² each independently represent a heterocyclic group containing nitrogen, oxygen or sulfur having 4 to 16 carbon atoms. R ³ and R ⁴ may each independently contain halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a plurality of hetero elements selected from these, and have 6 to 16 carbon atoms. It represents an aryl group, a heterocyclic group containing 6 to 16 carbon atoms, nitrogen, oxygen or sulfur. Further, X ¹ and Y ¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, or a halogenated group having 1 to 20 carbon atoms. Represents a hydrocarbon group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, Q ¹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, It represents a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms. ]

The heterocyclic group containing nitrogen, oxygen or sulfur having 4 to 16 carbon atoms of R ¹ and R ² is preferably a 2-furyl group, a substituted 2-furyl group, a substituted 2-thienyl group, It is a substituted 2-furfuryl group, and more preferably a substituted 2-furyl group.
Further, as the substituent of the substituted 2-furyl group, the substituted 2-thienyl group, and the substituted 2-furfuryl group, a methyl group, an ethyl group, an alkyl group having 1 to 6 carbon atoms such as a propyl group, Examples thereof include a halogen atom such as a fluorine atom and a chlorine atom, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, and a trialkylsilyl group. Of these, a methyl group and a trimethylsilyl group are preferable, and a methyl group is particularly preferable.
Further, R ¹ and R ² are particularly preferably a 2-(5-methyl)-furyl group. Further, it is preferable that R ¹ and R ² are the same as each other.
The above R ³ and R ⁴ may contain halogen, silicon, oxygen, sulfur, nitrogen, boron, phosphorus, or a plurality of hetero elements having 6 to 16 carbon atoms, or a plurality of hetero elements selected from these. As the aryl group, within the range of 6 to 16 carbon atoms, one or more hydrocarbon groups having 1 to 6 carbon atoms, silicon-containing hydrocarbon groups having 1 to 6 carbon atoms, and carbon atoms on the aryl cyclic skeleton. It may have 1 to 6 halogen-containing hydrocarbon groups as a substituent.

As R ³ and R ⁴ , at least one is preferably a phenyl group, a 4-methylphenyl group, a 4-i-propylphenyl group, a 4-t-butylphenyl group, a 4-trimethylsilylphenyl group, 2,3-dimethyl. Phenyl group, 3,5-di-t-butylphenyl group, 4-phenyl-phenyl group, chlorophenyl group, naphthyl group, or phenanthryl group, more preferably phenyl group, 4-i-propylphenyl group, 4- t-butylphenyl group, 4-trimethylsilylphenyl group, and 4-chlorophenyl group. Further, it is preferable that R3 and R4 are the same.

In the general formula (k1), X ¹ and Y ¹ are auxiliary ligands, which react with the cocatalyst of the catalyst component (L) to form an active metallocene having olefin polymerization ability. Therefore, as long as this object is achieved, X ¹ and Y ¹ are not limited in the kind of ligand, and each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms. , A silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group or a nitrogen-containing hydrocarbon having 1 to 20 carbon atoms Indicates a group.
Further, in the general formula (k1), Q ¹ may have a divalent hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms, which bonds two five-membered rings. It represents either a good silylene group or a germylene group. When two hydrocarbon groups are present on the silylene group or germylene group, they may be bonded to each other to form a ring structure.

Specific examples of Q ¹ include alkylene groups such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene; arylalkylene groups such as diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, di( alkylsilylene groups such as n-propyl)silylene, di(i-propyl)silylene and di(cyclohexyl)silylene, (alkyl)(aryl)silylene groups such as methyl(phenyl)silylene; arylsilylene groups such as diphenylsilylene; tetra Alkyloligosilylene group such as methyldisilylene; Germylene group; Alkylgermylene group obtained by substituting germanium for silicon of silylene group having a divalent hydrocarbon group having 1 to 20 carbon atoms; (alkyl)(aryl)germylene Group; an arylgermylene group and the like can be mentioned.

Among these, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms is preferable, and an alkylsilylene group and an alkylgermylene group are particularly preferable.

Specific examples of the compound represented by the above general formula (k1) include dichloro[1,1′-dimethylsilylenebis{2-(2-furyl)-4-phenyl-indenyl}]hafnium and dichloro[1, 1'-Dimethylsilylenebis{2-(2-thienyl)-4-phenyl-indenyl}] hafnium, dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-phenyl -Indenyl}]hafnium, dichloro[1,1'-diphenylsilylenebis{2-(5-methyl-2-furyl)-4-phenyl-indenyl}]hafnium, dichloro[1,1'-dimethylgermylenebis{ 2-(5-Methyl-2-furyl)-4-phenyl-indenyl}]hafnium, dichloro[1,1′-dimethylgermylenebis{2-(5-methyl-2-thienyl)-4-phenyl-indenyl }] Hafnium, dichloro[1,1′-dimethylsilylenebis{2-(5-t-butyl-2-furyl)-4-phenyl-indenyl}]hafnium, dichloro[1,1′-dimethylsilylenebis{2 -(5-Trimethylsilyl-2-furyl)-4-phenyl-indenyl}]hafnium, dichloro[1,1'-dimethylsilylenebis{2-(5-phenyl-2-furyl)-4-phenyl-indenyl}] Hafnium, dichloro[1,1'-dimethylsilylenebis{2-(4,5-dimethyl-2-furyl)-4-phenyl-indenyl}] hafnium dichloride, dichloro[1,1'-dimethylsilylenebis{2- (2-benzofuryl)-4-phenyl-indenyl}] hafnium, dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-methylphenyl)-indenyl}] Hafnium, dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-ipropylphenyl)-indenyl}] hafnium, dichloro[1,1'-dimethylsilylenebis {2-(5-Methyl-2-furyl)-4-(4-trimethylsilylphenyl)-indenyl}]hafnium, dichloro[1,1′-dimethylsilylenebis{2-(2-furfuryl)-4-phenyl- Indenyl}]hafnium, dichloro[1,1′-dimethylsilylene bis{2-(5-methyl-2-furyl)-4-(4-chlorophenyl)-indenyl}]hafnium, dichloro[1,1′-dimethylsilylene Screw{ 2-(5-Methyl-2-furyl)-4-(4-fluorophenyl)-indenyl}]hafnium, dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4 -(4-Trifluoromethylphenyl)-indenyl}]hafnium, dichloro[1,1'-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-t-butylphenyl)-indenyl }] Hafnium, dichloro[1,1′-dimethylsilylenebis{2-(2-furyl)-4-(1-naphthyl)-indenyl}]hafnium, dichloro[1,1′-dimethylsilylenebis{2-( 2-furyl)-4-(2-naphthyl)-indenyl}]hafnium, dichloro[1,1′-dimethylsilylenebis{2-(2-furyl)-4-(2-phenanthryl)-indenyl}]hafnium, Dichloro[1,1'-dimethylsilylenebis{2-(2-furyl)-4-(9-phenanthryl)-indenyl}]hafnium, dichloro[1,1'-dimethylsilylenebis{2-(5-methyl- 2-furyl)-4-(1-naphthyl)-indenyl}]hafnium, dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(2-naphthyl)-indenyl }] Hafnium, dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(2-phenanthryl)-indenyl}]hafnium, dichloro[1,1′-dimethylsilylenebis {2-(5-Methyl-2-furyl)-4-(9-phenanthryl)-indenyl}] hafnium, dichloro[1,1′-dimethylsilylenebis{2-(5-t-butyl-2-furyl) -4-(1-Naphtyl)-indenyl}] hafnium, dichloro[1,1'-dimethylsilylenebis{2-(5-t-butyl-2-furyl)-4-(2-naphthyl)-indenyl}] Hafnium, dichloro[1,1'-dimethylsilylenebis{2-(5-t-butyl-2-furyl)-4-(2-phenanthryl)-indenyl}] hafnium, dichloro[1,1'-dimethylsilylenebis Examples include {2-(5-t-butyl-2-furyl)-4-(9-phenanthryl)-indenyl}]hafnium.

(Ii) Component [K-2]: compound represented by general formula (k2)

[In general formula (k2), R ⁵ and R ⁶ are each independently a hydrocarbon group having 1 to 6 carbon atoms, and R ⁷ and R ⁸ are each independently halogen, silicon, oxygen, An aryl group having 6 to 16 carbon atoms, which may contain sulfur, nitrogen, boron, phosphorus, or a plurality of hetero elements selected from these. X ² and Y ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon having 1 to 20 carbon atoms. Group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, Q2 represents a divalent hydrocarbon group having 1 to 20 carbon atoms, or 1 carbon atom. Represents a silylene group or a germylene group which may have a hydrocarbon group of 20. M is zirconium or hafnium. ]

R ⁵ and R ⁶ are each independently a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl, n-hexyl and the like, preferably methyl. , Ethyl and n-propyl.
Further, each of R ⁷ and R ⁸ independently contains halogen having 6 to 16 carbon atoms, preferably 6 to 12 carbon atoms, silicon, or a plurality of hetero elements selected from these. Is also an aryl group. Preferred examples are phenyl, 3-chlorophenyl, 4-chlorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-i-propylphenyl, 4-t-butylphenyl, 4-trimethylsilylphenyl, 4 -(2-Fluoro-4-biphenylyl), 4-(2-chloro-4-biphenylyl), 1-naphthyl, 2-naphthyl, 4-chloro-2-naphthyl, 3-methyl-4-trimethylsilylphenyl, 3, Examples thereof include 5-dimethyl-4-t-butylphenyl, 3,5-dimethyl-4-trimethylsilylphenyl, and 3,5-dichloro-4-trimethylsilylphenyl.

Further, X ² and Y ² are auxiliary ligands, which react with the promoter of the catalyst component (L) to produce active metallocene having olefin polymerization ability. Therefore, as long as this object is achieved, X ² and Y ² are not limited in the kind of ligand, and each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, Silicon-containing hydrocarbon group having 1 to 20 carbon atoms, halogenated hydrocarbon group having 1 to 20 carbon atoms, oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, amino group or nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms Indicates.

In addition, Q ² is a bonding group that bridges two conjugated five-membered ring ligands, and has a divalent hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms. It is a silylene group which may be substituted or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms, preferably a substituted silylene group or a substituted germylene group. The substituent bonded to silicon or germanium is preferably a hydrocarbon group having 1 to 12 carbon atoms, and two substituents may be linked.

Specific examples of Q2 include methylene, dimethylmethylene, ethylene-1,2-diyl, dimethylsilylene, diethylsilylene, diphenylsilylene, methylphenylsilylene, 9-silafluorene-9,9-diyl, dimethylsilylene, diethyl. Examples thereof include silylene, diphenylsilylene, methylphenylsilylene, 9-silafluorene-9,9-diyl, dimethylgermylene, diethylgermylene, diphenylgermylene and methylphenylgermylene.

Furthermore, M is zirconium or hafnium, preferably hafnium.

Specific examples of the metallocene compound represented by the above general formula (k2) include dichloro{1,1'-dimethylsilylenebis(2-methyl-4-phenyl-4-hydroazulenyl)}hafnium and dichloro[1,1. '-Dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)-4-hydroazurenyl}]hafnium, dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(4-t-butylphenyl) -4-Hydroazurenyl}]hafnium, dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(4-trimethylsilylphenyl)-4-hydroazurenyl}]hafnium, dichloro[1,1'-dimethylsilylenebis{ 2-Methyl-4-(3-chloro-4-t-butylphenyl)-4-hydroazurenyl}]hafnium, dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(3-methyl-4-) t-Butylphenyl)-4-hydroazurenyl}]hafnium, dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(3-chloro-4-trimethylsilylphenyl)-4-hydroazurenyl}]hafnium, dichloro[1. 1,1′-Dimethylsilylenebis{2-methyl-4-(3-methyl-4-trimethylsilylphenyl)-4-hydroazurenyl}]hafnium, dichloro[1,1′-dimethylsilylenebis{2-methyl-4- (1-Naphtyl)-4-hydroazurenyl}]hafnium, dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(2-naphthyl)-4-hydroazulenyl}]hafnium, dichloro[1,1′- Dimethylsilylenebis{2-methyl-4-(4-chloro-2-naphthyl)-4-hydroazurenyl}]hafnium, dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(2-fluoro-4) -Biphenylyl)-4-hydroazurenyl}]hafnium, dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(2-chloro-4-biphenylyl)-4-hydroazulenyl}]hafnium, dichloro[1,1 '-Dimethylsilylenebis{2-methyl-4-(9-phenanthryl)-4-hydroazurenyl}]hafnium, dichloro[1,1'-dimethylsilylenebis{2-ethyl-4-(4-chlorophenyl)-4- Hydroazurenyl}]hafnium, dichloro[1,1′-dimethylsilylenebis{2-n-propyl-4-(3- Chloro-4-trimethylsilylphenyl)-4-hydroazurenyl}]hafnium, dichloro[1,1′-dimethylsilylenebis{2-ethyl-4-(3-chloro-4-t-butylphenyl)-4-hydroazurenyl}] Hafnium, dichloro[1,1'-dimethylsilylenebis{2-ethyl-4-(3-methyl-4-trimethylsilylphenyl)-4-hydroazulenyl}]hafnium, dichloro[1,1'-dimethylgermylenebis{2 -Methyl-4-(2-fluoro-4-biphenylyl)-4-hydroazurenyl}]hafnium, dichloro[1,1'-dimethylgermylenebis{2-methyl-4-(4-t-butylphenyl)-4] -Hydroazurenyl}]hafnium, dichloro[1,1'-(9-silafluorene-9,9-diyl)bis{2-ethyl-4-(4-chlorophenyl)-4-hydroazulenyl}]hafnium, dichloro[1, 1'-Dimethylsilylenebis{2-ethyl-4-(4-chloro-2-naphthyl)-4-hydroazulenyl}]hafnium, dichloro[1,1'-dimethylsilylenebis{2-ethyl-4-(2- Fluoro-4-biphenylyl)-4-hydroazurenyl}]hafnium, dichloro[1,1′-(9-silafluorene-9,9-diyl)bis{2-ethyl-4-(3,5-dichloro-4-) Trimethylsilylphenyl)-4-hydroazurenyl}]hafnium and the like. Further, in the above, a compound in which the central metal is hafnium is described, but a compound in which zirconium is substituted can be similarly exemplified.

(L): Ion-exchange layered silicate An ion-exchange layered silicate (hereinafter sometimes simply referred to as silicate) means that planes formed by ionic bonds and the like are stacked in parallel with each other by a binding force. A silicate compound having a different crystal structure and having exchangeable ions contained therein. Since most silicates are naturally produced mainly as the main component of clay minerals, impurities other than ion-exchange layered silicates (quartz, cristobalite, etc.) are often contained, but even if they are included, Good. Depending on the type, amount, particle size, crystallinity, and dispersion state of these contaminants, it may be preferable to pure silicate or more, and such a complex is also included in the catalyst component (L).
The silicate to be used is not limited to a naturally occurring one, and may be an artificially synthesized one or may include them.

Specific examples of silicates include, for example, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, smectite group such as stevensite, vermiculite group such as vermiculite, mica, illite, sericite, and glaucolite Examples include mica, attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, and chlorite.
The silicate is preferably a silicate having a 2:1 type structure as a main component, more preferably a smectite group, and particularly preferably montmorillonite. The type of the interlayer cation is not particularly limited, but a silicate containing an alkali metal or an alkaline earth metal as a main component of the interlayer cation is preferable from the viewpoint of being relatively easily and inexpensively available as an industrial raw material.

The ion-exchange layered silicate (L) can be used as it is without any particular treatment, but it is preferably subjected to a chemical treatment. Here, the chemical treatment of the ion-exchange layered silicate may be either a surface treatment for removing impurities adhering to the surface or a treatment for affecting the structure of clay. Treatment, alkali treatment, salt treatment, organic matter treatment and the like. Further, these ion-exchange layered silicates usually contain adsorbed water and interlayer water, but it is preferable to remove the adsorbed water and interlayer water and use them as the catalyst component (L). Particularly preferred as the catalyst component (N) is an ion-exchange layered silicate having a water content of 3% by mass or less, which is obtained by performing a salt treatment and/or an acid treatment.

The ion-exchange layered silicate can be treated with a catalyst component (M) of an organoaluminum compound described below before forming a catalyst or using it as a catalyst. The amount of the catalyst component (M) used with respect to 1 g of the ion-exchange layered silicate is not limited, but is usually 20.0 mmol or less, preferably 0.5 mmol or more and 10.0 mmol or less. The treatment temperature and time are not limited, and the treatment temperature is usually 0° C. or higher and 70° C. or lower, and the treatment time is 10 minutes or longer and 3 hours or shorter. It is also possible and preferable to wash after the treatment. As the solvent, the same hydrocarbon solvent as the solvent used in the pre-polymerization or slurry polymerization described later is used.

(M): Organoaluminum Compound The organoaluminum compound used as the catalyst component (M) has the general formula:
Compounds represented by ^{_{(AlR 9 q Z 3-q}} ) p are preferred.
In the formula, R ⁹ represents a hydrocarbon group having 1 to 20 carbon atoms, and Z represents a halogen, a hydrogen atom, an alkoxy group or an amino group. q represents an integer of 1 to 3, and p represents an integer of 1 to 2.
R ⁹ is preferably an alkyl group, and Z is chlorine when it is a halogen, an alkoxy group having 1 to 8 carbon atoms when it is an alkoxy group, and a carbon atom of 1 when it is an amino group. -8 amino groups are preferred.
The compounds represented by this formula can be used alone, in combination of two or more, or in combination.

Specific examples of the organic aluminum compound include trimethyl aluminum, triethyl aluminum, trinormal propyl aluminum, trinormal butyl aluminum, triisobutyl aluminum, trinormal hexyl aluminum, trinormal octyl aluminum, trinormal decyl aluminum, diethyl aluminum chloride, diethyl aluminum. Examples thereof include sesquichloride, diethyl aluminum hydride, diethyl aluminum ethoxide, diethyl aluminum dimethylamide, diisobutyl aluminum hydride, diisobutyl aluminum chloride and the like.

The catalyst can be formed by contacting the above catalyst components (K) to (M) in the (preliminary) polymerization tank at the same time or continuously, or at once or plural times.
The contact of each component is usually carried out in an aliphatic hydrocarbon or aromatic hydrocarbon solvent. The contact temperature is not particularly limited, but it is preferably carried out between -20°C and 150°C. The order of contact may be any combination that is purposeful, but the particularly preferable ones will be shown below for each component.
When the catalyst component (L) is used, before contacting the catalyst component (K) with the catalyst component (L), the catalyst component (K), or the catalyst component (L), or the catalyst component (K) and the catalyst Contacting both the component (L) with the catalyst component (M), or contacting the catalyst component (K) with the catalyst component (L) and at the same time contacting the catalyst component (M), or the catalyst component Although it is possible to contact the catalyst component (M) after contacting (K) with the catalyst component (L), it is preferable to contact the catalyst before contacting the catalyst component (K) with the catalyst component (L). It is a method of contacting with any of the components (M).
Further, after bringing the respective components into contact with each other, it is possible to wash with an aliphatic hydrocarbon or aromatic hydrocarbon solvent.

The amounts of the catalyst components (K), (L) and (M) used are arbitrary. For example, the amount of the catalyst component (K) used with respect to the catalyst component (L) is preferably 0.1 μmol to 1000.0 μmol, and particularly preferably 0.5 μmol to 500.0 μmol with respect to 1 g of the catalyst component (L). It is a range. Further, the amount of the catalyst component (M) relative to the catalyst component (K) is preferably 0.01 to 5.00×10 ⁶ , particularly preferably 0.1 to 1.0×10 ⁴ in terms of a transition metal molar ratio. It is preferably within the range.

The proportion of the component [K-1] (compound represented by the general formula (k1)) and the component [K-2] (compound represented by the general formula (k2)) is such that polypropylene having a long chain branch is used. The molar ratio of the transition metal of [K-1] to the total amount of the respective components [K-1] and [K-2] is preferably 0. It is 30 or more and 0.99 or less.
By changing this ratio, it is possible to adjust the balance between the melt property and the catalytic activity. That is, a low molecular weight terminal vinyl macromer is produced from the component [K-1], and a high molecular weight product obtained by copolymerizing a part of the macromer is produced from the component [K-2]. Therefore, by changing the ratio of the component [K-1], the average molecular weight of the produced polymer, the molecular weight distribution, the deviation of the molecular weight distribution toward the high molecular weight side, the extremely high molecular weight component, the branch (amount, length, The distribution) can be controlled, and thereby the melt physical properties such as branching index g′, melt tension, and spreadability can be controlled.

In order to produce the polypropylene resin (A) having a long chain branch, the molar ratio is preferably 0.30 or more, more preferably 0.40 or more, and further preferably 0.50 or more. .. Further, the upper limit is preferably 0.99 or less, and preferably 0.95 or less, and more preferably in order to efficiently obtain a polypropylene resin (A) having a long chain branch with high catalytic activity. The range is 0.90 or less.
Further, by using the component [K-1] within the above range, it is possible to adjust the balance between the average molecular weight and the catalytic activity with respect to the hydrogen amount.

The catalyst is preferably subjected to a prepolymerization treatment, which comprises contacting it with an olefin and polymerizing in a small amount. By performing the prepolymerization treatment, it is possible to prevent the formation of gel during the main polymerization.

The olefin used in the prepolymerization is not particularly limited, but propylene, ethylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, Styrene etc. can be illustrated. The olefin feed method may be any method such as a feed method for maintaining the olefin in the reaction tank at a constant rate or in a constant pressure state, a combination thereof, or a stepwise change.
The prepolymerization temperature and time are not particularly limited, but are preferably in the range of -20°C to 100°C and 5 minutes to 24 hours, respectively. The amount of the prepolymerization is preferably 0.01 to 100, more preferably 0.1 to 50 in terms of the weight ratio of the prepolymerized polymer to the catalyst component (K). Further, the catalyst component (M) can be added or added during the prepolymerization. It is also possible to wash after completion of the preliminary polymerization.
In addition, a method in which a polymer such as polyethylene or polypropylene or a solid of an inorganic oxide such as silica or titania is allowed to coexist during or after the contact of each of the above components is also possible.

As the polymerization mode, any mode can be adopted as long as the olefin polymerization catalyst containing the catalyst component (K), the catalyst component (L) and the catalyst component (M) is in efficient contact with the monomer.
Specifically, a slurry method using an inert solvent, propylene as a solvent without substantially using an inert solvent, a so-called bulk method, a solution polymerization method or substantially without using a liquid solvent each monomer in a gaseous state A vapor phase method of keeping can be adopted. Further, a method of performing continuous polymerization or batch polymerization is also applied. In addition to single-stage polymerization, it is also possible to carry out multi-stage polymerization of two or more stages.
In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, or toluene is used alone or as a mixture as a polymerization solvent.

The polymerization temperature is usually 0°C or higher and 150°C or lower. In particular, when bulk polymerization is used, the temperature is preferably 40°C or higher, more preferably 50°C or higher. The upper limit is preferably 80°C or lower, more preferably 75°C or lower.
Further, when using gas phase polymerization, the temperature is preferably 40°C or higher, more preferably 50°C or higher. The upper limit is preferably 100°C or lower, more preferably 90°C or lower.
The polymerization pressure is preferably 1.0 MPa or more and 5.0 MPa or less. Particularly when using bulk polymerization, the pressure is preferably 1.5 MPa or more, more preferably 2.0 MPa or more. The upper limit is preferably 4.0 MPa or less, and more preferably 3.5 MPa or less.

Further, when using gas phase polymerization, the pressure is preferably 1.5 MPa or more, more preferably 1.7 MPa or more. The upper limit is preferably 2.5 MPa or less, more preferably 2.3 MPa or less.
Further, as a molecular weight regulator and for the effect of improving the activity, hydrogen is auxiliary in a molar ratio to propylene, preferably in the range of 1.0×10 ⁻⁶ or more and 1.0×10 ⁻² or less. Can be used.

Further, by changing the amount of hydrogen used, in addition to the average molecular weight of the polymer produced, the molecular weight distribution, the bias toward the high molecular weight side of the molecular weight distribution, very high molecular weight component, branching (amount, length, It is possible to control the melt properties which characterize the polypropylene (A) having a long-chain branched structure, such as MFR, branching index, melt tension, and ductility.
Therefore, hydrogen is preferably used in a molar ratio to propylene of 1.0×10 ⁻⁶ or more, preferably 1.0×10 ⁻⁵ or more, and more preferably 1.0×10 ⁻⁴ or more. Is good. Regarding the upper limit, it is preferable to use it at 1.0×10 ⁻² or less, preferably 0.9×10 ⁻² or less, and more preferably 0.8×10 ⁻² or less.

When propylene is polymerized by using the catalyst and the polymerization method exemplified here, one end of the polymer is mainly propenyl by a special chain transfer reaction generally called β-methyl elimination from the active species derived from the catalyst component [M-1]. Shows the structure, so-called macromers are generated. It is considered that this macromer can generate a higher molecular weight and is incorporated into the active species derived from the catalyst component [M-2] having a better copolymerizability, and the macromer copolymerization proceeds. Therefore, the branched structure of the polypropylene resin having a long-chain branched structure to be generated is considered to be mainly comb-shaped chains.
Further, by using the metallocene-based catalyst as described above, it is possible to obtain a structure having high stereoregularity as described above.

Furthermore, commercially available products that can be used as the propylene-based polymer (A) having a long-chain branched structure that can be used in the present invention include various grades of Weimax (trade name) (manufactured by Japan Polypro Corporation), MFX8, MFX6, MFX3, EX8000, EX6000, EX4000, PF814 (trade name) (manufactured by Lyondell Basel), Daploy (trade name) WB140HMS (manufactured by Borealis) and the like can be mentioned.

<<Propylene-based polymer (B) having no long-chain branched structure>>
In the thermoplastic foamed resin composition according to the present invention, a propylene polymer (B) having no long chain branching structure as a base component, together with the above-mentioned propylene polymer (A) having a long chain branching structure. Contains.

In the present specification, the term "propylene-based polymer having no long-chain branched structure" or "polypropylene having no long-chain-branched structure" means a linear propylene-based polymer or a linear polypropylene, or a methyl group. A straight-chain short-chain branched propylene polymer containing a short-chain branch derived from a chain-forming monomer or a straight-chain short-chain branched polypropylene, and more specifically, the above-mentioned "propylene-based polymer having a long-chain branched structure". It is a propylene-based polymer or polypropylene that does not meet the requirements of "combination" or "polypropylene having a long-chain branched structure".

The propylene-based polymer (B) having no such long-chain branched structure is not particularly limited as long as it satisfies the above-mentioned requirements. For example, by using a Ziegler-Natta type catalyst or a magnesium chloride-supported Ziegler-Natta catalyst in the presence of a co-catalyst such as triethylaluminum or diethylaluminum, propylene, or by polymerizing propylene and another α-olefin, The obtained product may be used, or the product may be polymerized using a Kaminsky type catalyst using a metallocene compound.

The stereoregularity of the propylene-based polymer (B) having no long-chain branched structure is not particularly limited, and may be isotactic, syndiotactic, atactic, or a mixed system of any of these ratios. Although not particularly limited, polypropylene having a crystalline isotactic polymer as a main component and an atactic polymer of about 0.5 to 2.0 mol% is used from the viewpoint of industrial availability. Can be done.

However, in order to obtain better moldability and melting characteristics as the thermoplastic foamed resin composition according to the present invention, the propylene-based polymer (B) that does not have a long-chain branched structure as a base is within a certain range. The melt flow rate (230° C.) measured under the same conditions as described above is preferably 0.3 to 50.0 g/10 minutes. It is more preferably 0.3 to 10.0 g/10 minutes, and even more preferably 0.3 to 1.0 g/10 minutes.

In the present invention, the blending of the propylene polymer (A) having a long-chain branched structure described above improves drawdown characteristics, spreadability and the like of the thermoplastic foamed resin composition. The propylene-based polymer (B) having no long-chain branched structure as the base has a melt flow rate of a certain high value so as not to deteriorate the fluidity and processability of the thermoplastic foaming resin composition. Is desirable.

The propylene-based polymer (B) having no long-chain branched structure is preferably a propylene homopolymer, and in this case, although not particularly limited, it may be an isotactic polymer measured by ¹³ C-NMR. The tic triad fraction (mm) is preferably about 90% or more.

In the propylene-based polymer (B) having no long chain branched structure, other α-olefins copolymerizable with propylene include, for example, ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene. , 1-octene, 1-decene, 1-hexene, and the like, among which ethylene, 1-butene and 1-hexene are particularly preferable. The propylene-based polymer (B) having no long-chain branched structure is not particularly limited, but may contain a structural unit derived from a monomer other than propylene in a proportion of less than 15% by mass. However, as described above, it is preferably a homopolymer of propylene.

<<Blending Ratio of Propylene Polymer (B) Having No Long Chain Branching and Propylene Polymer (A) Having Long Chain Branching Structure>>
However, in the thermoplastic composition according to the present invention, the propylene polymer (B) having no long chain branching and the propylene polymer (A) having a long chain branching structure described above have a mass ratio of 80. : 20 to 98:2. When the blending ratio is within this range, the thermoplastic composition containing the inorganic substance powder according to the present invention and the thermoplastic resin has (1) a propylene-based polymer (B) simple substance having no long chain branching; 2) a thermoplastic composition containing a propylene-based polymer (B) having no long-chain branching and an inorganic substance powder; and (3) a propylene-based polymer (B) having no long-chain branching and a long-chain branched structure. Compared with the polypropylene-based polymer blend containing the propylene-based polymer (A), the strength of the breaking point and the maximum elongation at 170° C. to 180° C. were significantly improved, and the thermoplastic foamed resin composition was obtained. When the product contains a large amount of inorganic substance powder and is foamed with a chemical foaming agent to be molded, the drawdown property and spreadability at the time of heating and melting are good, and good foam molding can be performed. Further, by containing the above-mentioned predetermined amount of polypropylene (A) having a long-chain branched structure, the heat resistance and flame retardancy of the molded product are improved.

The mass ratio of the propylene-based polymer (B) having no long chain branching and the propylene-based polymer (A) having a long chain branching structure is more preferably 80:20 to 98:2, It is more preferable that the ratio is 80:20 to 90:10.

≪Other thermoplastics≫
In the thermoplastic foamed resin composition according to the present invention, as the resin component, other than the above-mentioned propylene-based polymer (B) having no long chain branching and the above-mentioned propylene-based polymer (A) having a long chain branching structure. A thermoplastic resin is also contained as long as it does not significantly impair the predetermined effects of the propylene polymer (B) having no long chain branch and the propylene polymer (A) having a long chain branch structure. However, it is desirable that these other thermoplastic resins be about 0 to 30 mass% when the mass of the entire resin component is 100%. That is, when the total weight of the resin components in the thermoplastic foamed resin composition is 100%, the propylene polymer (B) having no long chain branch and the propylene polymer (A having the long chain branch structure) It is desired that the total amount of () be 70% by mass to 100% by mass. Other thermoplastic resins are not particularly limited, but examples thereof include polyolefin resins other than polypropylene (polyethylene, propylene-ethylene copolymer, polybutylene, etc.), biodegradable resins, polyamide resins, polybutylene terephthalate (PBT), polyethylene. Examples thereof include terephthalate (PET).

The polyolefin resin and polyamide resin refer to resins having polyolefin and polyamide as a main chain. More specifically, for example, polyethylene refers to a resin having ethylene as a main chain, and those resins having crystallinity are preferable and copolymers with other monomers may be used.

The biodegradable resin is a resin that is completely consumed by microorganisms in the natural world and is finally decomposed into water and carbon dioxide.
Specific examples thereof include polylactic acid, polycaprolactone, polybutylene succinate, polybutylene adipate, polyethylene succinate, and cellulose ester. Further, the crystalline polymer may be used alone or in combination of two or more, for example, a mixture of polypropylene and polyethylene may be used.

<<Inorganic substance powder>>
The inorganic substance powder that can be blended in the thermoplastic foamed resin composition according to the present invention is not particularly limited, and examples thereof include calcium, magnesium, aluminum, titanium, iron, zinc and other carbonates, sulfates, silicates, Examples thereof include powders of phosphates, borates, oxides, or hydrates thereof. Specific examples include calcium carbonate, magnesium carbonate, zinc oxide, titanium oxide, silica, alumina, and clay. , Talc, kaolin, aluminum hydroxide, magnesium hydroxide, aluminum silicate, magnesium silicate, calcium silicate, aluminum sulfate, magnesium sulfate, calcium sulfate, magnesium phosphate, barium sulfate, silica sand, carbon black, zeolite, molybdenum, Examples thereof include diatomaceous earth, sericite, shirasu, calcium sulfite, sodium sulfate, potassium titanate, bentonite, and graphite. These may be synthetic or derived from natural minerals, and these may be used alone or in combination of two or more.

Further, the shape of the inorganic substance powder is not particularly limited and may be any of particles, flakes, granules, fibers and the like. Further, the particles may have a spherical shape generally obtained by a synthetic method, or may have an irregular shape obtained by crushing a collected natural mineral. ..

As the inorganic substance powder, calcium carbonate, magnesium carbonate, zinc oxide, titanium oxide, silica, alumina, clay, talc, kaolin, aluminum hydroxide, magnesium hydroxide and the like are preferable, and calcium carbonate is particularly preferable. Further, as the calcium carbonate, any of those prepared by a synthetic method, so-called light calcium carbonate, and so-called heavy calcium carbonate obtained by mechanically pulverizing and classifying a natural raw material mainly containing CaCO ₃ such as limestone. It is also possible to combine these, but from the viewpoint of economic efficiency, ground calcium carbonate is preferable.

Further, in order to enhance the dispersibility or reactivity of the inorganic substance powder, the surface of the inorganic substance powder may be modified in advance by a conventional method. Examples of the surface modification method include a physical method such as plasma treatment and a method of chemically treating the surface with a coupling agent or a surfactant. Examples of the coupling agent include silane coupling agents and titanium coupling agents. The surfactant may be anionic, cationic, nonionic or amphoteric, and examples thereof include higher fatty acids, higher fatty acid esters, higher fatty acid amides and higher fatty acid salts.

The inorganic substance powder is preferably particles, and the average particle diameter is preferably 0.1 μm or more and 50.0 μm or less, more preferably 1.0 μm or more and 15.0 μm or less. The average particle size of the inorganic substance powder described in the present specification means a value calculated from the measurement result of the specific surface area by the air permeation method according to JIS M-8511. As the measuring device, for example, a specific surface area measuring device SS-100 type manufactured by Shimadzu Corporation can be preferably used. In particular, it is preferable that the particle size distribution does not include particles having a particle size of 50.0 μm or more. On the other hand, if the particles are too fine, the viscosity when kneaded with the above-mentioned thermoplastic resin increases significantly, which may make it difficult to manufacture a molded product. Therefore, the average particle diameter is preferably 0.5 μm or more.

The average particle diameter of the powdery, flake, or granular inorganic substance powder is preferably 10.0 μm or less, and more preferably 5.0 μm or less.

The average fiber length of the fibrous inorganic substance powder is preferably 3.0 μm or more and 20.0 μm or less. The average fiber diameter is preferably 0.2 μm or more and 1.5 μm or less. The aspect ratio is usually 10 or more and 30 or less. The average fiber length and the average fiber diameter of the fibrous inorganic substance powder are measured by an electron microscope, and the aspect ratio is the ratio of the average fiber length to the average fiber diameter (average fiber length/average fiber diameter). Is.

The ground calcium carbonate contained in the composition of the present invention is not particularly limited as long as it is ground calcium carbonate, and may be optionally surface-treated.
Here, the heavy calcium carbonate is obtained by mechanically crushing and processing natural limestone or the like, and is clearly distinguished from synthetic calcium carbonate produced by a chemical precipitation reaction or the like. The pulverizing method includes a dry method and a wet method, but the dry method is preferable from the viewpoint of economy.

The average particle size of the heavy calcium carbonate is preferably 15.0 μm or less, more preferably 1.0 to 5.0 μm, because the cured product of the composition of the present invention has a better tear strength.
The average particle diameter of the heavy calcium carbonate is a value calculated from the measurement result of the specific surface area by the air permeation method according to JIS M-8511. As a measuring instrument, it is preferable to use a specific surface area measuring device SS-100 type manufactured by Shimadzu Corporation.

The blending ratio (mass %) of the above-mentioned thermoplastic resin contained in the thermoplastic foamed resin composition according to the present invention and the inorganic substance powder is not particularly limited as long as it is a ratio of 50:50 to 10:90, The ratio is preferably 40:60 to 20:80, and more preferably 40:60 to 25:75. In the blending ratio of the thermoplastic resin and the inorganic substance powder, when the proportion of the inorganic substance powder is lower than 50% by mass, a predetermined texture and impact resistance of the thermoplastic foamed resin composition obtained by blending the inorganic substance powder are obtained. This is because physical properties such as properties cannot be obtained, and on the other hand, when the content is higher than 90% by mass, molding processing such as extrusion molding becomes difficult.

In the thermoplastic foamed resin composition according to the present invention, the mass ratio of the propylene-based polymer (B) having no long chain branching excluding the inorganic substance powder and the propylene-based polymer (A) having a long chain branching structure. As for (mass %), a ratio of 80:20 to 98:2 is preferable, and a ratio of 80:20 to 90:10 can be given as a more preferable example.

<< foaming agent >>
The thermoplastic foaming resin composition according to the present invention further contains a chemical foaming agent as a foaming agent.
Generally, as a method for foaming a resin composition, there are a chemical foaming method and a physical foaming method, as is known. Physical foaming is also called "gas foaming" and is a method of containing gas in a material under high pressure. Hydrocarbons, CFCs, etc. are available as physical blowing agents, but the problems of flammability and environmental load of the gas itself have been pointed out. On the other hand, chemical foaming is a method of chemically forming bubbles by the gas generated by the thermal decomposition of the compound added to the resin composition. A chemical foaming agent is used in the present invention in order to obtain a uniform closed cell foam which can be used.

As the chemical foaming agent, as long as it generates gas at a temperature near or above the melting temperature of the thermoplastic resin contained in the thermoplastic foaming resin composition, even an organic thermal decomposition type foaming agent may be an inorganic thermal decomposition agent. The foaming agent may be used without particular limitation, and it is possible to use not only a single type but also a combination of a plurality of types.

Although not particularly limited, examples of the organic thermal decomposition type foaming agent include azo compounds such as azodicarbonamide, metal salts of azodicarboxylic acid (barium azodicarboxylic acid, etc.), azobisisobutyronitrile, N , N'-dinitrosopentamethylenetetramine and other nitroso compounds, hydrazodicarbonamide, 4,4'-oxybis(benzenesulfonylhydrazide), hydrazine derivatives such as toluenesulfonylhydrazide, and semicarbazide compounds such as toluenesulfonylsemicarbazide. ..

The inorganic thermal decomposition type foaming agent is not particularly limited, and examples thereof include ammonium carbonate, sodium carbonate, ammonium hydrogen carbonate, sodium hydrogen carbonate, ammonium nitrite, sodium borohydride, and anhydrous monosodium citrate. Are listed. Further, so-called water foaming using water (steam) can be adopted, and examples of the foaming agent to be used include water, an inorganic substance containing crystal water, and the like.

It is preferable to select an appropriate chemical foaming agent in consideration of the melting temperature, melt viscosity and other physical properties of the thermoplastic resin component in the thermoplastic foaming resin composition. In particular, it is desirable that the thermoplastic resin component and the chemical foaming agent in the expandable thermoplastic resin composition satisfy the following formula (1) in order to maintain moldability in injection foam molding.
T _S <T _D <T _P (1)
T _S : Softening point of thermoplastic resin T _D : Decomposition temperature of chemical foaming agent T _P : Molding temperature

The thermoplastic resin according to the present invention contains polypropylene (B) having no long chain branching and polypropylene (A) having a long chain branching structure in a mass ratio of 80:20 to 98:2. Therefore, it is not particularly limited, but typically, it is preferable that T _S is about 140° C. at the maximum and the molding temperature T _P is about 180 to 210° C., so that Td is 140 to 180° C. What is desirable is. From this point, sodium hydrogen carbonate is particularly preferable as the chemical foaming agent. It is known that sodium hydrogen carbonate gradually decomposes at a temperature of about 50° C., but it is in this temperature range that it is actively decomposed and gas is generated.

Further, sodium hydrogen carbonate is also known as baking soda and is highly safe because it is also widely used as a food additive, and a molded article molded from the expandable thermoplastic resin composition according to the present invention is, for example, a food product. Since it can be used without any problems even for applications such as food packaging that comes into contact with, it is desirable from the viewpoint of safety.

The content of the chemical foaming agent contained in the thermoplastic foamed resin composition according to the present invention is the kind and amount of the thermoplastic resin, the inorganic substance powder, etc. contained in the composition, and the specific gravity of the foam to be obtained. It can be appropriately set depending on the bubble ratio and the like, but is 1.0 to 10.0% by mass, more preferably 2.0 to 6.0% by mass based on the total mass of the thermoplastic foaming resin composition. It is preferable to set it as the range. Within this range, when the thermoplastic foamed resin composition according to the present invention is used, for example, when molding is performed by foaming injection molding or the like, the total amount of gas generated by decomposition of the chemical foaming agent is set to an appropriate value. In addition, it becomes possible to easily obtain a molded product having a desired specific gravity and foaming degree while maintaining the closed cell structure in the molded product.

In addition, in the aspect in which the thermoplastic foaming resin composition according to the present invention contains a foaming agent, a propylene-based polymer (B) having no long chain branching excluding the inorganic substance powder+a propylene-based polymer having a long chain branching structure. As a mass ratio (mass %) of the two components of the combined (A) and the chemical foaming agent, a ratio of 80:20 to 98:2 is more preferable, and a ratio of 80:20 to 90:10 is preferable. , Can be mentioned as a preferable example.

In addition, as a usage mode of the chemical foaming agent, in order to enhance the uniform dispersibility in the foamable thermoplastic resin composition according to the present invention, for example, a small amount of a small amount which becomes a part of the thermoplastic resin blended in the composition is used. A mode in which a so-called masterbatch is prepared by mixing a thermoplastic resin with a high concentration of a chemical foaming agent in advance at a ratio of, for example, 5.0 to 50.0% by mass, and adding the composition to the composition is described. It is also possible to collect. As such a masterbatch foaming agent, a commercially available one may be used.

≪Other additives≫
If necessary, the thermoplastic foamed resin composition of the present invention may contain other additives as auxiliary agents. As other additives, for example, a colorant, a lubricant, a coupling agent, a fluidity improver, a dispersant, an antioxidant, an ultraviolet absorber, a flame retardant, a stabilizer, an antistatic agent, etc. may be blended. .. These additives may be used alone or in combination of two or more. Further, these may be blended in the kneading step described later, or may be blended in the resin composition in advance before the kneading step. In the thermoplastic foamed resin composition according to the present invention, the amount of these other additives added is such that the propylene-based polymer (B) having no long chain branching and the propylene-based polymer having a long chain branching structure ( The thermoplastic resin containing A) and the inorganic substance powder are not particularly limited as long as they do not impair the desired effect, but, for example, when the total mass of the thermoplastic foamed resin composition is 100%, It is desired that these other additives are blended in a proportion of about 0 to 5.0% by mass, respectively, and a proportion of 2.0% by mass or less in total of the other additives.

Below, of these, what is considered to be important will be described with examples, but the present invention is not limited to these.

As the colorant, any of known organic pigments, inorganic pigments and dyes can be used. Specifically, organic pigments such as azo, anthraquinone, phthalocyanine, quinacridone, isoindolinone, geoosazine, perinone, quinophthalone, perylene pigments, ultramarine blue, titanium oxide, titanium yellow, iron oxide. Inorganic pigments such as (valley), chromium oxide, zinc white, and carbon black can be used.

Examples of the lubricant include stearic acid, hydroxystearic acid, complex type stearic acid, fatty acid lubricants such as oleic acid, aliphatic alcohol lubricants, stearamide, oxystearoamide, oleylamide, erucylamide, ricinolamide, behenamide, methylol. Amides, methylenebisstearamide, methylenebisstearobehenamide, bisamic acids of higher fatty acids, aliphatic amide lubricants such as complex type amides, stearic acid-n-butyl, methyl hydroxystearate, polyhydric alcohol fatty acid ester, Examples thereof include saturated fatty acid esters, aliphatic ester lubricants such as ester wax, and fatty acid metal soap lubricants.

As the antioxidant, a phosphorus-based antioxidant, a phenol-based antioxidant, and a pentaerythritol-based antioxidant can be used. Phosphorus-based, more specifically, phosphorus-based antioxidant stabilizers such as phosphorous acid ester and phosphoric acid ester are preferably used. Examples of the phosphite include triphenyl phosphite, trisnonylphenyl phosphite, tris(2,4-di-t-butylphenyl)phosphite, and other phosphite triesters, diesters, monoesters, and the like. Are listed.

Examples of the phosphoric acid ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris(nonylphenyl)phosphate, 2-ethylphenyldiphenylphosphate and the like. These phosphorus-based antioxidants may be used alone or in combination of two or more.

As the phenolic antioxidant, α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2- t-Butyl-6-(3'-t-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-t-butyl-4-(N,N-dimethyl Aminomethyl)phenol, 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, and tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxymethyl]methane. Etc. are illustrated, and these can be used individually or in combination of 2 or more types.

The flame retardant is not particularly limited, but for example, a halogen-based flame retardant or a non-phosphorus halogen-based flame retardant such as a phosphorus-based flame retardant or a metal hydrate can be used. Specific examples of the halogen-based flame retardant include halogenated bisphenol-based compounds such as halogenated bisphenylalkane, halogenated bisphenylether, halogenated bisphenylthioether, halogenated bisphenylsulfone, brominated bisphenol A, and bromine. Bisphenol-bis(alkyl ether) compounds such as chlorinated bisphenol S, chlorinated bisphenol A, chlorinated bisphenol S, and phosphorus-based flame retardants such as tris(diethylphosphinic acid) aluminum and bisphenol A bis(diphenyl phosphate). , Triaryl isopropyl phosphate, cresyl di 2, 6-xylenyl phosphate, aromatic condensed phosphoric acid ester, and the like, and examples of the metal hydrate include aluminum trihydrate, magnesium dihydroxide, or a combination thereof. Etc. can each be illustrated, and these can be used individually or in combination of 2 or more types. It works as a flame retardant aid, and can more effectively improve the flame retardant effect. Furthermore, for example, antimony oxide such as antimony trioxide and antimony pentoxide, zinc oxide, iron oxide, aluminum oxide, molybdenum oxide, titanium oxide, calcium oxide, magnesium oxide and the like can be used together as a flame retardant aid. ..

≪Molded product manufacturing method≫
The method for producing a molded article according to the present invention is not particularly limited as long as it can form a desired foamed structure in the resin phase and decompose it into a desired shape by decomposing a chemical foaming agent in the composition. It is possible to use any of liquid phase foaming methods such as injection foaming, extrusion foaming, foam blowing, or solid phase foaming methods such as bead foaming, batch foaming, press foaming, atmospheric secondary foaming and the like. In particular, in the thermoplastic foaming resin composition of the present invention containing crystalline polypropylene as a carrier resin and sodium hydrogen carbonate as a chemical foaming agent, the injection foaming method and the extrusion foaming method, and further the injection foaming method is preferably used. obtain.

As the injection foaming method, generally, a short shot method and a full shot method are known as a filling method, and a core back method using a mold having a variable cavity volume is also known. It is also possible to use.

Furthermore, a gas counter pressure method is known in which the inside of the mold is pressurized with gas when filling the resin composition for injection molding, and can be preferably used. That is, in general, a molded article formed by injection foaming is a so-called structural foam in which a solid skin layer having no bubbles is formed in a portion in contact with a mold, and a foam core layer is formed so as to be sandwiched between solid skins. However, in the structural foam, bubbles, particularly swirl marks (flow patterns) derived from breakage are likely to occur on the surface, and the gas counter pressure as described above can effectively suppress the generation of swirl marks. ..

The molding temperature at the time of molding cannot be unconditionally specified because it varies to some extent depending on the molding method, but is, for example, 180 to 260°C, more preferably 180 to 230°C, and further preferably 180 to 210. At a temperature of ℃, the foamable thermoplastic composition according to the present invention has good drawdown characteristics and spreadability while exhibiting good foaming characteristics of forming uniform closed cells, and Can be molded into a predetermined shape without causing local modification.

≪Molded product≫
The molded product according to the present invention is a molded product foam-molded using the thermoplastic foamed resin composition.

The shape and the like of the molded product according to the present invention are not particularly limited and may be of various forms, for example, it can be molded as a sheet, a container body or the like.

The expansion ratio of the molded product according to the present invention is, for example, 1.2 to 3.0 times, preferably 1.6 to 2.5 times, and more preferably 1.8 to 2.3 times. In the present invention, the thermoplastic foamed resin composition having the composition as described above causes the foamed structure to be broken even when foamed at a relatively high expansion ratio (for example, about 2.0 to 3.0 times). It is possible to obtain a product having good surface quality by obtaining a uniform foamed structure without foaming, suppressing generation of swirl marks on the surface due to bubble breakage, and the like. The expansion ratio can be calculated by dividing the density of the expandable resin composition by the density of the foam. Here, the density (apparent density) of the foam can be measured by a measuring method according to JIS K 6767:1999.

Furthermore, the density (apparent density) of the molded product is not particularly limited, but is, for example, 0.80 to 1.30 g/cm ³ , preferably 0.80 to 1.10 g/cm ³ , and more preferably Is about 0.85 to 1.00 g/cm ³ . This is because if the apparent density is too low, the rigidity decreases and the body becomes brittle, and if the apparent density is too high, the desired weight reduction due to the foamed structure cannot be achieved.

The foam structure of the foamed product of the present invention is not particularly limited to the closed cell structure, and depending on the use of the molded product, an open cell structure, or a closed cell structure and an open cell structure. May be a mixed structure, but the composition constituting the molded article according to the present invention is a composition containing an inorganic filler with a high filling rate, relatively high strength product use and water resistance or The closed-cell structure is desirable from the viewpoint of mainly considering the application of products requiring liquid impermeability and the like.

The average diameter (μm) of the closed cells formed in the molded product is appropriately selected depending on the intended purpose without any limitation, but it is preferably about 10 to 500 μm. When the average diameter is within this range, the strength of the obtained molded product can be maintained as sufficient, and the surface properties can be kept good, and the weight can be reduced by foaming. The average diameter of the closed cells is measured according to ASTM D3576-3577.

Furthermore, in the embodiment having a closed-cell structure as the molded product according to the present invention, as described above, even when the thermoplastic foamed resin composition according to the present invention contains a large amount of the inorganic substance powder, it is heated and melted. Has good draw-down characteristics and spreadability, and is less likely to cause foam breakage in the formed foam structure. Therefore, in the molded product, the cross-sectional area of the foam breakage part should be less than 10%, more preferably less than 5%. You can In addition, the "broken cell cross-sectional area" here means cutting the foam that is a molded product, taking a cross-sectional photograph, measuring the area of the relevant region on the photograph, and measuring the area of all cell cross-sections in the same manner. Is calculated as a ratio with the sum of.

Further, the thermoplastic foamed resin composition according to the present invention, even if it contains a large amount of inorganic substance powder, has good drawdown characteristics and spreadability during heating and melting, so that the molding die, for example, may be deep-drawn. Since the molded product of the present invention can be molded with good followability even if it has it, the molded product of the present invention has a desired shape regardless of its shape and the quality is uniform at each part.

Furthermore, by containing the inorganic substance powder and the propylene-based polymer (A) having a predetermined amount of a long-chain branched structure, it becomes excellent in heat resistance and flame retardancy.
Specifically, regarding flame retardancy, for example, UL94 V-1 or higher, particularly UL94 V-0 standard in the UL94 standard defined by the American Underwriters Laboratories lnc. Can be satisfied even in the form of a foam, and by adding an appropriate flame retardant, it is possible to satisfy a higher flame retardant performance of UL 94 5V.

The thickness of the molded product according to the present invention is not particularly limited, and may be various from thin to thick depending on the form of the molded product. A molded product having a thickness of 01 mm or more and 100 mm or less, more preferably a thickness of 1 mm or more and 30 mm or less is shown. If the thickness is within this range, it is possible to form a homogeneous and defect-free molded product without causing moldability and workability and without causing uneven thickness.

Hereinafter, the present invention will be described more specifically based on Examples. It should be noted that these examples are specific aspects and implementations in order to make it easier to understand the concept and scope of the present invention disclosed in this specification and described in the appended claims. It is described only for the purpose of exemplifying the form, and the present invention is not limited to these examples.

(Evaluation method)
Each physical property value in the following examples and comparative examples is evaluated by the following methods.

Melt flow rate (MFR):
The propylene-based polymer (A) having a long-chain branched structure and the propylene-based polymer (B) not having a long-chain branched structure are in accordance with JIS K7210-1:2014 A method condition M, test temperature: 230° C., nominal load : 2.16 kg, die shape: diameter 2.095 mm, length 8.00 mm.

Melt tension:
The measurement was performed under the following conditions using a Capillograph manufactured by Toyo Seiki Seisakusho.
Capillary: diameter 2.0 mm, length 40 mm
Cylinder diameter: 9.55 mm
Cylinder extrusion speed: 20 mm/min Take-up speed: 4.0 m/min

Isotactic triad fraction (mm)
390 mg of a sample was used together with o-dichlorobenzene/deuterated benzene bromine (C ₆ D ₅ Br)=4/1 (volume ratio) 2.6 ml and hexamethyldisiloxane as a chemical shift reference substance, and an NMR sample having an inner diameter of 10 mm. It was put in a tube and dissolved, and ¹³ C-NMR measurement was performed. ¹³ C-NMR measurement was carried out using an AV400M type NMR apparatus of Bruker BioSpin Co., Ltd. equipped with a cryoprobe having a diameter of 10 mm.
Pulse angle: 90°
Pulse interval: 15 seconds Accumulation frequency: 128 times or more Observation area: -20 to 179 ppm
The chemical shift was set with the methyl carbon peak of hexamethyldisiloxane set to 1.98 ppm, and the chemical shifts of the peaks due to other carbons were based on this.

Branch index g′:
[Measuring method]
GPC: Alliance GPCV2000 (Waters)
Detector: Described in order of connection Multi-angle laser light scattering detector (MALLS): DAWN-E (Wyatt Technology)
Differential refractometer (RI): GPC attached Viscometer (Viscometer): GPC attached Mobile phase solvent: 1,2,4-trichlorobenzene (added at a concentration of 0.5 mg/mL)
Mobile phase flow rate: 1 mL/min Column: Tosoh GMHHR-H(S) Two HTs connected Sample injection part temperature: 140°C
Column temperature: 140℃
Detector temperature: All 140 ℃
Sample concentration: 1 mg/mL
Injection volume (sample loop volume): 0.2175 mL

[analysis method]
In obtaining the absolute molecular weight (Mabs), the root mean square radius of gyration (Rg), and the intrinsic viscosity ([η]) obtained from the Viscometer obtained from the multi-angle laser light scattering detector (MALLS), data processing attached to MALLS is performed. Soft ASTRA (version 4.73.04) was used.

Foaming ratio:
It was calculated by dividing the density of the foamable resin composition by the density of the foam. The density (apparent density) of the foam was measured by a measuring method according to JIS K 6767:1999.

Density (apparent density):
As described above, it was measured by the measuring method according to JIS K 6767:1999.

Tensile strength test:
The tensile strength was measured according to JIS K 7161-2:2014 using an autograph AG-100kNXplus (Shimadzu Corporation) under the conditions of 23° C. and 50% RH. As the test piece, a dumbbell shape cut out from a molded product shown below was used. The stretching speed was 10 mm/min.

Bending test:
The bending test was performed according to JIS K7171:2016, using an autograph AG-10TD (Shimadzu Corporation) under the conditions of 23° C. and 50% RH. As a test piece, a strip shape cut out from a molded product shown below was used. The test speed was 2 mm/min.

Surface quality:
The presence or absence of swirl marks on the surface of the molded product was visually inspected and evaluated according to the following evaluation criteria.
[Evaluation criteria]
◯: No swirl mark is observed on the surface.
Δ: Swirl marks are slightly observed on the surface.
X: Many swirl marks are observed on the surface.

Foam structure (breaking):
The molded product was cut, and the number of broken cells of 1 mm ² or more in a constant visual field (5 mm×4 mm) on the cut surface was examined and evaluated according to the following evaluation criteria.
[Evaluation criteria"
⊚: No breakage of 1 mm ² or more.
◯: There is one broken cell of 1 mm ² or more.
B: There are 2 to 5 broken cells of 1 mm ² or more.
×: There are 6 or more broken cells of 1 mm ² or more.

(material)
The components used in the following examples and comparative examples were as follows.

Polypropylene without long chain branch (B):
The following were used as the polypropylene (B) having no long-chain branch.
B1: Polypropylene homopolymer (Nippon Polypro Corporation: Novatec (trade name) PP EA9)
MFR (JIS K7210-1:2014, 230°C): 0.5 g/min B2: Polypropylene homopolymer (Nippon Polypro Co., Ltd.: Novatec (trade name) PP FY6C)
MFR (JIS K7210-1:2014, 230°C): 2.4 g/min B3: polypropylene homopolymer (Nippon Polypro Co., Ltd.: Novatec (trade name) PP MA1B)
MFR (JIS K7210-1:2014, 230°C): 21.0 g/min B4: Polypropylene homopolymer (Nippon Polypro Co., Ltd.: Novatec (trade name) PP BC06C)
MFR (JIS K7210-1:2014, 230°C): 60.0 g/min

Polypropylene (A) having long chain branching:
The following were used as the polypropylene (A) having a long chain branch.
A1: Metallocene-based long-chain branched polypropylene (manufactured by Nippon Polypro Co., Ltd.: Weimax (trade name) MFX 8)
MFR (JIS K7210-1:2014, 230°C): 1.1 g/min Melt tension (230°C): 25 g
Isotactic triad fraction (mm): 90% or more Branching index g': 0.30 or more, less than 1.00

A2: Metallocene long-chain branched polypropylene (manufactured by Nippon Polypro Co., Ltd.: Weimax (trade name) MFX 6)
MFR (JIS K7210-1:2014, 230°C): 2.5 g/min Melt tension (230°C): 17 g
Isotactic triad fraction (mm): 90% or more Branching index g': 0.30 or more, less than 1.00

A3: Metallocene-based long-chain branched polypropylene (manufactured by Nippon Polypro Co., Ltd.: Weimax (trade name) MFX 3)
MFR (JIS K7210-1:2014, 230°C): 9.0 g/min Melt tension (230°C): 5 g
Isotactic triad fraction (mm): 90% or more Branching index g': 0.30 or more, less than 1.00

A4: Metallocene long-chain branched polypropylene
MFR (JIS K7210-1:2014, 230°C): 12.0 g/min Melt tension (230°C): 3 g
Isotactic triad fraction (mm): 90% or more Branching index g': 0.30 or more, less than 1.00

Other resin (Z):
Z1: Ultra-high molecular weight polyethylene (Mitsui Chemicals, Lbmer (registered trademark) L3000)

Z2: polymethylpentene (TPX (registered trademark) DX845, manufactured by Mitsui Chemicals, Inc.)

Inorganic substance powder (C):
C1: Fatty acid surface-treated heavy calcium carbonate particles Average particle diameter 2.2 μm (Bihoku Kogaku Co., Ltd., Ryton S-4)
C2: Light calcium carbonate particles Average particle size 1.5 μm (PC, manufactured by Shiraishi Industry Co., Ltd.)

Foaming agent (D):
D1: Sodium hydrogen carbonate D2: Azodicarbonamide

Example 1
As the polypropylene (B) having no long chain branch, the above B1 is used, as the polypropylene (A) having a long chain branch structure, the above A1 is used, as the inorganic substance powder, the above C1 is used, as the foaming agent, the above D1 is further used, and as the above lubricant, E1 was used in the blending ratio shown in Table 1. In Table 1, the numerical value of each component is the value in parts by mass. Then, using a fully automatic injection molding machine (WD650WS-V, manufactured by Ube Industries, Ltd.), foam injection molding was performed under the following conditions.
Mold used: Mold for automobile interior miniature shape (see Fig. 1) with a grain pattern of about 40 cm x 30 cm Material mixture: Stirring for 5 minutes with an electric stirrer Screw temperature: 180-210°C
Mold temperature: 30°C.
Mold clamping force: 4000kN
Injection speed: 80 mm/sec Holding pressure: 35 MPa

A test piece was prepared under the above-mentioned conditions, and the tensile strength test, the bending test, the surface quality and the foam structure were examined. The obtained results are shown in Table 2.

Examples 2-20 and Comparative Examples 1-10
Foam injection molding was performed in the same manner as in Example 1 except that the type and amount of each component in the thermoplastic foam resin composition were changed as shown in Table 1 below. Then, a test piece was prepared under the above-mentioned conditions, and the tensile strength test, the bending test, the surface quality and the foam structure were examined. The obtained results are shown in Table 2.
Further, the thus obtained sheet was similarly subjected to a tensile test at 170°C and 180°C. The obtained results are shown in Table 2. In addition, in Example 2, since a lubricant was not blended, the extruded appearance had a slight roughness, but the obtained sheet itself had no practical problem and the same performance as that of Example 1 was obtained. Indicated.

As shown in the results shown in Table 2, in the examples according to the present invention, the injection molding operation can be stably performed without any particular problem, and the weight reduction can be achieved by the foamed structure at a desired magnification. Further, there was no swirl mark on the surface, the mechanical strength was good, uneven thickness did not occur in the molded product, and a molded product with good quality could be obtained.

Claims (12)

A thermoplastic foaming resin composition comprising at least a thermoplastic resin, an inorganic substance powder and a chemical foaming agent, wherein the thermoplastic resin comprises polypropylene (B) having no long chain branching and a long chain branching structure. A thermoplastic foamed resin composition containing the polypropylene (A) in a mass ratio of 80:20 to 98:2. The thermoplastic foaming resin composition according to claim 1, wherein the mixing ratio of the thermoplastic resin and the inorganic substance powder in the thermoplastic foaming resin composition is 50:50 to 10:90 by mass. The polypropylene (A) having a long chain branched structure is a polypropylene having a long chain branched structure having an isotactic triad fraction (mm) measured by ¹³ C-NMR of 90% or more. The thermoplastic foamed resin composition described. The polypropylene (A) having a long chain branched structure has a long chain branched structure having a melt flow rate (230° C.) of 1.0 to 3.0 g/10 minutes and a melt tension (230° C.) of 5 to 30 g. The thermoplastic foamed resin composition according to claim 1, which is propylene having. The thermoplastic foam according to any one of claims 1 to 4, wherein the polypropylene (B) having no long chain branched structure is a polypropylene having a melt flow rate (230°C) of 0.3 to 50.0 g/10 minutes. Resin composition. The thermoplastic foamed resin composition according to claim 1, wherein the inorganic substance powder has an average particle diameter of 0.1 μm or more and 50.0 μm or less. The thermoplastic foamed resin composition according to claim 1, wherein the inorganic substance powder is calcium carbonate. The thermoplastic foamed resin composition according to claim 7, wherein the inorganic substance powder is ground calcium carbonate. 9. The chemical foaming agent is at least any one selected from the group consisting of hydrogen carbonate, carbonate, nitrite, water or an inorganic substance containing water of crystallization, a water azo compound and a nitroso compound. The thermoplastic foamed resin composition according to any one of 1. The thermoplastic foaming resin composition according to claim 1, wherein the chemical foaming agent is sodium hydrogen carbonate. The thermoplastic foaming resin composition according to claim 10, which contains the sodium hydrogen carbonate as the chemical foaming agent in an amount of 1.00 to 10.00 mass% with respect to the total mass of the composition. A molded article comprising the thermoplastic foamed resin composition according to claim 1.