JP2021059677A - Polypropylene resin composition - Google Patents

Abstract

To provide a polypropylene resin composition which improves odor, suppresses plastic feeling and suppresses deterioration in melt spreadability.SOLUTION: A polypropylene resin composition contains 20-90 mass% of a polypropylene resin (A) having characteristic (a-1) a melt tension (MT) (unit: g) satisfying log(MT)≥-0.9×log(MFR)+0.7 or log(MT)≥1.15 and characteristic (a-2) a melting point of 110°C or higher and lower than 150°C, and 10-80 mass% of a biomass material (C) (total of masses of (A) and (C) is 100 mass%.).SELECTED DRAWING: None

Description

The present invention relates to a polypropylene resin composition containing a biomass material, and an extruded foam, an injection foam, a sheet and a thermoformed body made of the polypropylene resin composition, and a blow molded body.

Polypropylene is used in all industries because it has excellent various physical properties such as heat resistance and can be manufactured at low cost. In recent years, reduction of CO2 emissions has been required from the viewpoint of global warming and environmental protection, and as a countermeasure, utilization of biomass materials capable of adsorbing and immobilizing CO2 in the atmosphere has been proposed in various fields. For example, a composition in which a biomass material such as wood powder is compounded with polypropylene has been proposed (Patent Document 1). And the polypropylene resin composition, which is a composite of polypropylene and wood powder, is semi-plastic, such as making you feel the warmth of wood that cannot be expressed by plastic, but it can retain the properties of wood such as fragrance and color tone, so it is artificial. It is expanding its applications such as being used for wood.

When a biomass material is compounded with polypropylene and the composite polypropylene resin composition is molded into various molded products, for example, a processing temperature of about 180 to 200 ° C. is required. At such a high temperature, biomass is used. The problem is that a significant odor is generated from the material, which has a great adverse effect on the operator. If the processing temperature is lowered in order to suppress the generation of odor, there is a problem that the appearance quality of the obtained molded product deteriorates or the processing becomes difficult in the first place.

In order to solve such a problem during molding, a propylene resin composition comprising 10 to 90 parts by weight of a propylene resin having a melting point of 110 to 150 ° C. and 90 to 10 parts by weight of a lignocellulosic or cellulosic substance. A product has been proposed (Patent Document 2). According to the propylene-based resin composition of Patent Document 2, it is shown that not only the molding processing temperature can be lowered and the generation of odor can be suppressed, but also the odor can be improved even at a high molding temperature.

Japanese Unexamined Patent Publication No. 6-80832 JP-A-2007-169612

Although the propylene-based resin composition of Patent Document 2 has been improved in terms of odor, there is a problem that the feel of the plastic is strengthened in terms of color tone and the like. Further, there is a problem that the blending of lignocellulosic or cellulosic substances deteriorates the melt ductility of the propylene resin, which limits the molding process. Therefore, an object of the present invention is to provide a polypropylene resin composition in which the odor is improved, the plastic feeling is suppressed, and the deterioration of melt ductility is suppressed.

The first polypropylene resin composition of the present invention comprises 20 to 90% by mass of a polypropylene resin (A) having the following properties (a-1) and properties (a-2), and 10 to 80% by mass of a biomass material (C). It is characterized in that it contains% (provided that the total mass of (A) and (C) is 100% by mass).
Characteristic (a-1): A characteristic (a) in which the melt tension (MT) (unit: g) satisfies log (MT) ≧ −0.9 × log (MFR) +0.7 or log (MT) ≧ 1.15. -2): Melting point is 110 ° C or higher and lower than 150 ° C

Further, the second polypropylene resin composition of the present invention contains 5 to 85% by mass of the polypropylene resin (A) having the following characteristics (a-1) and (a-2), and the following characteristics (b-1). Contains 5 to 85% by mass of the polypropylene resin (B) and 10 to 80% by mass of the biomass material (C) (provided that the total mass of (A), (B) and (C) is 100% by mass. ).
Characteristic (a-1): A characteristic (a) in which the melt tension (MT) (unit: g) satisfies log (MT) ≧ −0.9 × log (MFR) +0.7 or log (MT) ≧ 1.15. -2): Melting point of 110 ° C. or higher and lower than 150 ° C. (b-1): Melt tension (MT) (unit: g) is log (MT) <-0.9 x log (MFR) +0.7, and log (MT) <1.15 is satisfied

The polypropylene resin (A) is a propylene / ethylene random copolymer, a propylene / 1-butene random copolymer, a propylene / ethylene / 1-butene random copolymer, a propylene / ethylene random block copolymer, a propylene / ethylene / It is preferable that it is one or more kinds of polypropylene resins selected from the group consisting of 1-butene random block copolymers.

Further, the polypropylene resin (B) is one or more kinds of polypropylene resins selected from the group consisting of propylene homopolymers, propylene / ethylene block copolymers, and propylene / ethylene / 1-butene block copolymers. Good.

Further, the polypropylene resin (A) may have the following properties (a-3) and / or (a-4).
(A-3) Strain hardening degree in measurement of extensional viscosity is 1.5 or more (a-4) Ratio of components with molecular weight of 2 million or more in the molecular weight distribution curve measured by GPC is 0.4% by mass or more

The biomass material (C) is preferably one or more plant-derived fillers selected from the group consisting of wood, pulp, bamboo, sugar cane (bagasse), rice husks, and rice (starch).

Further, with respect to 100 parts by mass of the total of the polypropylene resin (A) and the biomass material (C) described above, or 100% by mass of the total of the polypropylene resin (A), the polypropylene resin (B) and the biomass material (C). , A polypropylene resin composition containing 1 to 50 parts by mass of the thermoplastic elastomer (D) is preferable.

Further, the extrusion foam molded product, the injection foam molded product, the sheet molded product, the thermoformed product, or the blow molded product preferably comprises the polypropylene resin composition described above.

The polypropylene resin composition of the present invention is excellent in environmental protection performance, can suppress odor and plastic feeling, and can suppress deterioration of melt ductility.

The first polypropylene resin composition of the present invention contains 20 to 90% by mass of the polypropylene resin (A) and 10 to 80% by mass of the biomass material (C), and the total of these is 100% by mass.

The second polypropylene resin composition of the present invention contains 5 to 85% by mass of the polypropylene resin (A), 5 to 85% by mass of the polypropylene resin (B), and 10 to 80% by mass of the biomass material (C). The total is 100% by mass.

Both the first polypropylene resin composition and the second polypropylene resin composition contain a polypropylene resin (A) and a biomass material (C), and while improving the odor, the plastic feeling is suppressed, and the melt spreadability is suppressed. Deterioration is suppressed and it has excellent environmental protection ability.

Polypropylene resin (A)
The polypropylene resin (A) has the following characteristic (a-1) in the relationship between the melt tension and the MFR.
(A-1): The melt tension (MT) (unit: g) of the polypropylene resin (A) is
Satisfy log (MT) ≥ −0.9 × log (MFR) +0.7, or log (MT) ≥ 1.15

The melt tension (MT) of the polypropylene resin (A) preferably satisfies log (MT) ≧ −0.9 × log (MFR) +0.9, or log (MT) ≧ 1.15. More preferably, it satisfies log (MT) ≧ −0.9 × log (MFR) +1.1, or log (MT) ≧ 1.15.

There is no upper limit to the melt tension of the polypropylene resin (A), but if it is too large, the ductility will decrease, the shapeability to the mold will deteriorate during thermoforming, and in extreme cases the molded product will tear. The log (MT) ≤ 1.48 (MT ≤ 30.2) is preferable because there is a possibility that molding defects such as the above may occur.

Here, in the present specification, the melt tension (MT) is a value measured using a capillograph. The resin is placed in a cylinder having a diameter of 9.55 mm heated to a temperature of 230 ° C., and the molten resin is extruded from an orifice having a diameter of 2.0 mm and a length of 40 mm at a pushing speed of 20 mm / min. The tension detected by the pulley when the extruded resin is taken up at a speed of 4.0 m / min is measured, and this is defined as the melt tension (MT).

(A-2) The polypropylene resin (A) has a melting point of 110 or more and less than 150 ° C., preferably 115 to 145 ° C., and more preferably 120 to 140 ° C. By setting the melting point of the polypropylene resin (A) to 110 ° C. or higher, it becomes possible to reduce stickiness caused by low crystalline components. Further, by setting the melting point of the polypropylene resin (A) to less than 150 ° C., the temperature at the time of molding the polypropylene resin composition can be relatively lowered, the generation of odor can be suppressed, and the moldability and the product can be improved. Quality can be ensured. The melting point can be adjusted by adjusting the amount of comonomer such as ethylene or butene introduced during propylene polymerization.

Here, in the present specification, the melting point is a value measured by a differential scanning calorimeter (DSC). Using a differential scanning calorimeter manufactured by Seiko, take a sample of about 5 mg, hold it at 200 ° C. for 5 minutes, cool it to 40 ° C. at a temperature lowering rate of 10 ° C./min, and then raise the temperature at 10 ° C./min. The melting point is obtained from the heat of fusion curve obtained when melting in. That is, the maximum peak temperature of the heat of fusion curve is defined as the melting point.

The polypropylene resin (A) has a melt flow rate (MFR) measured at 230 ° C. and a load of 2.16 kg, preferably 0.1 to 150 g / 10 minutes, and more preferably 1 to 100 g / 10 minutes. Here, MFR is a value measured at 230 ° C. and a load of 2.16 kg in accordance with JIS K7210. The MFR of the polypropylene resin (A) can be adjusted by controlling the hydrogen concentration at the time of polymerization and the like. When the MFR is 0.1 g / 10 minutes or more, the load on the extruder is suppressed and the productivity is improved when the sheet is extruded, which is preferable.

In the polypropylene resin (A), ^{the mm fraction of the propylene unit 3 chain by 13} C-NMR is preferably 95% or more, more preferably 96% or more, and further preferably 97% or more.

The mm fraction is the ratio of the propylene unit 3 chain in which the direction of the methyl branch in each propylene unit is the same in any propylene unit 3 chain consisting of a head-tail bond in the polymer chain, and the upper limit is 100%. is there. This mm fraction is a value indicating that the three-dimensional structure of the methyl group in the polypropylene molecular chain is isotically controlled, and the higher the value, the more isotropically controlled. When the mm fraction is 95% or more, the drawdown resistance during thermoforming is improved.

The method for measuring the mm fraction of the propylene unit 3-chain by ¹³ C-NMR of the polypropylene resin (A) is as follows.
After completely dissolving 375 mg of the sample in 2.5 ml of deuterated 1,1,2,2-tetrachloroethane in an NMR sample tube (10φ), the measurement was carried out at 125 ° C. by the proton complete decoupling method under the following conditions. To do. The chemical shift sets the central peak of the three peaks of deuterated 1,1,2,2-tetrachloroethane to 74.2 ppm. Chemical shifts of other carbon peaks are based on this.
Flip angle: 90 degrees Pulse interval: 10 seconds Resonance frequency: 100 MHz or more Accumulation frequency: 10,000 times or more Observation range: -20 ppm to 179 ppm
Number of data points: 32,768

The mm fraction is determined ^{using the 13} C-NMR spectrum measured under the above conditions. The spectrum is assigned with reference to Macromolecules, (1975), Vol. 8, p. 687, and Polymer, Vol. 30, p. 1350 (1989). A more specific method for determining the mm fraction is described in detail in paragraphs [0053] to [0065] of JP-A-2009-275207, and this method is also used in the present invention. ..

The polypropylene resin (A) preferably has a Q value (Mw / Mn) of 3.5 to 10 determined from the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC). , More preferably 3.7 to 8, and even more preferably 4 to 6. When the Q value of the polypropylene resin (A) is in the above range, it is particularly excellent in molding processability when the sheet is extruded, which is preferable.

The polypropylene resin (A) preferably has a Z average molecular weight (Mz) measured by gel permeation chromatography (GPC) and a molecular weight distribution Mz / Mw determined from Mw, preferably 2.5 to 10, more preferably 2.8. It is preferably to 8, and more preferably 3 to 6. When the Mz / Mw of the polypropylene resin (A) is in the above range, the molding processability is particularly excellent when the sheet is extruded.

The polypropylene resin (A) preferably has the property (a-4).
(A-4) The ratio of components having a molecular weight of 2 million or more in the molecular weight distribution curve measured by GPC is 0.4% by mass or more. In the molecular weight distribution curve obtained by measuring GPC of the polypropylene resin (A), the molecular weight is 200. The ratio of the components of 10,000 or more is preferably 0.4% by mass or more, more preferably 0.5% by mass or more, and further preferably 0.6% by mass or more. When the ratio of the components having a molecular weight of 2 million or more is in the above range, the melt tension is high and the molding processability is excellent.

In this specification, the definitions of Mn, Mw, and Mz are based on the matters described in "Basics of Polymer Chemistry" (edited by Polymer Society, Tokyo Kagaku Dojin, 1978), and Mn, Mw, and Mz are defined as Mn, Mw, and Mz. It can be calculated from the molecular weight distribution curve by GPC.

In the present specification, the measurement method of GPC is as follows.
-Device: Waters GPC (ALC / GPC 150C)
-Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
-Column: Showa Denko AD806M / S (3)
-Mobile phase solvent: orthodichlorobenzene (ODCB)
-Measurement temperature: 140 ° C
-Flow velocity: 1.0 ml / min
・ Injection amount: 0.2 ml
-Sample preparation: As a sample, prepare a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and dissolve it at 140 ° C. for about 1 hour.

The conversion from the holding capacity obtained by GPC measurement to the molecular weight is performed using a calibration curve (calibration curve) made of standard polystyrene prepared in advance. The following brands manufactured by Tosoh Corporation are used as standard polystyrene.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000

A calibration curve is created by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each standard polystyrene is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximating with the least squares method.
The following numerical values are used for the viscosity formula [η] = K × M ^{α used for conversion to the molecular weight.}
PS: K = 1.38 × 10 ^-4 , α = 0.7
PP: K = 1.03 × 10 ^-4 , α = 0.78

The polypropylene resin (A) preferably has a long-chain branched structure.
As a direct index of whether or not the polypropylene resin has a long-chain branched structure, the branching index g'can be mentioned. The branch index g'is the ratio of the intrinsic viscosity [η] br of the polymer having a long-chain branched structure to the intrinsic viscosity [η] lin of the linear polymer having the same molecular weight, that is, [η] br / [η] lin, It can be said that it has a long-chain branched structure when g ′ <1.

The definition of the branching index g'is described in, for example, "Developments in Polymer Classification-4" (JV Dawkins ed. Applied Science Publicers, 1983) and is a well-known index to those skilled in the art.

The branching index g'can be obtained as a function of the absolute molecular weight Mabs, for example, by using a light scatterometer as described below and a GPC equipped with a viscometer as a detector.

The polypropylene resin (A) preferably has a branching index g'of 0.30 or more and less than 1.00, and more preferably 0.55 or more and 0.98 or more when the absolute molecular weight Mabs determined by light scattering is 1,000,000. Hereinafter, it is more preferably 0.75 or more and 0.96 or less, and most preferably 0.78 or more and 0.95 or less.

The calculation method of the branch index g'is as follows.
An Alliance GPCV2000 manufactured by Waters is used as a GPC apparatus equipped with a differential refractometer (RI) and a viscosity detector (Viscometer). Further, as the light scattering detector, DAWN-E manufactured by Wyatt Technology, a multi-angle laser light scattering detector (MALLS) is used. The detectors are connected in the order of MALLS, RI, and Viscometer. The mobile phase solvent is 1,2,4-trichlorobenzene (an antioxidant Irganox 1076 manufactured by BASF Japan Ltd. is added at a concentration of 0.5 mg / mL).

The flow rate of the mobile phase solvent is 1 mL / min, and the column is used by connecting two GMHHR-H (S) HTs manufactured by Tosoh Corporation. The temperature of the column, the sample injection part and each detector is 140 ° C. The sample concentration is 1 mg / mL, and the injection amount (sample loop volume) is 0.2175 mL.

In determining the absolute molecular weight (Mabs), root mean square radius (Rg) and intrinsic viscosity ([η]), use the data processing software ASTRA (version 4.73.04) attached to MALLS and refer to the following documents. And calculate.
References 1. Developments in Composer Charactization-4 (JV Dawkins ed. Applied Science Publics, 1983. Chapter 1.)
References 2. Polymer, 45, 6495-6505 (2004)
References 3. Macromolecules, 33, 2424-2436 (2000)
References 4. Macromolecules, 33, 6945-6952 (2000)

The branching index g'is the ratio ([η] lin) of the intrinsic viscosity ([η] br) obtained by measuring the sample with a Viscometer and the intrinsic viscosity ([η] lin) obtained by separately measuring the linear polymer. ] Br / [η] lin).

Here, as the linear polymer for obtaining [η] lin, commercially available homopolypropylene (Novatec (registered trademark) PP grade name: FY6 manufactured by Japan Polypropylene Corporation) is used. Since it is known as the Mark-Houwink-Sakurada formula that the logarithm of [η] lin of a linear polymer has a linear relationship with the logarithm of molecular weight, [η] lin is appropriately set on the low molecular weight side or the high molecular weight side. Numerical values can be obtained by extrapolation.

The polypropylene resin (A) preferably has the following characteristics (a-3) in terms of strain hardening.
(A-3) Strain hardening degree in measuring extensional viscosity is 1.5 or more The strain hardening degree in measuring elongational viscosity of polypropylene resin (A) is preferably 1.5 or more, more preferably 2 or more, still more preferably. 3 or more. Here, the strain hardening degree is ^{a value obtained by measuring the extensional viscosity at a strain rate of 0.1 s-1} , and may be expressed as λmax in the present specification.
The strain hardening degree (λmax) is an index showing the strength at the time of melting, and if this value is large, a defective phenomenon in which an excessive uneven thickness portion is formed even in a molded product having a complicated shape during thermoforming. This can prevent the above, improve the physical properties of the molded product, and contribute to the thinning (gauge down) of the original sheet thickness, so that industrial members such as automobile members can be suitably molded. When the strain hardening degree of the polypropylene resin (A) having a long-chain branched structure is 1.5 or more, a sufficient effect of suppressing uneven thickness is exhibited.

The calculation method of the strain hardening degree is described below.
The extensional viscosity at a temperature of 180 ° C. and a strain rate of 0.1 s- ¹ is plotted on a log-log graph with time t (seconds) on the horizontal axis and extensional viscosity ηE (Pa · seconds) on the vertical axis. On the log-log graph, the relationship between the time until just before strain curing occurs and the viscosity is approximated by a straight line, and an approximate straight line is obtained.
Specifically, first, the inclination at each time when the extensional viscosity is plotted against time is obtained, but in doing so, various measures are taken in consideration of the fact that the measurement data of the extensional viscosity is discrete. Use the average method. For example, a method of obtaining the slopes of adjacent data and taking a moving average of several surrounding points can be mentioned.

The extensional viscosity becomes a simple increasing function in the region of low strain rate, gradually approaches a constant value, and matches the Truton viscosity after a sufficient time without strain hardening, but is common in the case of strain hardening. From about 1 strain amount (= strain rate x time), the extensional viscosity begins to increase with time. That is, the slope tends to decrease with time in the low strain region, but on the contrary, it tends to increase from the strain amount of about 1, and there is an inflection point on the curve when the extensional viscosity is plotted against time. .. Therefore, in the range of the strain amount of about 0.1 to 2.5, find the point where the slope of each time obtained above takes the minimum value, draw a tangent line at that point, and draw a straight line with the strain amount of 4.0. Extrapolate until The maximum value (ηmax) of the extensional viscosity ηE until the strain amount reaches 4.0 and the time for reaching the maximum value are obtained, and the viscosity on the approximate straight line at that time is defined as ηlin. ηmax / ηlin is defined as the degree of strain hardening (λmax).

The polypropylene resin (A) is a propylene homopolymer obtained by homopolymerizing propylene by single-stage polymerization or multi-stage polymerization of two or more stages, and copolymerizing propylene and α-olefin by single-stage polymerization or multi-stage polymerization of two or more stages. A propylene / α-olefin random copolymer obtained by polymerization, a polymerization step (1) in which propylene is homopolymerized by single-stage polymerization or multi-stage polymerization of two or more stages to obtain a propylene homopolymer, and propylene and α-olefin In a copolymerization step (2-1) to obtain a propylene / α-olefin random copolymer by copolymerizing with single-stage polymerization or multi-stage polymerization of two or more stages, or single-stage polymerization or two-stage polymerization of two or more kinds of α-olefins. A propylene / α-olefin block copolymer obtained by polymerization including a copolymerization step (2-2) for obtaining a random copolymer between α-olefins by copolymerizing in the above multi-stage polymerization, propylene and α-olefin Copolymerization step (1) to obtain a propylene / α-olefin random copolymer obtained by copolymerization by single-stage polymerization or multi-stage polymerization of two or more stages, and single-stage polymerization or two-stage or more of propylene and α-olefin. Copolymerization step (2-1) to obtain a propylene / α-olefin random copolymer by copolymerization by multi-stage polymerization or copolymerization of two or more kinds of α-olefins by single-stage polymerization or multi-stage polymerization of two or more stages Examples thereof include a propylene / α-olefin random block copolymer obtained by polymerization including a copolymerization step (2-2) for obtaining an α-olefin random copolymer. Further, as the polypropylene resin (A), one kind or a combination of two or more kinds may be used.

The α-olefin is preferably ethylene or an α-olefin having 4 to 18 carbon atoms. Specifically, ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4-methyl-pentene-1, 4-methyl-hexene-1, 4,4-dimethylpentene- 1st grade can be mentioned. Further, the α-olefin may be one kind or a combination of two or more kinds.

The polypropylene resin (A) is a propylene / ethylene random copolymer, a propylene / 1-butene random copolymer, a propylene / ethylene / 1-butene random copolymer, a propylene / ethylene random block copolymer, a propylene / ethylene / It is preferably one or more polypropylene resins selected from the group consisting of 1-butene random block copolymers.

The polypropylene resin (A) contains 85 to 100 mol% of propylene units, preferably 90 to 99.5 mol%, more preferably 92 to 98.5 mol%, ethylene units and / or 1-butene units of 0 to 15. It contains mol%, preferably 0.5-10 mol%, more preferably 1.5-8 mol%.
Here, the propylene unit and the ethylene and / or 1-butene unit are values measured by Fourier transform infrared analysis.

Examples of the polypropylene resin (A) include those polymerized by a Ziegler-Natta catalyst, those polymerized by a metallocene catalyst, and those polymerized by a post-metallocene catalyst. Examples of the Ziegler-Natta catalyst include catalysts containing titanium, magnesium, a solid component requiring halogen, organoaluminum, and an electron donor used as needed. Examples of the metallocene catalyst include a transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton, a cocatalyst, and a catalyst containing an organometallic compound and a carrier used as needed. Be done. Examples of the post-metallocene catalyst include organometallic compounds such as bisamide compounds of metals of Group 4 of the periodic table, bisimino compounds of metals of Group 8 to 10 of the periodic table, and salicylaldehyde compounds of metals of Group 4 to 10 of the periodic table, cocatalysts. And a catalyst containing an organometallic compound or a carrier used as needed.
As the polypropylene resin (A), a commercially available product can be used, and for example, the WAYMAX (registered trademark) series manufactured by Japan Polypropylene Corporation can be used.

Polypropylene resin (B)
The polypropylene resin (B) has the following characteristic (b-1) in the relationship between the melt tension and the MFR.
Characteristic (b-1): Melt tension (MT) (unit: g) satisfies log (MT) <-0.9 × log (MFR) +0.7, and log (MT) <1.15.

The melt tension (MT) of the polypropylene resin (B) preferably satisfies log (MT) <−0.9 × log (MFR) +0.6 and log (MT) <1.04 (MT <11). , More preferably log (MT) <−0.9 × log (MFR) +0.5, and log (MT) <0.85 (MT <7).

The lower limit of the melt tension of the polypropylene resin (B) is not set, but if it is too small, the drawdown resistance may decrease and the temperature range that can be formed during thermoforming may be narrowed. Therefore, log (MT) is preferable. )> 0.48 (MT> 3). Here, the melt tension (MT) is a value measured by the same method as for measuring the melt tension of the polypropylene resin (A).

The polypropylene resin (B) has a melt flow rate (MFR) measured at 230 ° C. and a load of 2.16 kg, preferably 0.1 to 150 g / 10 minutes, and more preferably 1 to 100 g / 10 minutes. Here, MFR is a value measured at 230 ° C. and a load of 2.16 kg in accordance with JIS K7210. The MFR of the polypropylene resin (B) can be adjusted by controlling the hydrogen concentration at the time of polymerization and the like. When the MFR is 0.1 g / 10 minutes or more, the load on the extruder is suppressed and the productivity is improved when the sheet is extruded, which is preferable. The MFR of the polypropylene resin (B) can be adjusted by controlling the hydrogen concentration at the time of polymerization and the like.

The MFR of the polypropylene resin (B) preferably satisfies the following relationship. That is, when the melt flow rate of the polypropylene resin (A) is MFRa and the melt flow rate of the polypropylene resin (B) is MFRb, MFRa / MFRb preferably satisfies 30> MFRa / MFRb> 1, and more preferably 15>. Satisfy MFRa / MFRb> 1.5. When MFRa / MFRb is in the above range, a molded product having a smaller uneven thickness can be obtained.

As a preferred embodiment, the polypropylene resin (B) is selected from a polypropylene resin (B1) having a melting point of 150 ° C. or higher and a polypropylene resin (B2) having a melting point of 110 ° C. or higher and lower than 150 ° C. Hereinafter, the description will be given together with the characteristics other than the melting point.

Polypropylene resin (B1)
The polypropylene resin (B1) preferably has a melting point of 150 ° C. or higher, more preferably 153 ° C. or higher, and even more preferably 155 ° C. or higher. The melting point of the polypropylene resin (B1) is preferably 170 ° C. or lower. By setting the melting point of the polypropylene resin (B1) to 150 ° C. or higher, the rigidity and heat resistance are increased. The melting point can be adjusted by adjusting the amount of comonomer such as ethylene or butene introduced during propylene polymerization.

The melting point (Tm1 / ° C.) of the polypropylene resin (A) and the melting point (Tm2 / ° C.) of the polypropylene resin (B1) preferably satisfy Tm2-Tm1 ≧ 1, more preferably Tm2-Tm1 ≧ 3, and further. Preferably, it satisfies 10 ≧ Tm2-Tm1 ≧ 3.

The polypropylene resin (B1) preferably has a Q value (Mw / Mn) of 3.5 to 10 determined from the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC). , More preferably 3.7 to 8, and even more preferably 4 to 6. When the Q value of the polypropylene resin (B1) is in the above range, it is particularly excellent in molding processability when the sheet is extruded, which is preferable.

The polypropylene resin (B1) preferably does not have a long chain branched structure.
The polypropylene resin (B1) preferably has a branching index g'at 1,000,000 when the absolute molecular weight Mabs determined by a light scatterometer is 1.

The polypropylene resin (B1) is a propylene homopolymer obtained by homopolymerizing propylene by single-stage polymerization or multi-stage polymerization of two or more stages, and copolymerizing propylene and α-olefin by single-stage polymerization or multi-stage polymerization of two or more stages. A propylene / α-olefin random copolymer obtained by polymerization, a polymerization step (1) in which propylene is homopolymerized by single-stage polymerization or multi-stage polymerization of two or more stages to obtain a propylene homopolymer, and propylene and α-olefin In a copolymerization step (2-1) to obtain a propylene / α-olefin random copolymer by copolymerizing with single-stage polymerization or multi-stage polymerization of two or more stages, or single-stage polymerization or two-stage polymerization of two or more kinds of α-olefins. A propylene / α-olefin block copolymer obtained by polymerization including a copolymerization step (2-2) for obtaining a random copolymer between α-olefins by copolymerizing in the above multi-stage polymerization, propylene and α-olefin Copolymerization step (1) to obtain a propylene / α-olefin random copolymer obtained by copolymerization by single-stage polymerization or multi-stage polymerization of two or more stages, and single-stage polymerization or two-stage or more of propylene and α-olefin. Copolymerization step (2-1) to obtain a propylene / α-olefin random copolymer by copolymerization by multi-stage polymerization or copolymerization of two or more kinds of α-olefins by single-stage polymerization or multi-stage polymerization of two or more stages Examples thereof include a propylene / α-olefin random block copolymer obtained by polymerization including a copolymerization step (2-2) for obtaining an α-olefin random copolymer. Further, the polypropylene resin (B1) may be used alone or in combination of two or more.

The α-olefin is preferably ethylene or an α-olefin having 4 to 18 carbon atoms. Specifically, ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4-methyl-pentene-1, 4-methyl-hexene-1, 4,4-dimethylpentene- 1st grade can be mentioned. Further, the α-olefin may be one kind or a combination of two or more kinds.

The polypropylene resin (B1) is preferably one or more polypropylene resins selected from the group consisting of propylene homopolymers, propylene / ethylene block copolymers, and propylene / ethylene / 1-butene block copolymers. ..

Examples of the polypropylene resin (B1) include those polymerized by a Ziegler-Natta catalyst, those polymerized by a metallocene catalyst, those polymerized by a post-metallocene catalyst, and the like. Examples of the Ziegler-Natta catalyst include catalysts containing titanium, magnesium, a solid component requiring halogen, organoaluminum, and an electron donor used as needed. Examples of the metallocene catalyst include a transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton, a cocatalyst, and a catalyst containing an organometallic compound and a carrier used as needed. Be done. Examples of the post-metallocene catalyst include organometallic compounds such as bisamide compounds of metals of Group 4 of the periodic table, bisimino compounds of metals of Group 8 to 10 of the periodic table, and salicylaldehyde compounds of metals of Group 4 to 10 of the periodic table, cocatalysts. And a catalyst containing an organometallic compound or a carrier used as needed.
As the polypropylene resin (B1), a commercially available product can be used, and for example, Novatec (registered trademark) PP series manufactured by Japan Polypropylene Corporation can be used.

Polypropylene resin (B2)
The polypropylene resin (B2) has a melting point of 110 or more and less than 150 ° C, preferably 115 to 145 ° C, and more preferably 120 to 140 ° C. By setting the melting point of the polypropylene resin (B2) to 110 ° C. or higher, it becomes possible to reduce stickiness caused by low crystalline components. Further, by setting the melting point of the polypropylene resin (B2) to less than 150 ° C., the temperature at the time of molding the polypropylene resin composition can be relatively lowered, the generation of odor can be suppressed, and the moldability and the product can be improved. Quality can be ensured. The melting point can be adjusted by the amount of comonomer such as ethylene or butene introduced at the time of propylene polymerization as in the case of polypropylene resin (A1). Here, the melting point is a value measured by the same method as for measuring the melting point of the polypropylene resin (A1).

The polypropylene resin (B2) has a Q value determined by gel permeation chromatography (GPC) of preferably 5.0 or less, more preferably 2.0 to 4.0, still more preferably 2.3 to. It is 3.5, and even more preferably 2.6 to 3.3. Here, the Q value is defined by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by GPC. By setting the Q value of the polypropylene resin (B2) to 5.0 or less, a molded product having excellent mechanical properties can be obtained, which is preferable.

(B-2) Soluble mass of 40 ° C. or less measured by the temperature elution separation (TREF) method Polypropylene resin (B2) can be used as orthodichlorobenzene at 40 ° C. or less measured by the temperature elution separation (TREF) method. The amount of the dissolved component is preferably 4.0% by mass or less, more preferably 3.0% by mass or less, and further preferably 1.5% by mass or less. By reducing the soluble content at 40 ° C. or lower measured by the temperature elution fractionation (TREF) method to 4.0% by mass or less, the affinity with the biomass material (C) is improved and bleeding from the molded product is suppressed. And preferred.

The components soluble in orthodichlorobenzene at 40 ° C. include so-called low crystalline components such as components having a low molecular weight such as oligomers, components having low stereoregularity such as atactic polypropylene, and components having an extremely high comonomer content. .. Here, a component having low stereoregularity such as atactic polypropylene and a low crystalline component having an extremely high comonomer content can be soluble even if the molecular weight is high. Therefore, in order to obtain the polypropylene resin (B2) preferably used in the present invention, polypropylene having low stereoregularity and polypropylene having a wide composition distribution containing a low crystalline component having an extremely high comonomer content can be obtained. The use of catalysts and the adoption of polymerization methods should be avoided.

Here, the amount of the component soluble in orthodichlorobenzene at 40 ° C. or lower measured by the temperature elution fractionation (TREF) method is a value measured according to the following procedure.
The sample is dissolved in orthodichlorobenzene at 140 ° C. to prepare a solution. This is introduced into a TREF column at 140 ° C. under the following conditions, cooled to 100 ° C. at a temperature lowering rate of 8 ° C./min, and subsequently cooled to 40 ° C. at a temperature lowering rate of 4 ° C./min and then held for 10 minutes. .. Then, the solvent ortodichlorobenzene was flowed through the column at a flow rate of 1 mL / min, and the components dissolved in orthodichlorobenzene at 40 ° C. were eluted in the TREF column for 10 minutes, and then the heating rate was 100 ° C./hour. The column is linearly heated to 140 ° C. to obtain an elution curve.
Column size: 4.3 mm φ x 150 mm
Column filler: 100 μm surface-inactivated glass beads Solvent: Ortodichlorobenzene Sample concentration: 5 mg / mL
Sample injection volume: 0.2 mL
Solvent flow velocity: 1 mL / min Detector: Fixed wavelength infrared detector FOXBORO MIRAN 1A
Measurement wavelength: 3.42 μm
From the elution curve obtained according to the above conditions, the ratio (mass%) of the amount of the component eluted at 40 ° C. to the total amount of the sample is calculated.

The polypropylene resin (B2) is a propylene homopolymer obtained by homopolymerizing propylene by single-stage polymerization or multi-stage polymerization of two or more stages, and copolymerizing propylene and α-olefin by single-stage polymerization or multi-stage polymerization of two or more stages. A propylene / α-olefin random copolymer obtained by polymerization, a polymerization step (1) in which propylene is homopolymerized by single-stage polymerization or multi-stage polymerization of two or more stages to obtain a propylene homopolymer, and propylene and α-olefin In a copolymerization step (2-1) to obtain a propylene / α-olefin random copolymer by copolymerizing with single-stage polymerization or multi-stage polymerization of two or more stages, or single-stage polymerization or two-stage polymerization of two or more kinds of α-olefins. A propylene / α-olefin block copolymer obtained by polymerization including a copolymerization step (2-2) for obtaining a random copolymer between α-olefins by copolymerizing in the above multi-stage polymerization, propylene and α-olefin Copolymerization step (1) to obtain a propylene / α-olefin random copolymer obtained by copolymerization by single-stage polymerization or multi-stage polymerization of two or more stages, and single-stage polymerization or two-stage or more of propylene and α-olefin. Copolymerization step (2-1) to obtain a propylene / α-olefin random copolymer by copolymerization by multi-stage polymerization or copolymerization of two or more kinds of α-olefins by single-stage polymerization or multi-stage polymerization of two or more stages Examples thereof include a propylene / α-olefin random block copolymer obtained by polymerization including a copolymerization step (2-2) for obtaining an α-olefin random copolymer. Further, the polypropylene resin (B2) may be used alone or in combination of two or more.

The α-olefin is preferably ethylene or an α-olefin having 4 to 18 carbon atoms. Specifically, ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4-methyl-pentene-1, 4-methyl-hexene-1, 4,4-dimethylpentene- 1st grade can be mentioned. Further, the α-olefin may be one kind or a combination of two or more kinds.

The polypropylene resin (B2) is a propylene / ethylene random copolymer, a propylene / 1-butene random copolymer, a propylene / ethylene / 1-butene random copolymer, a propylene / ethylene random block copolymer, a propylene / ethylene / It is preferably one or more polypropylene resins selected from the group consisting of 1-butene random block copolymers.

The polypropylene resin (B2) contains 85 to 100 mol% of propylene units, preferably 90 to 99.5 mol%, more preferably 92 to 98.5 mol%, ethylene units and / or 1-butene units of 0 to 15. It contains mol%, preferably 0.5-10 mol%, more preferably 1.5-8 mol%.
Here, the propylene unit and the ethylene and / or 1-butene unit are values measured by Fourier transform infrared analysis.

Examples of the polypropylene resin (B2) include those polymerized by a Ziegler-Natta catalyst, those polymerized by a metallocene catalyst, those polymerized by a post-metallocene catalyst, and the like. Examples of the Ziegler-Natta catalyst include catalysts containing titanium, magnesium, a solid component requiring halogen, organoaluminum, and an electron donor used as needed. Examples of the metallocene catalyst include a transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton, a cocatalyst, and a catalyst containing an organometallic compound and a carrier used as needed. Be done. Examples of the post-metallocene catalyst include organometallic compounds such as bisamide compounds of metals of Group 4 of the periodic table, bisimino compounds of metals of Group 8 to 10 of the periodic table, and salicylaldehyde compounds of metals of Group 4 to 10 of the periodic table, cocatalysts. And a catalyst containing an organometallic compound or a carrier used as needed.
As the polypropylene resin (B2), a commercially available product can be used, and for example, the WINTEC (registered trademark) series manufactured by Japan Polypropylene Corporation can be used.

The polypropylene resin (B) is a combination of one or more selected from the polypropylene resin (B1) of the above preferred embodiment and one or more selected from the polypropylene resin (B2) of another preferred embodiment described above. It may be.

Biomass material (C)
The biomass material (C) is an organic resource derived from animals and plants excluding fossil resources, and is preferably an organic resource derived from plants excluding fossil resources. Examples of plant-derived organic resources excluding fossil resources include cellulosic materials, lignocellulosic materials, and starch-based materials.

Examples of the cellulosic material include alpha fiber flocs obtained by alkaline-treating wood pulp and mechanically shredding, cotton linters and cotton flocs obtained from cotton seeds, and rayon flocs obtained by shredding rayon. Examples of the lignocellulosic material include lignocellulosic fibers and lignocellulosic powder. Specific examples thereof include wood pulp, refiner graft pulp (RGP), paper pulp, used paper, crushed wood chips, wood flour, fruit husk flour and the like. The shapes of these cellulosic materials and lignocellulosic materials are not particularly limited, and fibrous and powdery ones can be used. Specific examples of wood flour include crushed products such as pine, fir, poplar, bamboo, bagas, and oil palm trunks, sawdust, and canna scrap, and fruit shell flour includes fruits such as walnuts, peanuts, and palms. There is a crushed product of.

Cellulose-based material or ligno Cellulose-based material is an esterified cellulose-based material or esterified lignocellulosic material, cellulose-based material or ligno, which is obtained by adding polybasic acid anhydride to the hydroxyl group of the cellulosic material or lignocellulosic material. To the hydroxyl groups of oligoesterified cellulose-based materials or oligoesterified lignocellulosic materials, and cellulose-based materials or lignocellulose-based materials, which are obtained by adding polybasic acid anhydride and monoepoxy compound to the hydroxyl groups of cellulosic materials. It may be an oligoesterified cellulosic material or an oligoesterified lignocellulosic material to which a polybasic acid anhydride and a polyhydric alcohol are added.

Examples of the polybasic acid anhydride include maleic anhydride, succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dichloromaleic anhydride, itaconic anhydride, tetrabromophthalic anhydride, and hetic anhydride. Maleic anhydride, pyromellitic anhydride, and the like can be mentioned, but maleic anhydride, succinic anhydride, and phthalic anhydride, which are industrially advantageous and inexpensive, are particularly preferable.

The monoepoxide compound may be a compound containing one epoxy group in the molecule. For example, phenylglycidyl ether, allyl glycidyl ether, styrene oxide, octylene oxide, methyl glycidyl ether, butyl glycidyl ether, and cresil. Examples include glycidyl ether and the like.

Examples of polyhydric alcohols include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol. , 1,9-Nonandiol, 1,10-decanediol, pinacol, hydrobenzoin, benzpinacol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, glycerin, Examples thereof include polyethylene glycol 400.

As a general method for performing esterification, the polybasic acid anhydride (or the polybasic acid anhydride and the monoepoxy compound, or the polybasic acid anhydride is used in the presence of a cellulosic material or a lignocellulosic material. The compound and the polyhydric alcohol) are mixed and reacted at a temperature of 60 to 150 ° C. for 0.5 to 8 hours.

In the case of a reaction in which the polybasic anhydride and the monoepoxy compound are alternately added and esterified to a hydroxyl group in a cellulose-based material or a lignocellulose-based material component, the reaction proceeds sufficiently even without a catalyst, but the reaction is promoted. Therefore, a basic catalyst such as sodium carbonate, dimethylbenzylamine, tetramethylammonium chloride, or viridine may be used. Alternatively, an addition esterification catalyst may be used.

The molecular weights of the polybasic acid anhydride and the oligomer of the monoepoxy compound are about 20 to 1000 which can be liquid (preferably the degree of polymerization is 5 or less, 1) from the viewpoint of ease of use and effect. Also included).

The blending amounts of the polybasic acid anhydride and the monoepoxy compound are as follows. First, the polybasic acid anhydride is used in an amount of 5 to 120 parts by mass, preferably 10 to 100 parts by mass, based on 100 parts by mass of the dried cellulosic material or lignocellulosic material. The monoepoxy compound is preferably 0.5 to 2.0 equivalents of an epoxy group with respect to 1 equivalent of the hydroxyl group-free of the polybasic anhydride used. This is because when the polybasic acid anhydride is used in an amount of more than 120 parts by mass with respect to 100 parts by mass of the dried cellulosic material or lignocellulosic material, the content of the lignocellulose-based or cellulosic substance component becomes low and the heat pressure is increased. This is because exudation occurs during molding, which is not preferable, and a small amount of less than 5 parts by mass lowers the thermal pressure fluidity, and further, a uniform molded product cannot be obtained, which is not preferable.

In the case of a reaction in which the polybasic acid anhydride and the polyhydric alcohol are alternately added and esterified to the hydroxyl groups of the cellulosic material or the lignocellulose-based material, the monoepoxy compound described above may be replaced with the polyhydric alcohol. ..

As specific examples of starch-based materials, for example, rice, wheat, corn, sugar cane, potato, sweet potato, tapioca, corn starch, potato starch, potato starch, tapioca starch and their mild acetylated products can be widely used. Any crop containing starch can be used without limitation. In addition, these starch-based materials are as simple as they are in the general state when they are stored, washed, removed from the starch-free parts such as the exodermis, and cut to an appropriate size. It can be used only by pretreatment. The starch-based material is usually obtained in the form of granules, but these can be used as they are.

Further, it is more preferable that the starch-based material used as a raw material is subjected to such a simple pretreatment and then subjected to a pregelatinization treatment in the following manner. That is, the starch that constitutes the starch-based material has a crystal structure (β structure) at the beginning, but when it is placed in a temperature environment of 70 ° C. or higher in the presence of an appropriate amount of water, this β structure collapses. It changes to an amorphous structure (α structure). In this way, it is said that when raw starch is heated with water, it gelatinizes the change from β structure to α structure. The starch granules showing the α structure of this gelatinized material are dissolved at the molecular level of starch in the heat-flowing polypropylene resin as compared with the case of the β structure in the initial heated state (raw state). It becomes easy to disperse finely and evenly.

As a specific treatment for converting starch having a β structure into an α structure, heat treatment generally performed when it is used for food, such as immersing it in water and boiling it or steaming it with steam, is added. The method can be mentioned.

By the way, when starch having an amorphous state of α structure is left at a low temperature while containing water, a phenomenon (called aging) that returns to the crystalline state of the original β structure with the passage of time is observed. It is generally known. On the other hand, it is known that if water is removed from starch having an amorphous state of α structure, the starch does not reversibly transfer to β structure (does not age) even if it is left at a low temperature for a long period of time. There is.

Therefore, the starch-based material used as the raw material of the present invention has a starch structure of an α structure (amorphous structure), and both contains water and does not contain water (dehydrated). Will also be included. In any case, if the starch structure of the starch-based material blended in the polypropylene resin is an α structure (amorphous structure), the molecular chains of starch are loosened in the polypropylene resin matrix during the kneading process described later. , It becomes finer and easier to disperse. This is an effect that cannot be obtained when an unheated starch-based material having a β structure (crystal structure) in the starch structure is blended.

By the way, the method for obtaining a dehydrated starch-based material having an α structure is specifically by heating in the presence of moisture to gelatinize and then decompressing the atmosphere with a vacuum device as it is. If such a dehydrated starch-based material having an α structure is used, it is difficult to age, so that the starch-based material can be stored alone for a long period of time, and the production period of the polypropylene resin composition can be shortened or manufactured. It will contribute to cost reduction.

It is assumed that trehalose is dissolved in the water used for converting the starch having a β structure into the α structure described above. The effect of this is that, for example, when rice is applied as a starch-based material, trehalose suppresses the decomposition of the lipid component of rice by impregnating the raw rice with an aqueous solution of trehalose, and is produced. This is to suppress the deterioration of the polypropylene resin composition using the rice with time. The reason for this is said to be that trehalose has the effect of coating rice components to protect fatty acids from oxidative decomposition.

It can be said that such an effect is exhibited not only in rice but also in general starch-based materials, and as those having such an effect, in addition to the above-mentioned trehalose, salts, sucrose, and antioxidants are also exhibited. Examples thereof include agents, protein decomposition accelerators, cellulose decomposition accelerators and the like. By blending a starch-based material having an α structure by adding these substances to water, the effect of preventing the peculiar odor, charring, and coloring of the produced polypropylene resin composition can also be obtained.

By the way, we have explained that the starch-based material to be blended as a raw material has already been pregelatinized, but the starch-based material having a β structure contains water by the manufacturing method described later. Can also be used.

Specifically, the raw rice is immersed in water for a predetermined time, drained, then put into a kneader together with the polypropylene resin, and kneaded at the heat flow temperature of the polypropylene resin. This heat flow temperature (usually 100 to 170 ° C.) is sufficient to transfer the starch structure of raw rice from the β structure to the α structure, so that the raw rice is pregelatinized in the process of kneading. become. As described above, after the raw rice has changed to the α structure, the molecular chains of starch are loosened, refined, and dispersed in the polypropylene resin matrix as described above.

Here, in order for raw rice having a β structure to be heated to have an pregelatinized structure, it is desirable that the water content be 17% by mass or more, and for this purpose, the immersion time in water is set to 5 minutes or more. There is a need to. In addition, starch-based materials such as potatoes, which contain enough water to make starch into an α structure by themselves, do not need to be immersed in water like rice and can be put into a kneader as they are. it can.

The biomass material (C) is preferably one or more plant-derived fillers selected from the group consisting of wood, pulp, bamboo, sugar cane (bagasse), rice husks, and rice (starch).

The first polypropylene resin composition of the present invention contains 20 to 90% by mass of polypropylene resin (A) and 10 to 80% by mass of biomass material (C), preferably 30 to 85% by mass of polypropylene resin (A). And the biomass material (C) 15 to 70% by mass, more preferably the polypropylene resin (A) 40 to 80% by mass, and the biomass material (C) 20 to 60% by mass, still more preferably the polypropylene resin (A). It contains 45-75% by mass and 25-55% by mass of the biomass material (C). Here, the total mass ratio of the polypropylene resin (A) and the biomass material (C) is 100% by mass.

The second polypropylene resin composition of the present invention contains 5 to 85% by mass of the polypropylene resin (A), 5 to 85% by mass of the polypropylene resin (B), and 10 to 80% by mass of the biomass material (C), preferably. It contains 10 to 75% by mass of polypropylene resin (A), 10 to 75% by mass of polypropylene resin (B), and 15 to 70% by mass of biomass material (C), more preferably 15 to 65% by mass of polypropylene resin (A). It contains 15 to 65% by mass of polypropylene resin (B) and 20 to 60% by mass of biomass material (C), more preferably 20 to 55% by mass of polypropylene resin (A) and 20 to 55% by mass of polypropylene resin (B). It also contains 25-55% by mass of the biomass material (C). Here, the total mass ratio of the polypropylene resin (A), the polypropylene resin (B), and the biomass material (C) is 100% by mass.

Thermoplastic elastomer (D)
The polypropylene resin composition may optionally contain a thermoplastic elastomer (D). Examples of the thermoplastic elastomer (D) include olefin-based elastomers and styrene-based elastomers. These can be used alone or in combination of two or more.

Examples of the olefin-based elastomer include ethylene-propylene copolymer elastomer (EPR), ethylene-butene copolymer elastomer (EBR), ethylene-hexene copolymer elastomer (EHR), and ethylene-octene copolymer elastomer (EOR). ), Ethylene / propylene / etilidennorbornene copolymer, ethylene / propylene / butadiene copolymer, ethylene / α-olefin / diene ternary copolymer elastomer such as ethylene / propylene / isoprene copolymer, ethylene-ethylene / butylene -Hydrohydrate polymer-based elastomers such as ethylene copolymer (CEBC) can be mentioned. Of these, ethylene / propylene copolymer elastomers, ethylene / butene copolymer elastomers, and ethylene / hexene copolymer elastomers are preferable.

Examples of the styrene-based elastomer include styrene / butadiene / styrene triblock copolymer elastomer (SBS), styrene / isoprene / styrene triblock copolymer elastomer (SIS), and styrene-ethylene / butylene copolymer elastomer (SEB). , Styrene-ethylene / propylene copolymer elastomer (SEP), styrene-ethylene / butylene-styrene copolymer elastomer (SEBS), styrene-ethylene / butylene-ethylene copolymer elastomer (SEBC), hydrogenated styrene / butadiene elastomer (HSBR), Styrene-Eethylene / Styrene-Styrene Copolymer Elastomer (SEPS), Styrene-Eethylene / Ethylene / Styrene-Styrene Copolymer Elastomer (SEEPS), Styrene-butadiene / Butylene-Styrene Copolymer Elastomer (SBBS) , Partially hydrogenated styrene-isoprene-styrene copolymer elastomer, partially hydrogenated styrene-isoprene butadiene-styrene copolymer elastomer and the like.

For the thermoplastic elastomer (D), the MFR measured at 190 ° C. and a load of 2.16 kg is preferably 0.01 to 10 g / 10 minutes, more preferably 0.1 to 3 g / 10 minutes. When the MFR of the thermoplastic elastomer (D) is 0.1 g / 10 minutes or more, the load on the extruder is suppressed and the productivity is improved when the sheet is extruded. Further, when the MFR is 10 g / 10 minutes or less, the melt tension of the sheet can be kept high, and the molded body does not drip due to its own weight during extrusion molding or thermoforming, which is preferable.

The polypropylene resin composition of the present invention is 100% by mass consisting of the total of the polypropylene resin (A) and the biomass material (C) or the total of 100% by mass of the polypropylene resin (A), the polypropylene resin (B) and the biomass material (C). It may contain 1 to 50 parts by mass, more preferably 2 to 44 parts by mass, still more preferably 4 to 38 parts by mass, and even more preferably 8 to 32 parts by mass of the thermoplastic elastomer (D). it can.

(3) Compatibility Agent In the polypropylene resin composition, a compatibility agent can be added, if necessary. Preferred compatibilizers include saturated carboxylic acids, unsaturated carboxylic acids or derivatives thereof, thermoplastic resins modified with unsaturated carboxylic acids or derivatives thereof, and modified with unsaturated carboxylic acids or derivatives thereof. Examples thereof include cellulose-based materials, lignocellulose-based materials, and starch-based materials. Further, an oil-modified alkyd resin or a derivative thereof, modified starch or a derivative thereof can also be used.

Examples of the saturated carboxylic acid include succinic anhydride, succinic anhydride, phthalic anhydride, phthalic acid, tetrahydrophthalic anhydride, adipic anhydride and the like. Examples of unsaturated carboxylic acids include maleic anhydride, maleic acid, nagic anhydride, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid, crotonic acid, isocrotonic acid, mesaconic acid, angelic acid, sorbic acid, acrylic acid and the like. Can be mentioned. As the saturated carboxylic acid or the derivative of the unsaturated carboxylic acid, a metal salt of the saturated carboxylic acid or the unsaturated carboxylic acid, an amide, an imide, an ester or the like can be used.

Further, a thermoplastic resin modified with an unsaturated carboxylic acid or a derivative thereof, a cellulosic material modified with an unsaturated carboxylic acid or a derivative thereof, a lignocellulosic material, a starch-based material, or the like can be used. The pre-modification thermoplastic resin used for the thermoplastic resin modified with unsaturated carboxylic acid or a derivative thereof is not particularly limited as long as it does not significantly impair the effects of the present invention. Examples thereof include ethylene-α-olefin copolymers, high-density polyethylenes, polypropylenes, propylene block copolymers, and propylene random copolymers. Of these, it is preferably the same as the polypropylene resin (A1), the polypropylene resin (A2) and / or the polypropylene resin (B).

These are obtained by heating and mixing a thermoplastic resin or cellulosic material, lignocellulosic material, starch-based material, etc., an unsaturated carboxylic acid or a derivative thereof, and a radical generator in the presence or absence of a solvent. Be done. The addition amount of the unsaturated carboxylic acid or its derivative is preferably 0.1 to 15% by mass, particularly preferably 1 to 10% by mass. The compatibilizer used in the present invention includes a thermoplastic resin modified with an unsaturated carboxylic acid or a derivative thereof having no odor and a low acidity, and a cellulosic material modified with an unsaturated carboxylic acid or a derivative thereof, Ligno. Cellulose-based materials, starch-based materials and the like are preferable.

In the polypropylene resin composition, various additives such as a nucleating agent, a heat-resistant stabilizer, an antioxidant, a weather-resistant stabilizer, and light are used as optional components as long as the effects of the present invention are not significantly impaired. Stabilizers, UV absorbers, antistatic agents, slip agents, anti-blocking agents, antifogging agents, neutralizers, metal deactivators, surfactants, solubilizers, colorants, antibacterial / antifungal agents, flame retardants , Plasticizers, dispersants, fillers, conductive agents, preservatives, fragrances, deodorants, insect repellents, elastomers and the like can be blended. Two or more of these optional components may be used in combination.
Further, these optional components may be blended in the polypropylene resin (A), may be blended in the polypropylene resin (B), and two or more kinds of each resin component can be used in combination. ..

The method for preparing the propylene resin composition of the present invention includes powdery or pelletized polypropylene resin (A), biomass material (C) or polypropylene resin (A), polypropylene resin (B), biomass material (C), and Examples thereof include a method of mixing other compounding agents to be used as needed with a dry blend, a polypropylene mixer, or the like. Further, depending on the situation, the biomass material (C) and the polypropylene resin (A) and / or the polypropylene resin (B) may be fixed in advance by a gelation method or the like. Further, these may be kneaded by a single-screw or twin-screw extruder or the like, or kneaded with a high-concentration filler content to form a masterbatch, which may be diluted to a required concentration at the time of molding.

The polypropylene resin composition of the present invention comprises a polypropylene resin (A) and a biomass material (C), or a polypropylene resin (A), a biomass material (C) and a thermoplastic elastomer (D), or a polypropylene resin (A), a polypropylene resin. (B) and biomass material (C), or polypropylene resin (A), polypropylene resin (B), biomass material (C) and thermoplastic elastomer (D), and any component to be blended, if necessary, are mixed. Alternatively, it can be produced by heating and kneading with a single-screw extruder, a twin-screw extruder, or the like. The resin temperature for heat kneading can be appropriately determined in the range of 100 ° C. to 300 ° C. in consideration of the kneading load, the color and odor of the resin composition, and the like.

The polypropylene resin composition of the present invention can be appropriately molded into a desired shape by means such as pressure molding, film molding, vacuum molding, extrusion molding, injection molding and the like to produce various molded products. The molding temperature at this time can be appropriately determined in the range of 100 ° C. to 300 ° C. in consideration of the kneading load, the color and odor of the resin composition, and the like.

The polypropylene resin composition of the present invention includes various film / sheet materials, disposable molded products (for example, containers, pipes, squares, bars, artificial wood, trays, concrete panels, foams, etc.), furniture, building materials, etc. It can be effectively used as a material for interior / exterior materials for automobiles, housings / housings for home appliances, civil engineering / building materials, materials for agriculture / dairy / fisheries, recreational materials, sports materials, etc.

Further, the polypropylene resin composition of the present invention is suitably used in the fields of electrically insulating materials, industrial parts materials, building materials and the like, and in particular, is preferably used as a raw material for housing members, building materials and home appliances. Specific examples include trays, tableware, speakers, bath unit floor pans, tubs, toilet seats, cabinets, stereo cabinets, skirts, door materials, counter materials, window frames, sound insulation boards, shelves, civil engineering squares, pillars, structures. Examples include materials, kitchen members, floors, baths, base plates, main plates for piano organs, fitting ceiling materials, and the like.

According to the polypropylene resin composition of the present invention, it is possible to effectively dispose of a large amount of excess inventory of agricultural products that are difficult to dispose of, and to reduce the amount of polypropylene resin produced from fossil fuels. Further, in the molded product of the polypropylene resin composition of the present invention, charcoal remains as a residue even if it is incinerated after use, so that the amount of heat of combustion and carbon dioxide generated is small, which greatly contributes to the conservation of the global environment. Moreover, even when it is disposed of in landfill, the rate of return to soil is high and it can be said that it is environmentally friendly.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

1. 1. Evaluation method (1) Melting point (Tm)
The measurement was performed using a differential scanning calorimeter DSC6200 manufactured by Seiko Corporation. Approximately 5 mg of the sheet-shaped sample is packed in an aluminum pan, the temperature is once raised from room temperature to 200 ° C. at a heating rate of 100 ° C./min, held for 5 minutes, and then lowered to 40 ° C. at 10 ° C./min. From the heat of fusion curve obtained when the temperature was raised to 200 ° C. at 10 ° C./min, the maximum melting peak temperature was defined as the melting point Tm (° C.).

(2) Melt flow rate (MFR)
The MFRs of polypropylene resins (A1), (A2) and (B) were measured at 230 ° C. and a load of 2.16 kg in accordance with JIS K7210. The MFR of the thermoplastic elastomer (D) was measured at 190 ° C. and a load of 2.16 kg according to JIS K6922-2. The unit is g / 10 minutes.

(3) Melt tension MT
The measurement was performed using a capillograph manufactured by Toyo Seiki Seisakusho.
(Measurement condition)
・ Capillaries: diameter 2.0 mm, length 40 mm
・ Cylinder diameter: 9.55 mm
・ Cylinder extrusion speed: 20 mm / min ・ Pickup speed: 4.0 m / min ・ Temperature: 230 ° C
When the melt tension MT is extremely high, the resin may break at a take-up speed of 4.0 m / min. In such a case, the take-up speed was reduced by 0.1 m / min, and the melt tension at the maximum take-up speed was set to MT. The unit is grams.

(4) Q value (Mw / Mn)
It was determined by GPC measurement according to the following method.
-Device: Waters GPC (ALC / GPC 150C)
-Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
-Column: Showa Denko AD806M / S (3)
-Mobile phase solvent: orthodichlorobenzene (ODCB)
-Measurement temperature: 140 ° C
・ Flow velocity: 1.0 ml / min ・ Injection amount: 0.2 ml
-Sample preparation: As a sample, prepare a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT) and dissolve it at 140 ° C. for about 1 hour.
The conversion from the holding capacity obtained by GPC measurement to the molecular weight is performed using a calibration curve (calibration curve) made of standard polystyrene prepared in advance. The following brands manufactured by Tosoh Corporation are used as standard polystyrene.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000

(5) Soluble content at 40 ° C. or lower measured by the temperature elution fractionation (TREF) method was measured according to the method described above.

(6) Pellet odor 100 g of pellets were weighed, sealed in a 500 ml glass container, held at 80 ° C. for 3 hours, and then the lid of the glass container was opened to sensually evaluate the odor of the pellets inside. The strength of the odor is determined as follows.
⊚: Almost no odor is felt.
◯: A slight odor is felt.
Δ: I feel an odor.
×: A strong odor is felt.

(7) Extruded sheet molded product and its plastic feeling Pellets are put into an extruder with a screw diameter of 40 mm and extruded from a T-shaped die at a resin temperature of 200 ° C. to make a mirror-finished metal cast roll with a surface temperature of 60 ° C. A sheet of polypropylene resin composition having a width of 500 mm and a thickness of 1.0 mm was obtained by sandwiching the mixture and continuously taking it up at a speed of 1.2 m / min while cooling and solidifying.
The plastic feeling of the obtained molded product was evaluated by the decrease in gloss caused by the biomass material and the addition of patterns. The judgment of the strength of the plastic feeling is as follows.
◯: There is almost no plastic feeling.
Δ: There is a slight plastic feeling.
X: It is a plastic feeling itself.
Further, the die outlet ductility was evaluated in the extruded sheet molding when the take-up speed was increased and a sheet having a thickness of 0.5 mm was obtained. The determination of ductility is as follows.
◯: The thickness of the sheet is uniform.
Δ: A part of the sheet is thinned and the thickness is uneven.
X: The sheet is torn and it is difficult to pick it up.

(8) Thermoformed product The minimum thickness of the thermoformed product was measured as follows.
A test piece having a size of 200 mm × 200 mm was cut out from the polypropylene resin sheets obtained in each Example and each Comparative Example, and fixed to a circular frame having an internal radius of 80 mm. Using a dripping tester manufactured by Misuzu Erie, the heaters are guided to the heating furnace in the tester arranged one above the other, heated at an atmospheric temperature of 200 ° C, and the plug installed on the upper part of the seat 2 seconds after the maximum tension is returned. The sheet was deeply drawn by lowering it at 0.1 m / sec by air cylinder pressure. With respect to the obtained cone-shaped molded product having a height of 200 mm, the thickness of the body portion at 11 reference points provided at intervals of 25 mm between 25 mm and 175 mm in the height direction was measured with a micrometer, and the minimum measurement was performed. The value was taken as the minimum thickness of the body.

The drawdown property of the thermoformed product was measured as follows.
A test piece having a size of 300 mm × 300 mm was cut out from the polypropylene resin sheets obtained in each Example and each Comparative Example, and fixed horizontally to a frame having an inner size of 260 mm × 260 mm. Using a drooping tester manufactured by Misuzu Erie, the heaters are guided to the heating furnace in the tester arranged one above the other and heated at an ambient temperature of 200 ° C., and the vertical displacement of the central part of the sample changes with time from the start of heating. Was measured sequentially with a laser beam.
With heating, the sheet hangs down once (displaces in the minus direction), regains tension due to stress relaxation (displaces in the plus direction), and then hangs down again. The seat position (displacement) at the start of heating is A (mm), the position (displacement) at maximum tension return is B (mm), and the position (displacement) 10 seconds after maximum tension return is C (mm). The drawdown resistance was evaluated according to the following criteria.
⊚: BA ≧ 0 mm and CB ≧ -5 mm
◯: B−A ≧ -5 mm and CB ≧ -10 mm (excluding cases where BA ≧ 0 mm and CB ≧ -5 mm)
Δ: BA ≧ -5 mm and CB <-10 mm, or B-A <-5 mm and CB ≧ -10 mm
X: BA <-5 mm and CB <-10 mm
Here, the fact that BA ≧ -5 mm means that the sheet is tense during container molding, and a beautiful appearance without wrinkles can be formed, and that CB ≧ -10 mm is good. This means that the molding time range for obtaining a compact molded product is sufficiently wide.

(9) Extruded foam molded product and its plastic feeling 100 parts by mass of pellets of polypropylene resin composition and 0.5 parts by mass of chemical foaming agent (trade name: Hydrocerol CF40E-J, manufactured by Clariant Japan Co., Ltd.) as a bubble adjusting agent. The mixture was uniformly stirred and mixed by a ribbon blender, and the obtained mixture was put into a single-screw extruder having a barrel hole for injecting a physical foaming agent in the middle of the barrel. After heating and melting in the pre-stage of the extruder to plasticize and decompose the bubble conditioner, 0.50 parts by mass of liquefied carbon dioxide is injected and kneaded with a high pressure pump with respect to 100 parts by mass of the polypropylene resin composition. The polypropylene resin foam molding material was rapidly cooled in the subsequent stage of the extruder and extruded from a T-shaped die having a width of 750 mm and a lip width of 0.4 mm. One side of the extruded foam sheet is first cooled by a roll installed near the die, then both sides are cooled by three rolls installed after that, and the foam sheet is picked up at a constant speed by a pinch roll and has a thickness of 1.3 mm. Got The operating conditions of the extruder are as follows.
・ Extruder diameter: 65 mmφ, L / D = 42, physical foaming agent injection port: L / D = 20 position Screw rotation speed: 75 rpm
Discharge rate: Approximately 65 kg / h
The evaluation of the obtained plastic feeling was performed as described in (7) above.
For the porosity, after cutting the foams, they are filled in a cylindrical container having a bottom surface with a radius of 1.9 cm and a height of 4.5 cm without any gaps, and the mass, volume, density of the foams are measured and gas is used. The foaming ratio was calculated by measuring the porosity by compression.
For the foamed form, a sample was cut out from the foamed sheet, the cross section of the foamed layer was magnified and projected using a stereomicroscope (Nikon Corporation: SMZ-1000-2 type), and the following determination was made for the bubble form in the cross section. ..
◯: Fine and uniform.
X: Coarse bubbles are present.

(10) Injection foam molded product and its plastic feeling 100 parts by mass of pellets of polypropylene resin composition and 0.5 parts by mass of chemical foaming agent (trade name: Hydrocerol CF40E-J, manufactured by Clariant Japan Co., Ltd.) as a bubble adjusting agent. The mixture was uniformly stirred and mixed with a ribbon blender, and the obtained mixture was used for injection foam molding by the mold opening injection foam molding method as follows.
As an injection molding machine, "α-300" manufactured by FANUC was used, and injection molding was carried out at a cylinder temperature of 200 ° C. and an injection time of 1.0 second. As a mold for injection molding, a flat plate shape having a molded part size of 400 mm × 200 mm and a variable thickness for molding a foam molded body (this time, the mold cavity clearance (T0) was set to 2.0 mmt). Foam molding was carried out using what was possessed. The mold temperature was set to 40 ° C.
The evaluation of the obtained plastic feeling was performed as described in (7) above.
The foaming ratio was the ratio of the thickness of the molded body after foaming by the mold opening operation to the mold cavity clearance (T0).
For the bubble morphology, a sample was cut out from the foam, the cross section of the foam layer was magnified and projected using a stereomicroscope (Nikon: SMZ-1000-2 type), and the following determination was made for the cell morphology in the cross section. ..
◯: Fine and uniform.
X: Coarse bubbles are present.

(11) Blow molded product and its plastic feeling Using a small direct blow molding machine JB105 manufactured by Japan Steel Works, Ltd., which has a cross-head structure for screws and dies with a diameter of 50 mmφ and L / D22, blow at a molding temperature of 200 ° C. A polypropylene blow molded article (cylindrical bottle) having a bottle weight of 30 g and an internal capacity of 550 cc was molded under the conditions of a mold cooling temperature of 15 ° C. and a cooling time of 24 seconds.
The evaluation of the obtained plastic feeling was performed as described in (7) above.
The degree of parison descent was determined as follows from the ratio of the parison upper wall thickness to the parison lower wall thickness when the parison extruded from the small direct blow molding machine was extruded by 0.5 m in length.
◯: The ratio of the upper parison wall thickness to the lower parison wall thickness is 0.8 to 1.0.
Δ: The ratio of the parison upper wall thickness to the parison lower wall thickness is 0.6 to less than 0.8 ×: The ratio of the parison upper wall thickness to the parison lower wall thickness is less than 0.6 The minimum thickness is the center of the body of the cylindrical bottle. The wall thickness in four directions around the circumference was measured with a Mitutoyo micrometer (at a height of 15 cm from the bottom surface), and the difference between the maximum value and the minimum value was determined. The smaller this value is, the more uniform the wall thickness of the cylindrical bottle is, the smaller the uneven wall thickness is, and the better the product is.

(12) Tensile elastic modulus Using a molding machine (EC20 type injection molding machine manufactured by Toshiba Machine Co., Ltd.) and the following mold, a flat plate-shaped test piece for physical property evaluation is prepared under the following conditions, and the "tensile elastic modulus" described later is used. Used for evaluation.
-Mold = Take two flat plate-shaped test pieces (10 x 80 x 4t (mm)) for evaluation of physical properties.
-Molding conditions = molding temperature 220 ° C., mold temperature 30 ° C., injection pressure 50 MPa, injection time 5 seconds, cooling time 20 seconds.
Using the flat plate-shaped test piece prepared above, the measurement was performed at a test temperature of 23 ° C. in accordance with JIS K7162. Judgment of high or low tensile elastic modulus is as follows.
◯: Tension elastic modulus is 1,200 MPa or more ×: Tension elastic modulus is less than 1,200 MPa

2. The raw materials used for raw material evaluation are as follows. Table 1 summarizes the physical characteristics of raw materials.
-Polypropylene resin (A-1): Prepared according to Production Example 1-Polypropylene resin (A-2): Prepared according to Production Example 2-Polypropylene resin (B-1): Novatec BC6C (trade name) manufactured by Japan Polypropylene Corporation.
-Polypropylene resin (B-2): Novatec BC03C (trade name) manufactured by Japan Polypropylene Corporation
-Polypropylene resin (B-3): Wintech WFX6 (trade name) manufactured by Japan Polypropylene Corporation
-Polypropylene resin (B-4): Wintech WSX03 (trade name) manufactured by Japan Polypropylene Corporation
-Biomass material (C-1): Wood flour (100 mesh), manufactured by Casino-Biomass material (C-2): Wood flour (45 mesh), manufactured by Casino-Thermoplastic elastomer (D-1): Mitsui Chemicals Toughmer (registered trademark) AO405

Examples of catalyst production (1) Synthesis of complex (1-a) rac-dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) Indenyl}] Hafnium synthesis:
Synthesis of rac-dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indenyl}] hafnium, JP2012-149160 It was synthesized according to the method of Example 1.
(1-b) rac-dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] Hafnium synthesis:
rac-dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium was synthesized according to the method of Example 7 of JP-A-11-240909. did.

(2-a) Chemical treatment of ion-exchangeable layered silicate Add 645.1 g of distilled water and 82.6 g of 98% sulfuric acid to a 1 L three-necked flask equipped with a stirring blade and a reflux device, and raise the temperature to 95 ° C. It was warm.
Commercially available montmorillonite (Mizusawa Industrial Chemicals, Inc. Benclay KK, Al = 9.78% by mass, Si = 31.79% by mass, Mg = 3.18% by mass, Al / Si (molar ratio) = 0.320, 100 g (average particle size 14 μm) was added, and the mixture was reacted at 95 ° C. for 320 minutes. After 320 minutes, 0.5 L of distilled water was added to stop the reaction, and the mixture was filtered to obtain 255 g of a cake-like solid.
1 g of this cake contained 0.31 g of chemically treated montmorillonite (intermediate). The chemical composition of the chemically treated montmorillonite (intermediate) was Al = 7.68% by mass, Si = 36.05% by mass, Mg = 2.13% by mass, and Al / Si (molar ratio) = 0.222. ..
1545 g of distilled water was added to the cake to form a slurry, and the temperature was raised to 40 ° C. 5.734 g of lithium hydroxide / hydrate was added as a solid and reacted at 40 ° C. for 1 hour. After 1 hour, the reaction slurry was filtered and washed 3 times with 1 L of distilled water to give a cake-like solid again.
The recovered cake was dried to obtain 80 g of chemically treated montmorillonite. The chemical composition of this chemically treated montmorillonite is Al = 7.68% by mass, Si = 36.05% by mass, Mg = 2.13% by mass, Al / Si (molar ratio) = 0.222, Li = 0.53. It was% by mass.

To (2-b) reactor prepolymerized inner volume 1 m ^3, put chemically treated montmorillonite 150kg obtained as described above, the slurry was added hexane 2832L, which triisobutylaluminum 74.4kg (375mol) Was added over 85 minutes and stirred for 60 minutes. Then, it was washed with hexane to 1/32, and the total volume was adjusted to 900 L.
The slurry solution containing the chemically treated montmorillonite was kept at 50 ° C., and 0.65 kg of triisobutylaluminum (4.25 kg, 3.28 mol of a hexane solution having a concentration of 15.3% by mass) was added thereto.
After stirring for 5 minutes, 0.657 kg (0.81 mol) of rac-dichloro [1,1'-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4-hydroazurenyl}] hafnium and 96 L of toluene were added. , Stirring was continued for 60 minutes.
Then, 9.758 kg (26.61 mol) of trinormal octyl aluminum was added and stirred for 6 minutes, and then 0.064 kg of triisobutylaluminum (concentration: 0.648 mass%) of toluene was added to 240 L of toluene in a container with another stirring device. To the place where 9.88 kg, 0.32 mol) was added, rac-dichloro [1,1'-dimethylsilylenebis {2- (5-methyl-2-furyl) -4- (4-i-propylphenyl) indenyl. }] The prepared solution was added by adding 1.768 kg (1.89 mol) of phenylium, 100 L of toluene was added, and stirring was continued for another 20 minutes.
After that, 2387 L of hexane was added to bring the internal temperature of the reactor to 40 ° C., and then 328.1 kg of propylene was fed over 240 minutes to carry out prepolymerization while maintaining 40 ° C. Then, the propylene feed was stopped and residual polymerization was carried out at 40 ° C. for 80 minutes.
After completion of the residual polymerization, stirring was stopped and the contents were allowed to settle and settled. The supernatant was removed to a solution volume of 1500 L, 12.7 kg of triisobutylaluminum was added, 3974 L of hexane was added again, and the mixture was stirred and then settled, and the supernatant was removed until the solution volume was 1500 L.
To this, 8.9 kg of triisobutylaluminum (42.9 kg of a hexane solution having a concentration of 20.8 mass%) and 205 L of hexane were added.
Then, the reaction solution was transferred to a dryer and dried at 40 ° C. for 9 hours.
As a result, 465 kg of a dry prepolymerization catalyst was obtained. The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 2.1. This prepolymerization catalyst was designated as catalyst 1.

Manufacturing example 1
The 20 L autoclave was dried well in advance by circulating nitrogen under heating, and then the inside of the tank was replaced with propylene and cooled to room temperature. After introducing 18.7 mL of a heptane solution of triisobutylaluminum (140 mg / mL), 213 g of ethylene, _{and 0.34 N (normal) L of H 2} , 5000 g of liquid propylene was introduced, and the temperature was raised to 60 ° C. Then, 100 mg of the catalyst 1 excluding the prepolymerized polymer was pressure-fed to the polymerization tank with high-pressure argon to start polymerization, and the temperature was rapidly raised to 70 ° C. It was kept as it was at 70 ° C., and 1 hour after the start of polymerization, unreacted propylene was quickly purged to stop the polymerization. As a result, 1876 g of the polymer (polypropylene resin (A-1)) was obtained. The polypropylene resin (A-1) was a random polypropylene having a long-chain branched structure, and had a melting point (Tm) of 135 ° C. and an MFR of 3 g / 10 minutes.

Manufacturing example 2
The amount of H ₂ to be introduced was increased, and the catalyst 1 was polymerized according to Production Example 1 except that the mass excluding the prepolymerized polymer was 80 mg. As a result, a 1634 g polymer (polypropylene resin (A-2)) was obtained. The polypropylene resin (A-2) was a random polypropylene having a long-chain branched structure, and had a melting point (Tm) of 135 ° C. and an MFR of 30 g / 10 minutes.

(Examples 1-32, Comparative Examples 1-6)
The 38 types of polypropylene resin compositions shown in Tables 2 and 3 (Examples 1 to 32 and Comparative Examples 1 to 6) were weighed and uniformly stirred and mixed with a ribbon blender. The obtained mixture was put into a twin-screw extruder having a screw diameter of 15 mm, kneaded at a resin temperature of 200 ° C., extruded into a strand shape, cooled with water, and pelletized to obtain a polypropylene resin composition.

Pellet odor of the obtained polypropylene resin composition, extruded sheet molded product (plastic feeling, die outlet spreadability), thermoformed product (drawdown property, minimum thickness), extruded foam molded product (plastic feeling, expansion ratio, bubble morphology) ), Injection foam molded product (plastic feeling, foaming ratio, bubble morphology), blow molded product (plastic feeling, degree of parison drop, minimum thickness), and strength were evaluated by the above-mentioned method. The evaluation results are summarized in Tables 2 and 3.

Claims (8)

It contains 20 to 90% by mass of a polypropylene resin (A) having the following properties (a-1) and properties (a-2), and 10 to 80% by mass of a biomass material (C) (provided that (A) and (C). The total mass of the polypropylene resin composition is 100% by mass.).
Characteristic (a-1): A characteristic (a) in which the melt tension (MT) (unit: g) satisfies log (MT) ≧ −0.9 × log (MFR) +0.7 or log (MT) ≧ 1.15. -2): Melting point is 110 ° C or higher and lower than 150 ° C 5 to 85% by mass of polypropylene resin (A) having the following characteristics (a-1) and (a-2), 5 to 85% by mass of polypropylene resin (B) having the following characteristics (b-1), and A polypropylene resin composition comprising 10 to 80% by mass of the biomass material (C) (provided that the total mass of (A), (B) and (C) is 100% by mass).
Characteristic (a-1): A characteristic (a) in which the melt tension (MT) (unit: g) satisfies log (MT) ≧ −0.9 × log (MFR) +0.7 or log (MT) ≧ 1.15. -2): Melting point of 110 ° C. or higher and lower than 150 ° C. (b-1): Melt tension (MT) (unit: g) is log (MT) <-0.9 x log (MFR) +0.7, and log (MT) <1.15 is satisfied The polypropylene resin (A) is a propylene / ethylene random copolymer, a propylene / 1-butene random copolymer, a propylene / ethylene / 1-butene random copolymer, a propylene / ethylene random block copolymer, a propylene / ethylene / The polypropylene resin composition according to claim 1 or 2, wherein it is one or more polypropylene resins selected from the group consisting of 1-butene random block copolymers. The polypropylene resin (B) is characterized by being one or more kinds of polypropylene resins selected from the group consisting of propylene homopolymers, propylene / ethylene block copolymers, and propylene / ethylene / 1-butene block copolymers. The polypropylene resin composition according to claim 2 or 3. The polypropylene resin composition according to any one of claims 1 to 4, wherein the polypropylene resin (A) has the following properties (a-3) and / or (a-4).
(A-3) Strain hardening degree in measurement of extensional viscosity is 1.5 or more (a-4) Ratio of components with molecular weight of 2 million or more in the molecular weight distribution curve measured by GPC is 0.4% by mass or more A claim that the biomass material (C) is one or more plant-derived fillers selected from the group consisting of wood, pulp, bamboo, sugar cane (bagasse), rice husks, and rice (denpnum). The polypropylene resin composition according to any one of 1 to 5. Further thermoplasticity with respect to 100 parts by mass of the total of polypropylene resin (A) and biomass material (C) or 100% by mass of total of polypropylene resin (A), polypropylene resin (B) and biomass material (C). The polypropylene resin composition according to any one of claims 1 to 6, wherein the polypropylene resin composition contains 1 to 50 parts by mass of the elastomer (D). An extruded foam molded article, an injection expanded molded article, a sheet molded article, a thermoformed article, or a blow molded article made of the polypropylene resin composition according to any one of claims 1 to 7.