JP7306207B2 - Polypropylene resin composition - Google Patents

Description

The present invention relates to a polypropylene resin composition containing a biomass material, and to extruded foams, injection foams, sheets, thermoformed articles, and blow molded articles made from the polypropylene resin composition.

Polypropylene is used in all industries because it is excellent in various physical properties including heat resistance and can be produced at low cost. In recent years, from the viewpoint of global warming and environmental protection, the reduction of CO2 emissions is required, and as a countermeasure, the use of biomass materials that can adsorb and fix CO2 in the atmosphere has been proposed in many fields. For example, a composition has been proposed in which a biomass material such as wood flour is combined with polypropylene (Patent Document 1). The polypropylene resin composition, which is made by compounding wood flour with polypropylene, gives a feeling of the warmth of wood that cannot be expressed with plastic. It is used for wood, etc., and its applications are expanding.

When a biomass material is composited with polypropylene and the composite polypropylene resin composition is molded into various molded products, a processing temperature of, for example, about 180 to 200 ° C. is required. A significant odor is generated from the material, which poses a problem of having a great adverse effect on workers. When the processing temperature is lowered in order to suppress the generation of odor, problems arise in that the appearance quality of the resulting molded product deteriorates, and processing becomes difficult in the first place.

In order to solve such problems 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 lignocellulose or cellulosic material. has been proposed (Patent Document 2). According to the propylene-based resin composition of Patent Document 2, it is shown that not only can the molding temperature be lowered and the generation of odor can be suppressed, but also odor can be improved even at high molding temperatures.

JP-A-6-80832 JP 2007-169612 A

Although the propylene-based resin composition of Patent Document 2 is improved in terms of odor, there is a problem that the feel of plastic is enhanced in color tone and the like. Moreover, there is a problem that the blending of lignocellulose-based or cellulose-based materials worsens the melt spreadability of the propylene-based resin, resulting in restrictions on molding methods. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a polypropylene resin composition in which the odor is improved, the feeling of plastic is suppressed, and the deterioration of the melt spreadability is suppressed.

The first polypropylene resin composition of the present invention includes a polypropylene resin (A1) 5 to 85% by mass having the following properties (a1-1) and properties (a1-2), the following properties (a2-1) and properties 5 to 85% by mass of polypropylene resin (A2) having (a2-2) and 10 to 80% by mass of biomass material (C) (where the total mass of (A1), (A2) and (C) is 100 % by mass.).
Property (a1-1): Melt tension (MT) (unit: g) is a property (a1 -2): Melting point is 150 ° C. or higher Property (a2-1): Melt tension (MT) (unit: g) is log (MT) ≥ -0.9 × log (MFR) + 0.7, or log (MT) Property (a2-2) satisfying ≧1.15: melting point of 110° C. or more and less than 150° C.
The melt tension (MT) is measured under the conditions of a capillary diameter of 2.0 mm, a length of 40 mm, a cylinder diameter of 9.55 mm, a temperature of 230° C., a cylinder extrusion speed of 20 mm/min, and a take-up speed of 4.0 m/min. The MFR shall be measured at 230°C with a load of 2.16 kg according to JIS K7210.

In addition, the second polypropylene resin composition of the present invention includes a polypropylene resin (A1) having the following properties (a1-1) and properties (a1-2) and the following properties (a2-1) and properties (a2- 2) in total 5 to 85% by mass of polypropylene resin (A2), 5 to 85% by mass of polypropylene resin (B) having the following properties (b-1), and 10 to 80% by mass of biomass material (C) (However, the total mass of (A1), (A2), (B) and (C) is 100% by mass.).
Property (a1-1): Melt tension (MT) (unit: g) is a property (a1 -2): Melting point is 150 ° C. or higher Property (a2-1): Melt tension (MT) (unit: g) is log (MT) ≥ -0.9 × log (MFR) + 0.7, or log (MT) Property satisfying ≧1.15 (a2-2): Melting point of 110° C. or higher and less than 150° C. Property (b-1): Melt tension (MT) (unit: g) is log (MT) <-0.9×log (MFR) + 0.7 and log(MT) < 1.15
The melt tension (MT) is measured under the conditions of a capillary diameter of 2.0 mm, a length of 40 mm, a cylinder diameter of 9.55 mm, a temperature of 230° C., a cylinder extrusion speed of 20 mm/min, and a take-up speed of 4.0 m/min. The MFR shall be measured at 230°C with a load of 2.16 kg according to JIS K7210.

The polypropylene resin (A1) 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.

The polypropylene resin (A2) includes 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/ It is preferably one or more polypropylene resins selected from the group consisting of ethylene/1-butene random block copolymers.

Furthermore, the polypropylene resin (A2) preferably has the following properties ( a2-4) .
( a2-4) The ratio of components having a molecular weight of 2,000,000 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, sugarcane (bagasse), rice husks, and rice (starch).

In addition, the total of polypropylene resin (A1), polypropylene resin (A2) and biomass material (C) described above, or the total of polypropylene resin (A1), polypropylene resin (A2), polypropylene resin (B) and biomass material (C) A polypropylene resin composition containing 1 to 50 parts by mass of the thermoplastic elastomer (D) per 100 parts by mass of 100% by mass is preferred.

Further, it is preferable that the extruded foam molded product, the injection foam molded product, the sheet molded product, the thermoformed product, or the blow molded product is made of the polypropylene resin composition described above.

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

The first polypropylene resin composition of the present invention contains 5 to 85% by mass of polypropylene resin (A1), 5 to 85% by mass of polypropylene resin (A2), and 10 to 80% by mass of biomass material (C), The total is 100% by mass.

The second polypropylene resin composition of the present invention comprises a total of 5 to 85% by mass of polypropylene resin (A1) and polypropylene resin (A2), 5 to 85% by mass of polypropylene resin (B), and 10 biomass materials (C). ~80% by weight, the sum of which is 100% by weight.

Both the first polypropylene resin composition and the second polypropylene resin composition contain the polypropylene resin (A1), the polypropylene resin (A2) and the biomass material (C) to improve the odor and suppress the feeling of plastic. The deterioration of the melt spreadability is suppressed, and the environmental protection performance is excellent. In the present specification, the "blend of polypropylene resin (A1) and polypropylene resin (A2)" constituting the first polypropylene resin composition and the second polypropylene resin composition is simply referred to as "polypropylene resin (A) ” may be stated.

Polypropylene resin (A1)
The polypropylene resin (A1) has the following properties (a1-1) regarding the relationship between melt tension and MFR.
(a1-1): The melt tension (MT) (unit: g) of the polypropylene resin (A1) is
Satisfies log(MT)≧−0.9×log(MFR)+0.7 or log(MT)≧1.15

The melt tension (MT) of the polypropylene resin (A1) preferably satisfies log(MT)≧−0.9×log(MFR)+0.9 or log(MT)≧1.15. More preferably, log(MT)≧−0.9×log(MFR)+1.1 or log(MT)≧1.15 is satisfied.

The upper limit of the melt tension of the polypropylene resin (A1) is not defined, but if it is too large, the extensibility will decrease, the moldability will deteriorate during thermoforming, and in extreme cases the molded product will tear. It is preferable that log (MT) ≤ 1.48 (MT ≤ 30.2).

As used herein, melt tension (MT) is a value measured using a capillograph. The resin is placed in a cylinder with a diameter of 9.55 mm heated to a temperature of 230° C., and the molten resin is extruded through an orifice with 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 off at a speed of 4.0 m/min is measured and defined as the melt tension (MT).

(a1-2) The polypropylene resin (A1) has a melting point of 150° C. or higher.
The melting point of the polypropylene resin (A1) is preferably 153°C or higher, more preferably 155°C or higher. Also, the melting point of the polypropylene resin (A1) is preferably 170° C. or lower. By setting the melting point of the polypropylene resin (A1) to 150° C. or higher, rigidity and heat resistance are enhanced. Also, the melting point can be adjusted by adjusting the amount of comonomers such as ethylene and butene introduced during propylene polymerization.

Here, in this specification, the melting point is a value measured by a differential scanning calorimeter (DSC). Using a differential scanning calorimeter manufactured by Seiko, about 5 mg of a sample was taken, held at 200 ° C. for 5 minutes, cooled to 40 ° C. at a temperature decrease rate of 10 ° C./min, and then heated at a temperature increase rate of 10 ° C./min. The melting point is obtained from the heat of fusion curve obtained when melting at . That is, let the maximum peak temperature of a heat-of-melting curve be a melting point.

The polypropylene resin (A1) preferably has a melt flow rate (MFR) of 0.1 to 150 g/10 minutes, more preferably 1 to 100 g/10 minutes, measured at 230° C. under a load of 2.16 kg. As used herein, MFR is a value measured at 230° C. under a load of 2.16 kg according to JIS K7210. The MFR of the polypropylene resin (A1) can be adjusted by controlling the hydrogen concentration during polymerization. When the MFR is 0.1 g/10 minutes or more, the load on the extruder can be suppressed during extrusion molding of the sheet, and the productivity is improved, which is preferable.

The polypropylene resin (A1) preferably has a mm fraction of 3 chains of propylene units measured by ¹³ C-NMR of 95% or more, more preferably 96% or more, and still more preferably 97% or more.

The mm fraction is the ratio of 3 chains of propylene units having the same methyl branch direction in each propylene unit among arbitrary 3 chains of propylene units consisting of head-to-tail bonds in the polymer chain, and the upper limit is 100%. be. This mm fraction is a value indicating that the steric structure of the methyl groups in the polypropylene molecular chain is isotactically controlled, and the higher the value, the more isotactically controlled it means. When the mm fraction is 95% or more, the drawdown resistance during thermoforming is improved.

In the present specification, the method for measuring the mm fraction of 3 chains of propylene units by ¹³ C-NMR of polypropylene is as follows.
After completely dissolving 375 mg of a sample in 2.5 ml of deuterated 1,1,2,2-tetrachloroethane in an NMR sample tube (10φ), measurement was performed at 125°C under the following conditions by the proton complete decoupling method. do. Chemical shifts set the middle peak of the three peaks for deuterated 1,1,2,2-tetrachloroethane at 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 times: 10,000 times or more Observation range: -20 ppm to 179 ppm
Number of data points: 32,768

Determination of the mm fraction is performed using the ¹³ C-NMR spectrum measured under the conditions described above. Spectral assignment is performed 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. .

The polypropylene resin (A1) preferably has a Q value (Mw/Mn) determined from the weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of 3.5 to 10. , more preferably 3.7-8, more preferably 4-6. When the Q value of the polypropylene resin (A1) is within the above range, it is particularly excellent in moldability when extruding a sheet, which is preferable.

The polypropylene resin (A1) preferably has a molecular weight distribution Mz/Mw determined from the Z-average molecular weight (Mz) and Mw measured by gel permeation chromatography (GPC) of 2.5 to 10, more preferably 2.8. to 8, more preferably 3 to 6. When the Mz/Mw of the polypropylene resin (A1) is within the above range, the moldability is particularly excellent when the sheet is extruded.

In the present specification, the definitions of Mn, Mw, and Mz are based on the matters described in "Basics of Polymer Chemistry" (Kobunshi Gakkai ed., Tokyo Kagaku Dojin, 1978), etc., and Mn, Mw, and Mz are It can be calculated from the molecular weight distribution curve by GPC.

In the present invention, the measurement method of GPC is as follows.
・Apparatus: GPC manufactured by Waters (ALC/GPC 150C)
・ Detector: FOXBORO MIRAN 1A IR detector (measurement wavelength: 3.42 μm)
・Column: Showa Denko AD806M/S (3 columns)
・ Mobile phase solvent: ortho-dichlorobenzene (ODCB)
・Measurement temperature: 140°C
・Flow rate: 1.0 ml/min
・Injection volume: 0.2 ml
-Sample preparation: A 1 mg/mL solution of the sample is prepared using ODCB (containing 0.5 mg/mL of BHT) and dissolved at 140°C for about 1 hour.

Conversion from the retention volume obtained by GPC measurement to the molecular weight is carried out using a previously prepared standard polystyrene calibration curve (calibration curve). As standard polystyrene, the following brands manufactured by Tosoh Corporation are used.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000

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

Polypropylene resin (A1) preferably has a long-chain branched structure.
As a direct indicator of whether or not the polypropylene resin has a long-chain branched structure, the branching index g' can be mentioned. The branching index g′ is the ratio of the intrinsic viscosity [η]br of a polymer having a long-chain branched structure to the intrinsic viscosity [η]lin of a linear polymer having the same molecular weight, that is, [η]br/[η]lin, and when g′<1, it can be said to have a long-chain branched structure.

The definition of the branching index g' is described, for example, in "Developments in Polymer Characterization-4" (JV Dawkins ed. Applied Science Publishers, 1983), and is an index known 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 GPC with a viscometer as the detector.

The polypropylene resin (A1) preferably has a branching index g' of 0.30 or more and less than 1.00, more preferably 0.55 or more and 0.98 when the absolute molecular weight Mabs obtained by light scattering is 1,000,000. 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.

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

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

In determining the absolute molecular weight (Mabs), the root mean square radius of inertia (Rg) and the intrinsic viscosity ([η]), use the data processing software ASTRA (version 4.73.04) attached to MALLS and refer to the following literature. calculation.
References 1. Developments in Polymer Characterization-4 (JV Dawkins ed. Applied Science Publishers, 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 ]br/[η]lin).

Here, as a linear polymer for obtaining [η]lin, commercially available homopolypropylene (Novatec (registered trademark) PP grade name: FY6, manufactured by Nippon Polypropylene Co., Ltd.) is used. 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 the molecular weight. A numerical value can be obtained by extrapolation.

The polypropylene resin (A1) preferably has a strain hardening degree of 6.0 or more, more preferably 8.0 or more, as measured by extensional viscosity. Here, the degree of strain hardening is a value determined by measurement of elongational viscosity at a strain rate of 0.1 s ⁻¹ and may be expressed as λmax in this specification.
The degree of strain hardening (λmax) is an index that represents the strength when melted, and if this value is large, even if the molded body has a complicated shape, it is a defective phenomenon in which an excessive uneven thickness is formed during thermoforming. can be prevented, and the physical properties of the molded product can be improved, and the thickness of the sheet material can be reduced (gauge down), so industrial members such as automobile members can be suitably molded. When the strain hardening degree of the polypropylene resin (A1) having a long-chain branched structure is 6.0 or more, a sufficient thickness unevenness suppressing effect is exhibited. Further, when the strain hardening degree is 8.0 or more, even when the amount of filler and the amount of thermoplastic elastomer are large, a sufficient thickness unevenness suppressing effect is exhibited.

The method for calculating the strain hardening degree λmax(0.1) in the measurement of extensional viscosity at a strain rate of 0.1 s ⁻¹ is described below.
The elongational 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 elongational viscosity ηE (Pa·s) on the vertical axis. On the log-log graph, the relationship between the time immediately before strain hardening occurs and the viscosity is approximated by a straight line to obtain an approximate straight line.
Specifically, first, the slope at each time when the elongational viscosity is plotted against time is obtained. Use the average method. For example, there is a method in which the slopes of adjacent data are obtained and a moving average of several surrounding points is taken.

The elongational viscosity becomes a simple increasing function in the region of low strain amount, gradually approaches a constant value, and agrees with the Trouton viscosity after a sufficient period of time if there is no strain hardening. When the strain amount (=strain rate x time) is about 1, the elongational viscosity begins to increase with time. That is, the above slope tends to decrease with time in the low strain region, but tends to increase from a strain amount of about 1, and an inflection point exists on the curve when plotting the extensional viscosity against time. . Therefore, the strain amount is in the range of about 0.1 to 2.5, and the point where the slope at each time obtained above takes the minimum value is obtained, a tangent line is drawn at that point, and a straight line is drawn when the strain amount is 4.0. Extrapolate until . The maximum value (ηmax) of the elongational viscosity ηE until the amount of strain reaches 4.0 and the time at which the maximum value is obtained are determined, and the viscosity on the approximate straight line at that time is defined as ηlin. ηmax/ηlin is defined as λmax(0.1).

The polypropylene resin (A1) is a propylene homopolymer obtained by homopolymerizing propylene in a single-stage polymerization or a multi-stage polymerization of two or more stages, or a copolymer of propylene and an α-olefin in a 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) of obtaining a propylene homopolymer by homopolymerizing propylene in a single-stage polymerization or a multi-stage polymerization of two or more stages, and propylene and an α-olefin Copolymerization step (2-1) to obtain a propylene/α-olefin random copolymer by single-stage polymerization or multi-stage polymerization of two or more stages, or two or more types of α-olefins by single-stage polymerization or two-stage The propylene/α-olefin block copolymer obtained by the polymerization including the copolymerization step (2-2) to obtain a random copolymer between α-olefins by copolymerization in the above multistage polymerization, propylene and α-olefin are Copolymerization step (1) for obtaining a propylene/α-olefin random copolymer obtained by copolymerization by single-stage polymerization or multi-stage polymerization of two or more stages, and Copolymerization step (2-1) of obtaining a propylene/α-olefin random copolymer by multi-stage polymerization or copolymerization of two or more α-olefins by single-stage polymerization or multi-stage polymerization of two or more stages A propylene/α-olefin random block copolymer obtained by polymerization including a copolymerization step (2-2) for obtaining a random copolymer between α-olefins can be mentioned. Also, the polypropylene resin (A1) may be one kind or a combination of two or more kinds.

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- 1 etc. can be mentioned. Also, the α-olefin may be one or a combination of two or more.

The polypropylene resin (A1) 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 (A1) include those polymerized by a Ziegler-Natta catalyst, those polymerized by a metallocene catalyst, those polymerized by a post-metallocene catalyst, and the like. Ziegler-Natta catalysts include catalysts containing titanium, magnesium, a solid component essentially containing halogen, organic aluminum, and optionally an electron donor. The metallocene catalyst includes a transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton, a co-catalyst, and a catalyst comprising an organometallic compound and a carrier used as necessary. be done. Examples of post-metallocene catalysts include organometallic compounds such as bisamide compounds of metals of Group 4 of the periodic table, bisimino compounds of metals of Groups 8 to 10 of the periodic table, and salicylaldiminate compounds of metals of Groups 4 to 10 of the periodic table, promoters, and a catalyst containing an organic metal compound and a carrier, which are used as necessary.
The polypropylene resin (A1) can be a commercially available product, such as the WAYMAX (registered trademark) series manufactured by Japan Polypropylene Corporation.

Polypropylene resin (A2)
The polypropylene resin (A2) has the following properties (a2-1) regarding the relationship between melt tension and MFR.
(a2-1): The melt tension (MT) (unit: g) of the polypropylene resin (A2) is
Satisfies log(MT)≧−0.9×log(MFR)+0.7 or log(MT)≧1.15

The melt tension (MT) of the polypropylene resin (A2) preferably satisfies log(MT)≧−0.9×log(MFR)+0.9 or log(MT)≧1.15. More preferably, log(MT)≧−0.9×log(MFR)+1.1 or log(MT)≧1.15 is satisfied.

The upper limit of the melt tension of the polypropylene resin (A2) is not defined, but if it is too large, the extensibility will decrease, the moldability will deteriorate during thermoforming, and in extreme cases the molded product will tear. It is preferable that log (MT) ≤ 1.48 (MT ≤ 30.2).

(a2-2) The polypropylene resin (A2) has a melting point of 110 to 150°C. The melting point of the polypropylene resin (A2) is preferably 115-145°C, more preferably 120-140°C. By setting the melting point of the polypropylene resin (A2) to 110° C. or higher, it becomes possible to reduce the stickiness caused by the low-crystalline component. In addition, by setting the melting point of the polypropylene resin (A2) to less than 150°C, the temperature when molding the polypropylene resin composition can be relatively low, the generation of odor is suppressed, and moldability and product quality are improved. Quality can be ensured. Also, the melting point can be adjusted by adjusting the amount of comonomers such as ethylene and butene introduced during propylene polymerization.

The melting point (Tm1/° C.) of the polypropylene resin (A1) and the melting point (Tm2/° C.) of the polypropylene resin (A2) preferably satisfy Tm2−Tm1≧1, more preferably satisfy Tm2−Tm1≧3, and further Preferably, 10≧Tm2−Tm1≧3 is satisfied.

The polypropylene resin (A2) preferably has a melt flow rate (MFR) of 0.1 to 150 g/10 minutes, more preferably 1 to 100 g/10 minutes, measured at 230° C. under a load of 2.16 kg. Here, MFR is a value measured at 230° C. under a load of 2.16 kg according to JIS K7210. The MFR of the polypropylene resin (A2) can be adjusted by controlling the hydrogen concentration during polymerization. When the MFR is 0.1 g/10 minutes or more, the load on the extruder can be suppressed during extrusion molding of the sheet, and the productivity is improved, which is preferable.

The polypropylene resin (A2) preferably has a mm fraction of 3 chains of propylene units determined by ¹³ C-NMR of 95% or more, more preferably 96% or more, and still more preferably 97% or more.

The mm fraction is the ratio of 3 chains of propylene units having the same methyl branch direction in each propylene unit among arbitrary 3 chains of propylene units consisting of head-to-tail bonds in the polymer chain, and the upper limit is 100%. be. This mm fraction is a value indicating that the steric structure of the methyl groups in the polypropylene molecular chain is isotactically controlled, and the higher the value, the more isotactically controlled it means. When the mm fraction is 95% or more, the drawdown resistance during thermoforming is improved.

The polypropylene resin (A2) preferably has a Q value (Mw/Mn) of 3.5 to 10 determined from the weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC). , more preferably 3.7-8, more preferably 4-6. When the Q value of the polypropylene resin (A2) is within the above range, it is particularly excellent in moldability when extruding a sheet, which is preferable.

The polypropylene resin (A2) preferably has a molecular weight distribution Mz/Mw determined from the Z-average molecular weight (Mz) and Mw measured by gel permeation chromatography (GPC) of 2.5 to 10, more preferably 2.8. to 8, more preferably 3 to 6. When the Mz/Mw of the polypropylene resin (A2) is within the above range, the moldability is particularly excellent when the sheet is extruded.

The polypropylene resin (A2) preferably has the following properties (a2-4).
(a2-4) The ratio of components having a molecular weight of 2,000,000 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 GPC measurement of polypropylene resin (A), the molecular weight is 200 The ratio of 10,000 or more components is preferably 0.4% by mass or more, more preferably 0.5% by mass or more, and still more preferably 0.6% by mass or more. When the ratio of the component having a molecular weight of 2,000,000 or more is within the above range, the melt tension is increased and the moldability is excellent.

Polypropylene resin (A2) preferably has a long-chain branched structure.
As a direct indicator of whether or not the polypropylene resin has a long-chain branched structure, the branching index g' can be mentioned. The branching index g′ is the ratio of the intrinsic viscosity [η]br of a polymer having a long-chain branched structure to the intrinsic viscosity [η]lin of a linear polymer having the same molecular weight, that is, [η]br/[η]lin, and when g′<1, it can be said to have a long-chain branched structure.

The polypropylene resin (A2) preferably has a branching index g' of 0.30 or more and less than 1.00, more preferably 0.55 or more and 0.98 when the absolute molecular weight Mabs obtained by light scattering is 1,000,000. 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 polypropylene resin (A2) preferably has the following strain hardening properties (a2-3).
(a2-3) The degree of strain hardening in measurement of extensional viscosity is 1.5 or more The polypropylene resin (A2) preferably has a degree of strain hardening in measurement of extensional viscosity of 1.5 or more, more preferably 2 or more, and still more preferably is 3 or more. Here, the degree of strain hardening is a value determined by measurement of elongational viscosity at a strain rate of 0.1 s ⁻¹ and may be expressed as λmax in this specification.
The degree of strain hardening (λmax) is an index that represents the strength when melted, and if this value is large, even if the molded body has a complicated shape, it is a defective phenomenon in which an excessive uneven thickness is formed during thermoforming. can be prevented, and the physical properties of the molded product can be improved, and the thickness of the sheet material can be reduced (gauge down), so industrial members such as automobile members can be suitably molded. When the strain hardening degree of the polypropylene resin (A2) having a long-chain branched structure is 1.5 or more, a sufficient thickness unevenness suppressing effect is exhibited.

The polypropylene resin (A2) is a propylene homopolymer obtained by homopolymerizing propylene in a single-stage polymerization or a multi-stage polymerization of two or more stages, or a copolymer of propylene and an α-olefin in a 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) of obtaining a propylene homopolymer by homopolymerizing propylene in a single-stage polymerization or a multi-stage polymerization of two or more stages, and propylene and an α-olefin Copolymerization step (2-1) to obtain a propylene/α-olefin random copolymer by single-stage polymerization or multi-stage polymerization of two or more stages, or two or more types of α-olefins by single-stage polymerization or two-stage The propylene/α-olefin block copolymer obtained by the polymerization including the copolymerization step (2-2) to obtain a random copolymer between α-olefins by copolymerization in the above multistage polymerization, propylene and α-olefin are Copolymerization step (1) for obtaining a propylene/α-olefin random copolymer obtained by copolymerization by single-stage polymerization or multi-stage polymerization of two or more stages, and Copolymerization step (2-1) of obtaining a propylene/α-olefin random copolymer by multi-stage polymerization or copolymerization of two or more α-olefins by single-stage polymerization or multi-stage polymerization of two or more stages A propylene/α-olefin random block copolymer obtained by polymerization including a copolymerization step (2-2) for obtaining a random copolymer between α-olefins can be mentioned. Further, the polypropylene resin (A2) may be one type or a combination of two or more types.

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- 1 etc. can be mentioned. Also, the α-olefin may be one or a combination of two or more.

The polypropylene resin (A2) 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/ One or more polypropylene resins selected from the group consisting of 1-butene random block copolymers are preferred.

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

Examples of the polypropylene resin (A2) include those polymerized by a Ziegler-Natta catalyst, those polymerized by a metallocene catalyst, those polymerized by a post-metallocene catalyst, and the like. Ziegler-Natta catalysts include catalysts containing titanium, magnesium, a solid component essentially containing halogen, organic aluminum, and optionally an electron donor. The metallocene catalyst includes a transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton, a co-catalyst, and a catalyst comprising an organometallic compound and a carrier used as necessary. be done. Examples of post-metallocene catalysts include organometallic compounds such as bisamide compounds of metals of Group 4 of the periodic table, bisimino compounds of metals of Groups 8 to 10 of the periodic table, and salicylaldiminate compounds of metals of Groups 4 to 10 of the periodic table, promoters, and a catalyst containing an organic metal compound and a carrier, which are used as necessary.
The polypropylene resin (A2) can be a commercially available product, such as the WAYMAX (registered trademark) series manufactured by Japan Polypropylene Corporation.

Polypropylene resin (B)
The polypropylene resin (B) has the following property (b-1) regarding the relationship between melt tension and MFR.
Property (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 defined, but if it is too small, the drawdown resistance may decrease, and the moldable temperature range during thermoforming may be narrowed. )>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) preferably has a melt flow rate (MFR) of 0.1 to 150 g/10 minutes, more preferably 1 to 100 g/10 minutes, measured at 230° C. under a load of 2.16 kg. Here, MFR is a value measured at 230° C. under a load of 2.16 kg according to JIS K7210. The MFR of the polypropylene resin (B) can be adjusted by controlling the hydrogen concentration during polymerization. When the MFR is 0.1 g/10 minutes or more, the load on the extruder can be suppressed during extrusion molding of the sheet, and the productivity is improved, which is preferable. The MFR of the polypropylene resin (B) can be adjusted by controlling the hydrogen concentration during polymerization.

The MFR of the polypropylene resin (B) preferably satisfies the following relationship. That is, when the melt flow rate of polypropylene resin (A) is MFRa and the melt flow rate of polypropylene resin (B) is MFRb, MFRa/MFRb preferably satisfies 30>MFRa/MFRb>1, more preferably 15>. MFRa/MFRb>1.5 is satisfied. When MFRa/MFRb is in the range of the above values, it is possible to obtain a compact with a smaller uneven thickness.

The polypropylene resin (B) is, as a preferred embodiment, 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 or higher and lower than 150°C. The properties other than the melting point will be described below.

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, rigidity and heat resistance are enhanced. Also, the melting point can be adjusted by adjusting the amount of comonomers such as ethylene and butene introduced during propylene polymerization.

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 number average molecular weight (Mn) measured by gel permeation chromatography (GPC). , more preferably 3.7-8, more preferably 4-6. When the Q value of the polypropylene resin (B1) is within the above range, it is particularly excellent in moldability when extruding a sheet, which is preferable.

Polypropylene resin (B1) preferably does not have a long-chain branched structure.
The polypropylene resin (B1) preferably has a branching index g' of 1 at an absolute molecular weight Mabs of 1,000,000 determined by a light scattering meter.

The polypropylene resin (B1) is a propylene homopolymer obtained by homopolymerizing propylene in a single-stage polymerization or a multi-stage polymerization of two or more stages, or a copolymer of propylene and an α-olefin in a 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) of obtaining a propylene homopolymer by homopolymerizing propylene in a single-stage polymerization or a multi-stage polymerization of two or more stages, and propylene and an α-olefin Copolymerization step (2-1) to obtain a propylene/α-olefin random copolymer by single-stage polymerization or multi-stage polymerization of two or more stages, or two or more types of α-olefins by single-stage polymerization or two-stage The propylene/α-olefin block copolymer obtained by the polymerization including the copolymerization step (2-2) to obtain a random copolymer between α-olefins by copolymerization in the above multistage polymerization, propylene and α-olefin are Copolymerization step (1) for obtaining a propylene/α-olefin random copolymer obtained by copolymerization by single-stage polymerization or multi-stage polymerization of two or more stages, and Copolymerization step (2-1) of obtaining a propylene/α-olefin random copolymer by multi-stage polymerization or copolymerization of two or more α-olefins by single-stage polymerization or multi-stage polymerization of two or more stages A propylene/α-olefin random block copolymer obtained by polymerization including a copolymerization step (2-2) for obtaining a random copolymer between α-olefins can be mentioned. Also, the polypropylene resin (B1) may be one or a 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- 1 etc. can be mentioned. Also, the α-olefin may be one or a combination of two or more.

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. Ziegler-Natta catalysts include catalysts containing titanium, magnesium, a solid component essentially containing halogen, organic aluminum, and optionally an electron donor. The metallocene catalyst includes a transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton, a co-catalyst, and a catalyst comprising an organometallic compound and a carrier used as necessary. be done. Examples of post-metallocene catalysts include organometallic compounds such as bisamide compounds of metals of Group 4 of the periodic table, bisimino compounds of metals of Groups 8 to 10 of the periodic table, and salicylaldiminate compounds of metals of Groups 4 to 10 of the periodic table, promoters, and a catalyst containing an organic metal compound and a carrier, which are used as necessary.
The polypropylene resin (B1) can be a commercially available product such as Novatec (registered trademark) PP series manufactured by Japan Polypropylene Corporation.

Polypropylene resin (B2)
The polypropylene resin (B2) has a melting point of 110 to 150°C, preferably 115 to 145°C, 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 the stickiness caused by the low-crystalline component. In addition, by setting the melting point of the polypropylene resin (B2) to less than 150°C, the temperature when molding the polypropylene resin composition can be relatively low, the generation of odor is suppressed, and moldability and product quality are improved. Quality can be ensured. The melting point can be adjusted by adjusting the amount of comonomers such as ethylene and butene introduced during propylene polymerization in the same manner as the 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).

(b-1) Q value 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, It is more preferably 2.3 to 3.5, and even more preferably 2.6 to 3.3. Here, the Q value is defined as the ratio (Mw/Mn) between 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 article having excellent mechanical properties can be obtained, which is preferable.

(b-2) Soluble content below 40 ° C measured by temperature programmed elution fractionation (TREF) method Polypropylene resin (B2) is soluble in ortho-dichlorobenzene below 40 ° C measured by temperature programmed elution fractionation (TREF) method The amount of soluble components is preferably 4.0% by mass or less, more preferably 3.0% by mass or less, and even more preferably 1.5% by mass or less. By keeping the soluble content at 40°C or lower measured by the temperature programmed elution fractionation (TREF) method to 4.0 mass% or less, the compatibility with the biomass material (C) is improved and bleeding from the molded product is suppressed. and preferred.

Components soluble in ortho-dichlorobenzene at 40°C include so-called low crystal components such as components with low molecular weight such as oligomers, components with low stereoregularity such as atactic polypropylene, and components with extremely high comonomer content. . Here, components with low stereoregularity such as atactic polypropylene and low crystallinity components with extremely high comonomer content can become soluble components even if they have high molecular weights. Therefore, in order to obtain the polypropylene resin (B2) preferably used in the present invention, a polypropylene with low stereoregularity or a polypropylene with a wide composition distribution that contains a low-crystalline component with an extremely high comonomer content is obtained. The use of catalysts and polymerization methods should be avoided.

Here, the amount of components soluble in ortho-dichlorobenzene at 40° C. or less measured by the temperature rising elution fractionation (TREF) method is a value measured according to the following procedure.
A sample is dissolved in ortho-dichlorobenzene at 140° C. to obtain a solution. Under the following conditions, this is introduced into a TREF column at 140° C., cooled to 100° C. at a temperature decrease rate of 8° C./min, then cooled to 40° C. at a temperature decrease rate of 4° C./min, and held for 10 minutes. . Thereafter, the solvent ortho-dichlorobenzene was passed through the column at a flow rate of 1 mL/min, and the components dissolved in the ortho-dichlorobenzene at 40°C in the TREF column were eluted for 10 minutes, and then the temperature was raised at a rate of 100°C/hour. The temperature of the column is linearly raised to 140°C at , and an elution curve is obtained.
Column size: 4.3mmφ×150mm
Column packing material: 100 μm surface-deactivated glass beads Solvent: ortho-dichlorobenzene Sample concentration: 5 mg/mL
Sample injection volume: 0.2 mL
Solvent flow rate: 1 mL/min Detector: Fixed wavelength infrared detector MIRAN 1A manufactured by FOXBORO
Measurement wavelength: 3.42 μm
From the elution curve obtained under 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 in a single-stage polymerization or a multi-stage polymerization of two or more stages, or a copolymer of propylene and an α-olefin in a 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) of obtaining a propylene homopolymer by homopolymerizing propylene in a single-stage polymerization or a multi-stage polymerization of two or more stages, and propylene and an α-olefin Copolymerization step (2-1) to obtain a propylene/α-olefin random copolymer by single-stage polymerization or multi-stage polymerization of two or more stages, or two or more types of α-olefins by single-stage polymerization or two-stage The propylene/α-olefin block copolymer obtained by the polymerization including the copolymerization step (2-2) to obtain a random copolymer between α-olefins by copolymerization in the above multistage polymerization, propylene and α-olefin are Copolymerization step (1) for obtaining a propylene/α-olefin random copolymer obtained by copolymerization by single-stage polymerization or multi-stage polymerization of two or more stages, and Copolymerization step (2-1) of obtaining a propylene/α-olefin random copolymer by multi-stage polymerization or copolymerization of two or more α-olefins by single-stage polymerization or multi-stage polymerization of two or more stages A propylene/α-olefin random block copolymer obtained by polymerization including a copolymerization step (2-2) for obtaining a random copolymer between α-olefins can be mentioned. Also, the polypropylene resin (B2) may be one or a 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- 1 etc. can be mentioned. Also, the α-olefin may be one or a combination of two or more.

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/ One or more polypropylene resins selected from the group consisting of 1-butene random block copolymers are preferred.

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%, and 0 to 15 ethylene units and/or 1-butene units. mol %, preferably 0.5 to 10 mol %, more preferably 1.5 to 8 mol %.
Here, propylene units and ethylene and/or 1-butene units are values measured by Fourier transform infrared analysis.

Examples of the polypropylene resin (B2) include those polymerized with a Ziegler-Natta catalyst, those polymerized with a metallocene catalyst, those polymerized with a post-metallocene catalyst, and the like. Ziegler-Natta catalysts include catalysts containing titanium, magnesium, a solid component essentially containing halogen, organic aluminum, and optionally an electron donor. The metallocene catalyst includes a transition metal compound of Group 4 of the periodic table containing a ligand having a cyclopentadienyl skeleton, a co-catalyst, and a catalyst comprising an organometallic compound and a carrier used as necessary. be done. Examples of post-metallocene catalysts include organometallic compounds such as bisamide compounds of metals of Group 4 of the periodic table, bisimino compounds of metals of Groups 8 to 10 of the periodic table, and salicylaldiminate compounds of metals of Groups 4 to 10 of the periodic table, promoters, and a catalyst containing an organic metal compound and a carrier, which are used as necessary.
As the polypropylene resin (B), commercially available products such as 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 above preferred polypropylene resins (B1) and one or more selected from the above another preferred polypropylene resins (B2). may

Biomass material (C)
The biomass material (C) is an animal or plant-derived organic resource excluding fossil resources, preferably a plant-derived organic resource excluding fossil resources. Plant-derived organic resources other than fossil resources include cellulose-based materials, lignocellulose-based materials, and starch-based materials.

Examples of cellulosic materials include alpha fiber flock obtained by treating wood pulp with alkali and mechanically shredding, cotton linters obtained from cottonseed, cotton flock, and rayon flock obtained by shredding rayon. Lignocellulosic materials include lignocellulosic fibers and lignocellulosic powders. Specific examples include wood pulp, refiner graft pulp (RGP), paper pulp, waste paper, pulverized wood pieces, wood powder, and fruit shell powder. The shape of these cellulose-based materials and lignocellulose-based materials is not particularly limited, and fibrous or powdery materials can be used. Specific examples of wood flour include pulverized products such as pine, fir, poplar, bamboo, bagasse, and oil palm trunks, sawdust, and sawdust, and fruit shell powder includes fruits such as walnuts, peanuts, and palms. There is a pulverized product of

A cellulosic material or a lignocellulosic material is an esterified cellulosic material or an esterified lignocellulosic material obtained by adding a polybasic acid anhydride to a hydroxyl group of a cellulosic material or a lignocellulosic material, a cellulosic material or a lignocellulosic material. An oligoesterified cellulose-based material or an oligoesterified lignocellulose-based material obtained by adding a polybasic acid anhydride and a monoepoxy compound to a hydroxyl group of a cellulose-based material, and to a hydroxyl group of the cellulose-based material or a lignocellulose-based material, An oligoesterified cellulose-based material or an oligoesterified lignocellulose-based material obtained by adding a polybasic acid anhydride and a polyhydric alcohol may be used.

Polybasic acid anhydrides include maleic anhydride, succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dichloromaleic anhydride, itaconic anhydride, tetrabromophthalic anhydride, hetic anhydride, Examples include trimetic anhydride, pyromellitic anhydride, etc. Among them, industrially advantageous and inexpensive maleic anhydride, succinic anhydride and phthalic anhydride are particularly preferred.

The monoepoxy compound may be a compound containing one epoxy group in the molecule. Examples include phenyl glycidyl ether, allyl glycidyl ether, styrene oxide, octylene oxide, methyl glycidyl ether, butyl glycidyl ether, cresyl glycidyl ether and the like.

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-nonanediol, 1,10-decanediol, pinacol, hydrobenzoin, benzpinacol, cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, glycerin, Polyethylene glycol 400 and the like are mentioned.

As a general method for 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 lignocellulose material. 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 the reaction of alternately adding and esterifying the polybasic acid anhydride and the monoepoxy compound to the hydroxyl groups in the cellulosic material or lignocellulose material component, the reaction proceeds sufficiently even without a catalyst, but the reaction is accelerated. For this purpose, basic catalysts such as sodium carbonate, dimethylbenzylamine, tetramethylammonium chloride and pyridine may be used. An addition esterification catalyst may also be used.

The molecular weight of the oligomer of the polybasic acid anhydride and the monoepoxy compound is about 20 to 1000 (the degree of polymerization is preferably 5 or less, and 1 is also included).

Also, 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 weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the dry cellulosic material or lignocellulose material. The monoepoxy compound is preferably used in an amount of 0.5 to 2.0 equivalents of the epoxy group per equivalent of the anhydride group of the polybasic acid anhydride used. This is because when more than 120 parts by mass of the polybasic acid anhydride is used with respect to 100 parts by mass of the dry cellulosic material or lignocellulosic material, the content of the lignocellulosic or cellulosic material component becomes low, and the hot pressing process is performed. Exudation occurs unfavorably during molding, and a small amount of less than 5 parts by mass lowers the hot-pressure fluidity and makes it impossible to obtain a uniform molded article, 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 material, the polyhydric alcohol may be substituted for the above-mentioned monoepoxy compound. .

Specific examples of starch-based materials include, for example, rice, wheat, corn, sugar cane, potato, sweet potato, tapioca, corn starch, potato starch, potato starch, tapioca starch, and lightly acetylated products thereof. Any crop containing starch can be used without being limited to these. In addition, these starch-based materials can be stored as they are in the general state in which they are stored, or can be easily processed by washing, removing non-starch parts such as outer skins, and cutting into suitable sizes. It can be used as long as it is subjected to pretreatment. The starch-based material is usually obtained in the form of granules, and these can be used as they are.

Further, it is more preferable that the starch-based material used as the raw material is subjected to a pregelatinization treatment in the following manner after being subjected to such a simple pretreatment. In other words, the starch that constitutes the starch-based material initially has a crystalline structure (β structure), but when placed in an environment at a temperature of 70°C or higher in the presence of an appropriate amount of moisture, this β structure collapses. changes to an amorphous structure (α structure). In this way, when raw starch contains moisture and is heated, the change from β structure to α structure is called gelatinization. The starch granules exhibiting the α-structure of this gelatinized system material are unraveled at the molecular level of the starch in the heat-fluidized polypropylene resin, compared to the case of the β-structure in the initial heated state (raw state). It becomes a state in which it is easy to disperse finely and uniformly.

As a specific treatment to convert starch having a β structure into an α structure, a heat treatment that is generally performed when edible is added, such as immersing the starch in water and boiling it, or steaming it with steam. method.

By the way, when starch having an amorphous state with an α structure is left at a low temperature while still containing moisture, a phenomenon (referred to as aging) in which it returns to the original crystalline state with a β structure over time is observed. commonly known. On the other hand, it is known that if water is removed from starch that has an amorphous state with an α structure, the starch will not undergo a reversible transition to a β structure (no aging) while maintaining the α structure even when left at 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 α structure (amorphous structure), and is in both a water-containing state and a water-free (dehydrated) state. shall also include In any case, if the starch structure of the starch-based material to be blended with the polypropylene resin is an α structure (amorphous structure), the molecular chains of the starch are loosened in the matrix of the polypropylene resin during the kneading treatment described later. , becomes finer and easier to disperse. This is an effect that cannot be obtained when an unheated starch-based material having a β-structure (crystalline structure) is blended.

By the way, a specific method for obtaining a dehydrated α-structure starch-based material is to gelatinize the material by heating in the presence of moisture, and then reduce the pressure of the atmosphere using a vacuum apparatus. Using such a dehydrated α-structured starch-based material makes it possible to store the starch-based material alone for a long period of time because it is resistant to aging. This will contribute to cost reduction.

It should be noted that trehalose is dissolved in the water used for converting the starch having the β structure into the α structure. The effect of this is that, for example, when rice is used as a starch-based material, trehalose suppresses the decomposition of the lipid components of the rice by impregnating the uncooked rice with the trehalose aqueous solution. The purpose is to suppress deterioration over time of the polypropylene resin composition using the fermented rice. The reason for this is said to be that trehalose has the effect of coating rice ingredients and protecting fatty acids from oxidative decomposition.

It can be said that such an effect is exhibited not only in rice but also in common starch-based materials. agents, protein decomposition accelerators, cellulose decomposition accelerators, and the like. By adding these substances to water to form a starch-based material having an α structure, it is possible to obtain the effect of preventing the peculiar odor, scorching and coloring of the produced polypropylene resin composition.

So far, we have explained the use of a starch-based material that has already been pregelatinized as the starch-based material to be blended as a raw material. can also be used.

Specifically, uncooked rice is soaked in water for a predetermined period of time, drained, put into a kneader together with a polypropylene resin, and kneaded at the thermal flow temperature of the polypropylene resin. This thermal fluidization temperature (usually 100 to 170°C) is a temperature sufficient to convert the starch structure of uncooked rice from β structure to α structure, so the uncooked rice is alpha-processed during the kneading process. become. As described above, after the uncooked rice has changed to the α-structure, the molecular chains of the starch are loosened, finely divided, and dispersed in the polypropylene resin matrix.

Here, in order for the uncooked rice of the β structure to be heated to the α structure, it is desired that the water content is 17% by mass or more. There is a need to. In addition, for starch-based materials, such as potatoes, which contain sufficient moisture to convert the starch itself into an α-structure, there is no need to soak the starch in water, as is the case with rice. can.

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

The first polypropylene resin composition of the present invention contains 5 to 85% by mass of polypropylene resin (A1), 5 to 85% by mass of polypropylene resin (A2), and 10 to 80% by mass of biomass material (C), preferably Polypropylene resin (A1) 10 to 75% by mass, polypropylene resin (A2) 10 to 75% by mass, and biomass material (C) 15 to 70% by mass, more preferably polypropylene resin (A1) 15 to 65% by mass, 15 to 65% by mass of polypropylene resin (A2) and 20 to 60% by mass of biomass material (C), more preferably 20 to 55% by mass of polypropylene resin (A1), 20 to 55% by mass of polypropylene resin (A2), and 25 to 55% by mass of biomass material (C). Here, the total mass ratio of (A1), (A2) and (C) is 100% by mass. Further, the mass ratio of polypropylene resin (A1) and polypropylene resin (A2) is, for example, preferably polypropylene resin (A1): polypropylene resin (A2) = 5:95 to 95:5, more preferably polypropylene resin (A1) : polypropylene resin (A2) = 10:90 to 85:15, more preferably polypropylene resin (A1): polypropylene resin (A2) = 15:85 to 70:30.

The second polypropylene resin composition of the present invention comprises a total of 5 to 85% by mass of polypropylene resin (A1) and polypropylene resin (A2), 5 to 85% by mass of polypropylene resin (B), and biomass material (C) 10 to 80% by mass, preferably a total of 10 to 75% by mass of polypropylene resin (A1) and polypropylene resin (A2), 10 to 75% by mass of polypropylene resin (B), and 15 to 70% by mass of biomass material (C) containing, more preferably a total of 15 to 65% by mass of polypropylene resin (A1) and polypropylene resin (A2), 15 to 65% by mass of polypropylene resin (B), and 20 to 60% by mass of biomass material (C), and further It preferably contains 20 to 55% by mass of polypropylene resin (A1) and polypropylene resin (A2) in total, 20 to 55% by mass of polypropylene resin (B), and 25 to 55% by mass of biomass material (C). Here, the total mass ratio of (A1), (A2), (B) and (C) is 100% by mass. Further, the mass ratio of polypropylene resin (A1) and polypropylene resin (A2) is, for example, preferably polypropylene resin (A1): polypropylene resin (A2) = 5:95 to 95:5, more preferably polypropylene resin (A1) : polypropylene resin (A2) = 10:90 to 85:15, more preferably polypropylene resin (A1): polypropylene resin (A2) = 15:85 to 70:30.

Thermoplastic elastomer (D)
Optionally, a thermoplastic elastomer (D) may be added to the polypropylene resin composition. Examples of the thermoplastic elastomer (D) include olefin elastomers and styrene elastomers. These can be used alone or in combination of two or more.

Examples of olefinic elastomers include ethylene/propylene copolymer elastomer (EPR), ethylene/butene copolymer elastomer (EBR), ethylene/hexene copolymer elastomer (EHR), ethylene/octene copolymer elastomer (EOR ), ethylene-propylene-ethylidenenorbornene copolymer, ethylene-propylene-butadiene copolymer, ethylene-α-olefin-diene terpolymer elastomer such as ethylene-propylene-isoprene copolymer, ethylene-ethylene-butylene - hydrogenated polymer elastomers such as ethylene copolymers (CEBC); Of these, ethylene/propylene copolymer elastomers, ethylene/butene copolymer elastomers, and ethylene/hexene copolymer elastomers are preferred.

Styrene-based elastomers include, for example, 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-ethylene/propylene-styrene copolymer elastomer (SEPS), styrene-ethylene/ethylene/propylene-styrene copolymer elastomer (SEEPS), styrene-butadiene/butylene-styrene copolymer elastomer (SBBS) , a partially hydrogenated styrene-isoprene-styrene copolymer elastomer, a partially hydrogenated styrene-isoprene-butadiene-styrene copolymer elastomer, and the like.

The thermoplastic elastomer (D) preferably has an MFR of 0.01 to 10 g/10 minutes, more preferably 0.1 to 3 g/10 minutes, measured at 190° C. under a load of 2.16 kg. 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 product does not sag under its own weight during extrusion molding or thermoforming, which is preferable.

The polypropylene resin composition of the present invention is a total of polypropylene resin (A1), polypropylene resin (A2) and biomass material (C), or polypropylene resin (A1), polypropylene resin (A2), polypropylene resin (B) and biomass material The thermoplastic elastomer (D) is preferably 1 to 50 parts by mass, more preferably 2 to 44 parts by mass, still more preferably 4 to 38 parts by mass, and further More preferably, it can contain 8 to 32 parts by mass.

(3) Compatibilizer In the polypropylene resin composition, a compatibilizer may be blended as needed. Compatibilizers preferably used include saturated carboxylic acids, unsaturated carboxylic acids or derivatives thereof, thermoplastic resins modified with unsaturated carboxylic acids or derivatives thereof, and thermoplastic resins modified with unsaturated carboxylic acids or derivatives thereof. Examples include cellulosic materials, lignocellulosic materials, starch-based materials, and the like. Furthermore, oil-modified alkyd resins or derivatives thereof, modified starches or derivatives thereof can also be used.

Saturated carboxylic acids include succinic anhydride, succinic acid, phthalic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and adipic anhydride. Examples of unsaturated carboxylic acids include maleic anhydride, maleic acid, nadic anhydride, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid, crotonic acid, isocrotonic acid, mesaconic acid, angelic acid, sorbic acid, acrylic acid, etc. is mentioned. As the derivative of saturated carboxylic acid or unsaturated carboxylic acid, metal salts, amides, imides, esters, etc. of saturated carboxylic acid or unsaturated carboxylic acid can be used.

Thermoplastic resins modified with unsaturated carboxylic acids or derivatives thereof, and cellulose-based materials, lignocellulose-based materials, starch-based materials modified with unsaturated carboxylic acids or derivatives thereof, and the like can also be used. The thermoplastic resin before modification used for the thermoplastic resin modified with an unsaturated carboxylic acid or derivative thereof is not particularly limited as long as it does not significantly impair the effects of the present invention. Specifically, low-density polyethylene, Examples include ethylene-α-olefin copolymers, high-density polyethylene, polypropylene, propylene block copolymers, propylene random copolymers, and the like. Among these, it is preferably the same as polypropylene resin (A1), polypropylene resin (A2) and/or polypropylene resin (B).

These are obtained by heating and mixing a thermoplastic resin, a cellulose-based material, a lignocellulose-based material, a starch-based material, an unsaturated carboxylic acid or a derivative thereof, and a radical generator in the presence or absence of a solvent. be done. The amount of unsaturated carboxylic acid or derivative thereof added is preferably 0.1 to 15% by mass, particularly preferably 1 to 10% by mass. Examples of compatibilizers used in the present invention include thermoplastic resins modified with unsaturated carboxylic acids or derivatives thereof that have no odor and low acidity, cellulosic materials modified with unsaturated carboxylic acids or derivatives thereof, ligno Cellulose-based materials, starch-based materials, and the like are preferred.

The polypropylene resin composition may optionally contain various additives such as nucleating agents, heat stabilizers, antioxidants, weather stabilizers, light Stabilizers, UV absorbers, antistatic agents, slip agents, antiblocking agents, antifog agents, neutralizers, metal deactivators, surfactants, compatibilizers, colorants, antibacterial/antifungal agents, flame retardants , a plasticizer, a dispersant, a filler, a conductive agent, an antiseptic, an aromatic, a deodorant, an insect repellent, an elastomer, and the like. Two or more of these optional components may be used in combination.
Further, these optional components may be blended in the polypropylene resin (A) or may be blended in the polypropylene resin (B), and each resin component may be used in combination of two or more. .

As a method for preparing the propylene resin composition of the present invention, powdery or pellet-like polypropylene resin (A1), polypropylene resin (A2), biomass material (C) or polypropylene resin (A1), polypropylene resin (A2), polypropylene A method of mixing the resin (B), the biomass material (C), and optionally other compounding agents using a dry blend, a Henschel mixer, or the like can be mentioned. Depending on the situation, the biomass material (C) and the polypropylene resin (A), the polypropylene resin (A2) 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 extruder or a twin-screw extruder or the like, or may be kneaded as a high-concentration filler content to prepare a masterbatch, which may be diluted to a required concentration during molding.

The polypropylene resin composition of the present invention includes polypropylene resin (A1), polypropylene resin (A2) and biomass material (C), or polypropylene resin (A1), polypropylene resin (A2), biomass material (C) and thermoplastic elastomer ( D), or polypropylene resin (A1), polypropylene resin (A2), polypropylene resin (B) and biomass material (C), or polypropylene resin (A1), polypropylene resin (A2), polypropylene resin (B), biomass material ( C), the thermoplastic elastomer (D), and optional components blended as necessary can be mixed or heated and kneaded by a single-screw extruder, a twin-screw extruder, or the like. The resin temperature for heating and kneading can be appropriately determined in the range of 100° C. to 300° C., taking into consideration 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 of pressure molding, film molding, vacuum molding, extrusion molding, injection molding, or the like to produce various molded articles. 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 can be used for various film and sheet materials, disposable molded products (for example, containers, pipes, square timbers, bars, artificial timbers, trays, concrete panels, foams, etc.), furniture, building materials, It can be effectively used as a material for interior and exterior materials for automobiles, casings and housings for home electric appliances, civil engineering and construction materials, agricultural, dairy and fisheries materials, recreational materials, sports materials, and the like.

In addition, the polypropylene resin composition of the present invention is also suitably used in the fields of electrical insulating materials, industrial parts materials, building materials, etc., and is particularly suitably used as raw materials for housing members, building materials, and home electric appliances. Specific examples include trays, tableware, speakers, bath unit floor pans, buckets, toilet seats, cabinets, stereo cabinets, baseboards, door materials, counter materials, window frames, sound insulation boards, shelf boards, civil engineering square timbers, pillars, structures. materials, kitchen materials, floors, baths, baseboards, piano organ parent boards, fitting ceiling materials, and the like.

INDUSTRIAL APPLICABILITY According to the polypropylene resin composition of the present invention, it is possible to effectively dispose of a large amount of excess stock of agricultural products that are difficult to dispose of, and to reduce the amount of polypropylene resin that is produced from fossil fuels. Furthermore, since the molded article of the polypropylene resin composition of the present invention leaves charcoal as a residue even if it is incinerated after use, the amount of combustion heat and carbon dioxide generated is small, and it greatly contributes to the conservation of the global environment. Moreover, even if it is landfilled, the rate of return to the soil is high and it can be said that it is environmentally friendly.

EXAMPLES The present invention will be described in more detail below using examples, but the present invention is not limited to these examples.

1. Evaluation method (1) Melting point (Tm)
It was measured using a differential scanning calorimeter DSC6200 manufactured by Seiko. About 5 mg of the sheet-shaped sample is packed in an aluminum pan, heated from room temperature to 200 ° C. at a temperature increase rate of 100 ° C./min, held for 5 minutes, and then cooled to 40 ° C. at 10 ° C./min. , the maximum melting peak temperature was taken as the melting point Tm (°C) from the heat of melting curve obtained when the temperature was raised to 200°C at 10°C/min.

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

(3) Melt tension MT
It was measured using a capilograph manufactured by Toyo Seiki Seisakusho.
(Measurement condition)
- Capillary: diameter 2.0 mm, length 40 mm
・Cylinder diameter: 9.55mm
・Cylinder extrusion speed: 20 mm/min ・Take-up speed: 4.0 m/min ・Temperature: 230°C
If 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 decreased by 0.1 m/min, and the melt tension at the maximum take-up speed was defined as MT. Units are grams.

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

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

(6) Pellet Odor 100 g of pellets were weighed, enclosed in a 500 ml glass container, held at 80°C for 3 hours, the lid of the glass container was opened, and the odor of the pellets inside was sensory evaluated. The determination of the strength of the odor is as follows.
(double-circle): Almost no odor is sensed.
◯: A slight odor is sensed.
△: Odor is detected.
x: A strong odor is sensed.

(7) Extruded sheet molded product and its plastic feel Pellets are put into an extruder with a screw diameter of 40 mm, extruded from a T-shaped die at a resin temperature of 200 ° C., and onto a mirror-finished metal cast roll with a surface temperature of 60 ° C. The sheet was sandwiched between the two, and was continuously taken off at a speed of 1.2 m/min while cooling and solidifying to obtain a polypropylene resin composition sheet having a width of 500 mm and a thickness of 1.0 mm.
The plastic feeling of the obtained molded article was evaluated by the decrease in gloss attributed to the biomass material and the impartation of a pattern. The determination of the strength of the plastic feeling is as follows.
◯: Almost no feeling of plasticity.
Δ: Slightly plastic feel.
x: It is the plastic feeling itself.
Further, the extensibility at the die outlet was evaluated by increasing the take-up speed in the extrusion sheet molding to obtain a sheet with a thickness of 0.5 mm. Determination of spreadability 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 difficult to pick up.

(8) Thermoformed article The minimum thickness of the thermoformed article was measured as follows.
A test piece having a size of 200 mm×200 mm was cut out from the polypropylene resin sheet obtained in each example and each comparative example, and fixed to a circular frame having an inner radius of 80 mm. Using a sagging tester manufactured by Misuzu Erie Co., Ltd., the heater is led to a heating furnace in the tester arranged vertically and heated at an atmospheric temperature of 200 ° C. After 2 seconds from the maximum tension, the plug installed on the upper part of the seat is removed. The sheet was deep drawn by lowering the pressure of the air cylinder at a rate of 0.1 m/sec. For the resulting cone-shaped molded body with a height of 200 mm, the thickness of the body 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 The value was taken as the minimum thickness of the trunk.

The drawdown properties of thermoformed articles were measured as follows.
A test piece having a size of 300 mm×300 mm was cut out from the polypropylene resin sheet obtained in each example and each comparative example, and horizontally fixed to a frame with an inner dimension of 260 mm×260 mm. Using a sagging tester manufactured by Misuzu Erie Co., Ltd., heaters are arranged vertically in a heating furnace inside the tester and heated at an ambient temperature of 200 ° C. The change in vertical displacement of the central part of the sample from the start of heating over time. was measured successively by a laser beam.
When heated, the sheet once hangs down (displaced in the negative direction), stretches back (displaces in the positive direction) due to stress relaxation, and then hangs down again. The sheet position (displacement) at the start of heating is A (mm), the position (displacement) at the time of maximum tension is B (mm), and the position (displacement) 10 seconds after the maximum tension is C (mm), Drawdown resistance was evaluated according to the following criteria.
◎: BA ≥ 0 mm and CB ≥ -5 mm
○: BA ≥ -5 mm and CB ≥ -10 mm (excluding cases where BA ≥ 0 mm and CB ≥ -5 mm)
△: BA ≥ -5 mm and CB < -10 mm, or BA < -5 mm and CB ≥ -10 mm
×: BA <-5 mm and CB <-10 mm
Here, BA≧−5 mm means that the sheet is tense during container molding, and a wrinkle-free and beautiful appearance can be formed, and CB≧−10 mm is good. It means that the molding time range for obtaining a good molded article is sufficiently wide.

(9) Extruded foam molded product and its plastic feel 100 parts by mass of polypropylene resin composition pellets and 0.5 parts by mass of a chemical foaming agent (trade name: Hydrocerol CF40E-J, manufactured by Clariant Japan Co., Ltd.) as a cell regulator. The mixture was stirred and mixed uniformly with a ribbon blender, and the resulting mixture was put into a single-screw extruder having a barrel hole for injecting a physical foaming agent in the middle of the barrel. 0.50 parts by mass of liquefied carbon dioxide is injected into 100 parts by mass of the polypropylene resin composition with a high-pressure pump while plasticizing by heating and melting in the front stage of the extruder while decomposing the cell control agent. The polypropylene resin foam molding material was rapidly cooled in the latter stage of the extruder and extruded through a T-shaped die having a width of 750 mm and a lip width of 0.4 mm. The extruded foam sheet is first cooled on one side by rolls installed in the vicinity of the die, then cooled on both sides by three rolls installed, and picked up by pinch rolls at a constant speed to form a foam sheet with a thickness of 1.3 mm. got The operating conditions of the extruder are as follows.
・Extruder caliber: 65mmφ, L/D = 42, physical foaming agent injection port: position of L/D = 20, screw rotation speed: 75rpm
Discharge rate: about 65kg/h
Evaluation of the obtained plastic feel was performed as described in (7) above.
After cutting the foams, they were filled into a cylindrical container with a height of 4.5 cm and a bottom surface with a radius of 1.9 cm without gaps, and the mass, volume and density of the foams were measured and the gas expansion ratio was measured. The expansion ratio was calculated by measuring the porosity by compression.
For the morphology of the foam, a sample was cut out from the foam sheet, and the cross section of the foam layer was enlarged and projected using a stereoscopic microscope (manufactured by Nikon: SMZ-1000-2 type), and the morphology of the foam in the cross section was evaluated as follows.
○: Fine and uniform.
x: Coarse air bubbles are present.

(10) Injection foam molded product and its plastic feel 100 parts by mass of polypropylene resin composition pellets and 0.5 parts by mass of a chemical foaming agent (trade name: Hydrocerol CF40E-J, manufactured by Clariant Japan Co., Ltd.) as a cell regulator. The mixture was uniformly stirred and mixed with a ribbon blender, and the resulting mixture was subjected to 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 an injection molding mold, a flat plate shape with a molded part size of 400 mm × 200 mm and a variable thickness for molding a foam molded product (this time, the mold cavity clearance (T0) was 2.0 mmt) Foam molding was carried out using those having. The mold temperature was set at 40°C.
Evaluation of the obtained plastic feel was performed as described in (7) above.
The foaming ratio was defined as the ratio between the thickness of the molded article after foaming by the mold opening operation and the mold cavity clearance (T0).
For the bubble morphology, a sample was cut out from the foam, and the cross section of the foam layer was enlarged and projected using a stereoscopic microscope (manufactured by Nikon Corporation: SMZ-1000-2 type), and the bubble morphology in the cross section was evaluated as follows. .
○: Fine and uniform.
x: Coarse air bubbles are present.

(11) Blow-molded product and its plastic feel Using a small direct blow molding machine JB105 manufactured by Japan Steel Works, Ltd., which has a screw and die with a crosshead structure of a diameter of 50 mmφ and an L/D of 22, the molding temperature is 200 ° C. A polypropylene-based blow-molded product (cylindrical bottle) having a bottle weight of 30 g and an internal volume of 550 cc was molded under conditions of a mold cooling temperature of 15° C. and a cooling time of 24 seconds.
Evaluation of the obtained plastic feel was performed as described in (7) above.
The degree of parison descent was determined as follows from the ratio of the thickness of the upper part of the parison to the thickness of the lower part of the parison when the parison extruded from the small direct blow molding machine was extruded to a length of 0.5 m. Upper wall thickness ratio is 0.8 to 1.0
△: The ratio of the parison top thickness to the parison bottom thickness is 0.6 to less than 0.8 ×: The parison top thickness ratio to the parison bottom thickness is less than 0.6 The minimum thickness is the center of the barrel of the cylindrical bottle. At (15 cm in height from the bottom), the wall thickness in four peripheral directions was measured with a Mitutoyo micrometer, and the difference between the maximum and minimum values was determined. A smaller numerical value means that the thickness of the cylindrical bottle is more uniform, the uneven thickness is smaller, and the product is of better quality.

(12) Tensile modulus Using a molding machine (EC20 type injection molding machine manufactured by Toshiba Machine Co., Ltd.) and the following mold, a flat test piece for physical property evaluation was prepared under the following conditions, and the "tensile modulus" described later was obtained. Used for evaluation.
·Mold = two flat test pieces for evaluating physical properties (10 x 80 x 4t (mm)).
· 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 test piece prepared above, the measurement was performed at a test temperature of 23° C. according to JIS K7162. The determination of whether the tensile modulus is high or low is as follows.
○: Tensile modulus is 1,200 MPa or more ×: Tensile modulus is less than 1,200 MPa

2. Raw materials The raw materials used for the evaluation are as follows. Table 1 summarizes the physical properties of the raw materials.
-Polypropylene resin (A1-1): Waymax MFX6 (trade name) manufactured by Japan Polypropylene Co., Ltd.
-Polypropylene resin (A2-1): prepared according to Production Example 1 -Polypropylene resin (A2-2): prepared according to Production Example 2 -Polypropylene resin (B-1): Novatec BC6C (trade name) manufactured by Nippon Polypropylene Co., Ltd.
-Polypropylene resin (B-2): Novatec BC03C (trade name) manufactured by Japan Polypropylene Corporation
-Polypropylene resin (B-3): Wintec 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) A4050 manufactured by

Catalyst Production Example (1) Complex Synthesis (1-a) rac-dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-i-propylphenyl) Synthesis of indenyl}]hafnium:
rac-dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-i-propylphenyl)indenyl}]hafnium was synthesized in JP-A-2012-149160. Synthesized according to the method of Example 1.
(1-b) Synthesis of rac-dichloro[1,1′-dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}]hafnium:
Synthesis of rac-dichloro[1,1'-dimethylsilylenebis{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}]hafnium according to the method of Example 7 of JP-A-11-240909. bottom.

(2) Preparation of catalyst (2-a) Chemical treatment of ion-exchange layered silicate 645.1 g of distilled water and 82.6 g of 98% sulfuric acid were placed in a 1 L three-necked flask equipped with a stirring blade and a reflux device. The temperature was raised to 95°C.
Commercially available montmorillonite (Benclay KK manufactured by Mizusawa Chemical Industry Co., Ltd., Al = 9.78 mass%, Si = 31.79 mass%, Mg = 3.18 mass%, Al / Si (molar ratio) = 0.320, An average particle size of 14 μm) was added, and the reaction was allowed to proceed at 95° C. for 320 minutes. After 320 minutes, 0.5 L of distilled water was added to stop the reaction and filtered to obtain 255 g of a solid cake.
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 wt%, Si = 36.05 wt%, Mg = 2.13 wt%, Al/Si (molar ratio) = 0.222. .
1545 g of distilled water was added to the above 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 with 1 L of distilled water three times to obtain a cake-like solid again.
The collected cake was dried to obtain 80 g of chemically treated montmorillonite. The chemical composition of this chemically treated montmorillonite is Al = 7.68 mass%, Si = 36.05 mass%, Mg = 2.13 mass%, Al / Si (molar ratio) = 0.222, Li = 0.53 % by mass.

(2-b) Prepolymerization 150 kg of the chemically treated montmorillonite obtained as described above was placed in a reactor having an internal volume of 1 m ³ , and 2832 L of hexane was added to form a slurry, and 74.4 kg (375 mol) of triisobutylaluminum was added thereto. was added over 85 minutes and stirred for 60 minutes. After that, it was washed with hexane to 1/32, and the total volume was adjusted to 900L.
A slurry solution containing this chemically treated montmorillonite was kept at 50° C., and 0.65 kg of triisobutylaluminum (4.257 kg of a hexane solution with a concentration of 15.3 mass %, 3.28 mol) 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-hydroazulenyl}]hafnium and 96 L of toluene were added. , stirring was continued for 60 minutes.
Then, 9.758 kg (26.61 mol) of tri-n-octylaluminum was added and stirred for 6 minutes, and then 0.064 kg of triisobutyl aluminum (a toluene solution with a concentration of 0.648% by mass) was added to 240 L of toluene in another vessel equipped with a stirrer. 9.88 kg, 0.32 mol) of rac-dichloro[1,1′-dimethylsilylenebis{2-(5-methyl-2-furyl)-4-(4-i-propylphenyl)indenyl }] A solution prepared by adding 1.768 kg (1.89 mol) of hafnium was added, 100 L of toluene was added, and stirring was continued for an additional 20 minutes.
After that, 2387 L of hexane was added to raise 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. Thereafter, the propylene feed was stopped and residual polymerization was carried out at 40° C. for 80 minutes.
After the residual polymerization was completed, the stirring was stopped and the content was allowed to settle and settle. The supernatant was removed so that the solution volume became 1,500 L, 12.7 kg of triisobutylaluminum was added, 3,974 L of hexane was added again, and the mixture was stirred.
8.9 kg of triisobutylaluminum (42.9 kg of a hexane solution having a concentration of 20.8% by mass) and 205 L of hexane were added thereto.
After that, the reaction liquid was transferred to a dryer and dried at 40° C. for 9 hours.
As a result, 465 kg of dry prepolymerized 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 prepolymerized catalyst was referred to as catalyst 1.

Production Example 1 of polypropylene resin (A2-1)
A 20 L autoclave was heated and dried well by circulating nitrogen, 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 (140 mg/mL) of triisobutylaluminum, 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. After that, 100 mg of the above catalyst 1, excluding the prepolymerized polymer, was pumped into the polymerization tank with high-pressure argon to initiate polymerization, and the temperature was quickly raised to 70°C. The temperature was maintained at 70° C., and one hour after the initiation of polymerization, unreacted propylene was quickly purged to stop the polymerization. As a result, 1876 g of polymer (polypropylene resin (A2-1)) was obtained. Polypropylene resin (A2-1) 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.

Production Example 2 of polypropylene resin (A2-2)
Polymerization was carried out according to Production Example 1, except that the amount of H ₂ to be introduced was increased and the mass of the catalyst 1 excluding the prepolymerized polymer was 80 mg. As a result, 1634 g of polymer (polypropylene resin (A2-2)) was obtained. Polypropylene resin (A2-2) 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 to 32, Comparative Examples 1 to 5)
Thirty-seven types of polypropylene resin compositions (Examples 1 to 32 and Comparative Examples 1 to 5) shown in Tables 2 and 3 were weighed and uniformly stirred and mixed with a ribbon blender. The resulting mixture was put into a twin-screw extruder with a screw diameter of 15 mm, kneaded at a resin temperature of 200° C., extruded into strands, cooled with water and pelletized to obtain a polypropylene resin composition.

Pellets odor of the obtained polypropylene resin composition, extrusion sheet molded product (plastic feel, die exit spreadability), thermoformed product (drawdown property, minimum thickness), extrusion foam molded product (plastic feel, expansion ratio, cell shape ), injection foam molded products (plastic feel, expansion ratio, cell morphology), blow molded products (plastic feel, degree of parison drop, minimum thickness), and strength were evaluated by the methods described above. The evaluation results are summarized in Tables 2 and 3.

Claims (8)

5 to 85% by mass of a polypropylene resin (A1) having the properties (a1-1) and (a1-2) below, and a polypropylene resin (A2) having the properties (a2-1) and (a2-2) below 5 to 85% by mass, and 10 to 80% by mass of biomass material (C) (where the total mass of (A1), (A2) and (C) is 100% by mass). Resin composition.
Property (a1-1): Melt tension (MT) (unit: g) is a property (a1 -2): Melting point is 150 ° C. or higher Property (a2-1): Melt tension (MT) (unit: g) is log (MT) ≥ -0.9 × log (MFR) + 0.7, or log (MT) Property (a2-2) satisfying ≧1.15: melting point of 110° C. or more and less than 150° C.
The melt tension (MT) is measured under the conditions of a capillary diameter of 2.0 mm, a length of 40 mm, a cylinder diameter of 9.55 mm, a temperature of 230° C., a cylinder extrusion speed of 20 mm/min, and a take-up speed of 4.0 m/min. The MFR shall be measured at 230°C with a load of 2.16 kg according to JIS K7210. Polypropylene resin (A1) having the following properties (a1-1) and properties (a1-2) and polypropylene resin (A2) having the following properties (a2-1) and properties (a2-2) in total from 5 to 85% by mass, 5 to 85% by mass of polypropylene resin (B) having the following properties (b-1), and 10 to 80% by mass of biomass material (C) (however, (A1), (A2), (B ) and (C) is 100% by mass.) A polypropylene resin composition characterized by the following.
Property (a1-1): Melt tension (MT) (unit: g) is a property (a1 -2): Melting point is 150 ° C. or higher Property (a2-1): Melt tension (MT) (unit: g) is log (MT) ≥ -0.9 × log (MFR) + 0.7, or log (MT) Property satisfying ≧1.15 (a2-2): Melting point of 110° C. or higher and less than 150° C. Property (b-1): Melt tension (MT) (unit: g) is log (MT) <-0.9×log (MFR) + 0.7 and log(MT) < 1.15
The melt tension (MT) is measured under the conditions of a capillary diameter of 2.0 mm, a length of 40 mm, a cylinder diameter of 9.55 mm, a temperature of 230° C., a cylinder extrusion speed of 20 mm/min, and a take-up speed of 4.0 m/min. The MFR shall be measured at 230°C with a load of 2.16 kg according to JIS K7210. The polypropylene resin (A1) is one or more polypropylene resins selected from the group consisting of a propylene homopolymer, a propylene/ethylene block copolymer, and a propylene/ethylene/1-butene block copolymer. The polypropylene resin composition according to claim 1 or 2. The polypropylene resin (A2) 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/ 4. The polypropylene resin composition according to any one of claims 1 to 3, which is one or more polypropylene resins selected from the group consisting of 1-butene random block copolymers. The polypropylene resin composition according to any one of claims 1 to 4, wherein the polypropylene resin (A2) has the following properties ( a2-4) .
( a2-4) The ratio of components having a molecular weight of 2,000,000 or more in the molecular weight distribution curve measured by GPC is 0.4% by mass or more The biomass material (C) is one or more plant-derived fillers selected from the group consisting of wood, pulp, bamboo, sugarcane (bagasse), rice husk, and rice (starch). 6. The polypropylene resin composition according to any one of 1 to 5. Total of polypropylene resin (A1), polypropylene resin (A2) and biomass material (C), or total 100% by mass of polypropylene resin (A1), polypropylene resin (A2), polypropylene resin (B) and biomass material (C) The polypropylene resin composition according to any one of claims 1 to 6, further comprising 1 to 50 parts by mass of a thermoplastic elastomer (D) with respect to 100 parts by mass of the polypropylene resin composition. An extrusion foam-molded article, an injection foam-molded article, a sheet-molded article, a thermoformed article, or a blow-molded article comprising the polypropylene resin composition according to any one of claims 1 to 7.