Resin sheet, laminated sheet and molded resin product made from these

Abstract

To provide a resin sheet with superior sheet moldability, container moldability, heat resistance and cold resistance.SOLUTION: A resin sheet comprises a resin composition containing: a resin component composed of a polypropylene resin and a polyethylene resin; and a biomass material. The resin component contains the polypropylene resin in the amount of 70 wt.% to 93 wt.% and the polyethylene resin in the amount of 7 wt.% to 30 wt.%. In the resin composition, the biomass material is contained in the amount of 0.1 pt.wt. to 20 pts.wt. relative to 100 pts.wt. of the resin component, with its melt flow rate of 0.5 g / 10 min to 1.1 g / 10 min.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a resin sheet containing a biomass material, a laminated sheet, and a resin molded product obtained by molding them. [Background technology]

[0002] Resin sheets containing polypropylene-based resins are excellent in heat resistance, formability, and chemical resistance, and are used for resin molded products such as containers for packaging various products such as food. Such resin sheets are generally produced by extrusion molding of a resin composition, and are then thermoformed, such as vacuum forming, to form resin molded products such as containers. On the other hand, in recent years, from the viewpoint of the environment, it is required to reduce the use of fossil fuels as much as possible, and a resin composition containing a biomass material and a resin sheet containing the same have attracted attention. However, it is known that a resin composition in which a biomass material is blended with a polypropylene resin has a lower fluidity than a resin composition not containing a biomass material, and also has a lower strength than a resin composition not containing a biomass material, and many studies have been conducted to improve these properties.

[0003] For example, Patent Document 1 discloses a resin composition for films, particularly for use in garbage bags, shopping bags, or fertilizer bags, that contains 30 to 90 parts by weight of an ethylene-α-olefin copolymer, 70 to 10 parts by weight of a propylene-based resin, and 12 to 100 parts by weight of rice per 100 parts by weight of the resin components. By adjusting the amounts of the above components, this resin composition for films is able to suppress the reduction in impact strength, tensile strength, and heat seal strength that would be caused by the inclusion of rice. Furthermore, Patent Document 2 discloses a laminated sheet using layers containing a polyolefin resin and a biomass material such as rice flour. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 5183455 [Patent Document 2] Patent Publication No. 2021-192977 Summary of the Invention [Problem to be solved by the invention]

[0005] However, containers for food and the like are used under various temperature conditions, such as heating in a microwave oven, etc. Therefore, resin sheets are required to have not only sheet formability from a resin composition to a sheet and container formability from the sheet to a container, but also heat resistance and cold resistance as a product. In particular, with the increase in demand for frozen foods in recent years, strict cold resistance is required to prevent cracks and the like from occurring when subjected to external impact in a frozen state.

[0006] The present invention has been made in consideration of the above circumstances, and has an object to provide a resin sheet, a laminated sheet, and a resin molded product obtained by molding them, which have excellent sheet formability, container formability, heat resistance, and cold resistance. [Means for solving the problem]

[0007] The present inventors have conducted intensive research in order to solve the above-mentioned problems, and have found that a resin sheet having excellent sheet formability, container formability, heat resistance, and cold resistance can be obtained by using a resin composition which contains a resin component including a predetermined amount of a polypropylene-based resin and a predetermined amount of a polyethylene-based resin, and a predetermined amount of a biomass material, and which has a melt flow rate of 0.5 g / 10 min to 1.1 g / 10 min, thereby completing the present invention.

[0008] That is, the present invention has the following configuration. [1] A resin sheet comprising a resin component including a polypropylene-based resin and a polyethylene-based resin, and a resin composition containing a biomass material, wherein the resin component contains 70% by weight to 93% by weight of the polypropylene-based resin and 7% by weight to 30% by weight of the polyethylene-based resin, the biomass material is contained in an amount of 0.1 parts by weight to 20 parts by weight per 100 parts by weight of the resin component, and the melt flow rate of the resin composition is 0.5 g / 10 min to 1.1 g / 10 min. [2] The resin sheet according to [1], wherein the polyethylene resin contains an ethylene-α-olefin copolymer, and the resin component contains the ethylene-α-olefin copolymer in an amount of 3% by weight to 30% by weight. [3] The resin sheet according to [1], wherein the resin sheet has a thickness of 0.3 mm and a DuPont impact strength at -40°C of 0.5 J or more. [4] The resin sheet described in [1], wherein the resin sheet is 0.3 mm thick and 395 mm x 395 mm long and fixed horizontally to a frame, and placed in an atmosphere at 250°C, and the central part of the resin sheet descends to a descent point, then returns and rises to a return point, and descends again. In the behavior of the resin sheet, the difference in vertical height from the top surface of the frame to the return point is 20 mm or less, and the retention time, which is the time from the return point until it descends 10 mm again divided by 2, is 3 seconds or more. [5] The resin sheet according to [4], wherein the descent time required for the resin sheet to reach the descent point after being placed in an atmosphere at 250°C is less than 15 seconds. [6] The resin sheet according to [1], wherein the polypropylene-based resin is random polypropylene, the polyethylene-based resin is a mixture of an ethylene-α-olefin copolymer and at least one of a low-density polyethylene and a high-density polyethylene, and the resin component contains 70% by weight to 90% by weight of the random polypropylene, 5% by weight to 25% by weight of the ethylene-α-olefin copolymer, and 5% by weight to 25% by weight of at least one of the low-density polyethylene and the high-density polyethylene. [7] The resin sheet described in [1], wherein the biomass material is a grain-derived component. [8] A laminated sheet in which at least one of a resin layer containing a different biomass material and a resin layer not containing a biomass material is laminated on at least one of the upper and lower surfaces of the resin sheet described in [1]. [9] A resin molded product obtained by molding the resin sheet according to any one of [1] to [7] or the laminate sheet according to [8]. Effect of the Invention

[0009] The resin sheet of the present invention is environmentally friendly and has excellent sheet formability, container formability, heat resistance, and cold resistance. The resin sheet of the present invention is preferable as a resin sheet for producing a resin molded product, for example, a resin sheet for containers such as food containers, blister packs, and various industrial trays. In particular, it is preferable as a resin sheet for food containers, and among them, a resin sheet for frozen food containers. Here, the resin sheet in the present invention also includes an embodiment as a part of a laminated sheet, unless otherwise specified in the application. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] "Resin sheet" The resin sheet of the present invention comprises a resin component including a polypropylene resin and a polyethylene resin, and a resin composition containing a biomass material, the resin component containing 70 to 93% by weight of a polypropylene resin and 7 to 30% by weight of a polyethylene resin, the resin composition containing 0.1 to 20 parts by weight of the biomass material per 100 parts by weight of the resin component, and the melt flow rate of the resin composition is 0.5 to 1.1 g / 10 min. The resin sheet of the present invention is a non-stretched extrusion molded product. The resin sheet of the present invention is a sheet for molding a resin molded product by thermoforming such as vacuum molding, and is preferably a resin sheet for a container suitable for molding a container, particularly preferably a resin sheet for a food container suitable for molding a container for packaging food, and most preferably a resin sheet for a frozen food container suitable for molding a container for packaging frozen food.

[0011] "Physical properties of resin sheets" The thickness of the resin sheet is appropriately selected depending on the application and purpose. For food containers, a thickness of 100 to 2000 μm is preferable. The melt flow rate (MFR) of the resin composition constituting the resin sheet at 190°C is 0.5 g / 10 min to 1.1 g / 10 min, preferably 0.55 g / 10 min to 1.0 g / 10 min, and particularly 0.6 g / 10 min to 0.9 g / min. The MFR is measured according to JIS K7210 (1999) at a temperature of 190°C and a load of 2.16 kgf. In order to suppress deterioration of the biomass material and maintain good sheet productivity (sheet moldability) by extrusion molding, the melt flow rate is preferably greater than 0.5 g / 10 min. On the other hand, in order to maintain good moldability of a resin molded product formed by thermoforming the resin sheet, the melt flow rate is preferably less than 1.1 g / min.

[0012] The tensile modulus of the resin sheet is preferably 400 MPa or more in the MD direction in order to maintain the shape of the container when used as a food container. The tensile modulus was measured according to JIS K7127 (1999). The tensile yield strength of the resin sheet is preferably 15 MPa or more in the MD direction in order to maintain the shape of the container when used as a food container. The tensile yield strength was measured according to JIS K7127 (1999). The DuPont impact strength of a 0.3 mm thick resin sheet at −40° C. is at least 0.5 J, preferably at least 0.6 J, and particularly at least 0.7 J. The DuPont impact strength (impact core R: 1 / 4) was measured by a DuPont impact strength tester according to the method described below. The total light transmittance of the resin sheet is appropriately selected depending on the application. The total light transmittance was measured in accordance with JIS K7361-1 (1997). The haze value of the resin sheet is appropriately selected depending on the application. The haze value was measured in accordance with JIS K7136 (2000).

[0013] The resin sheet is placed in an atmosphere at 250° C. in a state where a resin sheet having a thickness of 0.3 mm and a size of 395 mm×395 mm is fixed horizontally to a frame, and the resin sheet is dropped to a drop point at the center of the resin sheet, then returns to the return point, and then drops again. In the behavior of the resin sheet, the difference H in the vertical height between the frame upper surface position (reference height) and the return point is 20 mm or less, preferably 15 mm or less, and particularly 10 mm or less, and the retention time T, which is the value obtained by dividing the time from the return point to the return by 10 mm again by 2, is 3 seconds or more, preferably 4 seconds or more, and particularly 4.5 seconds or more. Here, the resin sheet is sandwiched and fixed between an upper frame and a lower frame for fixing a sample. The lower frame is in a box in an atmosphere of 250° C. and is fixed at a certain height from the lower surface inside the box. The height of the upper surface of the lower frame is the height of the part of the resin sheet that is fixed, and this is the reference height. In order to ensure the uniformity of the thickness of the container, it is preferable that the difference H in height is smaller than 20 mm. The retention time T is also related to the molding conditions. In order to maintain good moldability of the container through an appropriate molding cycle, the holding time T is preferably longer than 3 seconds. Furthermore, it is preferable that the descent time for a 0.3 mm thick resin sheet to reach the above-mentioned descent point after being placed in an atmosphere of 250°C is shorter than 15 seconds, as this suppresses deterioration of the biomass material and the generation of odor, reduces the energy required to mold the container, and improves production efficiency.

[0014] "Resin component" The resin components used in the present invention include polypropylene-based resins and polyethylene-based resins. These resins may be petrochemically obtained or may be biomass-derived resins obtained from biomass materials.

[0015] "Polypropylene resin" Examples of polypropylene-based resins include homopolypropylene and copolymers mainly composed of propylene. Examples of comonomers of copolymers mainly composed of propylene include ethylene, butene, and α-olefins having 5 to 20 carbon atoms. In particular, random polypropylene or block polypropylene copolymerized with propylene and ethylene is preferred, and random polypropylene is most preferred. Note that the polypropylene-based resin may be a mixture of two or more of the above. The melting point (DSC) of polypropylene resin is from 110°C to 170°C.

[0016] The content of the polypropylene resin in the resin component is 70% by weight to 93% by weight, preferably 70% by weight to 90% by weight, and particularly preferably 70% by weight (excluding 70% by weight) to 85% by weight. When using random polypropylene, the content in the resin component is preferably 70% by weight to 90% by weight, 70% by weight to 80% by weight, and particularly preferably 70% by weight to 75% by weight. On the other hand, when using block polypropylene, the content in the resin component is preferably 70% by weight to 95% by weight, preferably 70% by weight to 92% by weight, and particularly preferably 70% by weight (excluding 70% by weight) to 90% by weight.

[0017] "Polyethylene resin" The polyethylene resin may be at least one selected from the group consisting of high-density polyethylene, low-density polyethylene, and ethylene-α-olefin copolymers obtained by copolymerizing α-olefins with ethylene as the main component. In particular, one type of ethylene-α-olefin copolymer, or a mixture of two types of ethylene-α-olefin copolymers, that is, a high-density polyethylene or a low-density polyethylene, or a mixture of three types of ethylene-α-olefin copolymers, that is, a high-density polyethylene and a low-density polyethylene, is preferably used. The ethylene-α-olefin copolymer is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-octadecene, and 1-eicosene. The density of ethylene-α-olefin copolymer is 0.85 g / cm 3 from 0.95 g / cm 3 , preferably 0.86 g / cm 3 from 0.94 g / cm 3 , especially 0.87 g / cm 3 from 0.93 g / cm 3 It is. The melting point (DSC) of polyethylene resins is from 50°C to 140°C.

[0018] The content of the polyethylene resin in the resin component is 7% by weight to 30% by weight, preferably 10% by weight to 30% by weight, particularly 15% by weight to less than 30% by weight. When the resin component contains an ethylene-α-olefin copolymer, the content of the ethylene-α-olefin copolymer is 3% by weight to 30% by weight (or less than 30% by weight), preferably 3% by weight to 25% by weight, most preferably 3% by weight to 20% by weight.

[0019] For example, when random polypropylene is used as the polypropylene resin, the content of the polyethylene resin in the resin component is 10% by weight to 30% by weight, preferably 15% by weight to 30% by weight, and particularly 20% by weight to less than 30% by weight. In this case, it is preferable to mix an ethylene-α-olefin copolymer with at least one of low-density polyethylene and high-density polyethylene as the polyethylene resin. When an ethylene-α-olefin copolymer is mixed with at least one of a low-density polyethylene and a high-density polyethylene as the polyethylene-based resin, the content of the ethylene-α-olefin copolymer in the resin component is 5 to 25% by weight, preferably 10 to 20% by weight, and the content of at least one of the low-density polyethylene and the high-density polyethylene in the resin component is 5 to 25% by weight, preferably 10 to 20% by weight.

[0020] On the other hand, when a block polypropylene is used as the polypropylene-based resin, the content of the polyethylene resin in the resin component is 5 to 30% by weight, preferably 10 to 30% by weight, and particularly 15 to 25% by weight. In this case, it is also preferable to mix an ethylene-α-olefin copolymer with at least one of low-density polyethylene and high-density polyethylene as the polyethylene-based resin. When an ethylene-α-olefin copolymer and at least one of a low-density polyethylene and a high-density polyethylene are mixed as the polyethylene-based resin, the content of the ethylene-α-olefin copolymer in the resin component is 3 to 15% by weight, preferably 3 to 10% by weight, and particularly preferably 3 to 5% by weight, and the content of at least one of the low-density polyethylene and the high-density polyethylene in the resin component is 4 to 30% by weight, preferably 6 to 20% by weight, and particularly preferably 8 to 15% by weight.

[0021] [Biomass materials] Biomass materials are excluding bioplastics and are fillers derived from plants such as wood, pulp, bamboo, and grain-derived components. Grain-derived components are particularly preferred, and examples of grain-derived components include at least one or any combination of rice, barley, wheat, millet, foxtail millet, and corn. Rice is the most preferred. The rice is preferably rice that has been subjected to a gelatinization process (hereafter referred to as gelatinized rice), and dried gelatinized rice is particularly preferred. When raw rice is increased in moisture content and placed in a temperature environment of 70°C or higher, the original crystalline structure (β structure) of the starch that constitutes the raw rice breaks down and changes (gelatinizes) to an amorphous structure (α structure). This gelatinized rice is preferred because it can be uniformly dispersed at the molecular level in the continuous phase of the thermally flowing resin component. The resin composition constituting the resin sheet contains 0.1 to 20 parts by weight, preferably 1 to 17 parts by weight, and particularly 2 to 14 parts by weight of a biomass material relative to 100 parts by weight of the resin component. From an environmental standpoint, a larger content of the biomass material is preferable, but in order to maintain good container moldability, it is preferable that the content of the biomass material is less than 20 parts by weight relative to 100 parts by weight of the resin component.

[0022] "Other ingredients" In addition to the resin component and the biomass material, the resin composition may contain a compatibilizer, a foam inhibitor, and various additives within the scope of the present invention. The compatibilizer is intended to improve the affinity between the resin component and the biomass material (e.g., rice). The foam inhibitor prevents foaming caused by moisture generated from the biomass material by heating. Examples of various additives include nucleating agents, heat stabilizers, antioxidants, weather stabilizers, antistatic agents, slip agents, antiblocking agents, antifogging agents, colorants, fillers, deodorizers, and fragrances.

[0023] "Method of manufacturing resin sheet" The resin sheet can be manufactured by preparing polypropylene resin, polyethylene resin, and biomass material, respectively, and feeding them into an extrusion molding machine that mixes and melts and kneads them. The molding temperature of the extrusion molding machine is 140°C or higher, preferably 150°C or higher, and 220°C or lower, preferably 200°C or lower. In order to perform melt extrusion well, the molding temperature is preferably higher than 170°C. On the other hand, in order to suppress deterioration of the biomass material (especially pregelatinized rice), the molding temperature is preferably lower than 220°C.

[0024] "Laminated sheet" The laminated sheet of the present invention comprises the above-mentioned resin sheet of the present invention and another resin layer (another resin sheet) different from the resin sheet of the present invention laminated on at least one of the upper surface or the lower surface of the resin sheet. Examples of this laminated sheet include a resin sheet having another resin layer laminated on either the upper surface or the lower surface, or on both surfaces. Here, the other resin layer is not limited as long as it has a different structure from the main resin sheet, such as a resin layer containing a biomass material different from the biomass material of the resin sheet to be laminated, a resin layer not containing a biomass material, or various laminate films. The combination, layer structure, and number of layers of the resin layers to be laminated can be set arbitrarily. Laminating a resin layer not containing a biomass material as the outermost layer on both the upper and lower surfaces suppresses the odor derived from the biomass material during molding into a product or in the product itself, and is also preferable from the viewpoint of hygiene consideration. The laminate sheet also preferably satisfies the same physical properties (tensile modulus, tensile yield strength, DuPont impact strength at -40°C, heating behavior) as the above-mentioned resin sheet. The melt flow rate of the laminate sheet preferably satisfies the same physical property values ​​as the above-mentioned resin sheet (i.e., 0.5g / 10min to 1.1g / 10min, preferably 0.55g / 10min to 1.0g / 10min, particularly 0.6g / 10min to 0.9g / min), but is not particularly limited as long as the resin sheet constituting the laminate sheet exhibits the above-mentioned measured values. This is because the sheet productivity of the laminate sheet of the present invention depends on the resin sheet of the present invention containing a heat-sensitive biomass material that requires extrusion processing at low temperature and low shear. The method of laminating other resin layers onto the resin sheet is not particularly limited, but for example, when the main resin sheet is extruded, the resin sheet may be extruded integrally so that other resin layers are laminated on the upper or lower surface of the resin sheet, or the main resin sheet may be obtained as a single layer and then laminated by post-treatment. Lamination by a lamination method may also be used. Thus, the lamination method is not limited to this, and various methods may be used. EXAMPLES

[0025] The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. The measurement methods or definitions of the physical properties shown in the examples are shown below.

[0026] <mfr> The MFR was measured in accordance with JIS K7210 (1999) at a temperature of 190°C and a load of 2.16 kgf. When the MFR was 0.5 g / 10 min or more, the sheet productivity was evaluated as "◯", and when it was less than 0.5 g / 10 min, the sheet productivity was evaluated as "×". <Tensile modulus and tensile yield strength> The tensile modulus and tensile yield strength were measured according to JIS K7127 (1999). <DuPont impact strength> The DuPont impact strength (impact core R: 1 / 4) was measured by the following method using a DuPont impact strength tester (manufactured by Mize Testing Instruments Co., Ltd.). The impact core is placed on a resin sheet 0.3 mm thick and 50 x 50 mm in size, and a 1 kg weight is dropped onto the impact core. The first drop test is performed with the weight set at the height determined in the preliminary test. For the second and subsequent drop tests, if the resin sheet cracks in the previous drop test, the weight is set at a height 50 mm lower than in the previous drop test, and if no cracks occur, the weight is set at a height 50 mm higher than in the previous drop test. For the second and subsequent drop tests, the position where the weight is dropped is changed for each test. This drop test with the weight is performed a total of 20 times, and the average value of the potential energy of the weight before all 20 drops is taken as the measured value. The potential energy is calculated by converting the product of the weight's load (1 kgf) and the height (cm) from the top of the impact core into joules. The preliminary test is conducted by multiple preliminary drop tests. In detail, the first preliminary drop test is conducted with the weight set at an appropriate height, and if the sheet breaks in the first preliminary drop test, the position where the weight is dropped is changed and the height of the weight is lowered by 50 mm and the next preliminary drop test is conducted. The preliminary drop tests are then repeated until the sheet does not break, and the preliminary test is terminated. The "height of the weight in the first drop test" is the height of the weight in the preliminary drop test at which the sheet did not break. On the other hand, if the sheet does not break in the first preliminary drop test, the position where the weight is dropped is changed and the height of the weight is increased by 50 mm and the next preliminary drop test is conducted. The preliminary drop tests are then repeated until the sheet breaks, and the preliminary test is terminated. The "height of the weight in the first drop test" is the height just before (50 mm lower than) the height at which the sheet broke. When the measured values ​​at -30°C and -40°C were 0.5 or higher, the cold resistance was rated as "○", otherwise the cold resistance was rated as "×". <Haze value> The haze was measured in accordance with JIS K7136 (2000). <Total light transmittance> The total light transmittance was measured in accordance with JIS K7361-1 (1997). <Heating behavior> A resin sheet with a thickness of 0.3 mm and dimensions of 395 mm x 395 mm was fixed horizontally to a frame and placed in an atmosphere at 250°C. The central part of the resin sheet descended to the lowest descent point (descent time S), then returned and rose to the highest return point, and descended again. The difference in vertical height H from the top surface of the frame to the return point and the retention time T, which is the time it took for the resin sheet to descend 10 mm again from the highest return point divided by 2, were measured. When the height H in the heating behavior was 20 mm or less and the holding time was 3 seconds or more, the container formability was rated as "good." When the height H was 15 mm or less and the holding time was 4 seconds or more, the container formability was rated as "excellent." When the height H was greater than 20 mm or the holding time was less than 3 seconds, the container formability was rated as "poor." When the drop time in the heating behavior was less than 15 seconds, the container formability (low heat amount) was rated as "good", and otherwise the container formability (low heat amount) was rated as "poor". <Heat resistance evaluation> A weight (approximately 10mm x 22mm x 35mm, weighing approximately 12g) was placed on a resin sheet with a thickness of 0.3mm and dimensions of 50mm x 50mm, and heated in a microwave oven at 700W for 50s. The degree of deformation of the resin sheet after heating was evaluated visually. The weight used was half a Maruha Nichiro "Sauce Tonkatsu" (25g per piece (1.9g protein, 3.6g fat)). ◎: Almost no deformation 〇: Some deformation, but within practical range ×: There is a large overall deformation, and it is not practical. <Odor evaluation> Two resin sheets, each 0.3 mm thick and 20 mm x 50 mm in size, were placed in a 50 ml glass bottle, and the odor inside was evaluated by a sensory test after about one hour in a thermostatic chamber at 80°C. The evaluation was based on the following scores and was calculated as the average of five people. 0 points: Almost no odor 1 point: A weak odor is detected 2 points: Odor is detected 3 points: Slightly strong odor 4 points: Strong odor

[0027] The raw materials used in the examples and comparative examples are as follows. Prime Polymer E701G: Block polypropylene (Melting point: 163°C (DSC)) Prime Polymer E702MG: Block polypropylene (Melting point 164℃(DSC)) Japan Polypropylene BC3HF: Block polypropylene (Melting point 160℃ (DSC)) Japan Polypropylene EG7F: Random polypropylene (Melting point: 143°C (DSC)) Japan Polypropylene EG7FTB: Random polypropylene (Melting point: 147°C (DSC)) Keiyo Polyethylene B5203: High density polyethylene (HDPE) (Density 0.948g / cm 3 , melting point 131℃(DSC) Braskem SGF4950: Biomass-derived high density polyethylene (HDPE) (Density 0.956g / cm 3 , melting point 133℃(DSC) Ube Maruzen Polyethylene R300: Low-density polyethylene (LDPE) (Density 0.920g / cm 3 , melting point 109℃(DSC) Mitsui Chemicals A4085S: Ethylene-α-olefin copolymer (Density 0.885g / cm 3 , melting point 66℃(DSC) Biomass Resin R50E-4: Rice-blended resin composition (Ethylene-α-olefin copolymer is the base resin, with 50% by weight of rice.)

[0028] [Example 1] 95 parts by weight of block PP (E702MG manufactured by Prime Polymer Co., Ltd.), 5 parts by weight of ethylene-α-olefin copolymer (A4085S manufactured by Mitsui Chemicals Co., Ltd.), and 7.5 parts by weight of rice blended resin composition (R50E-4 manufactured by Biomass Resins Co., Ltd.) were each put into an extrusion molding machine, and a resin sheet having a thickness of 300 μm was produced at a molding temperature of 190° C. This is designated as Example 1.

[0029] [Example 2] 90 parts by weight of block PP (E702MG manufactured by Prime Polymer Co., Ltd.), 10 parts by weight of HDPE (B5203 manufactured by Keiyo Polyethylene Co., Ltd.), and 7.5 parts by weight of a rice-blended resin composition (R50E-4 manufactured by Biomass Resin Co., Ltd.) were each put into an extrusion molding machine, and a resin sheet having a thickness of 300 μm was produced at a molding temperature of 190° C. This is designated as Example 2.

[0030] [Example 3] 80 parts by weight of block PP (E702MG manufactured by Prime Polymer Co., Ltd.), 20 parts by weight of HDPE (B5203 manufactured by Keiyo Polyethylene Co., Ltd.), and 7.5 parts by weight of a rice-blended resin composition (R50E-4 manufactured by Biomass Resin Co., Ltd.) were each put into an extrusion molding machine, and a resin sheet having a thickness of 300 μm was produced at a molding temperature of 190° C. This is designated as Example 3.

[0031] [Example 4] 85 parts by weight of block PP (E702MG manufactured by Prime Polymer Co., Ltd.), 15 parts by weight of HDPE (B5203 manufactured by Keiyo Polyethylene Co., Ltd.), and 30 parts by weight of a rice-blended resin composition (R50E-4 manufactured by Biomass Resin Co., Ltd.) were each put into an extrusion molding machine, and a resin sheet having a thickness of 300 μm was produced at a molding temperature of 190° C. This is Example 4.

[0032] [Example 5] 76 parts by weight of random PP (EG7FTB manufactured by Japan Polypropylene), 12 parts by weight of LDPE (R300 manufactured by Ube Maruzen Polyethylene), 12 parts by weight of ethylene-α-olefin copolymer (A4085S manufactured by Mitsui Chemicals), and 7.5 parts by weight of rice blended resin composition (R50E-4 manufactured by Biomass Resins) were each put into an extrusion molding machine, and a resin sheet having a thickness of 300 μm was produced at a molding temperature of 190° C. This is Example 5.

[0033] [Example 6] 76 parts by weight of random PP (EG7FTB manufactured by Japan Polypropylene), 12 parts by weight of HDPE (B5203 manufactured by Keiyo Polyethylene), 12 parts by weight of ethylene-α-olefin copolymer (A4085S manufactured by Mitsui Chemicals), and 7.5 parts by weight of rice-blended resin composition (R50E-4 manufactured by Biomass Resin) were each put into an extrusion molding machine, and a resin sheet having a thickness of 300 μm was manufactured at a molding temperature of 190° C. This is Example 6.

[0034] [Example 7] 90 parts by weight of random PP (EG7F manufactured by Japan Polypropylene Corporation), 10 parts by weight of ethylene-α-olefin copolymer (A4085S manufactured by Mitsui Chemicals) and 50 parts by weight of rice blended resin composition (R50E-4 manufactured by Biomass Resins) were each put into an extrusion molding machine, and a resin sheet having a thickness of 300 μm was produced at a molding temperature of 190° C. This is Example 7.

[0035] [Example 8] 80 parts by weight of random PP (EG7F manufactured by Japan Polypropylene), 9 parts by weight of biomass-derived HDPE (SGF4950 manufactured by Braskem), 3 parts by weight of LDPE (R300 manufactured by Ube Maruzen Polyethylene), 8 parts by weight of ethylene-α-olefin copolymer (A4085S manufactured by Mitsui Chemicals) and 7.5 parts by weight of rice-blended resin composition (R50E-4 manufactured by Biomass Resins) were each put into an extrusion molding machine, and a resin sheet having a thickness of 300 μm was produced at a molding temperature of 190° C. This is Example 8.

[0036] [Comparative Example 1] 100 parts by weight of block PP (E702MG manufactured by Prime Polymer Co., Ltd.) was put into an extrusion molding machine, and a resin sheet having a thickness of 300 μm was produced at a molding temperature of 190° C. This was designated Comparative Example 1.

[0037] [Comparative Example 2] 95 parts by weight of block PP (E702MG manufactured by Prime Polymer Co., Ltd.), 5 parts by weight of ethylene-α-olefin copolymer (A4085S manufactured by Mitsui Chemicals Co., Ltd.), and 7.5 parts by weight of rice blended resin composition were each put into an extrusion molding machine, and a resin sheet having a thickness of 300 μm was produced at a molding temperature of 190° C. This is referred to as Comparative Example 2.

[0038] [Comparative Example 3] 50 parts by weight of block PP (E702MG manufactured by Prime Polymer Co., Ltd.), 40 parts by weight of block PP (BC3HF manufactured by Japan Polypropylene Corporation), 10 parts by weight of HDPE (B5203 manufactured by Keiyo Polyethylene Co., Ltd.), and 7.5 parts by weight of a rice-blended resin composition (R50E-4 manufactured by Biomass Resins Co., Ltd.) were each put into an extrusion molding machine, and a resin sheet having a thickness of 300 μm was produced at a molding temperature of 190° C. This is referred to as Comparative Example 3.

[0039] [Comparative Example 4] 80 parts by weight of block PP (BC3HF manufactured by Japan Polypropylene Corporation), 20 parts by weight of HDPE (B5203 manufactured by Keiyo Polyethylene Corporation) and 7.5 parts by weight of a rice-blended resin composition (R50E-4 manufactured by Biomass Resin Co., Ltd.) were each put into an extrusion molding machine, and a resin sheet having a thickness of 300 μm was produced at a molding temperature of 190° C. This is referred to as Comparative Example 4.

[0040] [Comparative Example 5] 55 parts by weight of block PP (E701G manufactured by Prime Polymer), 25 parts by weight of block PP (BC3HF manufactured by Japan Polypropylene), 20 parts by weight of HDPE (B5203 manufactured by Keiyo Polyethylene) and 7.5 parts by weight of rice blended resin composition (R50E-4 manufactured by Biomass Resin) were each put into an extrusion molding machine, and a resin sheet having a thickness of 300 μm was produced at a molding temperature of 190° C. This is referred to as Comparative Example 5.

[0041] [Comparative Example 6] 15 parts by weight of block PP (E701G manufactured by Prime Polymer), 25 parts by weight of block PP (BC3HF manufactured by Japan Polypropylene), 60 parts by weight of HDPE (B5203 manufactured by Keiyo Polyethylene) and 7.5 parts by weight of rice blended resin composition (R50E-4 manufactured by Biomass Resin) were each put into an extrusion molding machine, and a resin sheet having a thickness of 300 μm was produced at a molding temperature of 190° C. This is referred to as Comparative Example 6.

[0042] [Comparative Example 7] 100 parts by weight of HDPE (B5203 manufactured by Keiyo Polyethylene Co., Ltd.) and 7.5 parts by weight of a rice-blended resin composition (R50E-4 manufactured by Biomass Resin Co., Ltd.) were each put into an extrusion molding machine, and a resin sheet having a thickness of 300 μm was produced at a molding temperature of 190° C. This is referred to as Comparative Example 7.

[0043] [Comparative Example 8] 100 parts by weight of random PP (EG7F manufactured by Japan Polypropylene Corporation) was put into an extrusion molding machine, and a resin sheet having a thickness of 300 μm was produced at a molding temperature of 190° C. This was designated Comparative Example 8.

[0044] [Comparative Example 9] 100 parts by weight of random PP (EG7F manufactured by Japan Polypropylene Corporation) and 7.5 parts by weight of a rice-blended resin composition (R50E-4 manufactured by Biomass Resin Co., Ltd.) were put into an extrusion molding machine, and a resin sheet having a thickness of 300 μm was produced at a molding temperature of 190° C. This is Comparative Example 9.

[0045] [Comparative Example 10] 90 parts by weight of random PP (EG7F manufactured by Japan Polypropylene Corporation), 10 parts by weight of ethylene-α-olefin copolymer (A4085S manufactured by Mitsui Chemicals) and 100 parts by weight of rice blended resin composition (R50E-4 manufactured by Biomass Resins) were each put into an extrusion molding machine, and a resin sheet having a thickness of 300 μm was produced at a molding temperature of 190° C. This is referred to as Comparative Example 10.

[0046] Table 1 shows the resin composition ratios of the resin sheets of Examples 1 to 8 and Comparative Examples 1 to 10. [Table 1]

[0047] The physical properties of the resin sheets of Examples 1 to 8 and Comparative Examples 1 to 10 were measured. The results are shown in Table 2. [Table 2]

[0048] The physical properties of the resin sheets of Examples 1 to 8 and Comparative Examples 1 to 10 were evaluated based on Table 2. The results are shown in Table 3. [Table 3]

[0049] The resin sheets of Examples 1 to 8 were high in sheet productivity, container formability, cold resistance, and heat resistance. It was found that the resin sheets of Examples 5 to 8 could achieve container formability with a low amount of heat and had high thermoforming productivity. In particular, the resin sheet of Example 6 had a low odor evaluation of less than 1.5, and was found to be suitable for food containers. The resin sheets of Comparative Example 1 and Comparative Example 8, which do not contain biomass material (rice), also had high standards for sheet productivity, container formability, cold resistance, and heat resistance. In other words, as seen from the resin sheets of Comparative Examples 2 to 7 and 9 and 10, it was found that by blending biomass material (rice), any of the sheet productivity, container formability, cold resistance, and heat resistance was reduced. In addition, the resin sheets (Comparative Examples 2, 6, 7, 9, and 10) in which the polyethylene resin of the resin component was out of the range of 7% by weight to 30% by weight were insufficient in at least any of container formability, heat resistance, and cold resistance. Furthermore, the resin sheets (Comparative Examples 5 and 7) with a melt flow rate of less than 0.5 g / 10 min had insufficient sheet productivity. And the resin sheets (Comparative Examples 3 and 4) with a melt flow rate exceeding 1.1 g / 10 min did not have sufficient container formability. In particular, the resin sheet of Comparative Example 4 did not show an increase from the drop point, that is, a heating behavior.

[0050] [Example 9] Next, a laminated sheet of Example 9 was produced by laminating resin layers on the upper and lower surfaces of the resin sheet of Example 8. In detail, a resin layer (middle layer, resin sheet of Example 8) consisting of 80 parts by weight of random PP (EG7F manufactured by Japan Polypropylene), 9 parts by weight of biomass-derived HDPE (SGF4950 manufactured by Braskem), 3 parts by weight of LDPE (R300 manufactured by Ube Maruzen Polyethylene), 8 parts by weight of ethylene-α-olefin copolymer (A4085S manufactured by Mitsui Chemicals) and 7.5 parts by weight of rice-blended resin composition (R50E-4 manufactured by biomass resin) was co-extruded to laminate resin layers (upper and lower layers) consisting of 100 parts by weight of random PP (EG7F manufactured by Japan Polypropylene) on the upper and lower surfaces, respectively, at a molding temperature of 190°C, and a three-layer laminated laminated sheet having a thickness of 300 μm was produced so that the thickness ratio of the three layers was approximately 1:16:1. As shown in Table 2, the MFR (190° C.) of Example 8 (a resin sheet made of the same resin composition as the intermediate layer of Example 9) was 0.74 g / 10 min. The resin composition of the laminated sheet of Example 9 is shown in Table 4.

[0051] [Table 4]

[0052] The physical properties of the laminate sheet of Example 9 and the physical properties of laminate sheets based on it were evaluated. The respective results are shown in Tables 5 and 6.

[0053] [Table 5]

[0054] [Table 6]

[0055] The laminated sheet of Example 9 had excellent container formability, and also had excellent heat resistance and cold resistance. In addition, there was almost no odor generated from the biomass material. In Table 6, the sheet productivity is evaluated based on the MFR of the intermediate layer. However, the MFR of the laminated sheet of Example 9 was 0.5 g / 10 min or more.

[0056] [Example 10] A laminated sheet was obtained by laminating a polyethylene film having a thickness of 20 μm onto the resin sheet of Example 1. A circular flat plate having a diameter of 20 cm was formed from this laminated sheet. In this way, the laminated sheet of the present invention could be easily produced from the resin sheet of the present invention by lamination processing. [Industrial Applicability]

[0057] The resin sheet of the present invention can be preferably used as a resin sheet for molding various resin molded products such as food containers, blister packs, various industrial trays, etc. In particular, it can be preferably used as a resin sheet for food containers or frozen food containers.< / mfr>

Claims

1. The present invention comprises a resin composition containing a resin component including a polypropylene-based resin and a polyethylene-based resin, and a biomass material, The resin component contains 70% by weight to 93% by weight of the polypropylene-based resin and 7% by weight to 30% by weight of the polyethylene-based resin, The biomass material is contained in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the resin component, The melt flow rate of the resin composition is 0.5 g / 10 min to 1.1 g / 10 min; Resin sheet.

2. The polyethylene resin comprises an ethylene-α-olefin copolymer, The resin component contains the ethylene-α-olefin copolymer in an amount of 3% by weight to 30% by weight. The resin sheet according to claim 1 .

3. The resin sheet having a thickness of 0.3 mm has a DuPont impact strength of 0.5 J or more at −40° C. The resin sheet according to claim 1 .

4. The resin sheet, which is 0.3 mm thick and 395 mm x 395 mm, is placed in an atmosphere at 250°C while being fixed horizontally to a frame, and in the behavior of the resin sheet in which the center of the resin sheet descends to a descending point, then returns and rises to a return point, and then descends again, the difference in vertical height from the upper surface of the frame to the return point is 20 mm or less, and the retention time, which is the value obtained by dividing the time from the return point until the sheet descends again by 10 mm by 2, is 3 seconds or more. The resin sheet according to claim 1 .

5. After the resin sheet is placed in an atmosphere at 250° C., the descent time until the resin sheet reaches the descent point is less than 15 seconds. The resin sheet according to claim 4.

6. The polypropylene-based resin is a random polypropylene, the polyethylene-based resin is a mixture of an ethylene-α-olefin copolymer and at least one of a low-density polyethylene and a high-density polyethylene; the resin component comprises 70% by weight to 90% by weight of the random polypropylene, 5% by weight to 25% by weight of the ethylene-α-olefin copolymer, and 5% by weight to 25% by weight of at least one of the low-density polyethylene and the high-density polyethylene; The resin sheet according to claim 1 .

7. The biomass material is a grain-derived component; The resin sheet according to claim 1 .

8. At least one of a resin layer containing a different biomass material and a resin layer not containing a biomass material is laminated on at least one of the upper surface or the lower surface of the resin sheet according to claim 1. Laminated sheet.

9. A resin molded product obtained by molding the resin sheet according to any one of claims 1 to 7 or the laminate sheet according to claim 8.

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