JP2016190967A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To modify a container/package recycling material and obtain a resin composition having an excellent strength.SOLUTION: A resin composition contains a first rubber composition or a first resin, and a resin composition containing at least one of polypropylene and polyethylene as a main component. The first rubber composition includes a block type styrene butadiene rubber, a butadiene rubber, a random type styrene butadiene rubber, and nitrile rubber (NBR). The first resin includes an acrylic resin, EVA, an AS resin, polyethylene terephthalate (PET), polycarbonate (PC), polystyrene (PS), and acrylonitrile butadiene styrene (ABS).SELECTED DRAWING: None

Description

  The present invention relates to a resin composition, and more particularly to a resin composition containing a container material.

  In accordance with the enforcement of the Containers and Packaging Recycling Law, porpropylene (PP) and polyethylene (PE) are sorted and pelletized from discharged plastic containers and packaging, etc., and reused. However, waste plastic (container) contains impurities such as plastics other than PP and PE, wood chips, iron scraps, and paper scraps, and it is difficult to completely remove these from PP and PE. Moreover, the physical property fall by the heat history for commercialization or raw material formation (pelletization) is unavoidable, Therefore, the intensity | strength of the pellet of waste PP or waste PE is low compared with a virgin material.

  Patent Document 1 (Japanese Patent Application Laid-Open No. 2011-226261) discloses a block member used for a rainwater storage tank, which is formed using a container material. This block member has a base part and a leg part having a cylindrical peripheral wall protruding upward from the base part, and the peripheral wall of the leg part is partially formed thick. And it is described that according to this block member, it can be set as the block member which has the outstanding intensity | strength.

  Patent Document 2 (Japanese Patent Laid-Open No. 2007-138137) discloses a composite material containing a container / packaging recycle material made of a thermoplastic resin and an inorganic powder or a wood-based material.

JP 2011-226261 A JP 2007-138137 A

  The technique disclosed in Patent Document 1 obtains excellent strength by forming a part of the block member thick, and does not improve the strength of the resin composition itself.

  When the composite material disclosed in Patent Document 2 is used as a molded body, the composite material contains inorganic powder or wood-based material, and therefore, it is difficult to reuse the molded body after it is discarded. This is because it is necessary to remove the inorganic powder or the woody material from the composite material when reusing.

  An object of the present invention is to obtain a resin composition having an excellent strength by modifying a container material.

  The resin composition of the present invention that solves the above problems includes the first rubber composition or the first resin, and a resin composition containing at least one of polypropylene and polyethylene as a main component.

  According to the present invention, an excellent strength can be obtained in a resin composition obtained by modifying a container material.

FIG. 1 is a graph showing the test results of bending properties. FIG. 2 is a graph showing the impact resistance test results. FIG. 3 is a graph showing the test results of bending properties. FIG. 4 is a graph showing the impact resistance test results. FIG. 5 is a graph showing the relationship between the amount of deflection and the bending load of sample GM197. FIG. 6 is a graph showing the relationship between the amount of deflection of the sample GM147 and the bending load. FIG. 7 is a graph showing the relationship between the amount of deflection and the bending load of sample GM206. FIG. 8 is a graph showing the relationship between the amount of deflection of sample GM194 and the bending load. FIG. 9 is a graph showing the relationship between the amount of deflection and the bending load of sample GM138. FIG. 10 is a graph showing the relationship between the amount of deflection and the bending load of sample GM139. FIG. 11 is a graph showing the relationship between the amount of deflection and the bending load of sample GM189. FIG. 12 is a graph showing the relationship between the amount of deflection and the bending load of the sample GM126. FIG. 13 is a graph showing the test results of bending properties. FIG. 14 is a graph showing the impact resistance test results. FIG. 15 is a graph showing the test results of bending properties. FIG. 16 is a graph showing the impact resistance test results. FIG. 17 is a graph showing the relationship between the amount of deflection and the bending load of sample GM190. FIG. 18 is a graph showing the relationship between the amount of deflection and the bending load of sample GM220. FIG. 19 is a graph showing the relationship between the amount of deflection of sample GM184 and the bending load. FIG. 20 is a graph showing the test results of bending properties. FIG. 21 is a graph showing the impact resistance test results. FIG. 22 is a graph showing the test results of bending properties. FIG. 23 is a graph showing the impact resistance test results. FIG. 24 is a graph showing the test results of bending properties. FIG. 25 is a graph showing the impact resistance test results. FIG. 26 is a graph showing the test results of bending properties. FIG. 27 is a graph showing the impact resistance test results. FIG. 28 is a graph showing the relationship between the amount of deflection of sample GM198 and the bending load. FIG. 29 is a graph showing the relationship between the amount of deflection and the bending load of sample GM199. FIG. 30 is a graph showing the relationship between the amount of deflection of sample GM156 and the bending load. FIG. 31 is a graph showing the relationship between the amount of deflection of sample GM200 and the bending load. FIG. 32 is a graph showing the relationship between the amount of deflection and the bending load of sample GM201. FIG. 33 is a graph showing the relationship between the amount of deflection and the bending load of sample GM202. FIG. 34 is a graph showing the relationship between the amount of deflection and the bending load of sample GM212. FIG. 35 is a graph showing the relationship between the amount of deflection and the bending load of sample GM213. FIG. 36 is a graph showing the relationship between the amount of deflection and the bending load of sample GM214. FIG. 37 is a graph showing the relationship between the amount of deflection and the bending load of sample GM142.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

<Embodiment 1>
The resin composition R1 according to the first embodiment will be described. The resin composition R1 includes a resin composition mainly composed of polypropylene (PP) and polyethylene (PE), and a first resin.

  Specifically, the resin composition mainly composed of PP and PE is a container material that is a recycled product of containers and packaging. Container materials include resins such as polyvinyl acetate (PVC), polyethylene terephthalate (PET), polystyrene (PS), cellophane (PT), ethylene vinyl alcohol copolymer (EVOH), and nylon in addition to PP and PE. There is sometimes.

  It should be noted that the composition of the container material is determined by the configuration of the discharged container and packaging. Therefore, the composition varies greatly depending on the local government, region, and season in which the containers and packages to be discharged are collected.

  Examples of the first resin include acrylic resin, acrylonitrile / styrene resin (AS resin), acrylonitrile butadiene styrene resin (ABS resin), polycarbonate (PC), polyethylene terephthalate (PET), polystyrene (PS), and polylactic acid (PLA). ), Hard resin such as cycloolefin copolymer resin, and hard resin such as ethylene vinyl acetate copolymer (EVA), aliphatic copolymer polyester resin, elastomer such as styrene elastomer (TPS) or olefin elastomer (TPO) Resins other than are mentioned. Here, “hard resin” means “hard resin” defined in ASTM D8833.

  The first resin may be a virgin material or a recycled product. Moreover, as a 1st resin, 1 type may be mix | blended independently, 2 or more types of hard resins may be used together, and hard resin and resins other than hard resin may be used together.

  EVA is used, for example, as a sealing material for solar cell panels. The solar battery has a structure in which solar battery cells are arranged between a glass plate and a back sheet material, and the solar battery cells are sealed with a sealing material. The back sheet material is mainly formed of PET. This sealing material may be used when EVA is selected as the first resin to be blended in the resin composition R1.

  In addition, when using the sealing material of the panel of a solar cell as 1st resin, you may use the end material product of the sealing material discharged | emitted in the manufacturing process of a solar cell, and it seals when discarding a solar cell. The stopping material may be peeled off from the solar cell and used as the first resin. In addition, even if it is a case where the end material product of a sealing material is used, or it is a case where a sealing material is peeled from a waste solar cell, a part of backsheet material may adhere to a sealing material. However, the back sheet material may be used as the first resin without being completely removed from the sealing material. In this case, at least EVA and PET are included as the first resin.

  The first resin is blended in an amount of, for example, 5 to 30 parts by weight, with the amount of the filler being 100 parts by weight. When the blending amount of the first resin is 5 parts by weight or less, there is a possibility that the effect of modifying the container material does not sufficiently appear. Moreover, when the compounding quantity of 1st resin is 30 or more, there exists a possibility that bending strength or impact resistance may fall remarkably.

  In addition, the resin composition R1 may contain a crosslinking agent, a commercially available non-reactive system / reactive system compatibilizer, and the like as optional components. Examples of commercially available non-reacting / reactive compatibilizers include NOMODA Modiper A series, Sanyo Chemical Co., Ltd. Yumex series, Sumitomo Chemical Co., Ltd. Bond First series, and the like. Here, the non-reactive compatibilizing agent is, for example, one in which the main chain contains a polyolefin such as PE or PP, and the first component is chemically bonded to the side chain, or the first in the main chain. Examples thereof include those having a component and a polyolefin such as PE or PP chemically bonded to the side chain. Examples of the reaction system compatibilizer include those obtained by modifying a part of the main chain composed of polyolefin or the first component with a component capable of reacting with alcohol or acid (for example, maleic anhydride or glycidyl).

  Examples of the crosslinking agent that can be blended into the resin composition R1 include organic peroxides such as dicumyl peroxide and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane. For example, the cross-linking agent can be blended in an amount of 0.01 to 0.3 parts by weight per 100 parts by weight of the filler.

  The resin composition R1 can be produced, for example, by putting each material into a kneader and kneading, and then extruding them with a twin screw extruder. In addition, you may pelletize obtained resin composition R1 as needed, and you may process it into a sheet form.

  The resin composition R1 has excellent strength because the first resin is blended in addition to the bulk material.

  When a hard resin is blended as the first resin in the resin composition R1, the resin material is modified by improving the bending characteristics, and the resin composition R1 having excellent strength can be obtained. Further, when EVA is blended as the first resin in the resin composition R1, the container material is modified by improving the impact resistance, so that the resin composition R1 having excellent strength can be obtained. it can. Furthermore, when both EVA and hard resin are blended as the first resin in the resin composition R1, it is possible to improve both the bending characteristics and the impact resistance. Resin composition R1 is obtained.

  Since the resin composition R1 has excellent strength, for example, it is suitably used as a pallet material or synthetic wood.

<Embodiment 2>
Next, the resin composition R2 according to the second embodiment will be described. The resin composition R2 includes a resin composition mainly composed of at least one of polypropylene and polyethylene, and a first rubber composition. The resin composition containing at least one of polypropylene and polyethylene as a main component is a container material as in the first embodiment.

  Examples of the first rubber composition include block-type styrene butadiene rubber (B-SBR), butadiene rubber (BR), random copolymerized styrene butadiene rubber (SBR), nitrile rubber (NBR), and natural rubber (NR). ), Isoprene rubber (IR), butyl rubber (IIR), ethylene / propylene rubber (EPM, EPDM) and the like. The amount of the first rubber composition is, for example, 5 to 30 parts by weight with respect to 100 parts by weight of the container material.

  The resin composition R2 may further contain a second resin. Examples of the second resin include acrylic resin, AS resin, PET, PC, EVA and the like. The compounding quantity of 2nd resin is 5-30 weight part with respect to 100 weight part of container materials, for example.

  In addition, the resin composition R2 may contain a crosslinking agent, a commercially available non-reactive system / reactive system compatibilizer, and the like as optional components. Examples of commercially available non-reacting / reactive compatibilizers include NOMODA Modiper A series, Sanyo Chemical Co., Ltd. Yumex series, Sumitomo Chemical Co., Ltd. Bond First series, and the like. Here, the non-reactive compatibilizing agent is, for example, one in which the main chain contains a polyolefin such as PE or PP, and the first component is chemically bonded to the side chain, or the first in the main chain. Examples thereof include those having a component and a polyolefin such as PE or PP chemically bonded to the side chain. Examples of the reaction system compatibilizer include those obtained by modifying a part of the main chain composed of polyolefin or the first component with a component capable of reacting with alcohol or acid (for example, maleic anhydride or glycidyl).

  Examples of the crosslinking agent that can be blended in the resin composition R2 include organic peroxides such as dicumyl peroxide and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane. For example, the cross-linking agent can be blended in an amount of 0.01 to 0.3 parts by weight per 100 parts by weight of the filler.

  Resin composition R2 can be manufactured by, for example, putting each material into a kneader and kneading them, and then extruding them with a twin-screw extruder, as in resin composition R1 of the first embodiment. In addition, you may pelletize obtained resin composition R2 as needed, and you may process it into a sheet form.

  Since the first rubber composition is blended in the resin composition R2 in addition to the container material, the resin composition R2 has excellent strength. In particular, the resin composition R2 having excellent impact resistance can be obtained due to the excellent elasticity and excellent impact resistance of the rubber composition.

<Embodiment 3>
In the first and second embodiments, the resin compositions R1 and R2 as the material of the molded product have been described. However, the resin composition of the present invention is used as a resin modifier for modifying the properties of the container material. The resin composition used may be used. Hereinafter, as a third embodiment, a resin composition R3 when used as a resin modifier will be described.

  As in the first embodiment, the resin composition R3 includes a resin composition (contained material) mainly composed of polypropylene (PP) and polyethylene (PE), and a first resin. Examples of the first resin include the same resins as in the first embodiment. The blending amount of the first resin is, for example, 50 to 500 parts by weight with respect to 100 parts by weight of the container material. That is, compared with resin composition R1 of Embodiment 1, in resin composition R3, the mixture ratio of 1st resin is high.

  Resin composition R3 can be manufactured by the same method as resin composition R1 of Embodiment 1. The resin composition R3 is preferably formed into a pellet shape.

  As described above, the resin composition R3 is used as a resin modifier for a container. Specifically, the resin composition R3 is provided to the user in a pellet form, for example. And a user adjusts the compounding quantity of a resin modifier (resin composition R3) according to the composition of a container material, and the desired physical property, and knead | mixes to a container material. Thereby, the container material is modified by the resin modifier (resin composition R3), and a resin composition having excellent strength can be obtained.

  The case where the resin composition R3 includes the container material and the first resin as in the first embodiment has been described, but the resin material and the first rubber composition are included as in the second embodiment. Even a resin composition can be used as a resin modifier for a container. In this case, a resin modifier having a higher blending ratio of the first rubber composition than the resin composition R2 of Embodiment 2 is used.

  In addition, it is not essential to include a container as a modifier for modifying the container. For example, the container material may be modified using a composite material containing an AS resin and a rubber composition as a modifier.

<Other embodiments>
In the above embodiment, it has been described that the filler material constituting the resin compositions R1 to R3 is mainly composed of PP and PE. However, the filler material is a resin composition mainly composed of PP. Alternatively, it may be a resin composition mainly composed of PE. Therefore, in the embodiment of the present invention, the container material only needs to have at least one of PP and PE as a main component.

[1: Study of resin to be added (1)]
Samples GM147, GM206, GM194, GM138, GM139, GM189, and GM126 were prepared in order to investigate the effect of the type and amount of resin added to the container material on the physical properties. Further, as a comparative example, a sample made of 100% container material was prepared and used as GM197. Details of each formulation are shown in Table 1. And these bending physical properties (a bending elastic modulus, the maximum bending stress, the bending amount at the time of the maximum bending stress), and impact resistance (Izod impact value) were measured. A sample preparation method and a sample measurement method will be described below.

  In addition, as a container material, the discharged product (container packaging) from PAX Co., Ltd. was used. As the virgin acrylic resin, the trade name “Delpet 60N” manufactured by Asahi Kasei Chemicals Corporation was used (in Table 1, “Vir acrylic”; the same applies hereinafter). As the AS resin of the virgin material, a trade name “LyTac-A 120PCF” manufactured by Nippon A & L Co., Ltd. was used (indicated as “Vir AS” in Table 1; the same shall apply hereinafter). As the recycled polyethylene terephthalate (PET), a commercially-available pulverized product of a PET bottle of carbonated drinking water was used (indicated as “recycled PET” in Table 1). As the virgin ethylene-vinyl acetate copolymer resin (EVA), the trade name “Ultrasen 633” manufactured by Tosoh Corporation was used (in Table 1, “Vir EVA”, the same applies hereinafter). As the EVA of the recycled product, an end material in the manufacturing process of the solar cell panel encapsulant manufactured by Kyocera Corporation was used (in Table 1, “EVA end product”, the same applies hereinafter).

(Sample preparation method)
A method for manufacturing the sample will be described. In addition, when there existed the material which is not mix | blended in each sample, the process was suitably abbreviate | omitted and the following preparation methods were applied.

  First, as a preparation for each material, each material was processed into a shape that could be put into a hopper of a twin screw extruder. Specifically, what can be finely cut was processed into pellet-shaped granules of 5 mm square or less, for example. In addition, powders that could be processed into powder were pulverized with a mill.

  Next, before putting each material into the hopper of a twin-screw extruder, each material was mixed beforehand. When the radical initiator was blended, in addition to the powder or pellet material, the radical initiator was also mixed in advance in the container.

  Next, each material processed as described above was kneaded using a twin-screw extruder. As the twin screw extruder, “KZW15-45HG” (Φ = 15, L / D = 45) manufactured by Technobel Co., Ltd. was used. As operating conditions of the apparatus, the screw rotation speed was 250 rpm, and the feeder discharge amount was 15 g / min. The twin-screw extruder has first to sixth six cylinders. Regarding the set temperatures of the respective cylinders, the first cylinder is set to 100 ° C., and the second to sixth cylinders and the die are set to 180 ° C. Each material was heated and mixed with the twin-screw extruder, and the resin mixture was extruded from the die of the twin-screw extruder. The extruded mixture is in the form of strands (strings). In addition, when a radical initiator is included in the material, it is considered that the crosslinking reaction has proceeded simultaneously with heating and mixing in the twin-screw extruder.

  Subsequently, the strand-shaped resin mixture extruded from the die was cooled in a water tank and then pelletized with a pelletizer. Then, the obtained pellets were put in a bag and mixed to achieve uniform quality.

  Next, a test piece was molded using the obtained pellets. Prior to the molding of the test piece, the pellets were heated and dried in a thermostatic bath. The heating temperature at this time was about 80 ° C., and the drying time was about 2 hours. Thereby, it is thought that the water | moisture content in a pellet was removed.

  Subsequently, a multipurpose test piece (80 mm × 10 mm × 4 mm) based on JIS K7139 was produced using the produced pellets as a raw material using an injection molding machine. As the injection molding machine, “ES1000” manufactured by Nissei Plastic Industry Co., Ltd. was used. As operating conditions of the apparatus, the cylinder temperature is set to be constant at 180 ° C., the injection speed is a predetermined speed of 10 to 40 mm / sec, the holding pressure is a predetermined pressure of 25 to 40 MPa, and the holding time is 15 seconds. The mold temperature was 45 ° C. and the cooling time was 15 to 40 seconds.

  Note that samples described later were also produced by the same method as these samples (except samples GM144 and GM128 in which a crosslinking agent was blended).

(Measurement method of bending properties (flexural modulus, maximum bending stress and deflection amount at maximum bending stress))
Using the produced multipurpose test piece, a bending test was performed in an atmosphere of a temperature of 20 ° C. and a humidity of 65% using a “5966 type universal material testing machine” manufactured by Instron Japan Company Limited. The support span was 50 mm, the bending speed was 5.0 mm / min, and the amount of change was 20 mm at maximum.

(Measurement method of impact resistance (Izod impact value))
A 2 mm notch was put into the produced multipurpose test piece using “No. 189 PNCA notch processing machine” manufactured by Yasuda Seiki Seisakusho. Then, the Izod impact test was done at room temperature using "No.258-L-PC impact test machine" by Yasuda Seiki Seisakusho. The hammer load was 5.5 J.

  In addition, it measured by the method similar to these samples also about the bending physical property and impact resistance of the sample which are mentioned later.

  The measurement results measured by the above method are shown in Table 1 and FIGS. Moreover, the graph which shows the relationship between the bending amount when a bending test is done about each sample, and a bending load is shown in FIGS. 5-12, respectively.

  In Table 1, “Bending strength increase / decrease” and “Impact resistance increase / decrease” items show the increase / decrease of each value as a percentage when compared with sample GM197. Note that “Δ” indicates an increase, and “▼” indicates a decrease.

  In Table 1, “reforming effect” in the item “evaluation” is an evaluation relating to mechanical properties. Samples with improved physical properties of either bending strength or impact resistance improved by more than twice (up by 10%) before modification, and values of both physical properties of bending strength and impact resistance Samples modified by 30% or more were evaluated as “「 ”. Also, both the physical properties of bending strength and impact resistance are the same or modified, and either one is modified to 10% or more, and the physical properties of either bending strength or impact resistance. Among the samples in which the property was improved by 10% or more and the other physical property was lowered, the sample in which the modification rate of one physical property exceeded the decrease rate of the other physical property was evaluated as “◯”. A sample in which the modification ratios of the values of bending strength and impact resistance are both less than 10%, and one of the properties of bending strength and impact resistance is improved and improved by 10% or more, and the other Among those in which the physical properties of the samples were reduced, the samples in which the reforming rate of one physical property was equal to or less than the decreasing rate of the other physical property were evaluated as “Δ”.

  The evaluation criteria for the above “bending strength increase / decrease”, “impact resistance increase / decrease”, and “modification effect” are the same in the following Tables 2 and 3.

  1 and 2, it can be seen that, when a hard resin (acrylic resin, AS resin, PET) is added to the container material, although the impact resistance is lowered, the bending property is improved. As for each hard resin, it can be seen that an acrylic resin or an AS resin is preferable from the viewpoint of improving bending characteristics (see GM147 and GM206 in FIG. 1). Further, it can be seen that AS resin is preferable from the point of impact resistance (see GM206 in FIG. 2). Therefore, in total, it is considered that AS resin has the highest effect of reforming the container material among acrylic resin, AS resin, and PET.

  3 and 4, when EVA is selected as the resin to be added to the container, it can be seen that the impact resistance is improved while the bending characteristics are lowered (see GM138 and GM139 in FIG. 4). .) Also, the difference in the amount of EVA added is examined (samples GM138 and GM139, samples GM189 and GM126). It can be seen that the greater the amount of EVA added, the lower the bending characteristics and the higher the impact resistance. The decrease in bending characteristics is about 10% for both bending elasticity and maximum bending stress, which is a practically satisfactory level.

  Regarding toughness, according to FIGS. 5 to 12, it can be seen that, even in the case of a solid material containing a hard resin, no fracture or crack occurs up to a deflection amount of 20 mm, and good toughness is obtained.

[2: Study of resin to be added (2)]
From the above examination, it has been found that EVA contributes to the improvement of impact resistance of the container. When the solar cell panel sealing material is recycled and used as EVA, it is assumed that a back sheet (main component: PET) or the like is attached to the sealing material. Therefore, samples GM189 and GM190 examined the effect on physical properties due to the presence or absence of a small amount of PET. In addition, samples GM139, GM220, and GM184 examined how much the impact resistance reduction caused by the hard resin can be complemented by using a hard resin and EVA in combination. The composition of these samples is shown in Table 2. And these bending physical properties (a bending elastic modulus, the maximum bending stress, the bending amount at the time of the maximum bending stress), and impact resistance (Izod impact value) were measured.

  In addition, as the polyethylene terephthalate (PET) of the recycled product, the end product in the manufacturing process of the back sheet material adhered to the sealing material of the solar cell panel of Kyocera Corporation was used (in Table 2, “PET It is written as “Scrap material”.)

  The measurement results measured by the above method are shown in Table 2 and FIGS. Moreover, the graph which shows the relationship between the bending amount when a bending test is done about each sample, and a bending load is shown in FIGS. 17-19, respectively (For samples GM197, GM189, and GM139, FIG. 5, FIG. 11 and FIG.

  According to FIGS. 13 and 14, the sample GM190 containing a small amount of PET has a slightly lower impact resistance than the sample GM189 containing no PET, but has the same bending characteristics. I understand. From this, it can be seen that a resin composition that can be used satisfactorily in practice can be obtained even when PET is mixed with EVA. From the comparison of FIG. 11 and FIG. 15, it can be seen that a small amount of PET does not cause a practical problem even from the viewpoint of toughness.

  A recycled product of a sealing material for a solar cell panel usually has a back sheet material made of PET as a raw material, and it is difficult to completely separate the sealing material and the back sheet material. Therefore, the current situation is that the sealing material cannot be effectively reused. However, as a result of this study, it has been found that there is no problem even if PET is mixed in EVA, so that a sealing material that is not completely peeled off from the backsheet material (that is, an EVA material containing PET) can be used. It was found that it can be used effectively for the reforming of recycled materials. Thus, since the recycled product of the sealing material can be effectively reused, it is possible to reduce the disposal amount of the sealing material and to suppress the cost of reforming the container material.

  15 and 16, samples GM220 and GM184 to which hard resin is added in addition to EVA as a material to be added to the container are less impact resistant than sample GM139 to which only EVA is added. However, it can be seen that the bending characteristics are improved. Further, according to FIG. 10, FIG. 18 and FIG. 19, even when the additive to the container material is only EVA (GM139) or when it contains hard resin in addition to EVA (GM220 and GM184), the amount of deflection is It can be seen that no fractures or cracks occurred up to 20 mm, and good toughness was obtained. Thereby, it turns out that it is effective to add hard resin in addition to EVA according to the characteristic required for a resin composition.

[3: Examination of rubber composition to be added]
We examined the modification of the container using the excellent elasticity and impact resistance of rubber. Samples GM197, GM198, GM199, GM156, GM200, GM201, GM202, GM212, GM213, GM214, and GM142 having the compositions shown in Table 3 were prepared. And these bending physical properties (a bending elastic modulus, the maximum bending stress, the bending amount at the time of the maximum bending stress), and impact resistance (Izod impact value) were measured.

  As the block-type styrene butadiene rubber (SBR), a product name “Nipol NS380S” manufactured by Nippon Zeon Co., Ltd. was used (indicated as “block SBR” in Table 1). As the butadiene rubber (BR), one having a trade name “Nipol 1220SG” manufactured by Nippon Zeon Co., Ltd. was used (indicated as “BR” in Table 3).

  The measurement results measured by the above method are shown in Table 3 and FIGS. Moreover, the graph which shows the relationship between the deflection amount when a bending test is done about each sample, and a bending load is respectively shown in FIGS. 28-37 (refer FIG. 5 about the sample GM197).

  According to FIG. 20, it can be seen that the bending strength is slightly reduced by adding the block SBR to the container (samples GM198, GM199, GM156). On the other hand, according to FIG. 21, it can be seen that the impact value is remarkably improved as the addition amount of the block SBR is increased (the sample GM156 is maximum). Therefore, it can be seen that by adding the block SBR to the container, excellent impact resistance can be obtained while maintaining the same degree of bending characteristics.

  Further, according to FIGS. 28 to 30, in samples GM198, GM199, and GM156 in which the block SBR is added to the container material, a good toughness is obtained without causing breakage or cracking up to a deflection amount of 20 mm. I understand.

  22 and FIG. 24, even when block SBR is added to the container and acrylic resin (samples GM200, GM201, GM202) or AS resin (GM212, GM213, GM214) is further added to FIG. Similarly, it can be seen that the bending strength is only slightly reduced.

  On the other hand, according to FIG. 23 and FIG. 25, when the addition amount of the block SBR added to the container material is smaller than the addition amount of the hard resin (samples GM200 and GM212), the impact resistance is not improved. I understand. However, when the addition amount of the block SBR is increased (samples GM201, GM202, GM213, GM214), the impact value is greatly improved. From this, it is considered that the impact resistance decrease due to the hard resin (acrylic resin or AS resin) can be complemented by the addition of the block SBR.

  Further, according to FIGS. 31 to 36, in samples GM198, GM199, and GM156 in which the block material SBR is added to the container material, the toughness is obtained without causing breakage or cracking up to a deflection amount of 20 mm. I understand.

  According to FIG. 26 and FIG. 27, when the sample GM198 whose rubber composition to be added is block SBR is compared with the sample GM142 which is BR, the sample GM142 to which BR is added is superior in both bending characteristics and impact resistance. I understand that In addition, according to FIG. 37, it can be seen that the sample GM142 also has good toughness with no bending or cracking until the deflection amount is 20 mm.

  The cost efficiency in the production of the PVB resin composition will be examined. In general, EVA end materials have components such as PET (derived from the back sheet material) attached to the surface and are considered unsuitable for recycling, and can therefore be purchased at low cost. Therefore, for example, samples GM189, GM126 (Table 1), and GM190 (Table 2) can produce a PVB resin composition with very excellent cost efficiency.

  Since the PVB resin composition containing only a container and a resin as a composition does not contain a radical initiator or a rubber composition, the production process is not complicated and the production efficiency is good. In addition, since the sample GM206 contains an inexpensive AS resin (virgin material) as a resin, it can be said that the sample GM206 is an excellent PVB resin composition in terms of manufacturing cost.

  Butadiene rubber (BR) is an inexpensive general purpose rubber. In sample GM142 (Table 3), an inexpensive butadiene rubber was used, and even though the blending amount of the butadiene rubber was a small amount of 5.9 parts by weight with respect to 100 parts by weight of the filler material, in terms of impact resistance. Excellent reforming effect. For this reason, the sample GM142 is a PVB resin composition that can be formed at an excellent manufacturing cost, and it can be said that a very excellent reforming effect is obtained per manufacturing cost.

  As mentioned above, embodiment mentioned above is only the illustration for implementing this invention. Therefore, the present invention is not limited to the above-described embodiment, and can be implemented by appropriately modifying the above-described embodiment without departing from the spirit thereof.

  The present invention can be used for a resin composition, and in particular, can be used for a resin composition containing a container material.

Claims (5)

A first rubber composition or a first resin;
A resin composition mainly comprising at least one of polypropylene and polyethylene;
A resin composition comprising: The resin composition according to claim 1,
The first rubber composition is a resin composition which is a block type styrene butadiene rubber, a butadiene rubber, a random type styrene butadiene rubber, a nitrile rubber (NBR), or a natural rubber (NR). The resin composition according to claim 1,
The first resin is acrylic resin, ethylene vinyl acetate copolymer (EVA), acrylonitrile / styrene (AS) resin, polyethylene terephthalate (PET), polycarbonate (PC), polystyrene (PS), and acrylonitrile butadiene styrene (ABS). ) A resin composition which is at least one of resins. In the resin composition according to claim 3,
The first resin is an ethylene vinyl acetate copolymer (EVA) and polyethylene terephthalate (PET). A resin composition mainly comprising at least one of polypropylene and polyethylene;
A resin modifier comprising the resin composition according to any one of claims 1 to 4;
Including
In the resin modifier, the content of the first rubber composition or the first resin is 50 to 500 parts by weight with respect to 100 parts by weight of the resin composition containing at least one of the polypropylene and polyethylene as a main component. A resin composition.

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