Resin molding material and method for recycling thermosetting carbamate

Abstract

The resin molding material is characterized in that the resin molding material is obtained by mixing 5-60% by weight of (A) a recycled material obtained by mixing a thermosetting urethane, short glass fibers and polyethylene terephthalate with 40-95% by weight of (B) a thermoplastic resin (provided that the total amount of (A) and (B) is 100% by weight).

Description

TECHNICAL FIELD

[0001] The present application relates to a resin molding material and a recycling method of thermosetting urethane. BACKGROUND

[0002] In the invention patent document 1, a recycling method of recycling rigid urethane foam which is manufactured from a raw material containing diphenylmethane diisocyanate as an essential component is described. The recycling method includes: a regeneration step of regenerating a polyurethane raw material from the rigid urethane foam; an addition polymerization step of addition polymerizing an alkylene oxide with the polyurethane raw material to produce a polyol; and a foaming treatment step of adding isocyanate, other additives to the polyol to regenerate the rigid urethane foam.

[0003] PRIOR ART DOCUMENTS

[0004] PATENT DOCUMENTS

[0005] Patent document 1: Japanese Patent Application Laid-Open No. 2003-012759 SUMMARY

[0006] PROBLEMS TO BE SOLVED BY THE INVENTION

[0007] The thermosetting urethane does not melt even if heated. Therefore, as in the recycling method of the invention patent document 1, a step of restoring the thermosetting urethane to a polyurethane raw material by chemical treatment (chemical recycling) is required.

[0008] However, the chemical recycling requires a large-scale equipment, and therefore the cost of the recycling becomes high, which becomes an obstacle to practical use. In addition, if it is a polyurethane monomer, the recycling can be performed by the chemical recycling, but in the case of a composite material of the polyurethane, the recycling is difficult.

[0009] Therefore, the object of the present application is to recycle a composite material containing a thermosetting urethane by a comparatively simple equipment.

[0010] MEANS FOR SOLVING THE PROBLEMS

[0011] In order to achieve the above object, a first mode of the present application is a resin molding material characterized in that the resin molding material is obtained by mixing (A) a recycled material 5 to 60% by weight in (B) a thermoplastic resin 40 to 95% by weight (wherein the total amount of (A) and (B) is 100% by weight), the (A) recycled material being a mixture of a thermosetting urethane, glass short fibers, and polyethylene terephthalate.

[0012] The second aspect of the present application is a resin molding material characterized by being obtained by mixing 5 to 60% by weight of (A) a recycled material, which is a mixture of a thermosetting urethane, glass short fibers, and polyethylene terephthalate, and 0 to 30% by weight (except 0% by weight) of (C) an additive in 10 to 95% by weight of (B) a thermoplastic resin (wherein the total amount of (A), (B), and (C) is 100% by weight).

[0013] The third aspect of the present application is a recycling method of a thermosetting urethane characterized by comprising: a recycled material production step of producing a recycled material in which a thermosetting urethane, glass short fibers, and polyethylene terephthalate are mixed by crushing a composite material containing the thermosetting urethane, the glass fibers, and the polyethylene terephthalate; and a resin molding material production step of producing a resin molding material by mixing the recycled material in a thermoplastic resin.

[0014] The resin molding material of the first and second aspects and the resin molding material produced in the resin molding material production step of the third aspect can also contain 1.5 to 29% by weight of a thermosetting urethane, 1.15 to 24.6% by weight of glass short fibers, and 1.0 to 13.8% by weight of polyethylene terephthalate.

[0015] Effects of the Invention

[0016] According to the present application, a composite material containing a thermosetting urethane can be recycled by a relatively simple device. BRIEF DESCRIPTION OF DRAWINGS

[0017] Figure 1 is a view that explains a recycled material production step according to the first embodiment of the present application.

[0018] Figure 2 is a view that explains a resin molding material production step according to the first embodiment of the present application.

[0019] Figure 3 is a view that schematically shows a composition example of a composite material.

[0020] Figure 4 is a view that shows an example in which a resin molding material is used for injection molding.

[0021] Figure 5 is a view that shows an example of a relationship between a mixing ratio of a recycled material and a density of a resin molded product.

[0022] Figure 6FIG. 1 is a graph showing an example of the relationship between the blending ratio of the recycled material and the heat deflection temperature of the resin molded article.

[0023] Figure 7 FIG. 2 is a graph showing an example of the relationship between the blending ratio of the recycled material and the flexural modulus of the resin molded article.

[0024] Figure 8 FIG. 3 is a graph showing an example of the relationship between the blending ratio of the recycled material and the flexural strength of the resin molded article.

[0025] Figure 9 FIG. 4 is a graph showing an example of the relationship between the blending ratio of the recycled material and the tensile elongation at break of the resin molded article.

[0026] Figure 10 FIG. 5 is a graph showing an example of the relationship between the blending ratio of the recycled material and the tensile yield strength of the resin molded article.

[0027] Figure 11 FIG. 6 is a graph showing an example of the relationship between the blending ratio of the recycled material and the Izod impact value (23°C) of the resin molded article.

[0028] Figure 12 FIG. 7 is a graph showing an example of the relationship between the blending ratio of the recycled material and the Izod impact value (-30°C) of the resin molded article.

[0029] Figure 13 FIG. 8 is a graph showing a resin molded material production process according to the second embodiment of the present application.

[0030] Symbol explanation

[0031] 1 Compound

[0032] 2 Compound particles

[0033] 3 Recycled material

[0034] 4 Recycled material particles

[0035] 5 Base resin particles

[0036] 6, 9 Resin molded material

[0037] 7, 10 Molded material particles

[0038] 8 Additive

[0039] 11 Urethane layer

[0040] 12 Glass mat layer

[0041] 13 Film layer

[0042] 20 Pulverizer

[0043] 30 disc pelletizer

[0044] 40 kneader

[0045] 41 hopper

[0046] 50 injection molding machine

[0047] 51 hopper

[0048] 52 metal mold

[0049] 60 resin molded product DETAILED DESCRIPTION

[0050] (First Embodiment)

[0051] Hereinafter, a first embodiment of the present application will be described with reference to the drawings. The recycling method of the present embodiment is provided with a recycled material generating step (refer to Figure 1 ) and a resin molding material generating step (refer to Figure 2 ).

[0052] The composite material 1 of the recycling target contains a thermosetting urethane, glass fibers, and PET (polyethylene terephthalate). In the present embodiment, a case where a urethane roof of a scrap (roof scrap) that forms an interior of a roof of an automobile is recycled is described, but the recycling target is not limited to the roof scrap of the automobile, and is only required to be a composite material 1 containing a thermosetting urethane, glass fibers, and PET.

[0053] As shown in Figure 3 , the composite material 1 of the present embodiment is a member in which a plurality of layers (6 layers in the illustrated example) are stacked one on top of another and bonded to be integrated. The plurality of layers include a urethane layer 11, upper and lower glass mat layers 12 that overlap the upper and lower surfaces of the urethane layer 11, a film layer 13 that overlaps the upper surface of the upper glass mat layer 12, an upper surface layer 14 that overlaps the upper surface of the film layer 13, and a lower surface layer 14 that overlaps the lower surface of the lower glass mat layer 12.

[0054] The urethane layer 11 is composed of a semi-rigid urethane foam (thermosetting urethane). The glass mat layer 12 is composed of glass fibers (glass long fibers) and isocyanate. The film layer 13 is composed of a CPP (unstretched polypropylene) film and a PP (polypropylene) film. The surface layer 14 is composed of a nonwoven fabric or a fabric including PET fibers. That is, among the constituents of the composite material 1, the thermosetting urethane is contained in the urethane layer 11, the glass fibers are contained in the glass mat layer 12, and the PET is contained as PET fibers in the surface layer 14.

[0055] The content of each component in the composite material 1 is, for example, 30 to 49% by weight of the thermosetting urethane, 23 to 41% by weight of the glass fiber, 20 to 23% by weight of the PET, and 6 to 11% by weight of the other components (wherein the total amount of the thermosetting urethane, the glass fiber, the PET, and the other components is 100% by weight). Among the other components, in addition to the CPP film and the PP film of the film layer 13, an adhesive or the like that bonds between the layers is included.

[0056] As shown in Figure 1 , the regenerated material generation process includes a pulverization process and a regenerated material pellet generation process.

[0057] In the pulverization process, the composite material 1 including the thermosetting urethane, the glass fiber, and the PET is pulverized to be granulated, thereby generating the regenerated material 3 in which the thermosetting urethane, the glass short fiber, and the PET are mixed. In the present embodiment, the composite material 1 is fed to a pulverizer 20, is pulverized to a particle diameter of about 5 mm, and is mixed to generate the regenerated material 3. The regenerated material 3 is a collection of the particles (composite material particles) 2 of the pulverized composite material 1. Each composite material particle 2 contains at least one of the components of the composite material 1, and the regenerated material 3 as a whole contains all of the components of the composite material 1. In addition, the glass long fiber of the composite material 1 is included in the composite material particle 2 in a state of being cut by the pulverization to a short fiber (glass short fiber) of about 1 mm to 6 mm.

[0058] In the regenerated material pellet generation process, the regenerated material 3 is processed to be the regenerated material pellet 4. In the present embodiment, the regenerated material 3 is fed to a disc die granulator 30, is compacted to be pelletized, and is generated as the regenerated material pellet 4.

[0059] By sufficiently mixing and stirring the pelletized regenerated material 3 (composite material particles 2) to be processed to be the regenerated material pellet 4, it is possible to make the proportions of the contents of each component in a single regenerated material pellet 4 close to the proportions of the contents of each component in the composite material 1. In addition, by processing the pelletized regenerated material 3 to be the regenerated material pellet 4, it is possible to easily perform storage of the regenerated material 3, supply to the next process (resin molding material generation process), and the like.

[0060] As shown in Figure 2 , the resin molding material generation process includes a mixing process and a molding material pellet generation process.

[0061] In the mixing process, the regenerated material 3 (refer to Figure 1) mixed with a thermoplastic resin to produce a resin molding material 6. In the present embodiment, the recycled material particles 4 produced in the recycled material particle production step are mixed with base resin particles 5 at a prescribed mixing ratio to produce the resin molding material 6. The base resin particles 5 are a substance produced by processing a base resin including a thermoplastic resin into particles. The resin molding material 6 is a substance produced by mixing the solid recycled material 3 and the solid base resin at a prescribed mixing ratio, and the resin molding material 6 of the present embodiment is a collection of two kinds of particles produced by mixing the recycled material particles 4 and the base resin particles 5 at a prescribed mixing ratio.

[0062] The mixing ratio of the recycled material 3 (recycled material particles 4) and the base resin (base resin particles 5) is set so that the recycled material 3 is 5 to 60% by weight and the base resin is 40 to 95% by weight (wherein the total amount of the recycled material 3 and the base resin is 100% by weight).

[0063] In the present embodiment, a case in which PP (polypropylene) is used as the base resin is described, but other thermoplastic resins (for example, ABS resin (acrylonitrile-butadiene-styrene resin) and the like) can also be used. The shape of the base resin is not limited to particles, and can be other shapes. In addition, the base resin can be virgin material or recycled material.

[0064] In the molding material particle production step, the resin molding material 6 is processed into molding material particles 7. In the present embodiment, the resin molding material 6 is fed into a hopper 41 of a kneader (twin-screw extruder) 40, and the recycled material 3 (recycled material particles 4) and the base resin (base resin particles 5) are kneaded and compacted into particles to produce the molding material particles 7. By processing the resin molding material 6 into the molding material particles 7, it is possible to stabilize the mixing ratio of the recycled material 3 and the base resin.

[0065] The respective amounts of the base resin (PP), the thermosetting urethane, the glass short fibers, the PET, and the other constituents in the resin molding material 6 (molding material particles 7) are preferably 10 to 95% by weight for the base resin, 1.5 to 29% by weight for the thermosetting urethane, 1.15 to 24.6% by weight for the glass short fibers, 1.0 to 13.8% by weight for the PET, and 0.3 to 6.6% by weight for the other constituents (wherein the total amount of the base resin, the thermosetting urethane, the glass short fibers, the PET, and the other constituents is 100% by weight).

[0066] The molding material particles 7 produced in the resin molding material production step can be used in the production of resin molded products 60 by injection molding, extrusion molding, press molding, and the like. For example, in the case of injection molding, as shown in FIG. 4, the molding material particles 7 are fed into a hopper 51 of an injection molding machine 50, and the molding material particles 7 are melted and injected into a mold 52 to produce the resin molded product 60. Figure 4As shown, in the injection molding machine 50, the molding material particles 7 are fed into the hopper 51, heated and melted, and then injected into the metal mold 52. The resin molded product 60 is obtained by taking it out of the metal mold 52 and cooling and solidifying.

[0067] Next, refer to Figures 5-12 The relationship between the physical properties of the resin molded article 60 manufactured using the resin molding material 6 (molding material particles 7) of this embodiment and the proportion (by weight%) of the recycled material 3 in the resin molding material 6 will be explained. Figures 5-12 This is an example of generating 10 kinds of resin molding materials 6, manufacturing 10 kinds of resin molded articles 60 by injection molding of each resin molding material 6, and comparing the physical properties of each resin molded article 60. The 10 kinds of resin molding materials 6 are obtained by using PP as the base resin, increasing the proportion of recycled material 3 from 0% by weight in increments of 5% by weight until 30% by weight, and then increasing the proportion of recycled material 3 from 30% by weight in increments of 10% by weight until 60% by weight. In the figures, the horizontal axis represents the proportion of recycled material 3, and the vertical axis represents the physical property values.

[0068] like Figure 5 As shown, the density (g / cm³) of the resin molded article 60 3 The percentage increases with the increase in the proportion of recycled material 3. For example... Figure 6 As shown, the load flexural temperature (°C) of the resin molded article 60 under a load of 0.45 MPa increases with the increase of the proportion of recycled material 3. Figure 7 As shown, the flexural modulus (MPa) of the resin molded article 60 increases with the increase of the proportion of recycled material 3. Figure 8 As shown, the flexural strength (MPa) of the resin molded article 60 decreases with increasing proportion of recycled material 3. For example... Figure 9 As shown, the tensile elongation at break (%) of the resin molded article 60 decreases with increasing proportion of recycled material 3. Figure 10 As shown, the tensile yield strength (MPa) of the resin molded article 60 decreases with increasing proportion of recycled material 3. Figure 11 and Figure 12 As shown, the Izod impact values ​​(kJ / m²) of the resin molded article 60 at 23°C and -30°C are... 2 All of these are reduced according to the combination of recycled material 3.

[0069] The proportion of recycled material 3 (the content of thermosetting urethane, short glass fibers, and PET in the resin molding material 6) is determined by considering the required properties of the resin molded article 60 and the aforementioned characteristics. For example, the density and flexural modulus of the resin molded article 60 both increase with the increase of the proportion of recycled material 3 (refer to...). Figure 5 and Figure 7Therefore, given the required rigidity (flexural modulus) and lightweight properties of the resin molded article 60, the recycled material 3 can be blended at the minimum blending ratio that yields the required flexural modulus.

[0070] According to this embodiment, the composite material 1 containing thermosetting carbamate is crushed to generate recycled material 3, and the generated recycled material 3 is mixed with a solid base resin to generate resin molding material 6. Therefore, the composite material 1 containing thermosetting carbamate can be recycled with relatively simple equipment without the need for large equipment such as chemical recycling and without separating thermosetting carbamate from the composite material 1.

[0071] The resin molding material 6 contains glass fibers from the composite material 1, thus increasing the rigidity of the resin molded article 60 using the resin molding material 6. In other words, the strength of the resin molded article 60 can be increased through the glass fibers of the composite material 1.

[0072] Recycled material 3 also functions as an additive to resin molding material 6, thus reducing the amount of recycled material 3 used in addition to the amount of base resin, thereby reducing the amount of base resin used.

[0073] The composite material 1, which is a waste material, can be recycled without incineration, thus significantly reducing CO2 production compared to incinerating the composite material 1.

[0074] Furthermore, if waste is generated from the resin molded article 60, the waste resin molded article 60 can be pulverized into granules and mixed with the resin molding material 6 for recycling. In this case, although the rigidity decreases to some extent due to the recycling of the resin molded article 60, both the glass fibers contained in the resin molding material 6 and the pulverized resin molded article 60 are short fibers of about 1 to 6 mm. Therefore, unlike the case where the glass fibers contained in the resin molding material 6 are long fibers, the rigidity will not decrease significantly. That is, even when the resin molded article 60 is recycled, the reduction in rigidity can be suppressed compared to the case where only the resin molding material 6 is used.

[0075] (Second Implementation)

[0076] Next, refer to Figure 13 The second embodiment of the present invention will be described. This embodiment involves a mixing process with the resin molding material generation process of the first embodiment (see reference...). Figure 2 and Figure 13 The process is different from the mixed process, but the other processes are the same. Therefore, detailed descriptions of processes other than the mixed process are omitted.

[0077] like Figure 13As shown, in the mixing process of this embodiment, recycled material particles 4 and additives 8 are mixed in base resin particles 5 at a predetermined ratio to generate resin molding material 9. In the molding material particle generation process, resin molding material 9 is fed into the hopper 41 of the mixer 40, and recycled material 3 (recycled material particles 4), additives 8 and base resin (base resin particles 5) are mixed and compacted into particles to generate molding material particles 10.

[0078] The blending ratios of recycled material 3 (recycled material particles 4), additive 8 and base resin (base resin particles 5) are set as follows: recycled material 3 is 5-60% by weight, additive 8 is 0-30% by weight (excluding 0% by weight), and base resin is 10-95% by weight (wherein, the total amount of recycled material 3, additive 8 and base resin is 100% by weight).

[0079] To adjust the physical properties of the resin molded article 60, additive 8 is added. As additive 8, inorganic fillers such as talc and / or rubber components can be used. By adding talc as additive 8, the rigidity of the resin molded article 60 can be improved. Furthermore, by adding rubber components as additive 8, the Izod impact value of the resin molded article 60 can be increased, and the decrease in Izod impact value caused by the addition of recycled material 3 can be suppressed.

[0080] The present invention has been described above based on the embodiments described above, but the present invention is not limited to the contents of the above embodiments, and appropriate modifications can be made without departing from the scope of the present invention. That is, other embodiments, examples, and techniques made by those skilled in the art based on these embodiments are all included within the scope of the present invention.

[0081] For example, in the first and second embodiments, the molding material particle generation process can be omitted (see...). Figure 2 and Figure 13 In this case, molding compound particles 7 and 10 are not generated; instead, resin molding materials 6 and 9 generated during the mixing process are used to manufacture the resin molded article 60. For example, in the case of injection molding (see...). Figure 4 In the injection molding machine 50, resin molding material 6 and resin molding material 9 are directly fed into the hopper 51, heated and melted, and then injected into the metal mold 52. The resin molded product 60 is obtained by taking it out of the metal mold 52 and cooling and solidifying.

[0082] In addition, in the first and second embodiments, the recycled material pellet generation process may be omitted (see reference). Figure 1 In this case, the mixing process in the resin molding material production process (refer to...) Figure 2 and Figure 13In the process of mixing the granular recycled material 3 generated in the crushing process with the solid base resin at a specified ratio, or mixing the granular recycled material 3, the additive 8 and the solid base resin at a specified ratio, the resin molding material 6 and the resin molding material 9 can be generated.

[0083] In addition, in the second embodiment, the recycled material particles 4 and the additive 8 are mixed in the base resin particles 5 to generate the resin molding material 9. However, it is also possible to mix the recycled material particles 4 and the base resin particles 5 and compress them to generate granules (corresponding to the molding material particles 7 in the first embodiment) in the same way as in the first embodiment, and mix the additive 8 in the generated granules to generate the resin molding material.

[0084] Industrial availability

[0085] This invention is useful for the recycling of composites containing thermosetting urethanes.

Claims

1. A resin molding material, characterized in that, The resin molding material is made by mixing 5-60% by weight of (A) recycled material with 40-95% by weight of (B) thermoplastic resin (wherein the total amount of (A) and (B) is 100% by weight), and the (A) recycled material is a mixture of thermosetting urethane, glass short fiber and polyethylene terephthalate.

2. A resin molding material, characterized in that, The resin molding material is made by mixing 5-60% by weight of (A) recycled material and 0-30% by weight of (C) additives (excluding 0% by weight) with 10-95% by weight of (B) thermoplastic resin (wherein, the total amount of (A), (B) and (C) is 100% by weight), wherein the (A) recycled material is a mixture of thermosetting urethane, glass short fibers and polyethylene terephthalate.

3. A method for regenerating thermosetting carbamates, characterized in that, have: The recycled material generation process involves granulating a composite material containing thermosetting urethane, glass fiber, and polyethylene terephthalate by crushing it, thereby generating a recycled material composed of a mixture of thermosetting urethane, short glass fiber, and polyethylene terephthalate. as well as The resin molding material generation process involves mixing the recycled material with a thermoplastic resin to generate the resin molding material.

Images