Pellets and method for manufacturing pellets

Abstract

The present invention provides a pellet and a method for producing a pellet. The present invention aims to provide a pellet containing a reinforcing fiber and a thermoplastic resin, which is useful in recycling of a fiber-reinforced resin composite. The pellet of the present invention is characterized by containing a reinforcing fiber and a thermoplastic resin, and having a cross section with a ratio (L / P) of a length L along an outer periphery of the cross section to a circumference P of a circumscribed shape of the above cross section of 1.1 to 2.2.

Description

TECHNICAL FIELD

[0001] The present application relates to a pellet and a method for manufacturing a pellet. BACKGROUND

[0002] In structural members of various machines, automobiles, and the like, pressure vessels, and tubular structures, and the like, a composite molded body in which a reinforcing material such as glass fiber is added to a base resin material is used. In particular, from the aspect of strength, a fiber reinforced resin composite material in which the reinforcing fiber is a continuous fiber is required.

[0003] PRIOR ART DOCUMENTS

[0004] PATENT DOCUMENTS

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 2006-218793 SUMMARY

[0006] PROBLEMS TO BE SOLVED BY THE INVENTION

[0007] In recent years, the amount of use of fiber reinforced resin composite materials has increased, and the recycling thereof has been studied, and the handling and molding easiness of the recycled pellet material becomes important. As a recycling method of fiber reinforced resin composite materials, various methods have been proposed until now. For example, in Patent Document 1, the following recycling method is described: a recycled carbon fiber reinforced thermoplastic resin molded product is pulverized, and a pellet is prepared, and then the pellet is mixed with a virgin carbon fiber reinforced thermoplastic resin pellet, and is used in injection molding. However, the purpose of this document aims at closed loop recycling of carbon fiber reinforced thermoplastic resin, and only the content of mixing with virgin pellets at the time of molding after the pellet is prepared is disclosed, and since the proportion (L / P) of the length L along the outer periphery of the cross section with respect to the circumference P of the circumscribed shape of the above cross section does not satisfy 1.1 to 2.2, the handling and molding easiness of the pellet is not sufficient.

[0008] An object of the present application is to provide a pellet containing a reinforcing fiber and a thermoplastic resin, which is useful in recycling of fiber reinforced resin composite materials.

[0009] MEANS FOR SOLVING THE PROBLEMS

[0010] That is, the present application is as follows. [1]

[0012] A pellet characterized by,

[0013] containing a reinforcing fiber and a thermoplastic resin,

[0014] having a cross section in which the proportion (L / P) of the length L along the outer periphery of the cross section with respect to the circumference P of the circumscribed shape of the above cross section is 1.1 to 2.2. [2]

[0016] The pellet as described in [1], wherein

[0017] The reinforcing fiber is oriented in one direction in the pellet,

[0018] The ratio of the fiber length of the reinforcing fiber to the length of the pellet (fiber length of reinforcing fiber / length of pellet) is 0.9 to 1.1 times. [3]

[0020] The pellet as described in [1] or [2], wherein the void fraction is 0.5 to 5.0%. [4]

[0022] The method for producing the pellet as described in any one of [1] to [3], comprising:

[0023] a molding step of molding a continuous fiber-reinforced resin composite material containing continuous reinforcing fibers and a thermoplastic resin, the longest side having a length of 0.1 to 20 mm, and having an interlayer peeling portion extending in the extension direction of the continuous reinforcing fibers on the surface. [5]

[0025] The method for producing the pellet as described in [4], comprising:

[0026] a metal removing step of removing metal from the continuous fiber-reinforced resin composite material before the molding step. [6]

[0028] The method for producing the pellet as described in [4], comprising:

[0029] a moisture removing step of removing moisture from the continuous fiber-reinforced resin composite material before the molding step. [7]

[0031] The method for producing the pellet as described in any one of [1] to [3], comprising:

[0032] a metal removing step of removing metal from a continuous fiber-reinforced resin composite material containing continuous reinforcing fibers and a thermoplastic resin, the longest side having a length of 0.1 to 20 mm, and having an interlayer peeling portion extending in the extension direction of the continuous reinforcing fibers on the surface;

[0033] a moisture removing step of removing moisture from the continuous fiber-reinforced resin composite material; and

[0034] a molding step of molding the continuous fiber-reinforced resin composite material after the metal removing step and the moisture removing step.

[0035] Effects of the Invention

[0036] The pellet of the present invention is useful in recycling of fiber reinforced resin composite materials because of the above constitution. BRIEF DESCRIPTION OF DRAWINGS

[0037] Figure 1 is a photograph of an example of the pellet of the present embodiment.

[0038] Figure 2 is a photograph of a cross section of an example of the pellet of the present embodiment.

[0039] Figure 3 is an explanatory diagram of a cross section of an example of the pellet of the present embodiment.

[0040] Figure 4 (A) of is a diagram explaining a measuring method of void fraction of the pole interface. Figure 4 (B) of is a photograph of an example of high void fraction of the pole interface.

[0041] Figure 5 is a diagram explaining the accumulation of reinforcing fibers occurring at the discharge port when manufacturing the pellet of the present embodiment.

[0042] Figure 6 is a diagram explaining a measuring method of the length of the longest side.

[0043] Figure 7 is a photograph of an example of the pulverized composite material.

[0044] Figure 8 is an observation image of the polishing surface when judging the interlayer peeling portion of the pulverized composite material.

[0045] Figure 9 is a diagram explaining Lb / La, Lb’ / La’.

[0046] Explanation of Symbols

[0047] 1 Pellet

[0048] 2 Cross section of the pellet

[0049] 21 Circumscribed shape

[0050] 22 Shape along the outer periphery of the cross section

[0051] 23 Pore

[0052] 3 Discharge port

[0053] 31 Thread

[0054] 32 Accumulation of reinforcing fibers

[0055] 4 Pole interface portion

[0056] 41 Continuous reinforcing fiber

[0057] 5. Crushing composite materials

[0058] 51 Interlayer peeling section

[0059] 52. Voids (interlayer delamination)

[0060] 53. Length of the gap in the thickness direction

[0061] 54. The thickness of the void and its length in the orthogonal direction.

[0062] 55. A line (La) connecting the two endpoints of the edge along the extension direction of the continuous reinforcing fibers on the surface.

[0063] 56. Line (Lb) on the surface of the composite material between the two endpoints of the edge along the extension direction of the continuous reinforcing fiber.

[0064] 57. A line (La') connecting the two endpoints of the side orthogonal to the extension direction of the continuous reinforcing fiber.

[0065] 58. A line (Lb') on the surface of the composite material between the two endpoints of an edge orthogonal to the extension direction of the continuous reinforcing fiber.

[0066] 59. Smallest circle Detailed Implementation

[0067] The following provides a detailed description of specific embodiments of the present invention (hereinafter referred to as "this embodiment"). The present invention is not limited to this embodiment and can be implemented with various modifications within the scope of its key points.

[0068] [Granular material]

[0069] The granules of this embodiment contain reinforcing fibers and thermoplastic resin, and have a cross-section in which the ratio (L / P) of the length L along the outer perimeter of the cross section to the perimeter P of the circumference of the circumferential shape of the cross section is 1.1 to 2.2.

[0070] The granules of this embodiment can be prepared from a continuously fiber-reinforced resin composite material comprising reinforcing fibers and thermoplastic resin, or from a pulverized composite material obtained by pulverizing the continuously fiber-reinforced resin composite material. From the perspective of reusability, the granules of this embodiment are preferably granules prepared using the raw material composite material.

[0071] It should be noted that, in this specification, the pulverized composite material that can be used as the raw material for the granules in this embodiment can be a pulverized material obtained by pulverizing the raw material composite material, a substance obtained by cutting the raw material composite material, etc.

[0072] In addition, in the present specification, a post-production continuous fiber reinforced resin composite material that can be used in the production of the above-described crushed composite material is sometimes referred to as a "raw material composite material". Here, the raw material composite material includes a composite material produced using recycled materials, in addition to a virgin composite material.

[0073] As the reinforcing fiber included in the pellets of the present embodiment, the same substances as the continuous reinforcing fiber described later can be given. The above-described reinforcing fiber can be one kind, or two or more kinds can be used in combination. In addition, it is preferable to be the same as the continuous reinforcing fiber included in the crushed composite material or the raw material composite material used as a raw material. Note that the continuous reinforcing fiber refers to a reinforcing fiber that extends from one end of a composite material to the other end opposite the one end, and the reinforcing fiber refers to a reinforcing fiber including the continuous reinforcing fiber and a continuous reinforcing fiber that is cut in the middle.

[0074] As the thermoplastic resin included in the pellets of the present embodiment, the same substances as the thermoplastic resin described later can be given. The above-described thermoplastic resin can be one kind, or two or more kinds can be used in combination. In addition, it is preferable to be the same as the thermoplastic resin included in the crushed composite material or the raw material composite material used as a raw material, the thermoplastic resin included in the virgin pellets added at the time of production.

[0075] In the pellets of the present embodiment, in addition to the above-described reinforcing fiber and the above-described thermoplastic resin, an additive can be included. As the above-described additive, for example, the same substances as the additive included in the crushed composite material or the raw material composite material used as a raw material at the time of production, the additive included in the virgin pellets added at the time of production, and the like can be given.

[0076] In the pellets of the present embodiment, from the aspects of increasing the surface area of the pellets, making the heating and melting at the time of molding processing easy, forming a drag by giving the pellet surface a concave-convex shape and improving the handling properties, the pellets have a cross section in which the ratio (L / P) of the length L along the outer periphery of the cross section to the circumference P of the circumscribed shape of the above-described cross section is 1.1 to 2.2. The L / P in the above-described cross section is preferably 1.2 to 2.1, more preferably 1.2 to 2.0, further preferably 1.4 to 1.8, and particularly preferably 1.5 to 1.8.

[0077] Here, the circumscribed shape refers to a shape in which, with the center of gravity of the cross section of the pellets as the center, the distance L from the center of gravity to the outer periphery of the cross section is measured while rotating 360°, and each point on the outer periphery of the cross section at which the distance L becomes a maximum value is connected by a line segment to form a shape. Figure 2 、 Figure 3 ) Note that Figure 2 is a photograph of a cross section of an example of the pellets of the present embodiment, Figure 3is a schematic view for explaining a cross section of the pellets of the present embodiment.

[0078] In addition, the above cross section refers to an arbitrary cross section of the pellets, and for example, can be a cross section orthogonal to the extending direction of the reinforcing fibers included in the pellets.

[0079] In order to adjust the L / P to the above range, for example, a method of matching the material composition and ratio of the thermoplastic resin, the continuous reinforcing fibers, the additive material, and the like of the raw material composite, the size, the shape, and the water absorption of the raw material composite, and the like to the pelletization conditions can be mentioned.

[0080] The orientation direction of the reinforcing fibers included in the pellets of the present embodiment (i.e., the extending direction of the reinforcing fibers) can be one direction or multiple directions (for example, two directions). Among them, from the viewpoint of the handleability and the ease of processing of the pellets and the properties of the molded body after molding the pellets, one direction is preferable.

[0081] The above orientation direction can be adjusted, for example, by the fiber diameter and the fiber amount of the reinforcing fibers in the composite used in the raw material and the kneading and discharging conditions at the time of pelletization. As the raw material composite, in the case of using a material having a large amount of reinforcing fibers and a large fiber diameter, by making the kneading speed slower and the discharging amount faster, pellets in which the reinforcing fibers are oriented in one direction can be obtained. In addition, by making the kneading speed faster and the discharging amount smaller, pellets in which the reinforcing fibers are oriented in multiple directions can be obtained. In addition, in the case of using a material having a small amount of reinforcing fibers and a small fiber diameter, by making the kneading speed faster and the discharging amount larger, pellets in which the reinforcing fibers are oriented in one direction can be obtained.

[0082] Regarding the proportion of the fiber length of the above reinforcing fibers in the pellets of the present embodiment with respect to the length of the pellets (fiber length of the reinforcing fibers / length of the pellets), from the viewpoint of obtaining a molded body having excellent properties such as strength by making the fiber length of the reinforcing fibers included in the pellets longer, the proportion is preferably 0.90 to 1.10 times, more preferably 0.93 to 1.08 times, and further preferably 0.95 to 1.05 times.

[0083] Note that, regarding the length of the above pellets, in the case of the pellets being substantially cylindrical, it refers to the height of the cylinder. In addition, substantially cylindrical means that the cross section orthogonal to the height is not necessarily only circular, and the cross section can be substantially circular, substantially circular with a sawtooth-shaped outer periphery, or the like. In addition, the pellets of the present embodiment can be pellets manufactured by cutting a thread made by melt extrusion or the like. In this case, the length of the above pellets can be the length of 2 cross sections (for example, the maximum length between the cross sections). From the viewpoint of the handleability and the moldability, the length of the above pellets is preferably 0.5 to 15 mm, more preferably 1 to 10 mm, and further preferably 3 to 7 mm.

[0084] In addition, the fiber length of the reinforcing fiber refers to the length of the reinforcing fiber contained in the pellets. The above-mentioned fiber length of the reinforcing fiber can be the average length of the reinforcing fiber contained in the pellets. From the viewpoint of obtaining a molded body having excellent physical properties such as strength, the fiber length of the above-mentioned reinforcing fiber is preferably 0.45 to 16.5 mm, more preferably 3 to 7 mm.

[0085] From the viewpoint of improving the cushioning property of the pellets and reducing fiber breakage occurring in processing and the like, the porosity of the pellets of the present embodiment is preferably 0.5 to 5.0%, more preferably 1.0 to 4.0%, further preferably 1.5 to 3.0%.

[0086] The above-mentioned porosity can be adjusted, for example, by the porosity of the compounded material after pulverization, the size of interlayer peeling.

[0087] Note that the porosity can be measured using the method described in the Examples below. The above-mentioned porosity refers to the proportion of pores present at the cross section of the pellets and the voids between the reinforcing fiber and the thermoplastic resin.

[0088] In the pellets of the present embodiment, the porosity of the polar interface portion between one of the reinforcing fibers in the pellets and the portion (for example, the portion composed of the thermoplastic resin) surrounding the reinforcing fiber in the cross section orthogonal to the extending direction of the reinforcing fiber in the pellets is preferably 20% or less, more preferably 15% or less, further preferably 10% or less. When the above-mentioned porosity of the polar interface portion is 5% or less, the reinforcing fiber is tightly bonded to its surroundings, and the strength of the pellets and the molded product is excellent. The above-mentioned porosity of the polar interface portion can be adjusted by the kind of the raw material compounded material and the like.

[0089] Note that the polar interface portion refers to the portion between the points in the outer peripheral region of the above-mentioned reinforcing fiber in the above-mentioned orthogonal cross section from the outer periphery of one of the above-mentioned reinforcing fibers to the distance (1 / 10r) of one-tenth of the distance r from the center (may be the barycenter) of the reinforcing fiber to the point on the outer periphery (A of FIG. 1). Figure 4

[0090] In addition, the above-mentioned porosity refers to the proportion of the area occupied by the voids to the area of the polar interface portion 100%. Figure 4 B of FIG. 1 is an example in which the polar interface portion has a void, and peeling of the reinforcing fiber from its surroundings easily occurs in molding, and thus is not preferable. The porosity of the polar interface portion of one of the reinforcing fibers can be found from any one of the orthogonal cross sections of the extending direction of the reinforcing fiber.

[0091] ​The porosity of the above-described polar interface portion can be measured by the following method. The oriented orthogonal cross section of the reinforcing fiber is ground with a grinder (small precision sample making system IS-POLISHER ISPP-1000 (Ikegai Seimitsu Kikai Co., Ltd.)) under a grinding pressure of 1000 g / cm2 2 and a grinding condition to produce a ground surface. Thereafter, the ground surface is observed with a field emission type scanning electron microscope (FESEM (S-4700, Hitachi High-Technologies Corporation)) and the porosity of the polar interface portion is calculated. Note that, in the evaluation of the porosity of the polar interface, the cross section orthogonal to the extension direction of the reinforcing fiber can be ground so as to become the ground surface. As for the above-described grinding condition, it can be performed in the order of #2000 water-resistant sandpaper for 10 minutes, a 9 μm particle size silicon carbide film for 5 minutes, a 5 μm particle size aluminum oxide film for 5 minutes, a 3 μm particle size aluminum oxide film for 5 minutes, and a 1 μm particle size aluminum oxide film for 5 minutes. In addition, each grinding is performed while water is added at about 7 mL / min, and air can be blown onto the ground surface between each grinding to remove cutting chips.

[0092] From the viewpoint of ease of pelletization and the properties of the molded pellets, the mass ratio of the above-described reinforcing fiber is preferably 10 to 70 mass%, more preferably 20 to 60 mass%, and further preferably 30 to 50 mass% with respect to 100 mass% of the pellets of the present embodiment.

[0093] The shape of the pellets of the present embodiment can be, for example, a substantially cylindrical shape or a substantially spherical shape. The pellets of the present embodiment can be pellets obtained by cutting a wire material (for example, a substantially cylindrical wire material cutting pellet).

[0094] The mass ratio of the above-described thermoplastic resin is preferably 30 to 90 mass%, and more preferably 50 to 70 mass% with respect to 100 mass% of the pellets of the present embodiment.

[0095] The mass ratio of the reinforcing fiber in the pellets of the present embodiment with respect to 100 parts by mass of the above-described thermoplastic resin is preferably 25 to 150 parts by mass, and more preferably 40 to 100 parts by mass.

[0096] The total mass ratio of the above-described reinforcing fiber and the above-described thermoplastic resin is preferably 90 to 100 mass%, and more preferably 95 to 99.5 mass% with respect to 100 mass% of the pellets of the present embodiment.

[0097] [Method for manufacturing pellets]

[0098] The method for manufacturing the pellets of the present embodiment is not particularly limited as long as it is a method that can obtain the above-described pellets of the present embodiment.

[0099] As the manufacturing method described above, a method including a molding step of molding a continuous fiber-reinforced resin composite material including a continuous reinforcing fiber and a thermoplastic resin, a longest side having a length of 0.1 to 20 mm, and an interlayer peeling portion extending along an extension direction of the continuous reinforcing fiber on a surface can be given. The method preferably includes a metal removal step of removing a metal from the continuous fiber-reinforced resin composite material before the molding of the continuous fiber-reinforced resin composite material described above, and / or a moisture removal step of removing moisture from the continuous fiber-reinforced resin composite material described above. More preferably, both the metal removal step and the moisture removal step are included, that is, a method including a metal removal step of removing a metal from a continuous fiber-reinforced resin composite material including a continuous reinforcing fiber and a thermoplastic resin, a longest side having a length of 0.1 to 20 mm, and an interlayer peeling portion extending along an extension direction of the continuous reinforcing fiber on a surface; a moisture removal step of removing moisture from the continuous fiber-reinforced resin composite material; and a molding step of molding the continuous fiber-reinforced resin composite material after the metal removal step and the moisture removal step. The order of the metal removal step and the moisture removal step is not particularly limited, and from the viewpoint of manufacturing efficiency, the moisture removal step is preferably provided after the metal removal step, and more preferably, the moisture removal step is continuously provided after the metal removal step.

[0100] (Metal removal step)

[0101] As the continuous fiber-reinforced resin composite material including a continuous reinforcing fiber and a thermoplastic resin, a longest side having a length of 0.1 to 20 mm, and an interlayer peeling portion extending along an extension direction of the continuous reinforcing fiber on a surface used in the metal removal step described above, a pulverized composite material can be given, for example. The pulverized composite material can be prepared from the raw material composite material described above. The pulverized composite material can be a pulverized composite material before the moisture removal step described above, or a pulverized composite material after the moisture removal step described above.

[0102] As a method of removing a metal, a method of removing by attaching to a magnet or the like, a method of removing using a device such as a magnetic separator or a foreign matter removal device, or the like can be given. Among them, from the viewpoint of production efficiency, a method of attaching to a magnet is preferable.

[0103] As a method of attaching to a magnet, a method of passing the pulverized composite material through a magnetic stand or the like can be given, for example.

[0104] As the magnet described above, a magnet having a surface magnetic flux density of 4000 to 30000 Gauss, preferably 10000 to 20000 Gauss can be used.

[0105] The temperature for removing metal can be 10 to 100°C.

[0106] (Moisture removal process)

[0107] Methods for removing moisture include, for example, heating drying, vacuum drying, and vacuum heating drying. Among these, heating drying and vacuum heating drying are preferred from the perspective of production efficiency.

[0108] The temperature for removing moisture can be 50–150℃.

[0109] The pressure required to remove moisture can be 1–100 kPa.

[0110] The time for the moisture removal process can be 0.5 to 100 hours.

[0111] (Molding process)

[0112] In the above molding process, granules can be obtained by molding the above-mentioned continuous fiber reinforced resin composite material, which includes continuous reinforcing fibers and thermoplastic resin, has a longest side length of 0.1 to 20 mm, and has interlaminar delamination portions extending along the extension direction of the continuous reinforcing fibers on its surface. Regarding the above-mentioned continuous fiber reinforced resin composite material, which includes continuous reinforcing fibers and thermoplastic resin, has a longest side length of 0.1 to 20 mm, and has interlaminar delamination portions extending along the extension direction of the continuous reinforcing fibers on its surface, it can be a continuous fiber reinforced resin composite material after undergoing the above-mentioned metal removal process, a continuous fiber reinforced resin composite material after undergoing the above-mentioned moisture removal process, or a continuous fiber reinforced resin composite material after undergoing both the above-mentioned metal removal process and the above-mentioned moisture removal process.

[0113] The molding process described above is preferably the following process: molding the continuous fiber-reinforced resin composite material (i.e., the pulverized composite material after the metal removal process and the moisture removal process) that has undergone the metal removal process and the moisture removal process to produce granules, thereby obtaining the granules of this embodiment.

[0114] Examples of molding processes described above include extrusion molding.

[0115] The above extrusion molding can use only the continuous fiber-reinforced resin composite material that has undergone the above metal removal process and the above moisture removal process, or it can further add virgin particles for dilution.

[0116] The above primary particles preferably contain a thermoplastic resin. As the thermoplastic resin contained in the above primary particles, the same thermoplastic resin as that contained in the continuous fiber-reinforced resin composite used in the molding step is preferable. The mass ratio of the above thermoplastic resin is preferably 50 to 100 parts by mass, more preferably 70 to 99.99 parts by mass, and further preferably 90 to 99.9 parts by mass, with respect to 100 parts by mass of the above primary particles. The thermoplastic resin contained in the above primary particles can be one or a combination of two or more.

[0117] The above primary particles can further contain an additive. As the above additive, from the aspect of improving the function of the pellets, a flame retardant, a heat-resistant agent, a weather-resistant agent, a lubricant, and the like can be given. The mass ratio of the above additive is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 10 parts by mass, and further preferably 0.1 to 5 parts by mass, with respect to 100 parts by mass of the above primary particles. The additive contained in the above primary particles can be one or a combination of two or more.

[0118] In the case where the above primary particles are added, the mass ratio of the above primary particles is preferably 0 to 300 parts by mass, more preferably 10 to 150 parts by mass, and further preferably 20 to 80 parts by mass, with respect to 100 parts by mass of the continuous fiber-reinforced resin composite used in the molding step.

[0119] In the above molding step, an extruder can be used to produce a strand.

[0120] The extruded strand can be cooled by air cooling, water cooling, or the like. Among them, air cooling is preferable.

[0121] The cooled strand can be cut into an appropriate size using a pelletizer or the like to be made into a pellet.

[0122] In the above molding step, when a pulverized composite material is used as a raw material, a reinforcing fiber accumulation occurs at a discharge portion of the extruder from which the strand is discharged. In the case where a pellet of a thermoplastic resin is used and a continuous reinforcing fiber, a short fiber, and / or a long fiber is used to form a strand, the reinforcing fiber accumulation does not occur. In the case where a pulverized composite material is used, the material composition or ratio of the thermoplastic resin or the continuous reinforcing fiber, an additive material, or the like contained in the pulverized composite material, the size, shape, or water absorption of the pulverized composite material, and the like, and the pelletization conditions are adjusted so that the above reinforcing fiber accumulation occurs at the discharge portion Figure 5 ), whereby the outer periphery of the cross section of the strand and the shape of the discharge port of the discharge portion are different, and the outer peripheral surface of the cross section becomes a jagged sawtooth shape Figure 2 , Figure 3), so the handling of the pellets is improved. In addition, since the outer peripheral surface is jagged in a concave-convex sawtooth shape, pellets and strands having the L / P of 1.1 to 2.2 described above can be obtained.

[0123] Even if a continuous fiber-reinforced resin composite material is used as a raw material of the crushed composite material, in a case where interlayer peeling of the crushed composite material is insufficient or in a case where the fiber diameter of the continuous reinforcing fiber is too fine, there is a tendency that the L / P increases beyond the above range.

[0124] From the aspect of obtaining pellets and strands whose outer peripheral surface is jagged in a concave-convex sawtooth shape, the mass ratio of the crushed composite material to the material of 100 mass% fed into the extruder is preferably 10 mass% or more, more preferably 20 to 70 mass%, and further preferably 30 to 60 mass%.

[0125] As the temperature of the heater at the time of the molding step, a temperature of the melting point of the thermoplastic resin contained in the pellets + 5°C to a temperature of the melting point + 150°C, and more preferably a temperature of the melting point + 15°C to a temperature of the melting point + 45°C is preferable.

[0126] In addition, as the rotation speed of the screw at the time of molding, 10 to 150 rpm, and more preferably 20 to 110 rpm is preferable.

[0127] In addition, as the discharge amount at the time of molding, 2 to 200 kg / h, and more preferably 3 to 100 kg / h, and further preferably 5 to 90 kg / h is preferable.

[0128] The raw material composite material that can be used for the manufacturing method of the pellets of the present embodiment will be described below. Note that, as the thermoplastic resin, the reinforcing fiber, and the additive contained in the pellets of the present embodiment, the thermoplastic resin, the continuous reinforcing fiber, and the additive described below can be cited, and the appropriate examples described below are preferable.

[0129] (Raw material composite material)

[0130] The form of the raw material composite material described above can be cited, for example, a form in which a woven fabric, a knitted fabric, a non-crimp fabric, a braid, a tube of a continuous reinforcing fiber is compounded with a thermoplastic resin; a form in which a continuous reinforcing fiber aligned in one direction is compounded with a thermoplastic resin; a form in which a filament composed of a continuous reinforcing fiber and a thermoplastic resin is aligned in one direction to be shaped; a form in which a filament composed of a continuous reinforcing fiber and a thermoplastic resin is made into a woven fabric, a knitted fabric, a braid, a tube to be shaped, and the like. Among them, from the aspect of obtaining a firm molded product after recycling, a form in which a continuous reinforcing fiber aligned in one direction is compounded with a thermoplastic resin, and a form in which a woven fabric of a continuous reinforcing fiber intersecting in two directions approximately orthogonal is compounded with a thermoplastic resin are preferable.

[0131] The raw material composite can be a flat plate or a laminate including a layer of continuous reinforcing fibers and a layer of thermoplastic resin. For example, the continuous reinforcing fibers can be arranged so that the length direction thereof is substantially parallel to the surface of the flat plate. Note that the layer of continuous reinforcing fibers is a layer including continuous reinforcing fibers and can be a layer in which the continuous reinforcing fibers are impregnated with a thermoplastic resin.

[0132] The form of the intermediate material before the raw material composite is shaped is not particularly limited and examples include: a mixed yarn of continuous reinforcing fibers and resin fibers; a coated yarn in which a bundle of continuous reinforcing fibers is coated with a resin; a form in which continuous reinforcing fibers are impregnated with a resin in advance and are made into a tape; a form in which a film of a resin is sandwiched with continuous reinforcing fibers; a form in which a resin powder is attached to continuous reinforcing fibers; a form in which a bundle of continuous reinforcing fibers is made into a braid with a resin fiber around the bundle; a form in which a resin is impregnated in advance between reinforcing fibers; a form in which continuous reinforcing fibers are brought into contact with a molten resin; and the like.

[0133] The method of manufacturing the raw material composite is not particularly limited and various methods can be used.

[0134] For example, the following method can be used: the base material (e.g., a base material composed of continuous reinforcing fibers, a base material composed of a thermoplastic resin) that constitutes the pulverized composite is stacked in the desired number of pieces, is cut or shaped, and is placed in a mold in the number of pieces or the number of layers necessary for the thickness of the target product in accordance with the shape of the mold. At this time, the mold can be closed after the base material is placed in the mold and is compressed, the temperature of the mold can be adjusted to a temperature above the melting point of the thermoplastic resin that constitutes the raw material composite, the thermoplastic resin can be melted, and the shaping can be performed.

[0135] As another method, the following method can be used: the base material that constitutes the continuous fiber-reinforced resin composite is continuously supplied using a double-belt press or a continuous compression molding device, is heated to a temperature above the melting point of the thermoplastic resin, is compression molded at an arbitrary pressure, and is cooled to a temperature below the crystallization temperature or the glass transition temperature of the thermoplastic resin to manufacture.

[0136] The raw material composite can be a hybrid composite further filled with a hybrid thermoplastic resin composition. In the manufacturing process of the hybrid composite, the above-described base material is placed in a mold, the mold is closed, and is pressurized, a predetermined hybrid thermoplastic resin composition is further injected and filled after a predetermined time, and the base material is molded so that the thermoplastic resin of the base material is joined with the predetermined hybrid thermoplastic resin composition, whereby the hybrid composite can be manufactured. The thermoplastic resin included in the above-described hybrid thermoplastic resin composition can be the same as or different from the thermoplastic resin included in the raw material composite.

[0137] As a site where an interlayer peeling portion is easily formed in the composite material after the above-mentioned raw material composite material is pulverized, for example, the interlayer of a layer of continuous reinforcing fibers and a layer of a thermoplastic resin, the interlayer of two layers of continuous reinforcing fibers that are aligned in mutually different directions, the interlayer of a hybrid layer and a layer of a base material, and the like can be given.

[0138] Figure 8 is a ground surface of a continuous fiber-reinforced resin composite material. With respect to the interlayer peeling portion 52, an interlayer peeling portion 52 is formed between a layer in which continuous reinforcing fibers extend in a direction orthogonal to the ground surface of the continuous fiber-reinforced resin composite material and a layer in which continuous reinforcing fibers extend in parallel to the ground surface. Figure 8

[0139] (Method for manufacturing pulverized composite material)

[0140] The above-mentioned pulverized composite material can be manufactured by pulverizing the above-mentioned raw material composite material. Note that, in the present specification, a pulverized composite material refers to a raw material composite material after pulverization.

[0141] The above-mentioned pulverization can be performed using a pulverizer, a crusher, or the like.

[0142] As a condition for the above-mentioned pulverization, the type of a blade used, the rotational speed of the blade, the shape of the blade, the force applied to the raw material composite material at the time of pulverization, the amount of the raw material composite material fed, the size and shape of the raw material composite material, and the like can be given.

[0143] From the aspect of obtaining a pulverized composite material of uniform size, after the above-mentioned pulverization, large pulverized composite materials can be removed by a mesh screen having a mesh size of 0.1 to 3 mm, preferably 0.1 to 2 mm.

[0144] From the aspect of removing metals, carbon steels, and the like that constitute a blade used in the pulverization from the pulverized composite material, the pulverized material can be refined using a high-magnetic-power magnet, a magnetic separator, a foreign matter removing device, or the like.

[0145] As the rotational speed of the blade at the time of the above-mentioned pulverization, from the aspect of being able to process a continuous fiber-reinforced resin composite material in which peeling of the interface of the fiber and the thermoplastic resin is less and in which interlayer peeling is more easily formed, 100 to 3000 min -1 , more preferably 300 to 1500 min -1 , and further preferably 500 to 1000 min -1 are preferable.

[0146] ​The amount of the raw material composite at the time of the pulverization is preferably 5 to 150 kg / h, more preferably 15 to 80 kg / h, and further preferably 20 to 65 kg / h, from the viewpoint of processing the continuous fiber-reinforced resin composite in which the interface between the fiber and the thermoplastic resin is less likely to peel, and making it easier to form interlayer peeling.

[0147] The size and shape of the composite at the time of the pulverization are preferably a rectangular parallelepiped in which the long side is 10 to 300 mm, more preferably 20 to 100 mm, and further preferably 30 to 70 mm, and the short side is 5 to 50 mm, more preferably 15 to 35 mm, from the viewpoint of processing the continuous fiber-reinforced resin composite in which the interface between the fiber and the thermoplastic resin is less likely to peel, and making it easier to form interlayer peeling.

[0148] The water absorption of the composite at the time of the pulverization is preferably 0.01 to 2.0% by mass, more preferably 0.03 to 1.0% by mass, and further preferably 0.1 to 0.5% by mass, from the viewpoint of processing the continuous fiber-reinforced resin composite in which the interface between the fiber and the thermoplastic resin is less likely to peel, and making it easier to form interlayer peeling. Note that the water absorption can be measured by using a Karl Fischer moisture meter (Kyoto Electronics Manufacturing Co., Ltd., MKC610) to measure 0.3 g of the continuous fiber-reinforced resin composite in a nitrogen atmosphere.

[0149] The type of the blade used at the time of the pulverization is preferably alloy tool steel, wear-resistant blade, titanium aluminum nitride, or super-hard alloy, from the viewpoint of processing the continuous fiber-reinforced resin composite in which the interface between the fiber and the thermoplastic resin is less likely to peel, and making it easier to form interlayer peeling and remove foreign matter. In addition, the blade is preferably a combination of a rotary blade and a fixed blade, the rotary blade is preferably 1 to 20 blades, and the fixed blade is preferably 20 to 70°.

[0150] The mass ratio of the thermoplastic resin in 100% by mass of the raw material composite is preferably 15 to 65% by mass, and more preferably 25 to 50% by mass, from the viewpoint of processing the continuous fiber-reinforced resin composite in which the interface between the fiber and the thermoplastic resin is less likely to peel, and making it easier to form interlayer peeling. In addition, the mass ratio of the continuous reinforcing fiber is preferably 35 to 85% by mass, and more preferably 50 to 75% by mass, from the same viewpoint.

[0151] As the thermoplastic resin contained in the above-mentioned raw material composite, from the viewpoint of being able to process a continuous fiber-reinforced resin composite in which peeling at the interface between the fiber and the thermoplastic resin is less, being more likely to form interlayer peeling, and making it easy to remove foreign matter, a polyamide-based resin, a polyester-based resin, a polyolefin resin such as polypropylene, a polyacetal-based resin, a polycarbonate-based resin, a polyether ketone-based resin, a polyether ether ketone-based resin, a polyether ketone ketone-based resin, a polyimide-based resin, a polyether imide-based resin, a polyether-based resin, and more preferably a polyamide-based resin and a polyolefin-based resin are preferable. In addition, as the continuous reinforcing fiber, from the viewpoint of being able to process a continuous fiber-reinforced resin composite in which peeling at the interface between the fiber and the thermoplastic resin is less, being more likely to form interlayer peeling, and making it easy to remove foreign matter, a glass fiber, a carbon fiber, an aramid fiber, a plant fiber such as jute, cellulose, hemp, and ramie is preferable.

[0152] (Properties of the pulverized composite)

[0153] -Length of the longest side-

[0154] From the viewpoint of reducing fluctuations in the production of molded articles, the length of the longest side of the above-mentioned pulverized composite is preferably 0.1 to 20 mm, more preferably 0.5 to 15 mm, and further preferably 1.0 to 10 mm.

[0155] The length of the longest side can be adjusted, for example, by the pulverization conditions of the raw material composite, the conditions for removing large pulverized materials from the pulverized materials, and the like.

[0156] With respect to the length of the longest side, a minimum circle 59 into which the top view of the pulverized composite falls can be drawn, and the diameter thereof can be found as the length of the longest side (L). Figure 6 In addition, the above-mentioned top view is a top view obtained in such a manner that the length of the longest side of the composite is the longest, and can be obtained in the form of a projection view obtained by projecting parallel light from directly above a continuous fiber-reinforced resin composite that is placed on a horizontal plane.

[0157] -Interlayer peeling portion-

[0158] The above-mentioned pulverized composite preferably has at least one interlayer peeling portion on the surface that extends in the extension direction of the continuous reinforcing fiber in the pulverized composite. Here, the extension direction of the continuous reinforcing fiber in the surface can be the extension direction of the continuous reinforcing fiber that can be confirmed when the surface is visually observed (D). Figure 7 In the case where the extension direction of the continuous reinforcing fiber has a plurality of directions, the above-mentioned condition is satisfied in any one direction.

[0159] The above-mentioned interlayer peeling portion can have a plurality of portions on the same surface. In addition, the surface having the above-mentioned interlayer peeling portion preferably has at least two or more surfaces.

[0160] Note that the interlayer peeling portion can be measured by SEM observation of a cross section in the orthogonal direction of the fiber, and refers to a portion in which the length in the orthogonal direction of the thickness of the void / the length in the thickness direction of the void is 3 or greater and the length in the orthogonal direction of the thickness of the void / the length of the crushed composite material is 0.1 or greater.

[0161] The length in the orthogonal direction of the thickness of the void / the length in the thickness direction of the void is preferably 5 or greater, more preferably 10 or greater, further preferably 15 or greater, and particularly preferably 20 or greater. When the length in the orthogonal direction of the thickness of the void / the length in the thickness direction of the void is in the above range, it is preferable from the viewpoint that pelletization, molding processing of the crushed composite material becomes easier, and the viewpoint that fluctuation in the content of the reinforcing fiber after pelletization or molding processing is reduced.

[0162] The length in the orthogonal direction of the thickness of the void / the length of the crushed composite material is preferably 0.3 or greater, more preferably 0.6 or greater, further preferably 0.8 or greater, and particularly preferably 0.9 or greater. When the length in the orthogonal direction of the thickness of the void / the length of the crushed composite material is in the above range, it is preferable from the viewpoint that pelletization, molding processing of the crushed composite material becomes easier, and the viewpoint that fluctuation in the content of the reinforcing fiber after pelletization or molding processing is reduced.

[0163] The above interlayer peeling portion is a trace of the raw material composite material after the raw material composite material (for example, a raw material composite material as a laminate) is crushed. In addition, the above interlayer peeling portion can be formed by crushing the raw material composite material.

[0164] In addition, the void refers to a space portion included in the crushed composite material, in which the thermoplastic resin and the continuous reinforcing fiber, the additive material, and the like are not present. The crushed composite material preferably has a void as the interlayer peeling portion on the surface.

[0165] The thickness direction is a direction orthogonal to the orientation direction of the continuous reinforcing fiber, and is the stacking direction of the reinforcing fiber base material.

[0166] The length of the crushed composite material is the orthogonal direction to the thickness direction in the cross section observed by SEM.

[0167] The above interlayer peeling portion can be analyzed by the following method. The crushed composite material is ground with a grinder (small precision sample making system IS-POLISHER ISPP-1000 (Ikegai Seimitsu Machine Co., Ltd.)) with a grinding pressure of 1000 g / cm 2The grinding was performed under specific grinding conditions to create a ground surface. Then, the ground surface was observed using a field emission scanning electron microscope (FESEM (S-4700, Hitachi High Technology Co., Ltd.)) to examine the surface of the pulverized composite material visible on the ground surface. Figure 8 Using ImageJ, the lengths of the voids in the thickness direction and the lengths in the orthogonal direction of the thickness of the pulverized composite material were measured, and the ratio of "(length of voids in the orthogonal direction of thickness) / (length of voids in the thickness direction)" was calculated. Regions where the ratio of "(length of voids in the orthogonal direction of thickness) / (length of voids in the thickness direction)" is 3 or more, and the ratio of "(length of voids in the thickness direction) / (length of pulverized composite material)" is 1 / 10 or more, were identified as interlaminar delamination areas.

[0168] No interlayer delamination refers to the condition where the aforementioned interlayer delamination cannot be identified by grinding any side of the pulverized composite material.

[0169] Regarding the above grinding conditions, the grinding was performed in the following order: 10 minutes with #2000 water-resistant sandpaper, 5 minutes with a 9μm silicon carbide film, 5 minutes with a 5μm alumina film, 5 minutes with a 3μm alumina film, and 5 minutes with a 1μm alumina film. Water was added at approximately 7 mL / min during each grinding cycle, and air was blown onto the grinding surface between cycles to remove cutting chips.

[0170] In the aforementioned pulverized composite material, it is preferable that the ratio (Lb / La) of the edges surrounding any one surface is less than the ratio (Lb' / La'). This ratio (Lb / La) is the proportion of the length (Lb, in mm) of the line connecting the two endpoints of the composite material surface along the extension direction of the continuous reinforcing fibers to the length (La, in mm) of the line connecting those two endpoints. Similarly, the ratio (Lb' / La') is the proportion of the length (Lb', in mm) of the line connecting the two endpoints along the edges orthogonal to the extension direction of the continuous reinforcing fibers to the length (La', in mm) of the line connecting those two endpoints. That is, in this surface, it is preferable that the edges along the extension direction of the continuous reinforcing fibers are relatively straight, while the edges in the direction orthogonal to the extension direction are serrated.

[0171] use Figure 9 The following explanation is provided. An analysis is performed on any surface with an approximate quadrilateral shape, consisting of an edge (edge ​​55 or 56) with the extension direction of the continuous reinforcing fibers and an edge orthogonal to the extension direction of the continuous reinforcing fibers (edge ​​57 or 58). An image of this surface is obtained using SEM or similar methods. A line segment connecting the two endpoints of the edge with the extension direction is drawn. Figure 9 55), and measure its length La (mm). Additionally, draw the line segment along the edge of the surface at both endpoints ( Figure 956), and measure its length Lb (mm). Similarly, in the side perpendicular to the extension direction, draw the line segment connecting the two endpoints ( Figure 9 57), line segments along the edges of the surfaces at the two endpoints ( Figure 9 58), and its lengths La' (mm) and Lb' (mm) were measured.

[0172] It should be noted that the extension direction can be the direction in which the continuous reinforcing fibers of the surface can be visually confirmed. When multiple directions of continuous reinforcing fibers can be confirmed, the direction with the longest continuous reinforcing fiber can be used as the extension direction. The aforementioned surface can be the surface having the interlaminar delamination portion extending in the extension direction of the continuous reinforcing fibers. Furthermore, when there are multiple edges surrounding the surface, the analysis is performed using Lb / La or Lb' / La' as the largest edge.

[0173] From the perspective of making molding and processing easier, "Lb' / La'-Lb / La" is preferably greater than 0, more preferably 0.1 to 100, even more preferably 0.2 to 50, even more preferably 0.5 to 5, and particularly preferably 0.7 to 1.5.

[0174] In the above-mentioned pulverized composite material, preferably there is at least one surface that satisfies the above-mentioned "Lb' / La'-Lb / La", and more preferably there are two surfaces.

[0175] -Porosity of the polar interface-

[0176] In the aforementioned pulverized composite material, the porosity of the interfacial portion between one continuous reinforcing fiber in a section orthogonal to the extension direction of the continuous reinforcing fiber in the composite material and the portion surrounding the continuous reinforcing fiber (e.g., a portion composed of thermoplastic resin) is preferably 20% or less, more preferably 15% or less, and even more preferably 10% or less. When the porosity is 20% or less, the continuous reinforcing fiber is tightly bound to its surroundings, resulting in excellent strength of the molded article. The porosity can be adjusted by the type of raw material composite material, etc.

[0177] It should be noted that the polar interface portion refers to the portion within the outer periphery region of the aforementioned continuous reinforcing fiber in the orthogonal cross section that is one-tenth (1 / 10r) of the distance r (which is the distance from the center (which may be the centroid) of the continuous reinforcing fiber to a point on the outer periphery). Figure 4 (A).

[0178] In addition, the porosity mentioned above refers to the ratio of the area occupied by voids to 100% of the area of ​​the polar interface. Figure 4B is an example in which a gap is present at the polar interface portion, and peeling easily occurs between the continuous reinforcing fiber and its surroundings in molding, and thus is not preferred. The porosity of the polar interface portion of 1 continuous reinforcing fiber can be found from any one orthogonal cross section in the direction of extension of the continuous reinforcing fiber.

[0179] The porosity described above can be observed by FESEM in the same manner as the evaluation of the presence or absence of the interlayer peeling portion, and the porosity of the polar interface portion is measured for any 100 continuous reinforcing fibers, and the average value is calculated. Note that in the measurement of the porosity of the polar interface, polishing can be performed in such a manner that a cross section orthogonal to the direction of extension of the continuous reinforcing fiber becomes the polishing surface. Also, in the case where 100 continuous reinforcing fibers cannot be confirmed in the composite material, the average value can be the average of the values found for all the continuous reinforcing fibers that can be confirmed.

[0180] - Volume proportion of continuous reinforcing fiber -

[0181] From the viewpoint of the excellent strength of the molded article after recycling, the volume proportion of the continuous reinforcing fiber is preferably 35 to 70 vol%, more preferably 40 to 65 vol%, and further preferably 45 to 60 vol% with respect to 100 vol% of the pulverized composite material.

[0182] The volume proportion described above can be measured by the following method. 2 g of the pulverized composite material is charged into an electric furnace, and heated at 650°C for 3 hours, and the resin is burned off. After that, it is naturally cooled to room temperature, and the mass of the continuous reinforcing fiber remaining is measured, and thus the mass proportion of the continuous reinforcing fiber to the resin included in the pulverized composite material is found. Also, the volume proportion of the continuous reinforcing fiber with respect to 100 vol% of the pulverized composite material (Vf, vol%) is found by dividing the mass proportion found by the density.

[0183] (Continuous reinforcing fiber)

[0184] As the continuous reinforcing fiber included in the pulverized composite material, a substance ordinarily used in continuous fiber reinforced resin composite materials can be used. The continuous reinforcing fiber included in the pulverized composite material is preferably the same as the continuous reinforcing fiber included in the raw material composite described above.

[0185] As the continuous reinforcing fiber, for example, glass fiber, carbon fiber, plant fiber, aramid fiber, ultra-high-strength polyethylene fiber, polybenzazole fiber, liquid crystal polyester fiber, polyketone fiber, metal fiber, ceramic fiber, and the like can be given, but are not limited thereto.

[0186] From the viewpoints of mechanical properties, thermal properties, and versatility, glass fiber, carbon fiber, plant fiber, and aramid fiber are preferred, and from the viewpoint of productivity, glass fiber is preferred.

[0187] The continuous reinforcing fiber can be used alone or in combination with two or more kinds.

[0188] The continuous reinforcing fiber can be subjected to a surface treatment agent (preferably a bundling agent described later).

[0189] Bundling agent

[0190] The continuous reinforcing fiber preferably has the bundling agent attached thereto.

[0191] In the case where the continuous reinforcing fiber is glass fiber, the bundling agent can be used as the surface treatment agent.

[0192] The bundling agent (sizing agent) can contain one or more selected from the group consisting of a silane coupling agent, a lubricant, and a bundling agent, and preferably contains at least a bundling agent or a silane coupling agent. The bundling agent can be composed of a silane coupling agent and a bundling agent, or can be composed of a silane coupling agent, a lubricant, and a bundling agent.

[0193] By using the bundling agent that forms a strong bond between the continuous reinforcing fiber (e.g., glass fiber) and the resin covering the periphery thereof, a pulverized composite material having a small void ratio can be obtained.

[0194] The bundling agent can be externally added to the material used, or can be internally contained in the material used. For example, the lubricant is sometimes contained in a commercially available product of the thermoplastic resin used.

[0195] Silane coupling agent

[0196] The silane coupling agent is generally used as a surface treatment agent for the continuous reinforcing fiber (e.g., glass fiber), and is useful in improving the interfacial adhesion strength.

[0197] As the silane coupling agent, for example, amino silane such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, and the like; mercapto silane such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane, and the like; epoxy silane; vinyl silane; maleic acid; and the like can be mentioned, but are not limited thereto. When a polyamide is used as the thermoplastic resin, a substance that easily binds to a carboxyl group or an amino group, which is a terminal group of the polyamide-based resin, is preferably selected, and an amino silane is preferably selected.

[0198] Lubricant

[0199] The lubricant is useful in improving the fibrillation of the continuous reinforcing fiber (e.g., glass fiber).

[0200] As the lubricant, any lubricating material of a liquid or a solid, which is common to the purpose, can be used as long as it does not hinder the silane coupling agent and the bundling agent, and examples thereof include, but are not limited to, waxes of animal, plant or mineral origin such as carnauba wax, lanolin wax and the like; surfactants such as fatty amides, fatty acid esters, fatty acid ethers, aromatic esters, aromatic ethers and the like; and the like.

[0201] -- Bundling agent --

[0202] The bundling agent is effective in improving the bundling property of the continuous reinforcing fibers (e.g., glass fibers) and in improving the interfacial adhesion strength.

[0203] As the bundling agent, a polymer, other than the above-mentioned thermoplastic resin as the main material of the pulverized composite material, can be used in accordance with the purpose.

[0204] As the polymer of the bundling agent, examples include, but are not limited to, homopolymers of acrylic acid, copolymers of acrylic acid and other copolymerizable monomers, copolymers of acrylic ester and / or methacrylic ester and copolymerizable monomers, and salts of these with primary, secondary and tertiary amines, and the like. In addition, polyurethane-based resins synthesized from isocyanates such as m-xylene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate) and isophorone diisocyanate, and polyester-based or polyether-based diols can also be appropriately used.

[0205] As the homopolymer of acrylic acid, the weight average molecular weight is preferably 1,000 to 90,000, and more preferably 1,000 to 25,000.

[0206] As the copolymerizable monomer constituting the copolymer of acrylic acid and other copolymerizable monomers, examples include, but are not limited to, one or more selected from the group consisting of acrylic acid, maleic acid, methacrylic acid, vinylacetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid, among monomers having a hydroxyl group and / or a carboxyl group (excluding only acrylic acid). As the copolymerizable monomer, it is preferable to have one or more ester-based monomers.

[0207] As the acrylic ester in the copolymer of acrylic ester and / or methacrylic ester and copolymerizable monomers, examples include methyl acrylate and the like, and as the above-mentioned methacrylic ester, examples include methyl methacrylate and the like. As the above-mentioned copolymerizable monomer, examples include one or more monomers selected from the group consisting of acrylic acid, maleic acid, maleic anhydride, methacrylic acid, vinylacetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid (preferably maleic anhydride). Among these, a copolymer of one acrylic ester, one methacrylic ester and one copolymerizable monomer is preferable. As the weight average molecular weight of the above-mentioned copolymer, it is preferably 1,000 to 90,000, and more preferably 1,000 to 25,000.

[0208] As the salt of the homopolymer and copolymer of acrylic acid and a primary amine, a secondary amine and a tertiary amine, there can be mentioned, for example, but not limited to, triethylamine salt, triethanolamine salt, glycine salt, etc. From the viewpoint of improving the stability of the mixed solution with other chemical agents (silane coupling agent, etc.) and reducing the amine odor, the neutralization degree is preferably 20 to 90%, more preferably 40 to 60%.

[0209] The weight average molecular weight of the salt-forming polymer of acrylic acid is not particularly limited, and is preferably in the range of 3,000 to 50,000. It is preferably 3,000 or more from the viewpoint of improving the bundling property of the continuous reinforcing fiber (e.g., glass fiber), and is preferably 50,000 or less from the viewpoint of improving the properties when the formed body is produced.

[0210] When a polyamide is used as the thermoplastic resin, as the bundling agent, a resin having good wettability with the polyamide resin or a close surface tension is preferably used. Specifically, for example, an emulsion of a polyurethane resin, an emulsion of a polyamide resin, or a modified product thereof can be selected.

[0211] As the thermoplastic resin used as the bundling agent, there can be mentioned, for example, but not limited to, a polyolefin-based resin, a polyamide-based resin, a polyurethane-based resin, a polyacetal-based resin, a polycarbonate-based resin, a polyester-based resin, a polyether ketone, a polyether ether ketone, a polyether sulfone, a polyphenylene sulfide, a thermoplastic polyether imide, a thermoplastic fluorine-based resin, and a modified thermoplastic resin obtained by modifying them, etc.

[0212] Further, from the viewpoint of further improving the adhesion of the continuous reinforcing fiber to the thermoplastic resin covering the fiber, reducing the proportion of the emulsifier component in the case where the bundling agent is attached to the continuous reinforcing fiber (e.g., glass fiber) as an aqueous dispersion, or not requiring an emulsifier, etc., as the thermoplastic resin used as the bundling agent, a modified thermoplastic resin is preferable.

[0213] Here, the modified thermoplastic resin means a substance in which, in addition to the monomer component forming the main chain of the thermoplastic resin, a different monomer component is copolymerized in order to change the properties of the thermoplastic resin, and the hydrophilicity, crystallinity, thermodynamic properties, etc. are modified.

[0214] As the modified thermoplastic resin used as the bundling agent, there can be mentioned, for example, but not limited to, a modified polyolefin-based resin, a modified polyamide-based resin, a modified polyester-based resin, etc.

[0215] The modified polyolefin-based resin as the bundling agent is a copolymer of an olefin-based monomer and a monomer copolymerizable with the olefin-based monomer such as an unsaturated carboxylic acid and / or an ester thereof, or a homopolymer of a monomer copolymerizable with the olefin-based monomer such as an unsaturated carboxylic acid and / or an ester thereof, and can be produced by a publicly known method. It can be a random copolymer of the olefin-based monomer and the unsaturated carboxylic acid and / or the ester thereof, or a graft copolymer of the olefin-based monomer grafted with the unsaturated carboxylic acid.

[0216] As the olefin-based monomer, there can be mentioned, but not limited to, for example, ethylene, propylene, 1-butene, and the like. They can be used alone as only one kind, or can be used in combination of two or more kinds.

[0217] As the monomer copolymerizable with the olefin-based monomer, there can be mentioned, for example, acrylic acid, maleic acid, maleic anhydride, methacrylic acid, vinylacetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and the like unsaturated carboxylic acids, and esterified bodies (methyl ester, ethyl ester, and the like) of these unsaturated carboxylic acids, and the like, which can be used alone as only one kind, or can be used in combination of two or more kinds.

[0218] In the case where the modified polyolefin-based resin is a copolymer of an olefin-based monomer and a monomer copolymerizable with the olefin-based monomer, as the monomer ratio, provided that the total mass of the copolymer is 100 mass%, the olefin-based monomer is preferably 60 to 95 mass%, and the monomer copolymerizable with the olefin-based monomer is preferably 5 to 40 mass%, and more preferably the olefin-based monomer is 70 to 85 mass%, and the monomer copolymerizable with the olefin-based monomer is 15 to 30 mass%. When the mass% of the olefin-based monomer is 60 mass% or more, the affinity with the matrix is good, and when the mass% of the olefin-based monomer is 95 mass% or less, the water dispersibility of the modified polyolefin-based resin is good, and the uniform application to the continuous reinforcing fiber is easy.

[0219] In the modified polyolefin-based resin used as the bundling agent, the modified group such as a carboxyl group introduced by copolymerization can be neutralized by a basic compound. As the basic compound, there can be mentioned, but not limited to, for example, alkalis such as sodium hydroxide, potassium hydroxide, and the like; ammonia; amines such as monoethanolamine, diethanolamine, and the like. The weight average molecular weight of the modified polyolefin-based resin used as the bundling agent is not particularly limited, and is preferably 5,000 to 200,000, and more preferably 50,000 to 150,000. It is preferably 5,000 or more from the viewpoint of improving the bundling property of the continuous reinforcing fiber (for example, glass fiber), and is preferably 200,000 or less from the viewpoint of the emulsion stability at the time of producing the water dispersion.

[0220] The modified polyamide-based resin used as the bundling agent is a modified polyamide compound in which a hydrophilic group such as a polyalkylene oxide chain, a tertiary amine component, and the like is introduced in the molecular chain, and can be produced by a publicly known method.

[0221] In the case of introducing a polyalkylene oxide chain into the molecular chain, for example, a part or all of polyethylene glycol or polypropylene glycol is modified into a diamine or a dicarboxylic acid and the resultant modified product is copolymerized to produce. In the case of introducing a tertiary amine component, for example, aminoethylpiperazine, bisaminopropylpiperazine, α-dimethylamino-ε-caprolactam, or the like is copolymerized to produce.

[0222] The modified polyester-based resin used as the bundling agent is a copolymer of a polycarboxylic acid or an anhydride thereof and a polyol, and is a resin having a hydrophilic group in a molecular skeleton including a terminal, and can be produced by a publicly known method.

[0223] As the hydrophilic group, for example, a polyalkylene oxide group, a sulfonate, a carboxyl group, a neutralized salt thereof, or the like can be given. As the polycarboxylic acid or an anhydride thereof, an aromatic dicarboxylic acid, an aromatic dicarboxylic acid containing a sulfonate, an aliphatic dicarboxylic acid, an alicyclic dicarboxylic acid, a polycarboxylic acid of 3 or more functions, or the like can be given.

[0224] As the aromatic dicarboxylic acid, for example, phthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, phthalic anhydride, or the like can be given, but are not limited thereto.

[0225] As the aromatic dicarboxylic acid containing a sulfonate, for example, a sulfoterephthalate, a 5-sulfoisophthalate, a 5-sulfoorthophthalate, or the like can be given, but are not limited thereto.

[0226] As the aliphatic dicarboxylic acid or the alicyclic dicarboxylic acid, for example, fumaric acid, maleic acid, itaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, 1,4-cyclohexane dicarboxylic acid, succinic anhydride, maleic anhydride, or the like can be given, but are not limited thereto.

[0227] As the polycarboxylic acid of 3 or more functions, for example, trimellitic acid, pyromellitic acid, trimellitic anhydride, pyromellitic dianhydride, or the like can be given, but are not limited thereto.

[0228] Among these, from the viewpoint of improving the heat resistance of the modified polyester-based resin, it is preferable that 40 to 99 mol% of the total polycarboxylic acid component be an aromatic dicarboxylic acid. In addition, from the viewpoint of emulsion stability in the case of producing the modified polyester-based resin as an aqueous dispersion, it is preferable that 1 to 10 mol% of the total polycarboxylic acid component be an aromatic dicarboxylic acid containing a sulfonate.

[0229] As the polyol constituting the modified polyester-based resin, a diol, a polyol of 3 or more functions, or the like can be given.

[0230] As the diol, there can be mentioned, but not limited to, for example, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, polytetramethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, polytetramethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A or its alkylene oxide adduct, and the like. As the polyol of 3 or more functions, there can be mentioned trimethylolpropane, glycerol, pentaerythritol, and the like.

[0231] As the copolymerization ratio of the polycarboxylic acid or its anhydride and the polyol constituting the modified polyester-based resin, provided that the total mass of the copolymerization component is 100 mass%, the polycarboxylic acid or its anhydride is preferably 40 to 60 mass%, and the polyol is preferably 40 to 60 mass%, and more preferably the polycarboxylic acid or its anhydride is 45 to 55 mass%, and the polyol is 45 to 55 mass%.

[0232] As the weight average molecular weight of the modified polyester-based resin, it is preferably 3,000 to 100,000, and more preferably 10,000 to 30,000. It is preferably 3,000 or more from the viewpoint of improving the bundling property of the continuous reinforcing fiber (for example, glass fiber), and 100,000 or less from the viewpoint of emulsion stability in the case of producing an aqueous dispersion.

[0233] The polymer, the thermoplastic resin used as the bundling agent can be used alone only one kind, or two or more kinds can be used in combination.

[0234] Provided that the total amount of the bundling agent is 100 mass%, one or more kinds of polymer selected from the group consisting of a homopolymer of acrylic acid, a copolymer of acrylic acid and other copolymerizable monomer, a copolymer of acrylic ester and / or methacrylic ester and copolymerizable monomer, and a salt of these and primary amine, secondary amine and tertiary amine is preferably used in an amount of 50 mass% or more, and more preferably 60 mass% or more.

[0235] In the case where the bundling agent is constituted by the silane coupling agent and the bundling agent, the bundling agent is applied and adhered in an amount of preferably 0.1 to 3 mass%, more preferably 0.2 to 2 mass%, and further preferably 0.2 to 1 mass% with respect to 100 mass% of the glass fiber, based on the total mass of the silane coupling agent and the bundling agent. From the viewpoint of controlling the bundling property of the glass fiber and improving the interfacial adhesion strength, the adhered amount of the bundling agent is preferably 0.1 mass% or more with respect to 100 mass% of the glass fiber, based on the total mass of the silane coupling agent and the bundling agent, and preferably 3 mass% or less from the viewpoint of the handleability of the yarn.

[0236] In addition, in the case where the bundling agent is composed of a silane coupling agent, a lubricant, and a bundling agent, the bundling agent is preferably adhered in an amount of 0.01 to 0.3% by mass, more preferably 0.02 to 0.2% by mass, and further preferably 0.03 to 0.15% by mass, based on 100% by mass of the continuous reinforcing fiber (e.g., glass fiber) in terms of the total mass of the silane coupling agent, the lubricant, and the bundling agent (total attached mass ratio). The amount of the bundling agent adhered is preferably 0.01% by mass or more, and preferably 0.3% by mass or less, based on 100% by mass of the continuous reinforcing fiber (e.g., glass fiber) in terms of the total mass of the silane coupling agent, the lubricant, and the bundling agent, from the viewpoint of controlling the bundling property of the continuous reinforcing fiber (e.g., glass fiber) and improving the interfacial adhesion strength, and from the viewpoint of the handleability of the yarn.

[0237] Composition of the bundling agent for glass fiber

[0238] The amount of the silane coupling agent in the bundling agent for glass fiber is preferably 0.1 to 2% by mass, more preferably 0.1 to 1% by mass, and further preferably 0.2 to 0.5% by mass, based on 100% by mass of the bundling agent, from the viewpoint of improving the bundling property of the glass fiber and improving the interfacial adhesion strength and the mechanical strength of the molded composite.

[0239] The amount of the lubricant in the bundling agent for glass fiber is preferably 0.01% by mass or more, and more preferably 0.02% by mass or more, from the viewpoint of imparting sufficient lubricity, and is preferably 1% by mass or less, and more preferably 0.5% by mass or less, from the viewpoint of improving the interfacial adhesion strength and the mechanical strength of the molded composite.

[0240] The amount of the bundling agent in the bundling agent for glass fiber is preferably 1 to 25% by mass, more preferably 3 to 15% by mass, and further preferably 3 to 10% by mass, from the viewpoint of controlling the bundling property of the glass fiber and improving the interfacial adhesion strength and the mechanical strength of the molded composite.

[0241] In the case where the continuous reinforcing fiber is glass fiber and the bundling agent is composed of a silane coupling agent, a lubricant, and a bundling agent, the bundling agent for the glass fiber preferably contains 0.1 to 2% by mass of the silane coupling agent, 0.01 to 1% by mass of the lubricant, and 1 to 25% by mass of the bundling agent, respectively, and the total mass is preferably adjusted to 100% by mass by diluting these components with water.

[0242] Usage mode of the bundling agent for glass fiber

[0243] The bundling agent for glass fiber can be adjusted to any one of an aqueous solution, a colloidal dispersion, an emulsion using an emulsifier, or the like, depending on the usage mode, and is preferably in the form of an aqueous solution from the viewpoint of improving the dispersion stability of the bundling agent and improving the heat resistance.

[0244] The glass fibers that constitute the continuous reinforcing fibers of the above-described composite material are obtained by applying the above-described bundling agent to the glass fibers using a known method such as a roll coater in a known glass fiber production process, and drying the produced glass fibers, thereby continuously obtaining.

[0245] In addition, as the continuous reinforcing fibers, a bundling agent can be used as in the case of selecting carbon fibers, and the bundling agent is preferably composed of a coupling agent (for example, a silane coupling agent), a lubricant, and a bundling agent. As the coupling agent, a substance that is compatible with the hydroxyl groups present on the surface of the carbon fibers can be selected, as the bundling agent, a substance that is wettable with the selected thermoplastic resin or a substance that has a surface tension close thereto can be selected, and as the lubricant, a substance that does not interfere with the coupling agent and the bundling agent can be selected.

[0246] The type of the bundling agent used in the carbon fibers is not particularly limited, and a known substance can be used. Specifically, for example, the substance described in Japanese Patent Application Publication No. 2015-101794 can be used.

[0247] In the case of using other continuous reinforcing fibers, the type and the amount of application of the bundling agent that can be used for glass fibers, carbon fibers are appropriately selected in accordance with the properties of the continuous reinforcing fibers, and the type and the amount of application of the bundling agent are preferably those corresponding to the bundling agent used in the carbon fibers.

[0248] - Shape of Continuous Reinforcing Fiber -

[0249] The continuous reinforcing fiber can be a multifilament formed of a plurality of filaments, and the number of filaments is preferably 30 to 15,000 from the aspect of handleability.

[0250] The filament diameter R of the continuous reinforcing fiber is preferably 2 to 30 μm, more preferably 4 to 25 μm, further preferably 6 to 20 μm, and most preferably 8 to 18 μm, from the aspect of strength and the aspect of handleability.

[0251] The product RD of the filament diameter R (μm) of the continuous reinforcing fiber and the density D (g / cm 3 ) of the continuous reinforcing fiber is preferably 5 to 100 μm·g / cm 3 , more preferably 10 to 50 μm·g / cm 3 , further preferably 15 to 45 μm·g / cm 3 , and still further preferably 20 to 45 μm·g / cm 3 , from the aspect of handleability of the continuous reinforcing fiber and the aspect of strength of the composite material.

[0252] The density D can be measured using an areometer.

[0253] On the other hand, the filament diameter R (μm) can be calculated from the density D (g / cm 3 ) and the fineness (dtex), the number of filaments (roots) by the following equation.

[0254] [Num. 1]

[0255]

[0256] In addition, the filament diameter R (μm) can be obtained, for example, by SEM observation of the continuous reinforcing fiber filaments.

[0257] In order to make the product RD of the continuous reinforcing fiber be within a prescribed range, the fineness (dtex) and the number of filaments (roots) can be appropriately selected in accordance with the density possessed by the continuous reinforcing fiber, with respect to the commercially available continuous reinforcing fiber. For example, in the case where glass fiber is used as the continuous reinforcing fiber, since the density is about 2.5 g / cm 3 , a fiber having a filament diameter of 2 to 40 μm can be selected. Specifically, in the case where the filament diameter of the glass fiber is 9 μm, by selecting glass fiber having a fineness of 660 dtex and a number of filaments of 400 roots, the product RD is 23. In addition, in the case where the filament diameter of the glass fiber is 17 μm, by selecting glass fiber having a fineness of 11,500 dtex and a number of filaments of 2,000 roots, the product RD is 43. In the case where carbon fiber is used as the continuous reinforcing fiber, since the density is about 1.8 g / cm 3 , a fiber having a filament diameter of 2.8 to 55 μm can be selected. Specifically, in the case where the filament diameter of the carbon fiber is 7 μm, by selecting carbon fiber having a fineness of 2,000 dtex and a number of filaments of 3,000 roots, the product RD is 13. In the case where aramid fiber is used as the continuous reinforcing fiber, since the density is about 1.45 g / cm 3 , a fiber having a filament diameter of 3.4 to 68 μm can be selected. Specifically, in the case where the filament diameter of the aramid fiber is 12 μm, by selecting aramid fiber having a fineness of 1,670 dtex and a number of filaments of 1,000 roots, the product RD is 17.

[0258] The continuous reinforcing fiber (for example, glass fiber) is manufactured by metering and mixing raw material glass, making molten glass using a melting furnace, spinning the same to make glass filaments, applying a bundling agent, and taking up in the form of direct winding roving (DWR), a cake, a twisted yarn, or the like using a spinning machine.

[0259] The continuous reinforcing fiber can be in any form, but if it is taken up in the form of a yarn, a cake, or DWR, the productivity and production stability in the resin-coated process are improved, and thus it is preferred. From the aspect of productivity, DWR is most preferred.

[0260] The form of the continuous reinforcing fiber is not particularly limited, and various forms such as woven fabric, knitted fabric, braids, tubulars, non-crimp fabric, unidirectional material, etc. can be given, and the form of woven fabric, non-crimp fabric, unidirectional material is preferable.

[0261] (Thermoplastic resin)

[0262] The thermoplastic resin contained in the above-mentioned pulverized composite material can be exemplified by, but not limited to, for example, polyolefin-based resins such as polyethylene, polypropylene, etc.; polyamide-based resins such as polyamide 6, polyamide 66, polyamide 46, polyamide 612, polyamide 6I, polyamide 1010, polyamide 12, polyamide 610, polyamide 410, polyamide 12, etc.; polyester-based resins such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, etc.; polyacetal-based resins such as polyformaldehyde, etc.; polycarbonate-based resins; polyether-based resins such as polyether ketone, polyether ether ketone, polyether glycol, polypropylene glycol, polytetramethylene ether glycol, etc.; polyether sulfone; polyphenylene sulfide; thermoplastic polyether imide; thermoplastic fluorine-based resins such as tetrafluoroethylene-ethylene copolymer, etc.; polyurethane-based resins; acrylic-based resins, and modified thermoplastic resins modified from them.

[0263] The thermoplastic resin contained in the above-mentioned pulverized composite material is preferably the same as the thermoplastic resin contained in the above-mentioned raw composite material.

[0264] Among these thermoplastic resins, polyolefin-based resins, polyamide-based resins, polyester-based resins, polyether-based resins, polyether sulfone, polyphenylene sulfide, thermoplastic polyether imide, thermoplastic fluorine-based resins are preferable, and from the aspects of mechanical properties and versatility, polyolefin-based resins, modified polyolefin-based resins, polyamide-based resins, polyester-based resins, polyurethane-based resins, and acrylic-based resins are more preferable, and from the consideration of thermal properties, polyamide-based resins and polyester-based resins are further preferable. In addition, from the aspect of durability against repeated load, polyamide-based resins are further more preferable.

[0265] -Polyester-based resin-

[0266] The polyester-based resin refers to a high molecular compound having a -CO-O- (ester) bond in the main chain.

[0267] As the polyester-based resin, polyethylene terephthalate, polybutylene terephthalate, poly-1,4-butylene terephthalate, poly-1,4-cyclohexyldimethylene terephthalate, polyethylene 2,6-naphthalate, etc. can be given, but not limited to them.

[0268] The polyester-based resin can be a homopolyester, and can also be a copolyester.

[0269] In the case of a copolymer polyester, a suitable third component is preferably copolymerized with the homopolymer polyester, and as the third component, a diol component such as, for example, diethylene glycol, neopentyl glycol, polyalkylene glycol, a dicarboxylic acid component such as, for example, adipic acid, sebacic acid, phthalic acid, isophthalic acid, 5-(sodium sulfonato) isophthalic acid, and the like can be given, but are not limited thereto.

[0270] In addition, a polyester resin using a raw material derived from a biological substance can also be used, and aliphatic polyester resins such as, for example, polylactic acid, polybutylene succinate, polybutylene succinate adipate, aromatic polyester resins such as, for example, polybutylene adipate terephthalate, and the like can be given, but are not limited thereto.

[0271] - Polyamide Resin -

[0272] A polyamide resin refers to a high molecular compound having a -CO-NH- (amide) bond in the main chain. For example, aliphatic polyamides, aromatic polyamides, wholly aromatic polyamides, and the like can be given.

[0273] As the polyamide resin, a polyamide obtained by ring-opening polymerization of a lactam, a polyamide obtained by self-condensation of an ω-amino carboxylic acid, a polyamide obtained by condensation of a diamine and a dicarboxylic acid, and a copolymer thereof can be given, but are not limited thereto.

[0274] The polyamide resin can be used alone or in the form of a mixture of two or more kinds.

[0275] As the lactam, a pyrrolidone, caprolactam, undecanolactam, lauryl lactam, and the like can be given, but are not limited thereto.

[0276] As the ω-amino carboxylic acid, an ω-amino fatty acid which is a ring-opening compound of a lactam based on water can be given, but is not limited thereto. Two or more kinds of monomers can be used respectively for condensation of the lactam or the ω-amino carboxylic acid.

[0277] As the diamine (monomer), a straight-chain aliphatic diamine such as, for example, hexamethylene diamine, pentamethylene diamine, a branched-chain aliphatic diamine such as, for example, 2-methyl pentamethylene diamine, 2-ethyl hexamethylene diamine, an aromatic diamine such as, for example, p-phenylene diamine, m-phenylene diamine, an alicyclic diamine such as, for example, cyclohexane diamine, cyclopentane diamine, cyclooctane diamine, and the like can be given, but are not limited thereto.

[0278] As the dicarboxylic acid (monomer), an aliphatic dicarboxylic acid such as, for example, adipic acid, pimelic acid, sebacic acid, an aromatic dicarboxylic acid such as, for example, phthalic acid, isophthalic acid, an alicyclic dicarboxylic acid such as, for example, cyclohexane dicarboxylic acid, and the like can be given, but are not limited thereto. One kind or two or more kinds of diamines and dicarboxylic acids as monomers can be used respectively for condensation.

[0279] As the polyamide-based resin, there can be mentioned, but not limited to, for example, aliphatic polyamides such as polyamide 4 (poly-α-pyrrolidone), polyamide 6 (polycaprolactam), polyamide 11 (polyundecanoamide), polyamide 12 (polydodecanoamide), polyamide 46 (polyazamacrylamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610, polyamide 612, etc., semi-aromatic polyamides such as polyamide 6T (poly-hexamethylene terephthalamide), polyamide 9T (poly-nonamethylene terephthalamide), polyamide 6I (poly-hexamethylene isophthalamide), etc., and copolyamides containing them as a constituent component, etc.

[0280] As the copolyamide, there can be mentioned, but not limited to, for example, a copolymer of hexamethylene adipamide and terephthalamide, a copolymer of hexamethylene adipamide and hexamethylene isophthalamide, and a copolymer of terephthalamide and 2-methylpentanediamine terephthalamide.

[0281] In the case of using the polyamide resin, the thermoplastic resin can contain 50 to 99 parts by mass of (A) aliphatic polyamide, and 1 to 50 parts by mass of (B) semi-aromatic polyamide containing a dicarboxylic acid unit containing at least 75 mole% of isophthalic acid unit, and a diamine unit containing at least 50 mole% of diamine unit having 4 to 10 carbon atoms.

[0282] When the thermoplastic resin contains (A) aliphatic polyamide and (B) semi-aromatic polyamide in the above-mentioned range, there is a tendency to improve the properties (strength, rigidity, high-temperature characteristics, water absorption characteristics, impact characteristics, appearance, etc.) of the composite material compared to the case of containing only (A) aliphatic polyamide as the polyamide.

[0283] The total content of (A) aliphatic polyamide and (B) semi-aromatic polyamide is preferably 70 to 100 mass%, more preferably 80 to 100 mass%, and further preferably 90 to 100 mass%, relative to 100 mass% of the thermoplastic resin.

[0284] As the above-mentioned (A) aliphatic polyamide, there can be mentioned, but not limited to, for example, polyamide 4, polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 610, polyamide 612, etc.

[0285] The content of (A) aliphatic polyamide is preferably 50 to 99 mass%, more preferably 60 to 90 mass%, and further preferably 70 to 80 mass%, in 100 mass% of the polyamide in the thermoplastic resin.

[0286] As the above-mentioned (B) semi-aromatic polyamide, there can be mentioned, but not limited to, for example, polyamide 6I, polyamide 9I, polyamide 10I, etc.

[0287] The total amount of the above-described isophthalic acid unit and the diamine unit having 4 to 10 carbon atoms is preferably 80 to 100 mol%, more preferably 90 to 100 mol%, further preferably 95 to 100 mol%, relative to 100 mol% of the total structural units of the (B) semi-aromatic polyamide.

[0288] Note that the proportion of the monomer unit constituting the (B) semi-aromatic polyamide can be measured by, for example, 13C nuclear magnetic resonance spectroscopy (NMR).

[0289] In the (B) semi-aromatic polyamide, the proportion of the isophthalic acid unit in the dicarboxylic acid unit is at least 75 mol%, preferably 85 mol% or more, more preferably 90 mol% or more. When the proportion of the isophthalic acid unit in the dicarboxylic acid unit is within the above-described range, there is a tendency for the high-temperature properties and the water absorption properties to improve.

[0290] In the (B) semi-aromatic polyamide, the proportion of the diamine unit having 4 to 10 carbon atoms in the diamine unit is at least 50 mol%, preferably 60 mol% or more, more preferably 70 mol% or more. When the proportion of the diamine unit having 4 to 10 carbon atoms in the diamine unit is within the above-described range, there is a tendency for the high-temperature properties and the water absorption properties to improve.

[0291] The content of the (B) semi-aromatic polyamide in 100 mass% of the polyamide in the thermoplastic resin is preferably 1 to 50 mass%, more preferably 10 to 40 mass%, further preferably 20 to 30 mass%.

[0292] The (A) aliphatic polyamide and the (B) semi-aromatic polyamide described above can be end-capped using a known end-capping agent. The total of the end-capped end amount of the (A) aliphatic polyamide and the (B) semi-aromatic polyamide, expressed in terms of the equivalent of 1 g of the polyamide in which the (A) aliphatic polyamide and the (B) semi-aromatic polyamide are combined together, is preferably 5 to 180 microequivalents / g (μeq / g), more preferably 10 to 170 microequivalents / g, further preferably 20 to 160 microequivalents / g, particularly preferably 30 to 140 microequivalents / g, most preferably 40 to 140 microequivalents / g. When the end-capped end amount is within the above-described range, there is a tendency for the physical properties (strength, rigidity, high-temperature properties, water absorption properties, impact properties, appearance, and the like) to improve.

[0293] Here, the end-capped end amount is the total amount of the amino end and the carboxyl end end-capped using an end-capping agent. The end-capped end amount can be measured using, for example, H-NMR. 1 H-NMR.

[0294] The terminal group concentration of the (A) aliphatic polyamide is preferably 1 / 2 or less, more preferably 2 / 5 or less, of the terminal group concentration of the (B) semi-aromatic polyamide. When the terminal group concentration of the (A) aliphatic polyamide is 1 / 2 or less of the terminal group concentration of the (B) semi-aromatic polyamide, there is a tendency for the physical properties (strength, rigidity, high temperature properties, water absorption properties, impact properties, and appearance, etc.) to improve.

[0295] The terminal group concentration of the (A) aliphatic polyamide and the (B) semi-aromatic polyamide can be measured using H-NMR. 1 H-NMR.

[0296] The difference between the peak temperatures of tan δ of the (A) aliphatic polyamide and the (B) semi-aromatic polyamide is preferably 45 to 100°C, more preferably 50 to 90°C, and further preferably 60 to 90°C. When the difference between the peak temperatures of tan δ of the (A) aliphatic polyamide and the (B) semi-aromatic polyamide is within the above range, there is a tendency for the high temperature properties and the water absorption properties to improve.

[0297] The peak temperatures of tan δ of the (A) aliphatic polyamide and the (B) semi-aromatic polyamide can be measured using, for example, a viscoelasticity measurement analysis device.

[0298] From the aspects of strength, rigidity, moldability, and appearance, the difference between the viscosities of the (A) aliphatic polyamide and the (B) semi-aromatic polyamide is preferably 3 times or more, and more preferably 4 times or more.

[0299] The viscosity of the thermoplastic resin can be measured by MFR measurement (according to ISO 1133).

[0300] (Additives)

[0301] An additive can be included in the above-described pulverized composite material as needed. As the above-described additive, for example, coloring agents, anti-aging agents, antioxidants, weathering agents, metal deactivators, light stabilizers, heat stabilizers, ultraviolet absorbers, antibacterial and antifungal agents, deodorants, electric conductivity imparting agents, dispersants, softening agents, plasticizers, crosslinking agents, co-crosslinking agents, vulcanizing agents, vulcanization aids, foaming agents, foaming aids, flame retardants, shock absorbing agents, nucleating agents, neutralizing agents, lubricants, anti-blocking agents, dispersants, flowability improvers, release agents, and the like can be mentioned. Note that the above-described additive refers to a component other than the above-described thermoplastic resin, the above-described continuous reinforcing fiber, and the contained components in the bundling agent.

[0302] The content of the additive can be 3% by mass or less with respect to 100% by mass of the composite material.

[0303] -Coloring Agents-

[0304] As the colorant, carbon black, nigrosine, aluminum pigment, titanium dioxide, phthalocyanine blue, cyanine blue, cyanine green, quinacridone, diatomaceous earth, monoazo salt, perylene, disazo, condensed azo, isoindoline, iron oxide red, nickel titanium yellow, diketopyrrolopyrrole, metal salt, perylene red, metal oxide, bismuth vanadate, cobalt green, cobalt blue, anthraquinone, phthalocyanine green, phthalocyanine blue, and the like can be given. Among them, a black colorant is preferred, and carbon black and nigrosine are more preferred.

[0305] In the above pulverized composite material, the content of the continuous reinforcing fiber is preferably 90 to 525 parts by mass and the content of the component other than them is 0 to 2 parts by mass, relative to 100 parts by mass of the thermoplastic resin, and more preferably the content of the continuous reinforcing fiber is 150 to 340 parts by mass and the content of the component other than them is 0 to 1 part by mass, relative to 100 parts by mass of the thermoplastic resin.

[0306] The pellets of the present embodiment can be used as a raw material of a composite material (for example, a recycled composite material) containing a thermoplastic resin and a reinforcing fiber.

[0307] Examples

[0308] The present application is explained in more detail based on examples below, but the present application is not limited by these examples.

[0309] [Evaluation]

[0310] The following measurements were performed on the composite materials obtained in the examples and comparative examples.

[0311] [L / P]

[0312] The pellets obtained in the examples and comparative examples were ground using a grinder (small precision sample making system IS-POLISHER ISPP-1000 (Ikeshima Seimitsu Jiki Co., Ltd.)) under a grinding pressure of 1000 g / cm2for the ground surface of the pellets, and the ground surface was observed using a field emission type scanning electron microscope (FESEM (S-4700, Hitachi High-Technologies Corporation)). The length L (mm) along the outer periphery of the above-mentioned cross section and the perimeter P (mm) of the circumscribed shape were measured using ImageJ, and L / P was calculated. 2

[0313] [Fiber length of reinforcing fiber / length of pellet]

[0314] After the length of the pellet was measured using a microscope, the pellet was placed in an electric furnace and heated at 650°C for 3 hours to burn off the resin. The length of the reinforcing fiber obtained was measured using a microscope, and (fiber length of reinforcing fiber) / (length of pellet) was calculated.

[0315] ​Note that the length of the pellets was set as the maximum length (mm) between two cross sections of the pellets obtained by cutting the strand. In addition, the fiber length of the reinforcing fibers was set as the length (mm) of the longest reinforcing fiber among the reinforcing fibers contained in the pellets.

[0316] [Mass proportion of reinforcing fibers]

[0317] After measuring the mass of the pellets obtained in the examples and comparative examples, the pellets were placed in an electric furnace and heated at a temperature of 650°C for 3 hours to burn off the resin, and the mass of the reinforcing fibers obtained was measured. The mass proportion of the reinforcing fibers (mass %) was then calculated by "(mass of reinforcing fibers) / (mass of pellets) x 100".

[0318] [Void fraction of pellets]

[0319] The ground surface was observed in the same manner as the L / P described above, the area of the cross section of the pellets and the voids observed in the cross section were measured by ImageJ, and "(area of voids) / (area of cross section of pellets) x 100" was calculated to thereby measure the void fraction of the pellets (%).

[0320] [Tensile strength]

[0321] The molded pieces of the A-type multipurpose test pieces produced in the examples and comparative examples were subjected to a tensile test using an INSTRON universal testing machine in accordance with ISO 527 to measure the tensile strength (MPa).

[0322] [Breakage of reinforcing fibers]

[0323] The molded pieces of the A-type multipurpose test pieces produced in the examples and comparative examples were placed in an electric furnace and heated at a temperature of 650°C for 3 hours to burn off the resin, and the length of the reinforcing fibers obtained (i.e., the fiber length of the reinforcing fibers of the molded pieces) was measured using a microscope. The length of the reinforcing fibers (i.e., the fiber length of the reinforcing fibers of the pellets) measured in the above [fiber length of reinforcing fibers / pellets] was then used to calculate the breakage proportion of the reinforcing fibers (%) by the following equation.

[0324] (Fiber length of reinforcing fibers of molded pieces) / (fiber length of reinforcing fibers of pellets) x 100

[0325] [Arching in molding]

[0326] After 0.1 wt% of polyethylene glycol (PEG 400, FUJIFILM and LIGHT PURE CO., LTD.) as a lubricant was added to the pellets obtained in the examples and comparative examples, dry mixing was performed, and after 5 kg was fed to the hopper of an injection molding machine, the absence of arching in the lower part of the hopper was evaluated as "none" (good), and the presence of arching was evaluated as "yes" (poor).

[0327] [Particle biting rotation speed]

[0328] To a mixing / extrusion test device (torque rheometer (LABO PLASTOMILL), Toyo Precision Machine Mfg. Co., Ltd.), 1 kg of the pellets produced in the examples and comparative examples was fed from a hopper, and the maximum rotation speed (rpm) of the screw biting the pellets was measured.

[0329] The materials used in the examples and comparative examples are described below.

[0330] [Glass fiber]

[0331] Glass fiber: a fiber made by attaching 0.3 mass% of a bunching agent to 100 mass% of glass fiber having fineness of 1.20 g / m and 2000 filaments. The take-up form was DWR, and the average filament diameter was about 17 μm. The above-mentioned bunching agent was produced as follows: deionized water was adjusted so as to be 0.1 mass% of γ-aminopropyl triethoxysilane (KBE-903, manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent, 0.5 mass% of carnauba wax as a lubricant, 1 mass% of polyurethane resin (Y65-55, manufactured by ADEKA Corporation) as a bunching agent, and 3 mass% of a copolymer compound (a copolymer compound having a weight average molecular weight of 20000, produced by copolymerizing 40 mass% of maleic anhydride, 50 mass% of methyl acrylate, and 10 mass% of methyl methacrylate) so as to produce the bunching agent.

[0332] [Production of continuous reinforcing fiber base material]

[0333] Glass cloth: a glass cloth was produced by weaving the above-mentioned glass fiber as warp and weft using a rapier loom (loom width 1 m). The weaving form of the obtained glass cloth was twill, the weaving density was 6.5 filaments / 25 mm, and the basis weight was 640 g / m 2 .

[0334] [Production of thermoplastic resin film]

[0335] PA66 (melting point 265°C) pellets were molded using a T-die extrusion molding machine (Soken Chemical & Engineering Co., Ltd.) to produce a thermoplastic resin film. The thickness of the thermoplastic resin film was 180 μm.

[0336] [Example 1]

[0337] Five sheets of glass cloth and six sheets of thermoplastic resin film were alternately stacked with the thermoplastic resin film on the surface to perform molding, and a prepreg was obtained. At this time, the proportion of the volume of the thermoplastic resin to be fed was 53%. As the molding machine, a continuous die molding machine was used. The obtained prepreg (i.e., raw material composite) was cut into about 50 mm x 20 mm using a crusher (KS-4040, Horai Co., Ltd.), and then was processed using a pulverizer (ZI-420, Horai Co., Ltd.) equipped with a mesh screen having a circular mesh size of 5 mm, and a pulverized composite was obtained. The obtained pulverized composite had interlayer peeling.

[0338] The obtained pulverized composite was passed through a magnetic stand (CM-7, Semco Co., Ltd.) 10 times to remove metal foreign matter. The foreign matter adhering to the magnet was removed after each 1 pass.

[0339] The pulverized composite was then put into a hot air circulating dryer, and was dried at 90°C for 18 hours.

[0340] The obtained pulverized composite and PA66 pellets were put into an extruder (SRV-L40 / 30, Japan Oil Machine Co., Ltd.) in a mass ratio of 1 :0.420, the two heaters near the inlet were set to a temperature of the melting point of the resin + 35°C, the remaining heaters were set to a temperature of the melting point + 25°C, the screw rotation speed was set to 31 rpm, the discharge amount was set to 4.2 kg / h, air cooling was performed, and pelletization was performed with a pellet length of 4 mm.

[0341] A molding piece in the shape of an A-type multipurpose test piece according to ISO 3167 was molded using an injection molding machine (SE50D, Sumitomo Heavy Industries, Ltd.). The specific molding conditions were set to a melt resin temperature of 295°C, 80°C below the hopper, a mold temperature of 100°C, a pressure holding of 40 MPa, an injection + pressure holding time of 25 seconds, and a cooling time of 15 seconds.

[0342] The obtained pellets were evaluated for arching in molding, pellet biting into the rotation speed, breakage of the reinforcing fibers, and tensile strength.

[0343] [Example 2]

[0344] Pellets and molding pieces were produced in the same manner as in Example 1, except that the circular mesh size of the mesh screen at the time of pulverization was 3 mm, and evaluation was performed.

[0345] [Example 3]

[0346] Pellets and molding pieces were produced in the same manner as in Example 1, except that pelletization was performed using a twin-screw kneader (TEM26SS, TOSHIBA MACHINE), and evaluation was performed.

[0347] [Example 4]

[0348] The pellets and molded pieces were produced in the same manner as in Example 1 except that the circular mesh size of the screen at the time of pulverization was 10 mm, and evaluation was performed.

[0349] [Example 5]

[0350] The pellets and molded pieces were produced in the same manner as in Example 1 except that the moisture removal process of being fed into a hot air circulating dryer and dried at 90°C for 18 hours was not performed, and evaluation was performed.

[0351] [Example 6]

[0352] The pellets and molded pieces were produced in the same manner as in Example 1 except that the pulverized composite material and PA66 pellets were fed into the extruder at a ratio of 1:1.35, and evaluation was performed.

[0353] [Example 7]

[0354] The pellets and molded pieces were produced in the same manner as in Example 1 except that the metal foreign matter removal process was not performed, and evaluation was performed.

[0355] [Example 8]

[0356] The pellets and molded pieces were produced in the same manner as in Example 1 except that the temperature of the heater was set to a temperature of the melting point of the resin + 40°C, and evaluation was performed.

[0357] [Example 9]

[0358] The pellets and molded pieces were produced in the same manner as in Example 1 except that the screw rotation speed was set to 10 rpm, and evaluation was performed.

[0359] [Example 10]

[0360] The pellets and molded pieces were produced in the same manner as in Example 1 except that the discharge amount was set to 30 kg / h, and evaluation was performed.

[0361] [Example 11]

[0362] The pellets and molded pieces were produced in the same manner as in Example 1 except that the cooling method was water cooling, and evaluation was performed.

[0363] [Example 12]

[0364] The pellets and molded pieces were produced in the same manner as in Example 1 except that the metal foreign matter removal process and the moisture removal process of being fed into a hot air circulating dryer and dried at 90°C for 18 hours were not performed, and evaluation was performed.

[0365] [Comparative Example 1]

[0366] A molded sheet was produced in the same manner as in Example 1, except that CM3001G-30 (Toray Industries, Inc., pellets containing 30 mass% glass fibers in a polyamide resin) was used as the pellets, and evaluation was performed.

[0367] [Comparative Example 2]

[0368] A crushed composite was obtained using "Tepex dynalite 101" (Bond Laminates) as a prepreg, which contains polyamide 66 impregnated in a glass cloth, and pellets, a molded sheet were produced in the same manner as in Example 1, except that the crushed composite was used, and evaluation was performed. The obtained crushed composite did not have interlayer peeling.

[0369] [Comparative Example 3]

[0370] Pellets, a molded sheet were produced in the same manner as in Example 1, except that the temperature of the heater was set to the melting point of the resin + 55°C, and evaluation was performed.

[0371] [Comparative Example 4]

[0372] Pellets, a molded sheet were produced in the same manner as in Example 1, except that the discharge amount was set to 100 kg / h, and evaluation was performed.

[0373]

Claims

1. A pellet characterized by, comprising a reinforcing fiber and a thermoplastic resin, having a cross section with a ratio L / P of a length L along an outer periphery of the cross section to a circumference P of a circumscribed shape of the cross section of 1.2 to 2.

2.

2. The pellet according to claim 1, wherein, the reinforcing fiber is oriented in one direction in the pellet, a ratio of a fiber length of the reinforcing fiber to a length of the pellet, i.e., fiber length of reinforcing fiber / length of pellet, is 0.9 to 1.1 times.

3. The pellets of claim 1 or 2, wherein, a void ratio is 0.5% to 5.0%.

4. The pellets of claim 1 or 2, wherein, the ratio L / P of the cross section is 1.2 to 2.

1.

5. The pellets of claim 1 or 2, wherein, a void ratio of an interface portion between one of the reinforcing fibers and a portion surrounding the reinforcing fiber in a cross section orthogonal to an extending direction of the reinforcing fiber is 20% or less.

6. The pellets of claim 1 or 2, wherein, a mass ratio of the reinforcing fiber with respect to 100 mass% of the pellet is 20 mass% to 60 mass%.

7. The pellets of claim 1 or 2, wherein, the reinforcing fiber is at least one selected from the group consisting of a glass fiber, a carbon fiber, a plant fiber, and an aramid fiber.

8. The pellets of claim 1 or 2, wherein, the thermoplastic resin is at least one selected from the group consisting of a polyamide-based resin and a polyester-based resin.

9. The granules of claim 8, wherein, the polyamide-based resin contains 50 mass% to 99 mass% of (A) an aliphatic polyamide, and 1 mass% to 50 mass% of (B) a semi-aromatic polyamide containing a dicarboxylic acid unit containing at least 75 mole% of isophthalic acid units, and a diamine unit containing at least 50 mole% of diamine units having 4 to 10 carbon atoms.

10. A pellet manufacturing method according to any one of claims 1 to 9, comprising: a molding step of molding a material containing a continuous fiber-reinforced resin composite containing a continuous reinforcing fiber and a thermoplastic resin, the longest side having a length of 0.1 mm to 20 mm, and having an interlayer peeling portion extending along an extending direction of the continuous reinforcing fiber on a surface.

11. The pellet manufacturing method according to claim 10, comprising: a metal removing step of removing a metal from the continuous fiber-reinforced resin composite before the molding step.

12. The pellet manufacturing method according to claim 10, comprising: a moisture removing step of removing moisture from the continuous fiber-reinforced resin composite before the molding step.

13. A pellet manufacturing method according to any one of claims 1 to 9, comprising: a metal removing step of removing a metal from a continuous fiber-reinforced resin composite containing a continuous reinforcing fiber and a thermoplastic resin, the longest side having a length of 0.1 mm to 20 mm, and having an interlayer peeling portion extending along an extending direction of the continuous reinforcing fiber on a surface; a moisture removing step of removing moisture from the continuous fiber-reinforced resin composite; and a molding step of molding a material containing the continuous fiber-reinforced resin composite after the metal removing step and the moisture removing step.

14. The method of manufacturing pellets as claimed in claim 11 or 13, wherein, The metal is removed by adhering the metal to a magnet.

15. The method of manufacturing pellets as claimed in claim 12 or 13, wherein, The water is removed by heat drying under conditions of a temperature of 50°C to 150°C and a time of 0.5 hours to 100 hours, or by vacuum heat drying under conditions of a temperature of 50°C to 150°C, a pressure of 1 kPa to 100 kPa, and a time of 0.5 hours to 100 hours.

16. The method of manufacturing pellets according to any one of claims 10 to 13, wherein, The material containing the continuous fiber-reinforced resin composite in the molding step further contains virgin particles, and the virgin particles contain a thermoplastic resin.

17. The method of manufacturing pellets as claimed in claim 16, wherein, The mass ratio of the virgin particles is 10 mass parts to 150 mass parts with respect to 100 mass parts of the continuous fiber-reinforced resin composite.

18. The method of manufacturing pellets according to any one of claims 10 to 13, wherein, The material containing the continuous fiber-reinforced resin composite contains 10 mass% or more of a crushed composite obtained by crushing the continuous fiber-reinforced resin composite.

19. The method of manufacturing pellets according to any one of claims 10 to 13, wherein, In the molding step, the temperature of the heater is a temperature of the melting point of the thermoplastic resin + 5°C to a temperature of the melting point + 150°C, the rotation speed of the screw is 10 rpm to 150 rpm, and the discharge amount is 2 kg / h to 200 kg / h.

20. The method of making pellets according to claim 18, wherein, The crushed composite is a material that has passed through a mesh screen having a mesh size of 0.1 mm to 3 mm.

21. The method of manufacturing pellets as recited in claim 18, wherein, When the pulverized composite material is obtained by pulverization, the rotational speed of the blade at the time of pulverization is 100 min -1 ~ 3000 min -1 .

22. The method of making pellets according to Claim 18, wherein, When the crushed composite is obtained by crushing, the water absorption of the composite is 0.01 wt% to 2.0 wt%.

23. The method of manufacturing pellets according to any one of claims 10 to 13, wherein, The continuous reinforcing fiber is at least one selected from the group consisting of glass fiber, carbon fiber, plant fiber, and aramid fiber.

24. The method of manufacturing pellets according to any one of claims 10 to 13, wherein, The thermoplastic resin is at least one selected from the group consisting of a polyamide-based resin and a polyester-based resin.

25. The method of manufacturing pellets as recited in claim 24, wherein, The polyamide-based resin contains 50 mass parts to 99 mass parts of (A) aliphatic polyamide and 1 mass part to 50 mass parts of (B) semi-aromatic polyamide, and the (B) semi-aromatic polyamide contains a dicarboxylic acid unit containing at least 75 mol% of isophthalic acid units and a diamine unit containing at least 50 mol% of diamine units having 4 to 10 carbon atoms.

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