JP2019093646A - Intermediate base material formed of composite material containing reinforcement fiber and resin and molded body, method for manufacturing the molded body - Google Patents

Abstract

To provide an intermediate base material which can effectively improve a mechanical strength such as a bending strength and an impact strength of a molded body while maintaining high production efficiency, and a molded body manufactured from the same.SOLUTION: A molded body 200 is formed of a composite material which contains an intermediate base material 100 containing a first portion 110 formed of a first material containing a first base material being a prepolymer of a thermosetting resin and a composite body composed of nanocellulose (NCe) and nanocarbon (NC) and a second portion 120 composed of a second material containing a second base material being a thermoplastic resin and a reinforcement fiber; and a composite material containing the first resin being the thermosetting resin and the second resin being the thermoplastic resin, the reinforcement fiber and the composite body 210 composed of the nanocellulose (NCe) and the nanocarbon (NC), which are mixed in the vicinity of the interface of both of the layers.SELECTED DRAWING: Figure 15

Description

  TECHNICAL FIELD The present invention relates to an intermediate substrate and a molded body made of a composite material containing a reinforcing fiber and a resin, and a method of manufacturing the molded body.

  In the art, for example, a carbon fiber reinforced plastic (CFRP), which is a composite material of resin as a matrix (CF) and carbon fiber (CF), as a material which is lightweight and has high mechanical strength. : Development of “composites containing reinforcing fibers and resins” (hereinafter sometimes referred to as “fiber-reinforced resin composites”) including carbon fiber reinforced resin composites such as Carbon Fiber Reinforced Plastics. It is popular. By mixing reinforcing fibers such as CF in a resin as a base material to make a composite material, mechanical strength such as bending strength and impact strength of the composite material can be improved.

  However, in the conventional carbon fiber reinforced resin composite material, the adhesion at the interface between the resin and CF is insufficient, and a gap at the nanometer (nm) level tends to occur. For this reason, as shown in FIG. 1, when stress is applied to the product made of the composite material 10, peeling occurs at the interface between the resin 20 and the CF 30, and the peeling develops into a crack to sufficiently function as the composite material. There were times when it could not be demonstrated.

  Therefore, in order to reduce the exfoliation of CF from the base material and solve the above problems, as shown in FIG. 2, the structure (network structure) including carbon nanotubes (CNT: Carbon NanoTube) 41 is made of resin 20 There has been proposed a technique for improving the adhesion between the resin 20 and the CF 30 by arranging it at the interface between the C. and the CF 30 (see, for example, Patent Document 1). Since both CF and CNT are made of carbon, they have good affinity (wettability) with each other, and the anchor effect of bonding CNT to the surface of CF via a covalent π bond improves adhesion between CF and resin. Also, slippage between the CF and the resin in the direction orthogonal to the CF fiber axis can be suppressed. As a result, delamination between CF and resin can be suppressed, and mechanical strength such as bending strength and impact strength can be improved.

  In the invention described in Patent Document 1, in addition to the adhesion portion where the network structure of CNTs directly connected to each other is directly connected to CF, CF and CNT are physically separated via the binding member. It is bonded and the bond between CF and CNT is reinforced. However, the affinity (wettability) between CNT and resin (particularly, epoxy resin frequently used in CFRP) is low, and CNT and resin hardly adhere to each other. Furthermore, it is difficult for air inside the CNT network structure to escape even by vacuum suction, and it is difficult to impregnate the resin to the inside of the unevenness of the CNT network structure.

  In addition, even if the resin once enters the inside of the unevenness of the network structure of CNT, for example, the resin is pulled out from the unevenness by the peripheral resin due to the contraction of the resin accompanying curing of the thermosetting resin, etc. There is also a problem that the air gap of the In addition, since the CNT network structure itself is hard and brittle, as shown in FIG. 3, when stress is applied to the product made of the composite material 10, peeling occurs at the interface between the resin 20 and CF 30 and the peeling develops into cracks. There was a case to do.

  On the other hand, in the art, there is known a chemical modification method of modifying functional groups in the CNT itself by, for example, surface treatment using strong acid such as aqua regia. There is a problem of damaging the structure and causing structural defects, and industrial practical application is difficult.

  Therefore, in the art, mechanical strength as CFRP is improved by incorporating nanocellulose (NCe: NanoCellulose) and nanocarbon (NC: NanoCarbon) modified by functional groups into a resin as a base material. A technology is disclosed (see, for example, Patent Document 2). According to this technique, the complex obtained by mixing NCe modified by a functional group having high affinity to the resin with NC having high affinity to CF is contained in the resin, thereby making the complex The adhesion between the resin and the CF can be enhanced and the cohesion of the NC can be reduced, and as a result, the mechanical strength of the CFRP can be stably and uniformly increased.

  Furthermore, the flexibility resulting from the physical bond (entanglement) of NCe and NC in the above composite enhances the impact strength of the CFRP, and joins the CFRP with dissimilar materials such as metals and / or other resins. The deformation and / or the dimensional change caused by the difference in linear expansion coefficient can be favorably mitigated.

  By the way, in the technical field of CFRP, for example, a prepreg which is an intermediate base material obtained by impregnating a thermosetting resin such as epoxy resin with a reinforcing fiber such as CF is widely used. The prepolymer has a low viscosity because it is in a stage before being cured as a final resin, and can be easily impregnated into reinforcing fibers. However, since it generally takes a long time to cure the prepolymer into the final resin, the production efficiency of the molded article made of thermosetting resin is higher than the production efficiency of the molded article made of thermoplastic resin. Low.

  From the above background, nowadays, for example, development of “composite material including reinforcing fiber and thermoplastic resin” including thermoplastic resin as a base material, such as carbon fiber reinforced thermoplastic (CFRTP), is under development. It is popular. By adopting a thermoplastic resin as a base material, CFRTP reduces the time required for molding as compared with a composite material containing a thermosetting resin as a base material, and has high production efficiency of a molded product.

  Also in the composite material including the thermoplastic resin as a base material and the reinforcing fiber as described above, by adding the above-described composite of NCe and NC, the reinforcing fiber and the resin can be obtained via the composite. The mechanical strength of the compact made of the composite material can be stably and uniformly increased. However, thermoplastic resins have high viscosity even during melting, and it is difficult to uniformly disperse the composite in the base material. As a result, for example, it can not sufficiently contribute to the improvement of the adhesion between the reinforcing fiber and the resin at the interface between the reinforcing fiber such as CF and the resin as the base material, and the mechanical strength of the molded body is sufficiently improved. It is difficult.

  As described above, in the relevant technical field, there is provided a technique capable of effectively improving the mechanical strength such as bending strength and impact strength of a molded article made of a fiber-reinforced resin composite material while maintaining high production efficiency. It has been demanded.

JP, 2016-190969, A Unexamined-Japanese-Patent No. 2017-110114

  As described above, in the relevant technical field, there is provided a technique capable of effectively improving the mechanical strength such as bending strength and impact strength of a molded article made of a fiber-reinforced resin composite while maintaining high production efficiency. It is required.

  In view of the above problems, as a result of earnest research, the inventor of the present invention has found that a part including a thermosetting resin prepolymer and a composite composed of nanocellulose (NCe) and nanocarbon (NC), a thermoplastic resin and a reinforcing fiber It has been found that the above requirements can be met by producing a molded article from an intermediate substrate comprising a portion comprising

  Therefore, the intermediate base material according to the present invention (hereinafter sometimes referred to as "the present invention base material") is a first base material which is a prepolymer of a thermosetting resin, nanocellulose (NCe) and nano An intermediate group comprising: a first portion comprising a first material comprising a composite comprising carbon (NC); and a second portion comprising a second material comprising a second matrix which is a thermoplastic resin and a reinforcing fiber It is a material. The nanocellulose (NCe) may be modified by a functional group.

  Preferably, the nanocellulose (NCe) is a cellulose nanofiber (CeNF), the nanocarbon (NC) is a carbon nanotube (CNT), and in the composite, the cellulose nanofiber (CeNF) is the carbon nanotube It is a complex entangled on the surface of (CNT).

  Material selected as reinforcing fiber, first base material, and second base material, disposition of composite in inventive substrate, disposition of reinforcing fiber in second portion, and first portion and second portion of the inventive substrate Details of the inventive substrate, such as placement with parts, will be described in detail in the description of the various embodiments of the invention.

  Furthermore, a molded article according to the present invention (hereinafter sometimes referred to as “the molded article of the present invention”) is a composite comprising a resin, a reinforcing fiber, nanocellulose (NCe) and nanocarbon (NC). And the resin is a molded body including a first resin which is a thermosetting resin and a second resin which is a thermoplastic resin. Typically, the inventive moldings are produced from the inventive substrates described above. In addition, the method for producing a molded article according to the present invention (hereinafter sometimes referred to as “the method of the present invention”) is a method for producing the molded article of the present invention described above. Specifically, the method of the present invention comprises heating the above-described substrate of the present invention to a predetermined temperature above the melting point of the second base material, and applying the intermediate substrate at a predetermined temperature by a predetermined pressure. It is a manufacturing method of a forming object including pressing.

  As described above, the substrate of the present invention comprises a portion comprising a thermosetting resin prepolymer and a composite comprising nanocellulose (NCe) and nanocarbon (NC), and a portion comprising a thermoplastic resin and reinforcing fibers. And an intermediate base material. The prepolymer has a low viscosity because it is in a stage before being cured as a final resin, and the thermoplastic resin in the molten state is in the process of heating and pressing the substrate of the present invention to produce a molded product having a desired shape. It can be easily mixed with the above complex in the resin. Therefore, the composite can be easily dispersed in the matrix constituting the molded body, and the composite can be made to reach the vicinity of the reinforcing fiber. As a result, mechanical strength such as bending strength and impact strength of the molded body can be effectively improved.

  In addition, the base material of the base material of the present invention is composed of a thermosetting resin prepolymer and a thermoplastic resin. That is, since the prepolymer of the thermosetting resin is only a part of the base material of the substrate of the present invention, compared to the intermediate base material made of the composite material according to the prior art including only the thermosetting resin as the base material, Since the prepolymer can be cured faster, the time required for molding is short, and the production efficiency of the molded body is high.

  As described above, according to the present invention, it is possible to effectively improve the mechanical strength such as bending strength and impact strength of a molded article made of a fiber-reinforced resin composite material while maintaining high production efficiency.

  Other objects, other features and attendant advantages of the present invention will be readily understood from the description of embodiments of the present invention which will be described with reference to the following drawings.

When stress acts on the product which consists of a composite material which concerns on a prior art, it is a schematic diagram which shows a mode that peeling generate | occur | produces in the interface of resin and a carbon fiber, and it develops to a crack. It is a schematic diagram explaining the prior art which improves the adhesiveness of resin and a carbon fiber by arrange | positioning the structure containing a carbon nanotube in the interface of resin and a carbon fiber. When stress acts on the product which consists of a composite material which concerns on the prior art shown in FIG. 2, it is a schematic diagram which shows a mode that peeling generate | occur | produces in the interface of resin and a carbon fiber, and it develops to a crack. It is a schematic diagram which shows one example of a structure of the 1st part of the intermediate | middle base material (1st base material) which concerns on 1st Embodiment of this invention. It is a schematic diagram which shows another example of a structure of the 1st part of a 1st base material. It is a schematic diagram which shows one example of a structure of the 2nd part of a 1st base material. It is a schematic diagram which shows another example of a structure of the 2nd part of a 1st base material. It is a schematic perspective view of the 2nd part shown in FIG. It is a schematic diagram which shows the several example of a structure of a 1st base material. It is a schematic diagram which shows another example of a structure of a 1st base material. It is a schematic diagram which shows the structure of the complex as a complex. It is a schematic diagram which shows the process in which this invention molded object is manufactured from this invention base material. It is a schematic diagram which shows the difference in the grade of mixing of the 1st part of this invention base material, and a 2nd part in the process in which this invention base material is manufactured from this invention base material. It is a schematic diagram which shows the process of further laminating the additional layer which consists of a different material on this invention base material comprised as a laminated body which consists of a sheet-like 1st part and 2nd part in the modification of this invention. It is a schematic diagram which shows one example of the manufacturing method of the molded object which concerns on this invention. It is a schematic diagram which shows another example of the manufacturing method of the molded object which concerns on this invention. It is a schematic diagram which shows another example of the manufacturing method of the molded object which concerns on this invention.

First Embodiment
Hereinafter, the intermediate base material (it may be called a "1st base material" hereafter) concerning a 1st embodiment of the present invention is explained.

<Constitution>
The first substrate comprises a first portion comprising a first material comprising a first base material, which is a prepolymer of a thermosetting resin, and a composite comprising nanocellulose (NCe) and nanocarbon (NC); It is an intermediate base material containing the 2nd portion which consists of the 2nd material which contains the 2nd base material and resin which are resin.

  The first base material is, for example, various fiber reinforcements such as carbon fiber reinforced plastic (CFRP) and glass fiber reinforced plastic (GFRP) according to the application and manufacturing conditions of the molded body manufactured from the first base material, etc. It can be suitably selected from a wide variety of thermosetting resin prepolymers including thermosetting resins used as a base material in resin composite materials. Specific examples of the first base material will be described in detail later.

  As nanocellulose (NCe), commercially available celluloses, such as alpha-cellulose, can be adopted, for example. Alternatively, for example, microfibrils obtained by forming cellulose into nanofibers by a technique such as TEMPO oxidation may be adopted as NCe. Preferably, NCe is a cellulose nanofiber (CeNF: Cellulose NanoFiber).

  It is desirable that the diameter of NCe be about 1 nm to 800 nm, and the average length be about 100 nm to 1000 μm. If the diameter and / or length of the obtained cellulose is too large, it can be refined using a micronizing apparatus (mill) such as a mill and attritor. Specific examples of the mill include, for example, a ball mill, a bead mill, a sand mill, and a blade mill.

  As nanocarbon (NC), for example, carbon nanotube (CNT), fullerene, graphene, graphene oxide, carbon black, and activated carbon, and a mixture thereof can be adopted. NC is preferably a carbon nanotube (CNT), more preferably a node-like carbon nanotube (a carbon nanotube in which a plurality of node-like or bell-like structures are connected). The average diameter of NC is preferably about 1 nm to 1 μm, and the average length is preferably about 1 nm to 100 μm, and more preferably the average length is about 1 nm to 1 μm).

  The above-mentioned complex can be obtained by mixing nanocellulose (NCe) and nanocarbon (NC) by the above-described micronizing treatment apparatus. The form of connection between NCe and NC is not particularly limited. Examples thereof include a bond formed by the reaction of a functional group possessed by NCe with a functional group present on the surface of NC and physical entanglement between NCe and NC. be able to.

  The configuration of the first part is not particularly limited as long as it is made of the first material including the first base material and the composite as described above. Specifically, the first portion may be, for example, a prepreg obtained by impregnating the above-described composite with a raw material (for example, a monomer or the like) of a thermosetting resin and then setting it in a semi-cured state. Alternatively, for example, as shown in FIG. 4, the first portion 110 may be a prepolymer in which the raw material is dispersed in the raw material of the thermosetting resin and then the raw material is in a semi-cured state (first base material 111). It may be In FIG. 4, the complex 112 is represented by black dots and curves. Alternatively, for example, as shown in FIG. 5, the first portion 110 may be one in which the surface of the thermosetting resin raw material (first base material 111) in a semi-cured state is covered with the above composite 112. Good. In FIG. 5, the complex 112 is represented as a layer having a darker color than the first base material 111.

  The second base material may be, for example, a carbon fiber reinforced thermoplastic (CFRTP), a glass fiber reinforced thermoplastic (GFRTP), etc., depending on the application and production conditions of the molded product produced from the first base material. It can be suitably selected from a wide variety of thermoplastic resins including thermoplastic resins used as a base material in various fiber reinforced resin composite materials. Specific examples of the second base material will be described in detail later.

  Reinforcing fibers are, for example, carbon fiber reinforced plastic (CFRP), glass fiber reinforced plastic (GFRP), carbon fiber reinforced thermoplastic (for example, depending on the application and production conditions of the molded body manufactured from the first base material, etc. It can be suitably selected from various reinforcing fibers used as reinforcing fibers in various fiber reinforced resin composite materials such as CFRTP) and glass fiber reinforced thermoplastic (GFRTP). Specific examples of the reinforcing fiber will be described in detail later.

  The configuration of the second portion is not particularly limited as long as it is made of the second material including the second base material and the reinforcing fiber as described above. Specifically, the second part may be, for example, one in which a thermoplastic resin in a molten state is impregnated into a reinforcing fiber and then cooled and solidified to integrate the thermoplastic resin and the reinforcing fiber. Alternatively, the second part may be, for example, a powder of thermoplastic resin, a mixture of fibers or sheets and reinforcing fibers. Alternatively, for example, the second part heats the mixture of thermoplastic resin powder, fiber or sheet, etc. and reinforcing fibers to melt the thermoplastic resin, and then cools and solidifies it to obtain thermoplastic resin and reinforcing fibers. It may be integrated.

  6 and 7 are schematic views illustrating the configuration of the second portion of the first base material. FIG. 6 shows the second portion 120 configured as an integral body in which the reinforcing fibers 122 are dispersed in the second base material 121 which is a thermoplastic resin. On the other hand, FIG. 7 shows a second portion 120 configured as a mixture of fibers (base material fibers) made of the second base material 121 which is a thermoplastic resin and the reinforcing fibers 122. Although FIGS. 6 and 7 are drawn as if all the fibers are in the same direction, it is not necessary for all the fibers to be in the same direction.

  In addition to the various components described above, the first material and / or the second material may further include an affinity binder. The affinity binder is not particularly limited as long as it has a function of enhancing the affinity between the various components described above. For example, specific examples of the affinity binder having the function of enhancing the affinity between NCe and NC include lignin, amylose, and amylopectin. In addition, the first material may further contain a curing agent for further curing the prepolymer as the first base material, for example, by polymerization and / or crosslinking, as necessary.

  For example, FIG. 9A shows a configuration of the first base 100 configured as a laminate of the sheet-like first portion 110 shown in FIG. 4 and the sheet-like second portion 120 shown in FIG. FIG. 9B is configured as a sandwich-like laminate in which the sheet-like first part 110 shown in FIG. 4 is sandwiched by the pair of sheet-like second parts 120 shown in FIG. FIG. 2 is a schematic view showing the configuration of the first base material 100. Furthermore, FIG. 9 (c) shows the third portion 130 made of a third material including a third base material which is a thermoplastic resin different from the second base material and reinforcing fibers, and the sheet-like shown in FIG. It is a schematic diagram which shows the structure of the 1st base material 100 comprised as a sandwich-like laminated body by which the sheet-like 1st part 110 shown in FIG. 4 was pinched | interposed by the 2nd part 120. FIG.

  In addition, in FIG. 9, as described above, the first base 100 is drawn as a laminate of the sheet-like first portion 110 and the second portion 120 (and the third portion 130). However, the first base 100 is not necessarily limited to the laminate, and the first portion 110 and the second portion 120 (and the third portion 130) are not necessarily limited to the sheet-like shape. In addition, the mixing form of the second base material 121 and the reinforcing fiber 122 in the second portion 120 is not particularly limited, and, for example, a thermoplastic resin as the second base material 121 as in the second portion 120 shown in FIG. Reinforcing fibers 122 may be dispersed in the

  Alternatively, in the second portion 120 (and the third portion 130), fibers of thermoplastic resin as the second base material 121 and reinforcing fibers 122 are mixed as in the second portion 120 shown in FIGS. 7 and 8. It may be a mixed fiber (e.g., commingle yarn). An example of the configuration of the first base material having the second portion configured as such a mixed fiber is shown in FIG. The first substrate 100 in the example shown in FIG. 10 includes a first portion 110 sandwiched by a second portion 120 configured as a mixed fiber.

  On the other hand, as shown in FIG. 4, the first portion 110 depicted in FIG. 9 is depicted as an integral in which the composite 112 is dispersed in the thermosetting resin prepolymer which is the first base material 111. It is done. However, as shown in FIG. 5, the first portion 110 may be one in which the surface of the thermosetting resin prepolymer which is the first base material 111 is covered with the composite 112.

<effect>
As described above, the first base material is made of the first material including the first base material, which is a prepolymer of a thermosetting resin, and the composite of nanocellulose (NCe) and nanocarbon (NC). And a second portion made of a second material including a second base material, which is a thermoplastic resin, and a reinforcing fiber. For example, FIG. 9A shows a configuration of the first base 100 configured as a laminate of the sheet-like first portion 110 shown in FIG. 4 and the sheet-like second portion 120 shown in FIG. FIG. 9B is configured as a sandwich-like laminate in which the sheet-like first part 110 shown in FIG. 4 is sandwiched by the pair of sheet-like second parts 120 shown in FIG. FIG. 2 is a schematic view showing the configuration of the first base material 100. Furthermore, FIG. 9 (c) shows the third portion 130 made of a third material including a third base material which is a thermoplastic resin different from the second base material and reinforcing fibers, and the sheet-like shown in FIG. It is a schematic diagram which shows the structure of the 1st base material 100 comprised as a sandwich-like laminated body by which the sheet-like 1st part 110 shown in FIG. 4 was pinched | interposed by the 2nd part 120. FIG. The configuration of the first base material is not limited to the above, and the above-described configurations may be further combined.

  The prepolymer of the thermosetting resin as the first base material has a low viscosity because it is at a stage before it is cured as a final resin, and the first base material is heated and pressed to form a molded body having a desired shape. In the production process, it can be easily mixed with the above-mentioned complex into the thermoplastic resin in the molten state. Therefore, the composite can be easily dispersed in the matrix constituting the molded body, and the composite can be made to reach the vicinity of the reinforcing fiber. As a result, mechanical strength such as bending strength and impact strength of the molded body can be effectively improved.

  Further, the base material of the first base material is composed of a thermosetting resin prepolymer and a thermoplastic resin. That is, since the prepolymer of the thermosetting resin is only a part of the base material of the first base material, the prepolymer of the thermosetting resin is more than the intermediate base material made of the composite material according to the prior art including only the thermoplastic resin as the base material. Since the prepolymer can be cured rapidly, the time required for molding is short, and the production efficiency of the molded body is high.

  Furthermore, in the molded article produced from the first base material, since the thermosetting resin and the thermoplastic resin are mixed as a base material, for example, due to the composite of these different types of resins, for example, Flexibility is enhanced, and impact strength and flexibility as a molded body are enhanced. In addition, since the nanocarbon (NC) is dispersed in the base material in the molded body produced from the first base material, an effect such as an increase in the mechanical strength of the molded body can be achieved.

  As described above, according to the first base material, it is possible to effectively improve the mechanical strength such as bending strength and impact strength of the molded product made of the fiber-reinforced resin composite material while maintaining high production efficiency. .

Second Embodiment
Hereinafter, an intermediate base material (hereinafter, may be referred to as “second base material”) according to the second embodiment of the present invention will be described.

  For example, in the case of employing an epoxy resin as the first base material, a polyamide resin as the second base material, and carbon fibers (CF) as the reinforcing fibers, as described above, adhesion at the interface between the resin and CF is not sufficient. It is enough. However, due to the hydroxyl group that NCe has in the molecular structure, the adhesion between NCe and the resin is enhanced, and the adhesion between the composite and the resin is enhanced. On the other hand, CF and NC are both carbon and have high affinity to each other. Therefore, the adhesion between CF and NC is enhanced, and the adhesion between the composite and CF is enhanced. That is, according to the base material of the present invention, good adhesion between CF and the matrix resin is achieved through the above-mentioned composite.

  However, for example, when using a prepolymer of a thermosetting resin having high hydrophobicity and / or a thermoplastic resin as the first base material and / or the second base material, the adhesion between the NCe and the resin is low, and It may be difficult to achieve good adhesion between CF and the matrix resin through the composite. Also, for example, when reinforcing fibers other than CF, such as glass fibers and resin fibers, are adopted, depending on the properties of the material constituting the reinforcing fibers, it is preferable to use the composite as a component of reinforcing fibers and resin as a base material. There is a risk that it will be difficult to achieve adhesion.

<Constitution>
Thus, the second base material is the above-described first base material, and the nanocellulose (NCe) is an intermediate base material modified by a functional group.

  As a functional group for modifying NCe, a functional group having high affinity to the first matrix is preferable. Specifically, when a prepolymer of a thermosetting resin having high hydrophilicity is adopted as the first base material, examples of the functional group include a hydroxyl group, an alcohol group, and the like ((primary, secondary) And hydrophilic groups such as amino group, carboxyl group, and carbonyl group. Conversely, when a prepolymer of a thermosetting resin having high hydrophobicity is adopted as the first base material, the functional group may be, for example, hydrophobicity such as alkyl group (especially long chain alkyl group) and aryl group. Mention may be made of the sex group.

  Furthermore, as long as the functional group does not adversely affect the properties of a molded article produced from the first base material, the molecule and / or the first base material constituting the first base material by reaction with the first base material Or a functional group capable of forming a covalent bond with a molecule constituting the thermosetting resin obtained by curing As a specific example of such a functional group, the alkoxy silyl group etc. which can form a siloxane bond, for example with a silicone resin can be mentioned. NCe may be modified by two or more different functional groups among such functional groups.

  In addition to the above, NCe may be further modified by a functional group having high affinity to the thermoplastic resin employed as the second base material. Specifically, when a thermoplastic resin having high hydrophilicity is adopted as the second base material, examples of the functional group include a hydroxyl group and an alcohol group (primary, secondary, tertiary) And hydrophilic groups such as amino groups, carboxyl groups, and carbonyl groups, which contain quaternary amino groups. Conversely, when a thermoplastic resin having high hydrophobicity is employed as the second base material, examples of the functional group include hydrophobic groups such as alkyl groups (particularly long-chain alkyl groups) and aryl groups. be able to.

  Furthermore, as long as the functional group does not adversely affect the properties of the molded article produced from the first base material, the functional group is reacted with the second base material in the process of producing the molded article from the first base material. It may be a functional group capable of generating a covalent bond with a molecule constituting a thermosetting resin as a base material. NCe may be modified by two or more different functional groups among such functional groups.

  When NCe is modified with two or more different functional groups, one NCe modified with these two or more different functional groups may be used, or these two or more different functional groups may be used. Two or more NCe modified with only one of the groups may be used.

<effect>
Since nanocellulose (NCe) has a hydroxyl group (OH group) in its molecular structure, it has relatively good affinity to a matrix having a highly polar functional group such as a carbonyl group and a hydroxyl group in its molecular structure. To have sex. However, as mentioned above, a wide variety of materials may be employed as the first and second matrix and reinforcing fibers. Therefore, the adhesion between these materials and NCe can be enhanced by modifying NCe with a functional group having high affinity to these materials. As a result, good adhesion between these materials is achieved via the above-mentioned composite.

  In addition, since the NCe is modified with a functional group having high affinity to the first base material, the second base material and / or the reinforcing fiber instead of performing the severe surface treatment to the CNT as described above, the CNT Good adhesion of the materials constituting the second substrate can be achieved without damaging the structure.

  Furthermore, when the NCe is modified with a functional group having a high affinity to the first matrix, the impregnation of the first matrix between NCs constituting the complex is promoted, so that the first matrix and the NC and Generation of a gap at the interface of (high anchor effect). In addition, since NCe is generally softer than NC, NCe can also function as a nanometer (nm) level buffer (cushion) in the composite. Since the delamination in the molded object manufactured from a 2nd base material can be suppressed by these, mechanical strengths, such as flexural strength and impact strength of the said molded object, can be raised.

  As described above, according to the second base material, it is possible to more effectively improve the mechanical strength such as the bending strength and the impact strength of the molded product made of the fiber-reinforced resin composite material while maintaining high production efficiency. it can.

Third Embodiment
Hereinafter, an intermediate base material (hereinafter, may be referred to as “third base material”) according to the third embodiment of the present invention will be described.

<Constitution>
The third substrate is the first or second substrate described above, wherein the nanocellulose (NCe) is a cellulose nanofiber (CeNF), and the nanocarbon (NC) is a carbon nanotube (CNT) The composite is an intermediate base material which is a complex in which the cellulose nanofibers (CeNF) are entangled on the surface of the carbon nanotubes (CNT).

  FIG. 11 is a schematic view showing the structure of the complex. As shown in FIG. 11, in the complex 112 a that is a complex 112 constituting the first portion of the third base, a plurality of CeNFs 113 are entangled on the surface of the CNTs 114. Such complex body 112a can also be obtained by mixing CeNF and CNT by a micronizing apparatus such as a mill and attritor, as described above.

<effect>
As described above, by intertwining CeNF and covering the surface of CNTs, the intermolecular force which is the cause of aggregation of CNTs is reduced, and the dispersibility of CNTs in the first portion is enhanced, and as a result, from the third base material The dispersibility of the CNTs in the molded body to be produced is enhanced. Thereby, as described above, the effect of enhancing the adhesion between the first base material, the second base material, and the reinforcing fiber can be favorably exhibited via the composite.

  Incidentally, there is an upper limit to the coverage of CNT by CeNF, and it is difficult to cover the entire surface of CNT with CeNF. However, if the CeNF excessively covers the surface of the CNT, the bonding between the carbon fiber (CF) and the CNT is hindered. Therefore, there is an appropriate value for the blending ratio of CeNF and CNT. For this appropriate value, for example, CeNF and CNT are mixed at various compounding ratios to prepare a complex (complex), and the mechanical strength and the like of the composite material prepared using each complex are measured. It can be confirmed by prior experiments.

  Further, in the portion where CeNF is physically entangled on the surface of CNT, when stress acts on the molded body produced from the third substrate, CeNF in close contact with the base material slides on the surface of CNT, It can absorb shocks. Thereby, compared with the case where only CNT is used as a binder without CeNF, the said molded object can exhibit higher flexibility and impact resistance.

  As described above, according to the second material, similar to the first material, mechanical strength such as bending strength and impact strength of carbon fiber reinforced resin composite materials such as CFRP and CFRTP can be effectively improved. . In addition to this, according to the second material, due to the structural feature of the complex as described above, a composite material molded body having high adhesion between the matrix resin and CF and having excellent impact resistance is manufactured. Can.

Fourth Embodiment
Hereinafter, an intermediate base material (hereinafter, may be referred to as “fourth base material”) according to the fourth embodiment of the present invention will be described. As described above, the reinforcing fibers constituting the second part of the substrate of the present invention are, for example, reinforcing fibers in a fiber-reinforced resin composite material according to the application and production conditions of a molded article produced from the substrate of the present invention. It can be appropriately selected from various reinforcing fibers used as Among such reinforcing fibers, carbon fibers (CF), glass fibers (GF), and resin fibers (RF) having sufficient strength in view of applications are particularly preferable.

<Constitution>
Therefore, the fourth base material is an intermediate base material corresponding to any of the first to third base materials described above, and the reinforcing fibers are carbon fibers (CF), glass fibers (GF), and The intermediate base material is at least one fiber selected from the group consisting of resin fibers (RF) including polyester fibers, polyamide fibers, polyimide fibers, and polyamideimide fibers.

  As CF, for example, PAN (PolyAcryloNitrile) carbon fiber which uses acrylic fiber as a raw material and pitch (PITCH) carbon fiber which uses pitch as a raw material In accordance with the above, one having a suitable thickness, length, strength and the like can be appropriately selected. GF and RF can also be appropriately selected from among those widely used as reinforcing fibers in the relevant technical field, depending on, for example, the use of the molded article produced from the fourth base material.

<effect>
The reinforcing fibers contained in the second portion of the fourth base can be appropriately selected from among those widely used as reinforcing fibers in the relevant technical field as described above. Therefore, for example, a reinforcing fiber having a suitable thickness, length, strength, and the like can be appropriately selected according to the application of the molded body produced from the fourth base material and the like. That is, the characteristics (for example, mechanical strength and the like) of the molded article produced from the fourth base material can be designed with a high degree of freedom without causing an excessive increase in cost.

  In the selection of the reinforcing fiber, for example, the affinity for the thermosetting resin derived from the first base material as the base material and the thermoplastic resin derived from the second base material in the molded article produced from the fourth base material It is desirable to select a highly reinforced fiber. Alternatively, when the affinity of the reinforcing fiber to the matrix in the molded body is low, the affinity to either the reinforcing fiber and the matrix of either one or both of the nanocellulose (NCe) and the nanocarbon (NC) constituting the composite is It is desirable to configure so as to have high quality.

Fifth Embodiment
Hereinafter, an intermediate base material (hereinafter, may be referred to as “fifth base material”) according to the fifth embodiment of the present invention will be described. As described above, the first base material constituting the first portion of the base of the present invention is, for example, in the fiber-reinforced resin composite material according to the application and production conditions of the molded article produced from the base of the present invention. It can be suitably selected from a wide variety of thermosetting resin prepolymers including thermosetting resins used as a base material. In addition, the second base material constituting the second portion of the base material of the present invention is also a base material in the fiber reinforced resin composite material according to, for example, the application and production conditions of the molded article produced from the first base material. It can be suitably selected from a wide variety of thermoplastic resins including thermoplastic resins used as

<Constitution>
Therefore, in the fifth base material, various materials that can be selected as the first base material and the second base material are specifically defined. The fifth base material is an intermediate base material corresponding to any of the first to fourth base materials described above.

  In the fifth base material, the first base material is a group consisting of epoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, vinyl ester resin, bismaleimide resin, cyanate resin, polyimide resin, and silicone resin. It is a prepolymer of at least one thermosetting resin selected from among these. The second base material is at least one thermoplastic resin selected from the group consisting of various general purpose plastics widely used in the art, various general purpose engineering plastics, and various super engineering plastics. .

  Specific examples of general purpose plastics include, for example, polyolefin resins including polyethylene (PE) resin and polypropylene (PP) resin, polyvinyl chloride (PVC) resin, polyvinylidene chloride (PVDC) resin, polyethylene terephthalate (PET) resin, Polymethyl methacrylate (PMMA) resin, polystyrene resin (PS), acrylonitrile-styrene resin (AS), styrene-based resin including acrylonitrile-butadiene-styrene (ABS) resin, and the like can be mentioned. In addition, as a specific example of the general-purpose engineering plastic, for example, a polyester type including polyamide (PA) resin, polyacetal (POM) resin, polycarbonate (PC) resin, polybutylene terephthalate (PBT) resin and polyethylene naphthalate (PEN) resin Resin, polyphenylene ether (PPE) resin, etc. can be mentioned. Furthermore, specific examples of super engineering plastics include, for example, polyphenylene sulfide (PPS) resin, polyarylate (PAR) resin, polyamide imide (PAI) resin, thermoplastic polyimide (TPI) resin, polyether imide (PEI) resin, Polyether ketone (PEK) resin, polyether ether ketone (PEEK) resin, polysulfone (PSF) resin, polyether sulfone (PES) resin etc. can be mentioned.

<effect>
The first and second base materials in the fifth base material can be appropriately selected from well-known materials widely distributed in the relevant technical field as described above. Therefore, for example, a material having suitable properties (for example, mechanical strength, heat resistance, durability, aesthetics, etc.) can be appropriately selected according to the application of the molded body produced from the fifth base material, etc. . That is, the characteristics (for example, mechanical strength, etc.) of the molded article produced from the fifth base material can be designed with a high degree of freedom without causing an excessive increase in cost.

  In general, for example, the affinity between the thermosetting resin derived from the first base material as the base material and the thermoplastic resin derived from the second base material in the molded article produced from the fifth base material is It is desirable to select the first and second base materials to be high. However, in some cases, the affinity between these resins may not necessarily be high as long as the properties required for a molded article produced from the fifth base material can be achieved, for example. From the viewpoint of achieving high mechanical strength in the molded article, it is desirable to select a first base material and a second base material having high affinity to reinforcing fibers. Also in this case, when the affinity of the matrix to the reinforcing fibers in the molded body is low, the reinforcing fibers and the matrix of either or both of nanocellulose (NCe) and nanocarbon (NC) constituting the complex It is desirable to be configured to have a high affinity to the material.

Sixth Embodiment
Hereinafter, the intermediate base material (it may be called a "sixth base material" hereafter) concerning a 6th embodiment of the present invention is explained. For example, as described above with reference to FIG. 5, the first part including the first base material and the composite has the surface of the first base material which is a prepolymer of the thermosetting resin in a semi-cured state. It may be coated by In this case, since the substrate of the present invention includes the first portion and the second portion made of the second material including the second base material that is a thermoplastic resin and the reinforcing fiber, the nanocellulose (NCe) and the nanocarbon (NC) The complex consisting of) is mainly present at the interface between the first part and the second part.

<Constitution>
Therefore, the sixth base material is an intermediate base material corresponding to any one of the first base material to the fifth base material described above, and at least a part of the interface between the first part and the second part is the intermediate base material. An intermediate substrate on which the composite is disposed.

<effect>
The composite provided at the interface between the first portion and the second portion as described above is also a thermosetting resin in the process of heating and pressing the sixth base material to produce a molded product having a desired shape. When the first base material, which is a prepolymer of (1), is mixed into the second base material (thermoplastic resin) in a molten state, it can be mixed with the first base material into the second base material.

  Therefore, according to the sixth base material, the composite can be easily dispersed in the base material constituting the molded body, and the composite can be made to reach the vicinity of the reinforcing fiber. As a result, mechanical strength such as bending strength and impact strength of the molded body can be effectively improved.

Seventh Embodiment
Hereinafter, an intermediate base material (hereinafter, may be referred to as “seventh base material”) according to the seventh embodiment of the present invention will be described. As described above, in the sixth base material, the composite of nanocellulose (NCe) and nanocarbon (NC) is disposed at least at part of the interface between the first portion and the second portion. This composite is a second base material in which the first base material, which is a prepolymer of a thermosetting resin, is in a molten state in the process of producing a molded product having a desired shape by heating and pressing the sixth base material. When it mixes in (thermoplastic resin), it can mix in a 2nd base material with a 1st base material. However, it is difficult to uniformly disperse in the second matrix because at least a part of the above-mentioned complex is directly (in the complex alone) mixed in the second matrix having high viscosity. .

  By the way, for example, as described above with reference to FIG. 4, the first portion made of the first material including the first base material and the composite is obtained by dispersing the composite in the thermosetting resin raw material. The raw material may be a semi-cured prepolymer (first base material). In this case, the composite composed of nanocellulose (NCe) and nanocarbon (NC) is present (dispersed) in the first base material mainly in the first part.

<Constitution>
Therefore, the seventh base material is an intermediate base material corresponding to any of the first base material to the sixth base material described above, and the composite is dispersed in the first base material in the first portion. It is an intermediate base material.

<effect>
As described above, in the seventh base material, the composite is dispersed in the first base material. The composite thus dispersed in the first base material is directly applied to the second base material having a high viscosity in the process of heating and pressing the seventh base material to produce a molded product having a desired shape. Rather than being incorporated (in the composite alone), it is incorporated into the second matrix together with a first matrix (prepolymer of a thermosetting resin) having a low viscosity. As a result, since aggregation of the complexes is reduced, it is easy to uniformly disperse the complexes in the second base material.

  Therefore, according to the seventh base material, the composite can be more easily dispersed in the base material constituting the molded body, and the composite can be made to reach the vicinity of the reinforcing fiber. As a result, mechanical strength such as bending strength and impact strength of the molded body can be effectively improved.

Eighth Embodiment
Hereinafter, an intermediate base material (hereinafter, may be referred to as “eighth base material”) according to the eighth embodiment of the present invention will be described. As described above, the mixing form of the second base material and the reinforcing fibers in the second portion is not particularly limited, and, for example, in the thermoplastic resin as the second base material as described above with reference to FIG. Reinforcing fibers may be dispersed.

<Constitution>
Therefore, the eighth base material is an intermediate base material corresponding to any of the first base material to the seventh base material described above, and in the second portion, the reinforcing fiber is mixed in the second base material It is an intermediate base material.

<effect>
As described above, in the second portion of the eighth base material, reinforcing fibers are mixed in the second base material. As such a second part, for example, it can be appropriately selected from among those distributed as so-called "prepreg", "preform", "stampable sheet" and the like. That is, the characteristics (for example, mechanical strength, etc.) of the molded article produced from the eighth base material can be designed with a high degree of freedom without causing an excessive increase in cost.

The ninth embodiment
Hereinafter, the intermediate base material (Hereafter, it may be called a "9th base material.") Which concerns on 9th Embodiment of this invention is demonstrated. As described above, the mixing form of the second base material and the reinforcing fibers in the second portion is not particularly limited. For example, as described above with reference to FIGS. 7 and 8, the thermoplastic resin as the second base material The fiber may be a mixed fiber (e.g., combing yarn) in which the fibers of the above and the reinforcing fiber are mixed.

<Constitution>
Therefore, the ninth base material is an intermediate base material corresponding to any of the first base material to the seventh base material described above, and the second portion is a fiber made of the second base material and the reinforcing fiber And an intermediate substrate configured as a commingle yarn.

<effect>
As described above, in the second portion of the ninth base material, the fibers made of the second base material and the reinforcing fibers are mixed as a commingle yarn. As a fiber which consists of such a 2nd base material, it can select suitably from what is distribute | circulating as a thermoplastic resin fiber, for example. In addition, by appropriately adjusting the mixing ratio of the fibers of the second base material and the reinforcing fibers, the orientation of the respective fibers, the method of weaving, and the like, the ninth base material can be obtained without causing an excessive increase in cost. Properties (for example, mechanical strength etc.) of the molded body to be manufactured can be designed with a high degree of freedom.

  For example, the ninth substrate can constitute the second portion such that the reinforcing fibers are oriented in a single direction. In a molded article produced by heating and pressing such a ninth base material, the reinforcing fibers are oriented in a single direction. Therefore, the molded body produced in this manner can be used as a so-called "UD material". Alternatively, the second portion can be configured such that the reinforcing fibers are not oriented in a single direction. In a molded article produced from such a ninth base material, since the reinforcing fibers are not oriented in a single direction, they do not exhibit anisotropy in properties such as mechanical strength. Accordingly, such a molded body can be used, for example, in applications where it is not desirable to have anisotropy in properties such as mechanical strength.

  Furthermore, the second part can also be configured such that the reinforcing fibers constitute the fabric. In a molded article produced from such a ninth base material, reinforcing fibers constitute a woven fabric. That is, such a molded body can be used as a so-called "cross material". Accordingly, such a shaped body can be used in applications where it is not desirable to have anisotropy in properties such as mechanical strength, and where higher mechanical strength is required.

Tenth Embodiment
Hereinafter, an intermediate base material (hereinafter, may be referred to as “tenth base material”) according to the tenth embodiment of the present invention will be described. The shape and size of the substrate of the present invention, and the shape, size and arrangement of the first portion and the second portion of the substrate of the present invention are applications of the molded article produced from the substrate produced from the substrate of the present invention And it can design suitably according to manufacturing conditions etc., and is not limited in particular. For example, the substrate of the present invention can be configured as a laminate of sheet-like (layered) first and second portions as described above with reference to FIG.

<Constitution>
Therefore, the tenth base material is an intermediate base material corresponding to any of the first base material to the ninth base material described above, and the second base material is composed of the first layer consisting of the first part and the second part A sheet-like intermediate substrate comprising a laminate in which layers are adjacently laminated.

  The thickness and thickness ratio of each of the first layer and the second layer are not particularly limited, but as the thickness of the first layer (first portion) containing the prepolymer of the thermosetting resin as the first base material increases, The proportion of the material requiring the curing treatment in the tenth base material increases, and the time required for the curing treatment becomes long. Therefore, from the viewpoint of maintaining the production efficiency of the molded body from the tenth base material, it is desirable that the thickness of the first layer be thin.

<effect>
As described above, the tenth base material is a sheet-like intermediate base material having a thermosetting resin prepolymer and a thermoplastic resin as a base material. Therefore, the tenth base material can be used as, for example, so-called "prepreg", "preform", and "stampable sheet".

Eleventh Embodiment
Hereinafter, the molded object (Hereafter, it may be called a "11th molded object.") Which concerns on 11th Embodiment of this invention is demonstrated. As mentioned at the beginning of this specification, the present invention relates not only to an intermediate substrate consisting of a composite material containing reinforcing fibers and a resin, but also to a molded body consisting of a composite material containing reinforcing fibers and a resin.

<Constitution>
The eleventh molded body is formed of a composite material including a resin, a reinforcing fiber, and a composite composed of nanocellulose (NCe) and nanocarbon (NC), and the resin is a thermosetting resin. It is a molded object containing 1st resin and 2nd resin which is a thermoplastic resin.

  Although the method for producing the eleventh molded article is not particularly limited, for example, the eleventh molded article is an intermediate base (the present invention base) according to the present invention including the first base to the tenth base described above. It can manufacture by shape | molding as a molded object which has a desired shape by heating and pressurizing.

  The “first resin” is derived from a prepolymer of a thermosetting resin as a first base material constituting the first portion of the present invention base, and the “second resin” is the first base material of the present invention It originates in the thermoplastic resin as a 2nd base material which constitutes 2 parts. Therefore, the first resin and the second resin are apparent from the description of the first base material and the second base material in the base material of the present invention, and thus the description herein is omitted.

  Further, the composite composed of nanocellulose (NCe) and nanocarbon (NC) and the reinforcing fiber are derived from the composite forming the first part of the substrate of the present invention and the reinforcing fiber forming the second part. Therefore, since the composite and the reinforcing fiber are also apparent from the description of the composite and the reinforcing fiber in the substrate of the present invention, the description herein is omitted.

<effect>
As described above, the eleventh molded body is a molded body formed of a so-called "fiber-reinforced resin composite material" including a resin and a reinforcing fiber, and further includes a composite formed of NCe and NC. Therefore, according to the eleventh molded body, as described above in relation to the substrate of the present invention, the affinity between the resin and the reinforcing fiber is enhanced, and the mechanical strength such as bending strength and impact strength is effectively improved.

  Furthermore, in the eleventh molded body, since a thermosetting resin and a thermoplastic resin are mixed as a base material, for example, the flexibility of the base material is increased due to the composite of these different types of resins, and molding is performed. The impact strength and flexibility as a body increase. In addition, in the eleventh molded body, since nanocarbon (NC) is dispersed in the resin, an effect such as an increase in hardness of the molded body can be achieved.

  As described above, according to the eleventh molded body, mechanical strength such as bending strength and impact strength of a molded body made of a fiber-reinforced resin composite material can be effectively improved. When the base material of the eleventh molded body exhibits thermoplasticity, the molded body can be subjected to a further processing step as an intermediate material. That is, the eleventh molded body can also be used as an intermediate base to be subjected to further processing.

<< 12th embodiment >>
Hereinafter, a molded body (hereinafter sometimes referred to as “the twelfth molded body”) according to the twelfth embodiment of the present invention will be described. The twelfth molded body corresponds to the above-described second base material. Accordingly, the structure of the twelfth molded body and the effects achieved by the twelfth molded body are apparent from the description of the second base material, so the description herein is omitted and only the structure of the twelfth molded body is described. Briefly describe.

<Constitution>
The twelfth molded body is the eleventh molded body described above, wherein the nanocellulose (NCe) is modified by a functional group.

<< 13th Embodiment >>
Hereinafter, a formed body according to the thirteenth embodiment of the present invention (hereinafter, may be referred to as "the thirteenth formed body") will be described. The thirteenth molded body corresponds to the above-described third base material. Therefore, the configuration of the thirteenth molded body and the effects achieved by the thirteenth molded body are apparent from the description of the third base material, so the description herein is omitted, and only the configuration of the thirteenth molded body is described. Briefly describe.

<Constitution>
A thirteenth molded body is the eleventh molded body or the twelfth molded body described above, wherein the nanocellulose (NCe) is a cellulose nanofiber (CeNF), and the nanocarbon (NC) is a carbon nanotube (CNT) The composite is a formed body in which the cellulose nanofibers (CeNF) are entangled on the surface of the carbon nanotubes (CNTs).

Fourteenth Embodiment
Hereinafter, the molded object (Hereafter, a "14th molded object" may be called.) Which concerns on 14th Embodiment of this invention is demonstrated. The fourteenth molded body corresponds to the fourth base described above. Accordingly, the configuration of the fourteenth molded body and the effects achieved by the fourteenth molded body are apparent from the description of the fourth base material, so the description herein is omitted and only the configuration of the fourteenth molded body is described. Briefly describe.

<Constitution>
The fourteenth molded article is a molded article corresponding to any of the eleventh molded article to the thirteenth molded article described above, wherein the reinforcing fiber is carbon fiber (CF), glass fiber (GF), and polyester fiber, It is a molded object which is at least one fiber selected from the group consisting of resin fibers (RF) including polyamide fibers, polyimide fibers, and polyamideimide fibers.

«Fifteenth embodiment»
Hereinafter, a formed body according to the fifteenth embodiment of the present invention (hereinafter sometimes referred to as “the 15th formed body”) will be described. The fifteenth formed body corresponds to the above-described fifth base material. Accordingly, the configuration of the fifteenth molded body and the effects achieved by the fifteenth molded body are apparent from the description of the fifth base material, so the description herein is omitted and only the configuration of the fifteenth molded body is given. Briefly describe. However, as described above, in the following description, the "first resin" is derived from the prepolymer of the thermosetting resin as the first base material constituting the first portion of the inventive substrate, and the "second resin""Is derived from the thermoplastic resin as a second base material constituting the second part of the base material of the present invention.

<Constitution>
The fifteenth molded body is a molded body corresponding to any of the eleventh molded body to the fourteenth molded body described above.

  In the fifteenth molded body, the first resin is a group consisting of an epoxy resin, a phenol resin, a urea resin, a melamine resin, an unsaturated polyester resin, a vinyl ester resin, a bismaleimide resin, a cyanate resin, a polyimide resin, and a silicone resin. It is at least one thermosetting resin selected. The second base material is at least one thermoplastic resin selected from the group consisting of various general purpose plastics widely used in the art, various general purpose engineering plastics, and various super engineering plastics. .

  Specific examples of general purpose plastics include, for example, polyolefin resins including polyethylene (PE) resin and polypropylene (PP) resin, polyvinyl chloride (PVC) resin, polyvinylidene chloride (PVDC) resin, polyethylene terephthalate (PET) resin, Polymethyl methacrylate (PMMA) resin, polystyrene resin (PS), acrylonitrile-styrene resin (AS), styrene-based resin including acrylonitrile-butadiene-styrene (ABS) resin, and the like can be mentioned. In addition, as a specific example of the general-purpose engineering plastic, for example, a polyester type including polyamide (PA) resin, polyacetal (POM) resin, polycarbonate (PC) resin, polybutylene terephthalate (PBT) resin and polyethylene naphthalate (PEN) resin Resin, polyphenylene ether (PPE) resin, etc. can be mentioned. Furthermore, specific examples of super engineering plastics include, for example, polyphenylene sulfide (PPS) resin, polyarylate (PAR) resin, polyamide imide (PAI) resin, thermoplastic polyimide (TPI) resin, polyether imide (PEI) resin, Polyether ketone (PEK) resin, polyether ether ketone (PEEK) resin, polysulfone (PSF) resin, polyether sulfone (PES) resin etc. can be mentioned.

Sixteenth to nineteenth embodiments
The molded articles according to the sixteenth to nineteenth embodiments of the present invention (hereinafter sometimes referred to as "the sixteenth molded article" to the "19th molded article") will be described. As described above, the molded product according to the present invention (the molded product according to the present invention) comprises heating the intermediate base according to the present invention (the base according to the present invention) including the first base to the tenth base described above. It can manufacture by pressurizing and shape | molding as a molded object which has a desired shape.

  In the manufacturing process, the first base material, which is a prepolymer of a thermosetting resin, and the second base material, which is a thermoplastic resin melted by heating, are at least partially mixed. At the same time, at least a part of the composite (made of nanocellulose (NCe) and nanocarbon (NC)) that made up the first part was mixed into the second part and made up the second part At least a portion of the reinforcing fibers are incorporated into the first portion. Thus, in the process of producing the molded article of the present invention from the substrate of the present invention, the first portion and the second portion, which constitute the substrate of the present invention, are at least partially mixed.

  The degree of mixing varies, for example, depending on various conditions (for example, temperature and pressure, characteristics of various materials constituting the present invention substrate, etc.) in the process of producing the formed article of the present invention substrate from the present invention substrate. . For example, as shown in FIG. 12, the first base material 100 configured as a sandwich-like laminate in which the sheet-like first part 110 is sandwiched between the pair of sheet-like second parts 120 is heated and pressed. The case of manufacturing the molded object of the present invention is assumed. In FIG. 12, there is an air gap between the first portion 110 and the second portion 120 constituting the first base material 100, but in the actual manufacturing process, the first portion 110 and the second portion 120 are They are brought into contact with each other and subjected to heat and pressure in the laminated state. At this time, the degree of mixing of the first portion and the second portion constituting the substrate of the present invention is various according to, for example, manufacturing conditions such as temperature and pressure, and the characteristics of various materials constituting the substrate of the present invention. Change to

  In (a) of FIG. 13, in the molded article of the present invention 200 manufactured, the first portion 110 and the second portion 120 constituting the base of the present invention are sufficiently mixed to form a mixed layer 210, thereby forming a composite The body 112 and the reinforcing fibers 122 also exhibit a substantially homogeneous dispersion throughout the mixed layer 210. Also, in (b), the entire first portion 110 is mixed into the second portion 120 to form the mixed layer 210, and the complex 112 mainly diffuses to the mixed layer 210 along with this, and the first portion Although the reinforcing fibers 122 are also diffused in the region 110, some of the second portions 120 do not mix with the first portions 110 and remain as the second portions 120. A state in which the complex 112 has not reached the area is shown. Furthermore, in (c), only a part of the first portion 110 is mixed into the second portion 120 to form the mixed layer 210, and the composite 112 mainly diffuses into the mixed layer 210, thereby Although the reinforcing fibers 122 are also diffused in the region that was the one portion 110, some of the first portions 110 and some of the second portions 120 remain unmixed, of which the second portion 120 A state in which the complex 112 has not reached the area is shown.

  As described above, even if the molded article of the present invention is produced from the same base material of the present invention, the base material of the present invention can be obtained, for example, according to manufacturing conditions such as temperature and pressure and characteristics of various materials constituting the base material of the present invention. The degree of mixing of the first part and the second part which have made up variously changes. As a result, inventive moldings with different internal structures and properties can be produced from the same inventive substrate.

  Therefore, for example, by adjusting the production conditions such as temperature and pressure, and the characteristics of various materials constituting the substrate of the present invention, the molded article of the present invention having various internal structures and characteristics is produced from the same substrate of the present invention be able to.

<Constitution>
Therefore, the sixteenth molded body is a molded body corresponding to any of the eleventh molded body to the fifteenth molded body described above, and in the resin, the first resin and the second resin are homogeneously mixed. A molded body that includes the
The seventeenth molded body is the sixteenth molded body described above, and the resin is a molded body further including a region formed of only the second resin.
Furthermore, an eighteenth molded body is the seventeenth molded body described above, and the resin is a molded body further including a region formed only of the first resin.
In addition, the nineteenth molded body is a molded body corresponding to any of the eleventh molded body to the fifteenth molded body described above, and the first resin and the second resin are provided over the entire resin. Is a compact which is homogeneously mixed.

In the sixteenth molded body, the first resin and the second resin are mixed at least partially homogeneously. Therefore, the states (a) to (c) described above with reference to FIG. 13 are all included in the sixteenth formed body.
In the seventeenth molded body, there is a second resin which remains unmixed with the first resin. Accordingly, the state shown in (b) of FIG. 13 corresponds to the seventeenth molded body.
In the eighteenth molded body, not only the second resin remaining unmixed with the first resin but also the second resin remaining unmixed with the second resin are present. Accordingly, the state shown in (c) of FIG. 13 corresponds to the eighteenth molded body.
In the nineteenth molded body, all the first resins and all the second resins are intimately mixed. Accordingly, the state shown in (a) of FIG. 13 corresponds to the nineteenth molded body.

<effect>
As described above, even the inventive molded article manufactured from the same inventive substrate of the present invention, the sixteenth molded article, for example, according to the production conditions such as temperature and pressure and the characteristics of various materials constituting the inventive substrate Various internal structures and characteristics can be achieved, including the nineteenth to nineteenth compacts. Therefore, for example, by adjusting the production conditions such as temperature and pressure, and the characteristics and the like of various materials constituting the substrate of the present invention, suitable properties (for example, a machine) can be obtained according to the application and required characteristics of the molded article of the present invention. Molded articles having the desired strength, heat resistance, durability and aesthetics) can be produced. That is, the characteristics (for example, mechanical strength, etc.) of the molded article produced from the substrate of the present invention can be designed with a high degree of freedom without causing an excessive increase in cost.

<< Twentieth embodiment >>
Hereinafter, a formed body according to the twentieth embodiment of the present invention (hereinafter, sometimes referred to as “twentieth formed body”) will be described. As described above, the nanocellulose (NCe) is modified by modifying the nanocellulose (NCe) with a functional group having a high affinity to the material adopted as the first base material, the second base material and the reinforcing fiber constituting the base material of the present invention. Good adhesion between these materials is achieved via the composite of cellulose (NCe) and nanocarbon (NC). As a result, good adhesion between the first resin, the second resin, and the reinforcing fibers that constitute the molded product produced from the base material of the present invention can be achieved, and delamination in the molded product can be suppressed. The mechanical strength such as bending strength and impact strength of the molded body can be improved.

  In order to achieve the above effects, at least a part of the interface between the first resin and the reinforcing fiber, a part of the interface between the second resin and the reinforcing fiber, and the first resin and the second resin It is desirable that the complex intervenes in any part of the interface.

<Constitution>
Thus, the twentieth formed body is a formed body corresponding to any of the above-described eleventh to nineteenth formed bodies, and at least a part of the interface between the first resin and the reinforcing fiber, the (2) A molded body in which the composite is disposed at a part of the interface between the resin and the reinforcing fiber, or at a part of the interface between the mixture of the first resin and the second resin and the reinforcing fiber .

  There is no particular limitation on the method for arranging the complex at the various interfaces as described above. For example, as described above, the first resin in the twentieth molded body is covered with the composite by covering the surface of the first base material that constitutes the first portion of the inventive base material used for producing the twentieth molded body It is possible to increase the proportion of the complex present at the interface between the carbon fiber and the reinforcing fiber and the interface between the first resin and the second resin. Alternatively, as described above, when the composite is dispersed in the first matrix in the substrate of the present invention, the amount of the composite added may be increased to result in the composite at various interfaces as described above. The probability of existence can be increased.

<effect>
As described above, in the twentieth molded body, at least a part of the interface between the first resin and the reinforcing fiber, a part of the interface between the second resin and the reinforcing fiber, or a mixture of the first resin and the second resin By arranging the composite on a part of the interface between the fiber and the reinforcing fiber, good adhesion between the first resin, the second resin and the reinforcing fiber constituting the molded body is achieved, and Delamination can be suppressed. That is, according to the twentieth molded body, mechanical strength such as bending strength and impact strength of the molded body can be improved.

<< Modification >>
In the above description of the substrate of the present invention and the molded article of the present invention, a laminate of the first portion of one layer and the second portion of one layer, the first portion of one layer being between the second portions of two layers Mainly the laminated body etc. in which the 1st part of one layer is sandwiched between the 2nd part of 1 layer and the other resin layer (3rd part) of 1 layer, etc. . However, the configuration of the molded body (the molded body of the present invention) according to the present invention is not limited to the above.

  For example, the inventive molding may be provided with an additional layer on the outermost surface of one or both of the various laminates described above. The material constituting the additional layer is not particularly limited, but, for example, iron-based metals such as stainless steel and metal materials such as nonferrous metals such as gold, silver, copper, aluminum and magnesium can be adopted. Alternatively, for the purpose of imparting excellent properties such as heat resistance, chemical resistance, corrosion resistance and insulation to the molded product of the present invention, etc., a resin layer made of super engineering plastic as described above is added as an additional layer May be

  FIG. 14 further includes polyetheretherketone (PEEK) resin, which is a super engineering plastic, as an additional layer 220 on the surface on the first portion 110 side of the first base 100 described above with reference to FIG. 9A. It is a schematic diagram which shows the process of manufacturing the molded object 200 by heating and pressurizing what was laminated | stacked. In general, super engineering plastics are expensive, but by laminating as an additional layer on the outermost layer in this way, the raw material cost can be reduced. Further, in the example shown in FIG. 14, the additional layer 220 is laminated on the surface on the side of the first portion 110 including the prepolymer of the thermosetting resin, but depending on the affinity with the material constituting the additional layer, etc. The additional layer 220 may be laminated on the surface on the second portion 120 side.

  For example, thermosetting resins such as epoxy resins and urethane resins are also used as good adhesives. Therefore, it can also be said that the intermediate substrate according to the present invention is a material suitable for joining dissimilar materials as described above.

  In the case of additionally laminating additional layers of different materials as described above, there are concerns about problems such as deformation and / or dimensional change due to differences in linear expansion coefficient between the molded article of the present invention and the additional layers. . However, in the molded article of the present invention, the flexibility of the composite of the thermosetting resin and the thermoplastic resin is additionally added to the flexibility of NCe and NC in the composite due to physical bonding (entanglement). Such deformation and / or dimensional change can be favorably mitigated.

The Twenty-first Embodiment
Hereinafter, a method for producing a molded product (hereinafter sometimes referred to as “the 21st method”) according to the twenty-first embodiment of the present invention will be described. As mentioned at the beginning of this specification, the present invention relates not only to an intermediate substrate and a molded body consisting of a composite material containing reinforcing fibers and a resin, but also to a method of manufacturing the molded body.

<Constitution>
A twenty-first method is a manufacturing method for producing any one of the eleventh to twentieth molded articles, wherein the melting point of the second base material is any of the first to tenth substrates. It is a manufacturing method of a forming object including heating to the above predetermined temperature, and pressurizing the above-mentioned middle base material by predetermined pressure at the above-mentioned predetermined temperature. Preferably, the twenty-first method includes heating the substrate of the present invention to a predetermined temperature which is higher than the curing temperature of the first base material and higher than the melting point of the second base material.

  As a method for heating and pressing the intermediate substrate in the twenty-first method, the present invention to be manufactured from the material constituting the substrate of the present invention and the substrate of the present invention among various methods well known to those skilled in the art It can be appropriately selected according to the shape, characteristics and the like of the molded body. For example, when using a sheet-like intermediate substrate as described above, the molded article of the present invention can be produced from the substrate of the present invention by so-called "hot stamping" (hot press).

  For example, FIG. 15 is a schematic view showing an example of a method of manufacturing a molded body according to the present invention by heating and pressing the first base 100 described with reference to FIG. 9A. The first base material 100 configured as a laminate of the first portion 110 of one layer and the second portion 120 of one layer has heat as a first base material constituting the first portion 110 by heating and pressing. The curing of the prepolymer of the effect resin proceeds, and the thermosetting resin as the second base material constituting the second portion 120 is melted and the first base material and / or the first base material is cured; A mixing and mixing layer 210 is formed.

  In the example shown in FIG. 15, although both the first portion 110 and the second portion 120 remain completely unmixed, as described above with reference to FIG. 13, the first portion The degree of mixing of the 110 and the second portion 120 is, for example, various conditions (for example, temperature and pressure, characteristics of various materials constituting the inventive substrate) in the process of producing the inventive molded article from the inventive substrate. And so on). In addition, when heating and pressing the substrate of the present invention as described above, not only the stacking direction of the first portion 110 and the second portion 120, but also other directions (for example, the first portion 110 and the second portion 120). The mixing of the first portion 110 and the second portion 120 may be promoted by applying stress also in the in-plane direction of

  Moreover, FIG. 16 is a schematic diagram which shows an example of the method of heating and pressurizing the 1st base material 100 demonstrated with reference to (b) of FIG. 9, and manufacturing the molded object which concerns on this invention. Furthermore, FIG. 17 is a schematic view showing an example of a method of manufacturing a molded article according to the present invention by heating and pressing the first base material 100 described with reference to FIG. 9C. In any of the examples, it is the same as the example shown in FIG. 15 described above except that the second part 120 and the third part 130 are respectively laminated on the surface of the first part 110 opposite to the second part 120. So I will omit the detailed explanation here.

<effect>
The base material of the substrate of the present invention is composed of a thermosetting resin prepolymer and a thermoplastic resin. That is, since the prepolymer of the thermosetting resin is only a part of the base material of the substrate of the present invention, compared to the intermediate base material made of the composite material according to the prior art including only the thermosetting resin as the base material, The prepolymer can be cured faster. Therefore, according to the twenty-first method, a compact can be obtained in a shorter time than in the prior art. That is, the production efficiency of the molded body is high.

  While certain embodiments have been described, and for the purpose of illustrating the invention, certain embodiments and modifications have been described, sometimes with reference to the accompanying drawings, the scope of the invention is to be considered as illustrative of those embodiments. It should not be construed as being limited to the embodiments and the modifications, and it is needless to say that appropriate modifications can be made within the scope of the matters described in the claims and the specification.

  DESCRIPTION OF SYMBOLS 10 ... Composite material, 20 ... (matrix) resin, 30 ... Carbon fiber (CF) 40 ... Binder layer, 40a ... Complex body, 41 ... Carbon nanotube (CNT) 42 ... Cellulose nanofiber (CeNF), 50 ... Clearance, 100: Intermediate base material, 110: First portion, 111: First base material, 112: Composite material, 112a: Complex body, 113: Cellulose nanofibers (CeNF), 114: Carbon nanotubes (CNT), 120: Second part, 121: second base material, 122: reinforcing fiber, 130: third part, 200: molded body, 210: mixed layer, and 220: additional layer.

Claims (21)

A first portion made of a first material comprising a first base material which is a prepolymer of a thermosetting resin, and a composite of nanocellulose (NCe) and nanocarbon (NC);
A second portion made of a second material including a second base material that is a thermoplastic resin and reinforcing fibers;
including,
Intermediate base material. An intermediate substrate according to claim 1,
The nanocellulose (NCe) is modified by a functional group,
Intermediate base material. An intermediate substrate according to claim 1 or claim 2, wherein
The nanocellulose (NCe) is cellulose nanofiber (CeNF),
The nanocarbon (NC) is a carbon nanotube (CNT),
The complex is a complex in which the cellulose nanofiber (CeNF) is entangled on the surface of the carbon nanotube (CNT),
Intermediate base material. An intermediate base material according to any one of claims 1 to 3, which is
The reinforcing fiber is at least one fiber selected from the group consisting of carbon fiber (CF), glass fiber (GF), and resin fiber (RF) including polyester fiber, polyamide fiber, polyimide fiber, and polyamideimide fiber. is there,
Intermediate base material. An intermediate substrate according to any one of claims 1 to 4, wherein
The first base material is at least one selected from the group consisting of epoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, vinyl ester resin, bismaleimide resin, cyanate resin, polyimide resin, and silicone resin. Is a prepolymer of thermosetting resin,
The second base material is a polyolefin resin including polyethylene (PE) resin and polypropylene (PP) resin, polyvinyl chloride (PVC) resin, polyvinylidene chloride (PVDC) resin, polyethylene terephthalate (PET) resin, polymethacrylic acid General-purpose plastic consisting of styrene resin including methyl (PMMA) resin, polystyrene resin (PS), acrylonitrile styrene resin (AS) and acrylonitrile butadiene styrene (ABS) resin, polyamide (PA) resin, polyacetal (POM) resin , A general-purpose engineer consisting of a polyester resin including a polycarbonate (PC) resin, a polybutylene terephthalate (PBT) resin, and a polyethylene naphthalate (PEN) resin, and a polyphenylene ether (PPE) resin Plastics, as well as polyphenylene sulfide (PPS) resin, polyarylate (PAR) resin, polyamide imide (PAI) resin, thermoplastic polyimide (TPI) resin, polyether imide (PEI) resin, polyether ketone (PEK) resin, polyether At least one thermoplastic resin selected from the group consisting of super engineering plastics consisting of ether ketone (PEEK) resin, polysulfone (PSF) resin, polyether sulfone (PES) resin,
Intermediate base material. An intermediate substrate according to any one of claims 1 to 5, wherein
The composite is disposed at a part of an interface between at least the first portion and the second portion,
Intermediate base material. An intermediate substrate according to any one of claims 1 to 6, wherein
Said composite is dispersed in said first matrix in said first part,
Intermediate base material. An intermediate base material according to any one of claims 1 to 7, which is
In the second portion, the reinforcing fiber is mixed in the second base material,
Intermediate base material. An intermediate base material according to any one of claims 1 to 7, which is
The second portion is configured as a commingle yarn made of fibers of the second base material and the reinforcing fibers.
Intermediate base material. An intermediate base material according to any one of claims 1 to 9, wherein
The laminated body by which the 1st layer which consists of a said 1st part, and the 2nd layer which consists of a said 2nd part adjoin and laminated | stacked is included.
Sheet-like intermediate base material. It is formed of a composite material including a resin, a reinforcing fiber, and a composite of nanocellulose (NCe) and nanocarbon (NC),
The resin includes a first resin which is a thermosetting resin and a second resin which is a thermoplastic resin.
Molded body. It is a molded object described in Claim 11,
The nanocellulose (NCe) is modified by a functional group,
Molded body. It is a molded object described in Claim 11 or Claim 12, and.
The nanocellulose (NCe) is cellulose nanofiber (CeNF),
The nanocarbon (NC) is a carbon nanotube (CNT),
The complex is a complex in which the cellulose nanofiber (CeNF) is entangled on the surface of the carbon nanotube (CNT),
Molded body. It is a molded object described in any one of Claims 11 thru | or 13, Comprising:
The reinforcing fiber is at least one fiber selected from the group consisting of carbon fiber (CF), glass fiber (GF), and resin fiber (RF) including polyester fiber, polyamide fiber, polyimide fiber, and polyamideimide fiber. is there,
Molded body. It is a molded object described in any one of Claim 11 thru | or 14, Comprising:
The first resin is at least one selected from the group consisting of epoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, vinyl ester resin, bismaleimide resin, cyanate resin, polyimide resin, and silicone resin. Thermosetting resin,
The second resin is a polyolefin resin including polyethylene (PE) resin and polypropylene (PP) resin, polyvinyl chloride (PVC) resin, polyvinylidene chloride (PVDC) resin, polyethylene terephthalate (PET) resin, polymethyl methacrylate (PMMA), general purpose plastic consisting of styrene resin including polystyrene resin (PS), acrylonitrile styrene resin (AS) and acrylonitrile butadiene styrene (ABS) resin, polyamide (PA) resin, polyacetal (POM) resin, A general-purpose engineer that consists of a polyester resin including polycarbonate (PC) resin, polybutylene terephthalate (PBT) resin and polyethylene naphthalate (PEN) resin, and polyphenylene ether (PPE) resin Plastics, as well as polyphenylene sulfide (PPS) resin, polyarylate (PAR) resin, polyamide imide (PAI) resin, thermoplastic polyimide (TPI) resin, polyether imide (PEI) resin, polyether ketone (PEK) resin, polyether At least one thermoplastic resin selected from the group consisting of super engineering plastics consisting of ether ketone (PEEK) resin, polysulfone (PSF) resin, polyether sulfone (PES) resin,
Molded body. It is a molded object as described in any one of Claims 11 thru | or 15, Comprising:
The resin includes a region in which the first resin and the second resin are homogeneously mixed.
Molded body. It is a molded object described in Claim 16, Comprising:
The resin further includes a region consisting only of the second resin,
Molded body. It is a molded object described in Claim 17, Comprising:
The resin further includes a region consisting only of the first resin,
Molded body. It is a molded object as described in any one of Claims 11 thru | or 15, Comprising:
The first resin and the second resin are homogeneously mixed over the entire resin.
Molded body. A molded article according to any one of claims 11 to 19, wherein
At least a part of an interface between the first resin and the reinforcing fiber, a part of an interface between the second resin and the reinforcing fiber, or a mixture of the first resin and the second resin and the reinforcing fiber The complex is disposed in part of the interface,
Molded body. A method for producing a molded body according to any one of claims 11 to 20, wherein
A method of heating the intermediate substrate according to any one of claims 1 to 10 to a predetermined temperature equal to or higher than the melting point of the second base material, and a predetermined temperature of the intermediate substrate at the predetermined temperature. Pressurizing by pressure,
including,
Method for producing a molded body.

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