JP6395050B2 - Compact - Google Patents

Description

  The present invention relates to a molded article having a desired joined state formed by joining and integrating different kinds of material layers, for example, different kinds of resin layers.

  When the molded body has a laminated structure, it can satisfy various required performances compared to a single layer such as a resin layer, and can improve moldability while ensuring desired mechanical properties. There are many. For example, Patent Document 1 discloses that a core material and a fiber-reinforced resin layer are integrated with a powder resin binder in order to efficiently manufacture a lightweight and high-strength fiber-reinforced resin laminate with high accuracy and low cost. A bonded laminate is disclosed.

  Patent Document 2 discloses a technique for forming a resin composite material having excellent vibration damping properties by encapsulating a resin film in carbon fiber reinforced plastic (CFRP).

  Patent Document 3 previously filed by the present applicant discloses a laminate in which a sheet made of a fiber reinforced resin or the like having higher rigidity than the thermoplastic sheet is laminated on at least one surface of a specific thermoplastic sheet. A laminate having a specific composition of the thermoplastic sheet has sufficiently high rigidity under a static load and can absorb a large amount of energy when subjected to a high-speed impact. It is disclosed.

  Furthermore, Patent Document 4 previously filed by the present applicant discloses a technique for melt-bonding preforms of thermoplastic resins to each other via another thermoplastic resin. Note that Patent Document 4 also describes that the preform can be injection-molded.

  On the other hand, when molding a molded body made of a kind of thermoplastic resin, it is generally known that injection molding is preferable from the viewpoints of excellent moldability, mass productivity, and accuracy of the molded body. Yes.

  Further, as a technique similar to the technique disclosed in Patent Document 4, as a technique for joining and integrating the thermoplastic resins A and B, one thermoplastic resin A is molded in advance, and the other thermoplastic resin is molded. Regarding the resin B, a technique of integrally molding both thermoplastic resins by injection molding with respect to the molded body of the thermoplastic resin A is conceivable. In this way, if an integrally molded product is obtained as a whole by injection molding of one of the thermoplastic resins B, the excellent moldability based on the good fluidity inherent in the injection molding method can be obtained, with high accuracy. While taking advantage of the fact that molding is possible, molding in a short time suitable for mass production becomes possible.

  In addition, when joining and integrating fiber reinforced resin materials, various reinforcing fibers such as carbon fiber, glass fiber and aramid fiber are known as the reinforcing fiber of the fiber reinforced resin. In addition, various forms are known, such as those in which discontinuous fibers are randomly included, those in which continuous fibers are oriented in one direction, and those in the form of a reinforced fiber fabric. These are appropriately selected according to the required characteristics of the final molded product. For example, in addition to weight reduction, when high mechanical properties are required for the molded product as a whole, carbon fiber reinforced resin is often used, and although not as high as carbon fiber reinforced resin, In comparison, when high mechanical properties are required and a relatively inexpensive molded product is required, glass fiber reinforced resin is often used. On the other hand, when molding is performed so as to be capable of mass production with excellent moldability, injection molding is often employed. However, in the case of injection molding, from the viewpoint of fluidity necessary for molding, it is usually required that the reinforcing fibers contained are discontinuous fibers.

  However, in general, fiber reinforced resins using discontinuous fibers as reinforcing fibers have lower mechanical properties than fiber reinforced resins using continuous fibers as reinforcing fibers. Therefore, high mechanical properties are expressed by using fiber reinforced resin with continuous fibers as reinforcing fibers for specific necessary parts of the molded product, and discontinuous fibers are reinforced at parts where mechanical characteristics may be lower than that part. It is conceivable to improve the overall moldability by using a fiber reinforced resin as a fiber and molding the fiber reinforced resin having the discontinuous fiber as a reinforced fiber by injection. For example, for parts that require high mechanical properties, fiber reinforced resin with carbon fibers oriented in one direction or fiber reinforced resin with reinforced fibers made of carbon fiber fabric is used. It is conceivable to injection-mold a fiber reinforced resin in which discontinuous fibers of glass fibers are used as reinforcing fibers. For example, in Patent Document 5, when a fiber reinforced resin is injected inside a shell portion having an open cross-sectional shape to form a rib portion, a material having a higher bending elastic modulus than the rib portion constituting material is used as the shell portion constituting material. A configuration to be used is disclosed. In principle, such molded products can provide high mechanical properties for specific required parts, and good moldability for other parts and even the whole. In addition, the cost of the molded product can be reduced by using glass fibers as reinforcing fibers.

JP 2006-347134 A JP 2011-11346 A JP 2009-154305 A WO2012 / 137554 JP 2013-933 A

  Under the present circumstances as described above, when producing a molded body made of a laminate of different types of resin layers, a method of simply bonding with an adhesive is usually employed. However, it is often difficult to obtain a high bonding strength simply by bonding via an adhesive layer. Particularly when at least one resin layer is made of a fiber reinforced resin layer, it is highly bonded to a resin layer different from that. It is often difficult to bond with strength.

  In addition, in a molded body having a laminated integrated structure, it can be molded with high accuracy while satisfying light weight and satisfying high mechanical properties, has excellent moldability suitable for mass production, and further excellent When it is required to have energy absorption performance, it is difficult to satisfy all of the required performance with the conventional technology similar to the technology disclosed in Patent Document 4 as described above.

  In the case where the above-mentioned fiber reinforced resin materials are joined and integrated, in the molded product in which the fiber reinforced resins using different types of reinforcing fibers as described above are joined together, particularly, for example, an adhesive The following problem appears when one fiber-reinforced resin is injected and integrated without joining through layers.

That is, in the combination example as described above, the fiber reinforced resin portion using carbon fibers made of continuous fibers as reinforced fibers and the fiber reinforced resin portion using glass fibers made of discontinuous fibers as reinforced fibers, Due to the difference in type and form, there is a relatively large difference in linear expansion coefficient, especially at the joint between the two, and the difference in the mechanical properties of the joint is locally low, or at the joint There is a risk of peeling between the two fiber reinforced resins.

  In view of the current situation as described above, the object of the present invention is to provide a high-bonding strength even in the case where at least one resin layer is made of a fiber reinforced resin layer in a molded body in which layers made of different kinds of resins are joined and integrated. An object of the present invention is to provide a molded body having high mechanical properties that can be molded.

  Further, the object of the present invention is to pay attention to the technique described in Patent Document 3 and the technique similar to the technique disclosed in Patent Document 4, and in a molded body having a laminated integrated structure, An object of the present invention is to provide a molded body that can satisfy all of high mechanical properties, high molding accuracy, excellent moldability, and excellent energy absorption performance.

  Furthermore, the problem of the present invention is to pay particular attention to the problems caused by the difference in the linear expansion coefficient due to the difference in the type and form of the reinforcing fibers as described above, and different fiber reinforced resins, particularly different kinds of different forms. Fiber reinforced resin that can secure excellent properties of joints when it is required to integrally join fiber reinforced resin using reinforced fibers through injection molding of one fiber reinforced resin It is to provide an injection-molded body.

In order to solve the above-mentioned problems, a molded article according to the present invention is a matrix resin in which resin A is used as a matrix resin, and the surface of a fiber-reinforced sheet-like molded product is bonded to an adhesive layer B. A molded body formed by integral molding with an injection material or a press material, wherein the resin A, the adhesive layer B, and the resin C are composed of any combination of the following (1) or (2): .
(1) Resin A: polyamide, adhesive layer B: acid anhydride-modified polypropylene having a reactive functional group that reacts with resin A , resin C: polypropylene (2) resin A: polyphenylene sulfide, adhesive layer B: reacts with resin A Imide-modified polyamide having a reactive functional group , resin C: polyamide Here, the adhesive layer B has a composition different from both the resin A and the resin C.

  In such a molded body according to the present invention, a layer having a thermoplastic resin A as a matrix resin and a fiber-reinforced sheet-like molded product and a resin C different from the thermoplastic resin A as a matrix is bonded. At this time, an adhesive layer B containing a component having a reactive functional group is interposed, and a layer of the resin C to be joined is formed by injection molding or press molding, and the entire molded body is formed through the molding. It is integrally molded. That is, it is a molded body that is joined and integrated with injection molding or press molding of the layer of the resin C to be joined, instead of joining through a conventional simple adhesive layer. By forming at least the sheet-shaped molded article as a fiber reinforced resin layer, it is possible to exhibit high mechanical properties as the entire molded body. And since the layer of resin C is shape | molded by injection molding or press molding, the layer part of resin C is shape | molded with high precision with the outstanding moldability, and the shaping | molding suitable for mass production is attained. Further, the resin C layer is formed into a sheet-like molded article composed of a fiber reinforced resin layer together with the resin C layer by injection molding or press molding through an adhesive layer B containing a component having a reactive functional group. Since the bonding is performed, the bonding itself is very easily performed, and a high bonding strength is easily achieved. Therefore, it is possible to obtain a molded body having a laminate structure having high mechanical strength and high bonding strength with good moldability in a short time suitable for mass production.

Further, in the molded body according to the present invention, particularly when excellent energy absorption performance is required, the adhesive layer B is made of a thermoplastic sheet, and the thermoplastic sheet has a thermoplastic resin and a reactive functional group. It is important to comprise a thermoplastic resin composition obtained by blending the resin D. When the thermoplastic sheet as the adhesive layer B is made of such a thermoplastic resin composition, excellent energy absorption performance can be obtained, and high energy absorption performance can be obtained for the entire molded body.

  As the resin serving as the base of the resin D having the reactive functional group, various resins as described below can be used, but in view of excellent energy absorption performance, it is particularly a rubber polymer. preferable.

In addition, various reactive functional groups as described below can be adopted as the reactive functional group of the resin D, but amino group, carboxyl group, carboxyl metal salt are particularly preferable from the standpoint of excellent energy absorption performance. It is important that it is at least one selected from an epoxy group, an acid anhydride group, and an oxazoline group.

  Further, as the thermoplastic resin constituting the thermoplastic sheet, various thermoplastic resins can be used, in particular, polyamide resin, polyester resin, polyphenylene sulfide resin, styrene resin, polyphenylene oxide resin, polycarbonate resin, It is preferably at least one selected from a polylactic acid resin and a polypropylene resin.

  Further, in the molded body according to the present invention, the resin C to be injection molded or press molded is not particularly limited, but from the viewpoint of ease of integral molding, for example, polyamide resin, polyester resin, polyphenylene sulfide resin, styrene It is preferably made of at least one selected from a series resin, a polyphenylene oxide resin, a polycarbonate resin, a polylactic acid resin, and a polypropylene resin.

  In such a molded body according to the present invention, it is preferable that the fibers in the sheet-shaped molded article are continuous reinforcing fibers. For example, it is preferable that the sheet-shaped molded article includes a unidirectional reinforcing fiber layer in which reinforcing fibers made of continuous fibers are oriented in one direction and a woven fabric of reinforcing fibers made of continuous fibers. When the reinforcing fiber is made of continuous fiber, the sheet-like molded product can express higher mechanical properties than when it is made of discontinuous fibers, and as a result, the molded product as a whole can express higher mechanical properties. become.

  In addition, the fiber in the sheet-like molded product is not particularly limited, and for example, carbon fiber, glass fiber, aramid fiber, or a reinforced fiber combining these can be used. By including, higher mechanical properties can be expressed.

Furthermore, as a preferred form of the molded body according to the present invention, the adhesive layer B containing the component having the reactive functional group is made of a thermoplastic sheet, and the elastic modulus (a) of the sheet-shaped molded product and the injection material or Mention may be made of molded products in which the elastic modulus (b) of the thermoplastic sheet as the adhesive layer B containing the component having a reactive functional group and the elastic modulus (c) of the press material has the following relationship.
a>c> b

  In the molded body according to such a preferable form, the elastic modulus (a) of the sheet-shaped molded product and the elastic modulus (c) of the injection material or the pressed material are between the sheet-shaped molded product and the injection material or the pressed material. Since a specific thermoplastic sheet having a low elastic modulus (b) is interposed, when the molded body receives an impact load, the load transmission can be appropriately attenuated by the thermoplastic sheet layer. As a result, it is possible to exhibit excellent energy absorption performance. And since this molded article has a sheet-like molded article made of fiber reinforced resin, it can exhibit high mechanical properties such as high rigidity, especially under static load, and is sufficiently good because it is made of resin as a whole. Since it is integrally molded by injection or press of a material using resin C as a matrix, at least high molding accuracy of the injection material or press material portion can be obtained, and the injection molding method or press molding method Can exhibit the excellent moldability inherently. Therefore, the entire molded body can satisfy all of excellent energy absorption performance, light weight, high mechanical properties, high molding accuracy, and excellent moldability, and a desired molded body is realized.

  In the molded body according to the preferred embodiment described above, in order to express the excellent energy absorption performance more reliably, the thermoplastic sheet has a tensile elastic modulus at the tensile speeds V1 and V2 in the tensile test as E (V1). , E (V2), it is preferable to satisfy E (V1)> E (V2) when V1 <V2.

  Further, the present invention is a preferred fiber reinforced resin injection-molded product, that is, the first fiber reinforced resin containing the first reinforced fiber composed of continuous fibers and having the first linear expansion coefficient, and the discontinuous fibers. A second fiber reinforced resin containing a second reinforcing fiber different from the first reinforcing fiber and having a second linear expansion coefficient different from the first linear expansion coefficient; A hybrid fiber reinforced resin injection molded body integrally joined and molded through resin injection molding, wherein the second fiber reinforced resin is formed from discontinuous fibers in addition to the second reinforced fibers. The first reinforcing fiber contains the same type of reinforcing fiber, and the second linear expansion coefficient is the first linear expansion coefficient, and the second fiber reinforced resin is the second reinforcing fiber as the reinforcing fiber. Between the third linear expansion coefficient when containing only fibers Having a coefficient of expansion also provides the fiber-reinforced resin injection molded article according to claim.

  In such a fiber reinforced resin injection-molded body according to the present invention, the second fiber reinforced resin to be injection-molded is composed of discontinuous fibers and the first reinforcing fibers in addition to the second reinforcing fibers composed of discontinuous fibers. Since the same type of reinforcing fiber as the fiber is contained, the first linear expansion coefficient of the first fiber reinforced resin and the second fiber reinforced resin as the reinforcing fiber are only the second reinforcing fiber as the linear expansion coefficient. The linear expansion coefficient between the third and the third linear expansion coefficient in the case of containing is contained. Therefore, the difference in the coefficient of linear expansion between the second fiber reinforced resin and the first fiber reinforced resin to be injection-molded becomes small, and the first fiber reinforced resin and the second fiber reinforced resin become the second Even in the case of being integrally joined via injection molding of fiber reinforced resin, a locally low part occurs in the mechanical properties of the joint, or separation occurs between the two fiber reinforced resins at the joint. The fear is removed, and excellent characteristics at the joint are ensured.

  In the fiber reinforced resin injection molded article, the type of the first reinforcing fiber and the second reinforcing fiber is not particularly limited, but as a particularly effective representative form, the first reinforcing fiber is made of carbon fiber, The form which the said 2nd reinforcement fiber consists of glass fiber can be mentioned. In such a form, high mechanical properties are ensured in the first fiber reinforced resin portion having carbon fibers made of continuous fibers, and the first reinforced fibers are made of second reinforced fibers made of glass fibers and discontinuous fibers. In the second fiber reinforced resin portion containing the same type of reinforcing fibers, high fluidity is obtained at the time of injection molding, and excellent moldability is ensured, and furthermore, glass fibers are used for the second reinforcing fibers. As a whole, an inexpensive fiber-reinforced resin injection molded body is realized.

  Further, the fiber reinforced resin injection-molded body has a heat shrinkage behavior changing portion showing a heat shrinkage behavior different from other parts in the vicinity of the joint surface of the second fiber reinforced resin with the first fiber reinforced resin. It is especially effective when it has. Regarding the change in the heat shrinkage behavior different from other parts, the larger the difference in the linear expansion coefficient between the first fiber reinforced resin and the second fiber reinforced resin, the more the change in the heat shrinkage behavior caused by the difference. Since the difference in the linear expansion coefficient between the second fiber reinforced resin and the first fiber reinforced resin is suppressed to be small, the change in the heat shrinkage behavior is also suppressed to a small level. The possibility that a portion where the mechanical properties of the joint portion are locally low or that the fiber reinforced resin is peeled off at the joint portion is removed is eliminated.

  Such a heat shrinkage behavior change part is generated as follows, for example. For example, there is a cross-sectional shape changing portion on the joint surface of the second fiber reinforced resin with the first fiber reinforced resin, and the presence of the cross-sectional shape changing portion generates a heat shrinkage behavior changing portion. Or a thickness changing portion where the thickness of the second fiber reinforced resin changes in the vicinity of the joint surface of the second fiber reinforced resin with the first fiber reinforced resin. And a form in which the heat shrinkage behavior changing portion is generated due to the presence of the thickness changing portion is exemplified.

  Moreover, in the said fiber reinforced resin injection molded object, the volume content ratio of the said 2nd reinforced fiber in the said 2nd fiber reinforced resin, the said 1st reinforced fiber, and the same kind of reinforced fiber is 1: 0.1. It is preferably in the range of ˜1: 1.5. If the volume content ratio of the first reinforcing fiber and the same type of reinforcing fiber is too low, the effect of reducing the difference in linear expansion coefficient between the first fiber reinforced resin and the second fiber reinforced resin is low. When the volume content ratio between the first reinforcing fiber and the same type of reinforcing fiber is too high, the advantage (for example, cost reduction) of using a reinforcing fiber of a different type from the first reinforcing fiber for the second reinforcing fiber is reduced.

  Furthermore, in the fiber reinforced resin injection-molded product, the first fiber reinforced resin contains the first reinforced fibers oriented in one direction with respect to the first reinforced fibers of the first fiber reinforced resin. The form in which the said 1st fiber reinforced resin contains the textile fabric of a 1st reinforcement fiber can be illustrated separately or with it. When the first reinforcing fiber oriented in one direction is contained, it becomes possible to enhance the mechanical properties of the fiber-reinforced resin injection molding material particularly in a specific direction, and the first reinforcing fiber fabric is contained. In some cases, the mechanical characteristics can be improved uniformly in a relatively unspecified direction.

Thus, according to the molded body according to the present invention, when a layer having a resin C different from the resin A as a matrix is bonded to the surface of the fiber-reinforced sheet-like molded product, the resin A is a matrix resin. A thermoplastic resin comprising a thermoplastic resin and a resin D having at least one reactive functional group selected from an amino group, a carboxyl group, a carboxyl metal salt, an epoxy group, an acid anhydride group, and an oxazoline group. The adhesive layer B, which is a thermoplastic sheet made of the composition, is interposed, and the layer of the resin C to be joined is molded by injection molding or press molding, and the entire molded body is integrally molded through the molding. Therefore, it can be joined and integrated with injection molding or press molding of the resin C layer, and has high joint strength and high mechanical properties of the sheet-like molded product layer. The molded article comprising utilizing laminate can be easily realized with good moldability.

  Further, by using a specific thermoplastic resin having a reactive functional group that reacts with the thermoplastic resin A as the thermoplastic resin constituting the adhesive layer B containing a component having a reactive functional group, higher bonding can be achieved. A molded body having strength is obtained.

  Moreover, according to the molded body according to the preferred embodiment of the present invention described above, the thermoplastic resin A is used as a matrix resin, and the fiber-reinforced sheet-like molded product is obtained by using the resin C as a matrix via a specific thermoplastic sheet. Because it is a molded body integrated by injection molding or press molding of the selected material, it is possible to achieve light weight, high mechanical properties, high molding accuracy, and excellent moldability, and at the same time, a sheet-like molded product and injection By interposing a specific thermoplastic sheet having an elastic modulus (b) lower than the elastic modulus (a) of the sheet-like molded article and the elastic modulus (c) of the injection material or the press material between the materials or the press material, The energy absorption performance excellent as the whole molded object can be expressed.

  Furthermore, according to the above-mentioned fiber reinforced resin injection-molded material according to the preferred embodiment of the present invention, in addition to the second reinforced fiber made of discontinuous fibers, the second fiber reinforced resin to be injection-molded is also made of discontinuous fibers. By including the same kind of reinforcing fiber as the first reinforcing fiber, the second fiber reinforced resin becomes the first linear expansion coefficient of the first fiber reinforced resin, and the second fiber reinforced resin becomes the reinforced fiber. Since it has a linear expansion coefficient between the third linear expansion coefficient in the case of containing only the second reinforcing fiber, the second fiber reinforced resin to be injection-molded and the first fiber reinforced resin The difference in the linear expansion coefficient between the first fiber reinforced resin and the second fiber reinforced resin can be locally reduced in the mechanical properties of the joint between the first fiber reinforced resin and the second fiber reinforced resin, or both fibers are reinforced at the joint. Remove the possibility of peeling between the resins, Excellent characteristics can be ensured that. Thereby, it is possible to realize preferable excellent characteristics over the entire molded product integrated by injection molding of the second fiber reinforced resin.

It is a schematic block diagram which shows the structural example of the molded object which concerns on one embodiment of this invention. It is a schematic block diagram which shows the structural example of the molded object which concerns on another embodiment of this invention. It is explanatory drawing of the lap shear test which measures the joint strength in this invention. It is a schematic block diagram which shows the comparison with the laminated structural example of the molded object which concerns on another embodiment of this invention, and the structural example of the conventional typical molded object. It is a schematic side view of the fiber reinforced resin injection molding which concerns on one embodiment of this invention. It is the schematic side view (A) and schematic front view (B) of the fiber reinforced resin injection molding which concern on another embodiment of this invention. It is the schematic side view (A) and schematic front view (B) of the fiber reinforced resin injection molding which concern on another embodiment of this invention.

Hereinafter, embodiments of the present invention will be described in detail.
The molded body according to the present invention is configured, for example, as shown in FIG. A molded body 1 according to an embodiment of the present invention includes an adhesive layer B (3 including a component having a reactive functional group on the surface of a fiber-reinforced sheet-shaped molded article 2 using a thermoplastic resin A as a matrix resin. ) Through an injection material or a press material 4 using a resin C different from the thermoplastic resin A as a matrix. The adhesive layer B (3) containing a component having a reactive functional group is preferably made of a thermoplastic resin having a reactive functional group that reacts with the thermoplastic resin A. FIG. 1 shows a molded body 1 having a three-layer structure including a sheet-like molded article 2, an adhesive layer B (3) containing a component having a reactive functional group, and an injection material or a press material 4. 2, for example, as shown in FIG. 2, a molded article 11 according to another embodiment, a sheet-like molded article 2, an adhesive layer B (3) containing a component having a reactive functional group, an injection material, or a press material 4. It is also possible to configure the adhesive layer B (3) containing a component having a reactive functional group, the five layers of the sheet-like molded product 2, and the like.

  The joint strength between the sheet-like molded product 2 and the layer made of the injection material or the press material 4 in the molded body according to the present invention can be measured by, for example, a lap shear test (shear test) as shown in FIG. In the test method shown in FIG. 3, an adhesive layer B containing a component having a reactive functional group on a part of the surface of a test piece of a fiber-reinforced sheet-like molded product 2 using a thermoplastic resin A as a matrix resin. Through (3), a test sample formed by integral molding with a test piece of injection material (injection molded product) or press material 4 using a resin C different from the thermoplastic resin A as a matrix, is formed into a sheet-like molded product. The end part on the 2 side and the end part on the injection material or press material 4 side are held by the chuck parts 5 and 6 of the tensile tester, and the adhesive layer B (3 containing a component having a reactive functional group is obtained by the tensile tester. The joint portion formed by the adhesive layer B (3) containing the component having a reactive functional group by pulling the sheet-like molded product 2 and the injection material or the press material 4 in the opposite directions so as to apply a shear load to the joint portion There is a break By measuring the tensile load when a predetermined amount or more modifications (e.g., interfacial failure) occurs, it is possible to quantitatively measure the bonding strength. The lapping allowance between the sheet-like molded product 2 and the injection material or the press material 4, the length, width and thickness of each test piece, and the length of each chuck portion were set to the dimensions shown in the figure.

  In the molded body according to the present invention as described above, the resin C constituting the injection material or the press material is not particularly limited. However, from the viewpoint of ease of integral molding, for example, as described above, polyamide resin, polyester, etc. It is preferably made of at least one selected from resins, polyphenylene sulfide resins, styrene resins, polyphenylene oxide resins, polycarbonate resins, polylactic acid resins, and polypropylene resins. Moreover, it does not specifically limit as the thermoplastic resin A which comprises the fiber-reinforced sheet-like molded product, The thermoplastic resin similar to the resin C can be used. These resin layers should just be joined via the contact bonding layer B containing the component which has a reactive functional group.

  The adhesive layer B containing a component having such a reactive functional group is particularly preferably made of a thermoplastic resin having a reactive functional group that reacts with the thermoplastic resin A. Examples of the thermoplastic resin constituting the adhesive layer B containing the component having a reactive functional group include polyamide resin, polyester resin, polyphenylene sulfide resin, styrene resin, polyphenylene oxide resin, polycarbonate resin, polylactic acid resin, and polypropylene resin. And at least one selected from those modified resins. Particularly, polyamide resins, polyester resins, polyphenylene oxide resins, and modified resins thereof are more preferably used because of high reactivity of terminal groups.

  In the present invention, the polyamide resin is a resin composed of a polymer having an amide bond, and mainly contains amino acids, lactams or diamines and dicarboxylic acids. Representative examples of the raw materials include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, lactams such as ε-caprolactam and ω-laurolactam, tetramethylenediamine, penta Methylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylene Diamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4 -Aminocyclohex Sil) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, aliphatic, alicyclic, aromatic Diamines, and adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid Examples thereof include aliphatic, alicyclic, and aromatic dicarboxylic acids such as acid, hexahydroterephthalic acid, and hexahydroisophthalic acid. In the present invention, polyamide homopolymers or copolymers derived from these raw materials are used individually or individually. It can be used in the form of a mixture.

  In the present invention, specific examples of polyamide resins particularly useful for the adhesive layer B containing a component having a reactive functional group include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66). ), Polypentamethylene adipamide (nylon 56), polytetramethylene adipamide (nylon 46), polyhexamethylene sebacamide (nylon 610), polypentamethylene sebacamide (nylon 510), polyhexamethylene dodeca Mido (nylon 612), polyundecanamide (nylon 11), polydodecanamide (nylon 12), polycaproamide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalate Amide copolymer (Niro 66 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene adipamide / polyhexamethylene isophthalamide / polycaproamide copolymer (nylon 66 / 6I / 6) , Polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polyhexamethylene terephthalamide / polydodecanamide copolymer (nylon 6T / 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide / Polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyxylylene adipamide (nylon XD6), polyhexamethylene terephthalamide / poly-2-methylpen Terephthalamide copolymer (nylon 6T / M5T), polyhexamethylene terephthalamide / poly pentamethylene terephthalamide copolymer (nylon 6T / 5T), and mixtures thereof or copolymers, and the like.

  Particularly preferable examples include polyamide 6, polyamide 66, polyamide 610, polyamide 11, polyamide 12, polyamide 6/66 copolymer, polyamide 6/12 copolymer and the like. Furthermore, it is also practically preferable to use these polyamide resins as a mixture depending on required properties such as moldability, heat resistance, toughness, and surface properties. Among these, polyamide 6, polyamide 66, polyamide 610, and polyamide 11 are suitable. Polyamide 12 is most preferred.

  The degree of polymerization of these polyamide resins is not particularly limited, and the relative viscosity measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a sample concentration of 0.01 g / ml is preferably in the range of 1.5 to 7.0. A polyamide resin in the range of 1.8 to 6.0 is preferred. When the relative viscosity is less than 1.5, it is difficult to express the excellent impact absorption characteristic of the molded article of the present invention. When the relative viscosity is greater than 5.0, the melt viscosity of the thermoplastic resin composition is difficult. Increases significantly, making it difficult to form a thermoplastic resin sheet.

  In the present invention, the polyester resin is a thermoplastic resin composed of a polymer having an ester bond in the main chain, and a dicarboxylic acid (or an ester-forming derivative thereof) and a diol (or an ester-forming derivative thereof). And a polymer or a copolymer obtained by a condensation reaction having as a main component thereof, or a mixture thereof.

  Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, and 4,4′-diphenyl ether dicarboxylic acid. Acid, aromatic dicarboxylic acid such as 5-sodiumsulfoisophthalic acid, adipic acid, sebacic acid, azelaic acid, aliphatic dicarboxylic acid such as dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc. And alicyclic dicarboxylic acids and ester-forming derivatives thereof. The diol component is an aliphatic glycol having 2 to 20 carbon atoms, that is, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol. , Cyclohexanedimethanol, cyclohexanediol and the like, or long-chain glycols having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol and the like, and ester-forming derivatives thereof.

  Preferred examples of these polymers or copolymers include polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxylate), Polybutylene naphthalate, polyethylene terephthalate, polyethylene (terephthalate / isophthalate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / 5-sodium sulfoisophthalate), polybutylene (terephthalate / 5-sodium sulfoisophthalate), polyethylene Naphthalate, polycyclohexanedimethylene terephthalate, etc. Polybutylene terephthalate, polybutylene (terephthalate / adipate), polybutylene (terephthalate / decane dicarboxylate), polybutylene naphthalate, polyethylene terephthalate, polyethylene (terephthalate / adipate), polyethylene naphthalate, polycyclohexanedimethylene terephthalate, etc. Particularly preferred is polybutylene terephthalate (polybutylene terephthalate resin).

  The polybutylene terephthalate resin has an intrinsic viscosity measured in a 0.5% o-chlorophenol solution at 25 ° C. in the range of 0.35 to 2.00, more preferably 0.50 to 1.50. A range is preferred. Moreover, you may use together polybutylene terephthalate resin from which intrinsic viscosity differs, and it is preferable that intrinsic viscosity exists in the range of 0.35-2.00.

  Further, the polybutylene terephthalate resin is durable if the COOH end group amount obtained by potentiometric titration of the m-cresol solution with an alkaline solution is in the range of 1 to 50 eq / t (end group amount per ton of polymer). From the point of anisotropy suppressing effect, it can be preferably used.

  Specific examples of the polyphenylene oxide resin include poly (2,6-dimethyl-1,4-phenylene oxide), poly (2-methyl-6-ethyl-1,4-phenylene oxide), and poly (2,6 -Diphenyl-1,4-phenylene oxide), poly (2-methyl-6-phenyl-1,4-phenylene oxide), poly (2,6-dichloro-1,4-phenylene oxide) and the like. Further, a copolymer such as a copolymer of 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol) can be mentioned. Among them, poly (2,6-dimethyl-1,4-phenylene oxide) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and in particular, poly (2,6-dimethyl) -1,4-phenylene oxide) is preferred.

  The polyphenylene oxide resin preferably has a reduced viscosity measured in a 0.5 g / dl chloroform solution at 30 ° C. in the range of 0.15 to 0.70.

  The method for producing such a polyphenylene oxide resin is not particularly limited, and those obtained by a known method can be used. For example, it can be easily produced by oxidative polymerization using as a catalyst a complex of cuprous salt and amine by Hay described in US Pat. No. 3,306,874.

  Specific examples of the polypropylene resin include a propylene homopolymer or a copolymer of propylene and at least one α-olefin, conjugated diene, non-conjugated diene, or the like.

  Examples of the monomer repeating unit constituting the α-olefin include ethylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl- 2-12 carbon atoms excluding propylene such as 1-hexene, 4,4 dimethyl-1-hexene, 1-nonene, 1-octene, 1-heptene, 1-hexene, 1-decene, 1-undecene and 1-dodecene Examples of the monomer repeating unit constituting the α-olefin, conjugated diene, and non-conjugated diene include butadiene, ethylidene norbornene, dicyclopentadiene, 1,5-hexadiene, and the like. One type or two or more types can be selected.

  The skeleton structure of polypropylene resin includes propylene homopolymer, propylene and one or more random or block copolymers of the above-mentioned other monomers, and copolymers of other thermoplastic monomers. A polymer etc. can be mentioned. For example, polypropylene, ethylene / propylene copolymer, propylene / 1-butene copolymer, ethylene / propylene / 1-butene copolymer, and the like are preferable.

  In general, a propylene homopolymer is used when rigidity is required, and one or two or more random or block polypropylenes of propylene and the other monomers are used when impact characteristics are required. .

  The resin having the above-mentioned reactive functional group used in the present invention is a resin having a reactive functional group in a molecular chain, and is obtained by introducing a reactive functional group into a base resin.

  The resin serving as the base of the resin having a reactive functional group is not particularly limited, but is preferably a polyamide resin, a polyester resin, a polyphenylene sulfide resin, a polyphenylene oxide resin, a polycarbonate resin, a polylactic acid resin, a polyacetal resin, a polysulfone resin, Polytetrafluoroethylene resin, polyetherimide resin, polyamideimide resin, polyimide resin, polyethersulfone resin, polyetherketone resin, polythioetherketone resin, polyetheretherketone resin, polyethylene resin, polypropylene resin, polystyrene resin and ABS resin At least one resin selected from styrene-based resins such as rubber polymers, polyalkylene oxide resins and the like can be used. Among these, polyethylene resin, polypropylene resin, styrene resin, and rubbery polymer are more preferable as the resin serving as the base of the resin having a reactive functional group because of easy introduction of the reactive functional group.

  The reactive functional group contained in the resin having a reactive functional group is not particularly limited as long as it reacts with the functional group present in the thermoplastic resin A, but is preferably an amino group, a carboxyl group, or a carboxyl metal. Examples thereof include at least one selected from a salt, a hydroxyl group, an acid anhydride group, an epoxy group, an isocyanate group, a mercapto group, an oxazoline group, a sulfonic acid group, and the like. Of these, amino groups, carboxyl groups, carboxyl metal salts, epoxy groups, acid anhydride groups, and oxazoline groups are more preferred because they are highly reactive and have few side reactions such as decomposition and crosslinking.

  The number of functional groups per molecular chain in the resin having a reactive functional group is not particularly limited but is usually preferably 1 to 10 and preferably 1 to 5 in order to reduce side reactions such as crosslinking. . Moreover, although the molecule | numerator which does not have a functional group at all may be contained, it is so preferable that the ratio is small.

  In the thermoplastic resin in the adhesive layer B containing a component having a reactive functional group in the molded article of the present invention, various components may be added as necessary within a range not impairing the characteristics. Examples of components that can be added include fillers, other thermoplastic resins, rubbers, and various additives.

  For example, a filler may be used as necessary to improve strength, dimensional stability, and the like. The filler may be fibrous or non-fibrous, or a combination of fibrous filler and non-fibrous filler may be used.

  Examples of the filler include glass fiber, glass milled fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone-kow fiber, metal Fibrous fillers such as fibers, wollastonite, zeolite, sericite, kaolin, mica, clay, pyrophyllite, bentonite, asbestos, talc, alumina silicate and other silicates, alumina, silicon oxide, magnesium oxide, zirconium oxide, Metal compounds such as titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, hydroxides such as magnesium hydroxide, calcium hydroxide and aluminum hydroxide, Rasubizu, ceramic beads, non-fibrous fillers such as boron nitride and silicon carbide and the like, which may be hollow, it is also possible to further combination of these fillers 2 or more. In addition, these fibrous and / or non-fibrous fillers are pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, an epoxy compound, This is preferable in terms of obtaining superior mechanical properties.

  In order to improve strength, dimensional stability and the like, when such a filler is used, the amount of the filler is not particularly limited, but it is preferably 30 to 400 parts by weight based on 100 parts by weight of the thermoplastic resin composition.

  Moreover, as long as it does not impair the characteristic of the contact bonding layer B containing the component which has a reactive functional group, as other thermoplastic resins mix | blended as needed, for example, a polyamide resin, a polyester resin, a polyphenylene sulfide resin, Polyphenylene oxide resin, polycarbonate resin, polylactic acid resin, polyacetal resin, polysulfone resin, polytetrafluoroethylene resin, polyetherimide resin, polyamideimide resin, polyimide resin, polyethersulfone resin, polyetherketone resin, polythioetherketone resin, Examples thereof include polyether ether ketone resins, polyethylene resins, polypropylene resins, styrene resins such as polystyrene resins and ABS resins, and polyalkylene oxide resins. Two or more of these thermoplastic resins can be used in combination. When such thermoplastic resins are used, the blending amount thereof is not particularly limited, but is preferably blended by 1 to 400 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition.

  Furthermore, rubbers and various additives can be blended as necessary within a range not impairing the properties of the adhesive layer B containing a component having a reactive functional group.

  Such rubbers include, for example, polybutadiene, polyisoprene, styrene-butadiene random copolymers and block copolymers, hydrogenated block copolymers, acrylonitrile-butadiene copolymers, butadiene-isoprene copolymers, and the like. Diene rubber, ethylene-propylene random copolymer and block copolymer, ethylene-butene random copolymer and block copolymer, ethylene and α-olefin copolymer, ethylene-acrylic acid, ethylene -Ethylene-unsaturated carboxylic acid copolymer such as methacrylic acid, ethylene-acrylic acid ester, ethylene-unsaturated carboxylic acid ester copolymer such as ethylene-methacrylic acid ester, part of unsaturated carboxylic acid is a metal salt A ethylene-acrylic acid-acrylic acid metal , Ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid metal salt copolymer such as ethylene-methacrylic acid-methacrylic acid metal salt, acrylic ester-butadiene copolymer such as butyl acrylate-butadiene copolymer Ethylene-propylene non-conjugated diene terpolymers such as elastic polymers, ethylene-fatty acid vinyl copolymers such as ethylene-vinyl acetate, ethylene-propylene-ethylidene norbornene copolymers, ethylene-propylene-hexadiene copolymers Preferred examples thereof include thermoplastic elastomers such as coalescence, butylene-isoprene copolymer, chlorinated polyethylene, polyamide elastomer, and polyester elastomer, and modified products thereof. Two or more kinds of such rubbers can be used in combination. When such rubbers are used, the blending amount thereof is not particularly limited, but is preferably blended by 1 to 400 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition.

  In addition, as various additives that can be added as necessary within a range that does not impair the characteristics of the adhesive layer B containing a component having a reactive functional group, preferably a crystal nucleating agent, a coloring inhibitor , Antioxidants such as hindered phenols and hindered amines, mold release agents such as ethylenebisstearylamide and higher fatty acid esters, plasticizers, heat stabilizers, lubricants, UV inhibitors, colorants, flame retardants, foaming agents, etc. It is done.

  These rubbers and various additives can be blended at any stage for producing the thermoplastic resin composition in the adhesive layer B containing the component having a reactive functional group in the molded article of the present invention. Yes, for example, when producing a thermoplastic resin composition with a twin screw extruder, a method of adding the resin at the same time when blending the resin, a method of adding the resin by means of side feed during melt kneading, or a resin in advance The method of adding after melt-kneading, and the method of adding to the resin of one side which comprises a thermoplastic resin composition first, melt-kneading, and mix | blending the remaining resin are mentioned.

  As a method for forming the adhesive layer B itself containing a component having a reactive functional group in the present invention, any method can be used. As a molding method, for example, extrusion molding, calendar molding, or the like is possible.

  Moreover, you may form simultaneously in the manufacture process of the sheet-like molded product 2 reinforced with fiber. Specifically, extrusion molding, calendar molding, and the like are possible.

  As described above, in the molded product according to another embodiment of the present invention, the adhesive layer B containing a component having a reactive functional group is made of a thermoplastic sheet, and the elastic modulus (a) of the sheet-shaped molded product and the injection material Alternatively, it is a molded product in which the elastic modulus (b) of the thermoplastic sheet as the adhesive layer B containing the component having a reactive functional group and the elastic modulus (c) of the press material has a relationship of a> c> b. That is, a specific thermoplastic sheet layer is interposed between a sheet-like molded product made of thermoplastic resin A and an injection material or press material using resin C as a matrix.

  FIG. 4 shows the above-described laminated configuration example of the molded body according to the present invention in comparison with the configuration example of the conventional molded body. The molded body 21 shown in FIG. 4 (A) has, for example, a configuration of only a laminated material obtained by laminating and integrating only a plurality of sheet-like molded products 22 reinforced with a thermoplastic resin (A) as a matrix. The molded body shown in FIG. 4B is composed of, for example, an injection material or a press material 23 having a thermoplastic resin (C) as a matrix, and the molded body 24 shown in FIG. 4) is a hybrid structure in which a sheet-like molded product 22 reinforced with a thermoplastic resin (A) as a matrix is laminated and integrated on both sides of a layer of an injection material or a press material 23 having a matrix). In the molded body 25 according to the embodiment of the present invention, the thermoplastic resin (A) is matted on both sides of the layer of the injection material or press material 23 using the thermoplastic resin (C) as a matrix. A material in which the thermoplastic resin (C) is used as a matrix through the thermoplastic sheet (26) containing the thermoplastic resin (B) and having the specific elastic modulus as described above. It has the structure integrally formed by 23 injection molding or press molding. In the example shown in FIG. 4D, a five-layer stacked structure of layer 22, layer 26, layer 23, layer 26, and layer 22 is used, but a three-layer stacked structure of layer 22, layer 26, and layer 23 is also used. Good.

  In the molded body having such a configuration, the types of the thermoplastic resin (A) and the thermoplastic resin (C) constituting the layers 22 and 23 are particularly limited as long as they can be joined and integrated with the thermoplastic sheet 26. It is not limited. By using the laminated structure as described above, as described above, it is possible to achieve lightness, high mechanical properties, high molding accuracy, and excellent moldability, as well as the sheet-like molded product 22 and the injection material or press material 23. Is formed by interposing a specific thermoplastic sheet 26 having an elastic modulus (b) lower than the elastic modulus (a) of the sheet-like molded product 22 and the elastic modulus (c) of the injection material or the press material 23. The energy absorption performance excellent as the whole body 25 can be expressed.

  Such a thermoplastic sheet is particularly preferably composed of a thermoplastic resin composition containing a thermoplastic resin and a resin D having a reactive functional group.

  The thermoplastic resin of the thermoplastic sheet used in the present invention is not particularly limited as long as it is a resin that can be molded by heating and melting. For example, polyamide resin, polyester resin, polyphenylene sulfide resin, polyphenylene oxide resin, polycarbonate resin , Polylactic acid resin, polyacetal resin, polysulfone resin, polytetrafluoroethylene resin, polyetherimide resin, polyamideimide resin, polyimide resin, polyethersulfone resin, polyetherketone resin, polythioetherketone resin, polyetheretherketone resin, Preferred is at least one thermoplastic resin selected from polyethylene resins, polypropylene resins, styrene resins such as polystyrene resins and ABS resins, rubbery polymers, polyalkylene oxide resins, and the like. Rukoto can.

  Among the thermoplastic resins shown above, polyamide resins, polyester resins, polyphenylene sulfide resins, styrene resins, polyphenylene oxide resins, polycarbonate resins, polylactic acid resins, and polypropylene resins are preferably used. Polyester resins and polyphenylene oxide resins are most preferably used because of their high end group reactivity. The polyamide resin, polyester resin, and polyphenylene oxide resin are as described in the description of the adhesive layer B containing the component having a reactive functional group.

  The resin D having a reactive functional group used in the present invention is a resin having a reactive functional group in a molecular chain, and is obtained by introducing a reactive functional group into a base resin.

  The resin serving as the base of the resin D having a reactive functional group is a thermoplastic resin different from the thermoplastic resin of the thermoplastic sheet described above, and is not particularly limited, but is preferably a polyamide resin, a polyester resin, or a polyphenylene sulfide. Resin, Polyphenylene oxide resin, Polycarbonate resin, Polylactic acid resin, Polyacetal resin, Polysulfone resin, Polytetrafluoroethylene resin, Polyetherimide resin, Polyamideimide resin, Polyimide resin, Polyethersulfone resin, Polyetherketone resin, Polythioetherketone Resin, polyether ether ketone resin, polyethylene resin, polypropylene resin, styrenic resin such as polystyrene resin and ABS resin, rubbery polymer, polyalkylene oxide resin, etc. It is possible to use at least one resin selected to differ from the bets thermoplastic resin. Among them, the resin serving as the base of the resin D having a reactive functional group is more preferably a polyethylene resin, a polypropylene resin, a styrene resin, or a rubbery polymer because of the ease of introduction of the reactive functional group, and further imparting shock absorption. In view of the above, a rubbery polymer is more preferable.

  The rubbery polymer generally contains a polymer having a glass transition temperature lower than room temperature, and a part of the intermolecular molecules are constrained by covalent bonds, ionic bonds, van der Waals forces, entanglements, etc. It is a coalescence. Examples of rubber polymers include polybutadiene, polyisoprene, styrene-butadiene random copolymers and block copolymers, hydrogenated products of the block copolymers, acrylonitrile-butadiene copolymers, butadiene-isoprene copolymers, and the like. Diene rubber, ethylene-propylene random copolymer and block copolymer, ethylene-butene random copolymer and block copolymer, ethylene and α-olefin copolymer, ethylene-acrylic acid, ethylene -Ethylene-unsaturated carboxylic acid copolymer such as methacrylic acid, ethylene-acrylic acid ester, ethylene-unsaturated carboxylic acid ester copolymer such as ethylene-methacrylic acid ester, part of unsaturated carboxylic acid is a metal salt A certain ethylene-acrylic acid-acrylic acid metal salt Acrylic elasticity such as ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid metal salt copolymer such as ethylene-methacrylic acid-methacrylic acid metal salt, acrylic ester-butadiene copolymer such as butyl acrylate-butadiene copolymer Polymers, copolymers of ethylene and fatty acid vinyl such as ethylene-vinyl acetate, ethylene-propylene non-conjugated diene terpolymers such as ethylene-propylene-ethylidene norbornene copolymer, ethylene-propylene-hexadiene copolymer Preferred examples include thermoplastic elastomers such as butylene-isoprene copolymer, chlorinated polyethylene, polyamide elastomer, and polyester elastomer.

  When a polyamide resin is used as the thermoplastic resin of the thermoplastic sheet, among these, from the viewpoint of compatibility, ethylene-unsaturated carboxylic acid ester copolymer, ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid metal salt copolymer A polymer is preferably used.

  The unsaturated carboxylic acid ester in the ethylene-unsaturated carboxylic acid ester copolymer is a (meth) acrylic acid ester, preferably an ester of (meth) acrylic acid and an alcohol. Specific examples of unsaturated carboxylic acid esters include (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-2-ethylhexyl, stearyl (meth) acrylate Examples include esters.

  The weight ratio of the ethylene component to the unsaturated carboxylic acid ester component in the copolymer is not particularly limited, but is preferably in the range of 90/10 to 10/90, more preferably 85/15 to 15/85.

  The number average molecular weight of the ethylene-unsaturated carboxylic acid ester copolymer is not particularly limited, but is preferably in the range of 1000 to 70000 from the viewpoint of fluidity and mechanical properties.

  Specific examples of the unsaturated carboxylic acid in the ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid metal salt copolymer include (meth) acrylic acid. Examples of unsaturated carboxylic acid metal salts include (meth) acrylic acid metal salts. Although the metal of unsaturated carboxylic acid metal salt is not specifically limited, Preferably, alkali metals, such as sodium, alkaline-earth metals, such as magnesium, zinc etc. are mentioned.

  The weight ratio of the unsaturated carboxylic acid component to the unsaturated carboxylic acid metal salt component in the ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid metal salt copolymer is not particularly limited, but preferably 95/5 to 5/95, More preferably, it is the range of 90/10-10/90.

  The number average molecular weight of the ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid metal salt copolymer is not particularly limited, but is preferably in the range of 1000 to 70000 from the viewpoint of fluidity and mechanical properties.

  The reactive functional group contained in the resin D having a reactive functional group is not particularly limited as long as it reacts with the functional group present in the thermoplastic resin (C) serving as a matrix of the injection material or the press material. However, preferably, at least one selected from an amino group, a carboxyl group, a carboxyl metal salt, a hydroxyl group, an acid anhydride group, an epoxy group, an isocyanate group, a mercapto group, an oxazoline group, a sulfonic acid group, and the like can be given. Of these, amino groups, carboxyl groups, carboxyl metal salts, epoxy groups, acid anhydride groups, and oxazoline groups are more preferred because they are highly reactive and have few side reactions such as decomposition and crosslinking.

  When the acid anhydride group is introduced into the rubbery polymer, the method can be carried out by a generally known technique and is not particularly limited. For example, maleic anhydride, itaconic anhydride, endic acid anhydride, A method of copolymerizing acid anhydrides such as citraconic anhydride and 1-butene-3,4-dicarboxylic acid anhydride and a monomer that is a raw material of the rubber polymer, grafting the acid anhydride onto the rubber polymer Or the like can be used.

  In addition, when the epoxy group is introduced into the rubbery polymer, the method can be carried out by a generally known technique and is not particularly limited. For example, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, itacon A method of copolymerizing a vinyl monomer having an epoxy group, such as a glycidyl ester compound of an α, β-unsaturated acid such as glycidyl acid, with a monomer which is a raw material of a rubbery polymer, having the above functional group A method of polymerizing a rubbery polymer using a polymerization initiator or a chain transfer agent, a method of grafting an epoxy compound onto a rubbery polymer, or the like can be used.

  Further, when the oxazoline group is introduced into the rubbery polymer, the method can be carried out by a generally known technique and is not particularly limited. For example, 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2 A method of copolymerizing a vinyl monomer having an oxazoline group such as -acryloyl-oxazoline or 2-styryl-oxazoline with a monomer which is a raw material of a rubbery polymer can be used.

  The number of functional groups per molecular chain in the resin (D) having a reactive functional group is not particularly limited, but usually 1 to 10 is preferable, and 1 to 5 in order to reduce side reactions such as crosslinking. Preferably. Moreover, although the molecule | numerator which does not have a functional group at all may be contained, it is so preferable that the ratio is small.

  Although there is no restriction | limiting in particular about the compounding ratio of the thermoplastic resin and the resin D which has a reactive functional group in the thermoplastic sheet in the said molded object, The weight Aw of the thermoplastic resin and the weight of the resin D which has a reactive functional group The ratio Aw / Bw to Bw is preferably in the range of 5/95 to 95/5, more preferably in the range of 10/90 to 90/10, and most preferably in the range of 15/85 to 85/15. When Aw / Bw is lower than 5/95, the reaction between resins D having reactive functional groups becomes remarkable, and there is a tendency that molding processing becomes difficult due to increase in viscosity, and Aw / Bw exceeds 95/5. In addition, the amount of the functional group that reacts with the thermoplastic resin is decreased, and the effect of improving the mechanical properties of the thermoplastic resin composition and the manifestation effect of unique viscoelastic behavior tend to be reduced, which is not preferable.

  Further, the thermoplastic resin composition used for the thermoplastic sheet in the molded article of the present invention has a tensile elastic modulus of E (V1) and E (V2) at tensile speeds V1 and V2 in a tensile test. When V <2, it is preferable that E (V1)> E (V2). The above relational expression is preferably established for all V1 and V2 within the range of the tensile speed of 10 mm / min to 500 mm / min, and more preferably any V1 within the range of 1 mm / min to 1000 mm / min. , V2 is preferably established.

  Further, when the tensile elongation at break is ε (V1) and ε (V2) at the tensile speeds V1 and V2, it is preferable that ε (V1) <ε (V2) when V1 <V2. The tensile elongation at break indicates the elongation at the moment of fracture. The above relational expression is preferably established for all V1 and V2 within the range of the tensile speed of 10 mm / min to 500 mm / min, and more preferably any V1 within the range of 1 mm / min to 1000 mm / min. , V2 is preferably established.

  As a method for producing a thermoplastic resin composition in the thermoplastic sheet in the molded article of the present invention, production in a molten state, production in a solution state, etc. can be used. Can be preferably used. For production in a molten state, melt kneading with an extruder, melt kneading with a kneader, or the like can be used. From the viewpoint of productivity, melt kneading with an extruder that can be continuously produced can be preferably used. For melt kneading by an extruder, one or more extruders such as a single screw extruder, a twin screw extruder, a multi screw extruder such as a four screw extruder, and a twin screw single screw compound extruder can be used. From the viewpoint of improvement in productivity, reactivity, and productivity, a multi-screw extruder such as a twin-screw extruder or a four-screw extruder can be preferably used, and a method by melt kneading using a twin-screw extruder is most preferable.

  In the case of using a twin screw extruder, there is no particular limitation, but from the viewpoint of improving kneadability and reactivity, the value of L / D0 is preferably 50 or more, more preferably 60 to 200, especially 80 to A range of 200 is more preferable. Even when a twin screw extruder having an L / D0 of less than 50 is used, the L / D0 through which the thermoplastic resin composition passes is preferably 50 or more by kneading a plurality of times. The L / D0 is a value obtained by dividing the screw length L by the screw diameter D0. The screw length is the length from the upstream end of the screw segment at the position (feed port) where the screw base material is supplied to the screw tip. Here, the raw material refers to the thermoplastic resin in the thermoplastic sheet, the resin D having a reactive functional group, a filler added as other components, thermoplastic resins, rubbers, various additives, and the like of the present invention. All the components necessary to obtain a thermoplastic resin composition are shown. The screw of the twin screw extruder is configured by combining screw segments having different lengths and shape characteristics such as full flight and kneading disc. In the extruder, the side to which raw materials are supplied may be referred to as upstream, and the side from which molten resin is discharged may be referred to as downstream.

  When an extruder having a sampling valve or the like is used for sampling from the middle of the extruder, the screw length L is “upstream of the screw segment at the position (feed port) where the raw material of the screw is supplied. It can be considered that it is the same as that kneaded by a normal extruder equal to the “length from the end portion to the sampling location” and having a screw diameter D0 equal to the screw diameter of an extruder having a sampling valve or the like. The sampling location here refers to a position on the screw shaft on the upstream side closest to the port through which the resin in the cylinder is discharged.

  Moreover, when using a twin screw extruder in the present invention, it is preferable that the screw of the twin screw extruder has a plurality of full flight zones and kneading zones from the viewpoint of improving kneadability and reactivity. . The full flight zone is composed of one or more full flights, and the kneading zone is composed of one or more kneading discs.

  When using a twin screw extruder in the present invention, among the resin pressures indicated by the resin pressure gauges installed in a plurality of kneading zones, the maximum kneading zone resin pressure is Pkmax (MPa), Of the resin pressures indicated by the resin pressure gauges installed in the full flight zone, assuming that the minimum resin pressure in the full flight zone is Pfmin (MPa), the value of Pkmax is set to (Pfmin + 0.3) or more. The thermoplastic resin composition of the invention is preferably produced, more preferably (Pfmin + 0.4) or more, and further preferably (Pfmin + 0.5) or more. A kneading zone composed of one or more kneading discs is more excellent in kneadability and reactivity of the molten resin than a full flight zone composed of one or more full flights. By filling the kneading zone with the molten resin, the kneading property and the reactivity are drastically improved. As an index indicating the state of filling of the molten resin, there is a value of the resin pressure, and the larger the resin pressure, the more standard the molten resin is filled. That is, when a twin screw extruder is used in the present invention, the reaction can be effectively promoted by increasing the resin pressure in the kneading zone within a certain range from the resin pressure in the full flight zone. In the tensile test, when the tensile elastic modulus is E (V1) and E (V2) at the tensile speeds V1 and V2, the characteristic of E (V1)> E (V2) is prominent when V1 <V2. It can be expressed.

  There are no particular restrictions on how to increase the resin pressure in the kneading zone, but there is an effect of accumulating the reverse screw zone and the molten resin between the kneading zones and downstream of the kneading zone, which has the effect of pushing the molten resin upstream. For example, a method of introducing a seal ring zone having a gap is preferably used. The reverse screw zone and the seal ring zone are composed of one or more reverse screws and one or more seal rings, which can be combined.

  In the thermoplastic resin composition in the thermoplastic sheet in the molded article of the present invention, other components other than the thermoplastic resin and the resin D may be added as necessary within the range not impairing the characteristics. Absent. Examples of other components include fillers, thermoplastic resins, rubbers, and various additives.

  For example, a filler may be used as necessary to improve strength, dimensional stability, and the like. The filler may be fibrous or non-fibrous, or a combination of fibrous filler and non-fibrous filler may be used.

  As the filler, as described above, glass fiber, glass milled fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber , Fibrous filler such as stone fiber, metal fiber, wollastonite, zeolite, sericite, kaolin, mica, clay, pyrophyllite, bentonite, asbestos, talc, alumina silicate and other silicates, alumina, silicon oxide, Metal compounds such as magnesium oxide, zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, magnesium hydroxide, calcium hydroxide and aluminum hydroxide Non-fibrous fillers such as hydroxides, glass beads, ceramic beads, boron nitride and silicon carbide, etc., may be hollow, and two or more of these fillers may be used in combination. Is possible. In addition, these fibrous and / or non-fibrous fillers are pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, an epoxy compound, This is preferable in terms of obtaining superior mechanical properties.

  When using such a filler in order to improve strength, dimensional stability, etc., the amount of the filler is not particularly limited, but as described above, 30 to 400 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition. It is preferable to mix.

  Moreover, in the thermoplastic resin composition in the thermoplastic sheet in the molded article of the present invention, other thermoplastic resins can be blended as necessary within a range not impairing the characteristics.

  Examples of such thermoplastic resins include polyamide resins, polyester resins, polyphenylene sulfide resins, polyphenylene oxide resins, polycarbonate resins, polylactic acid resins, polyacetal resins, polysulfone resins, tetrafluoropolyethylene resins, polyetherimide resins, polyamideimides. Resin, polyimide resin, polyethersulfone resin, polyetherketone resin, polythioetherketone resin, polyetheretherketone resin, polyethylene resin, polypropylene resin, styrene resin such as polystyrene resin and ABS resin, polyalkylene oxide resin, etc. It is done. Two or more of these thermoplastic resins can be used in combination. When such thermoplastic resins are used, the blending amount thereof is not particularly limited, but is preferably blended by 1 to 400 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition.

  Furthermore, in the thermoplastic resin composition in the thermoplastic sheet in the molded article of the present invention, other rubbers and various additives can be blended as necessary within the range not impairing the characteristics.

  Examples of the various additives that can be added to the rubber and the thermoplastic resin composition in the thermoplastic sheet in the molded body include the same as those exemplified for the adhesive layer B described above.

  Also, these rubbers and various additives can be blended at any stage for producing the thermoplastic resin composition in the thermoplastic sheet in the molded article of the present invention, as described above. For example, when a thermoplastic resin composition is produced by a twin screw extruder, a method of adding the resin at the same time when blending the resin, a method of adding the resin by a method such as side feed during melt kneading, Examples thereof include a method of adding after melt-kneading, and a method of first adding to one resin constituting the thermoplastic resin composition and blending the remaining resin after melt-kneading.

  When the thermoplastic resin composition in the thermoplastic sheet in the molded body of the present invention is produced by a twin screw extruder, a supercritical fluid is introduced from the viewpoint of improving the reactivity when melt kneading with the twin screw extruder. You can also Such a supercritical fluid is a fluid that exceeds the limit point (critical point) at which gas and liquid can coexist, and has both gas properties (diffusibility) and liquid properties (solubility). is there. Such supercritical fluids include supercritical carbon dioxide, supercritical nitrogen, supercritical water, etc., preferably supercritical carbon dioxide and supercritical nitrogen can be used, most preferably supercritical carbon dioxide can be used. .

  Any method can be used as the method for molding the thermoplastic sheet in the molded article of the present invention. As a molding method, for example, extrusion molding, calendar molding, or the like is possible.

  The elastic modulus of the thermoplastic sheet or the like in the molded body of the present invention is, for example, cut out a test piece of length × width × thickness = 85 mm × 20 mm × 0.5 mm from the sheet, and performs a bending test in accordance with ASTM D790, This bending elastic modulus can be used as an index of rigidity as an elastic modulus in the present invention.

  The resin in the resin composition constituting the portion having a higher elastic modulus (rigidity) than the thermoplastic sheet in the molded article of the present invention is not particularly limited. For example, polyamide resin, polyester resin, polyphenylene sulfide resin, polyphenylene Oxide resin, polycarbonate resin, polylactic acid resin, polyacetal resin, polysulfone resin, polytetrafluoroethylene resin, polyetherimide resin, polyamideimide resin, polyimide resin, polyethersulfone resin, polyetherketone resin, polythioetherketone resin, poly Ether ether ketone resin, polyethylene resin, polypropylene resin, styrene resin such as polystyrene resin and ABS resin, thermoplastic resin such as rubber polymer, polyalkylene oxide resin, epoxy resin, phenol resin , And the like thermosetting resin such as urea resin.

  Moreover, it is preferable that the resin composition which comprises a part with higher elastic modulus (rigidity) than the thermoplastic sheet in the molded object of this invention contains a filler for the purpose of improving rigidity. The shape of the filler may be fibrous or non-fibrous, and a combination of fibrous filler and non-fibrous filler may be used.

  Examples of the filler include glass fiber, glass milled fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone-kow fiber, metal Fibrous fillers such as fibers, wollastonite, zeolite, sericite, kaolin, mica, clay, pyrophyllite, bentonite, asbestos, talc, alumina silicate and other silicates, alumina, silicon oxide, magnesium oxide, zirconium oxide, Metal compounds such as titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, hydroxides such as magnesium hydroxide, calcium hydroxide and aluminum hydroxide, Rasubizu, ceramic beads, non-fibrous fillers such as boron nitride and silicon carbide and the like, which may be hollow, it is also possible to further combination of these fillers 2 or more.

  Among them, preferable fillers include fibrous fillers such as glass fiber, glass milled fiber, carbon fiber, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone koji fiber, metal fiber, etc. More preferable examples include glass fiber and carbon fiber.

  In addition, these fibrous and / or non-fibrous fillers are pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, an epoxy compound, This is preferable in terms of obtaining superior mechanical properties.

  When such a filler is used, the amount of the filler is not particularly limited, but it is preferably 10 to 400 parts by weight based on 100 parts by weight of the resin composition.

  The molded body of the present invention has the laminated structure as described above, has a sufficiently high rigidity under a static load, has a low maximum load applied to an object when subjected to a high-speed impact, and has a large energy. To absorb.

  The thermoplastic sheet in the molded article of the present invention is characterized by a large peak value of loss tangent (tan δ), and exhibits excellent characteristics such as vibration energy absorption performance. For this reason, it is particularly useful for applications that require sound absorption, heat absorption, vibration control, seismic isolation, and the like.

Next, an embodiment of the fiber-reinforced resin injection molded body of the present invention will be described with reference to the drawings.
FIG. 5 shows a fiber-reinforced resin injection molded body according to one embodiment of the present invention. In the present embodiment, the fiber reinforced resin injection molded body 31 includes a flat fiber or sheet-like first fiber reinforced resin 32 and a flat or sheet-like second fiber reinforced resin 33 formed from the second fibers. The reinforcing resin 33 is integrally joined and molded through injection molding. The first fiber reinforced resin 32 is made of a fiber reinforced resin containing a first reinforced fiber (for example, carbon fiber) made of continuous fibers and having a first linear expansion coefficient, and the second fiber reinforced resin 33 is A fiber reinforced resin comprising discontinuous fibers and containing a second reinforcing fiber (for example, glass fiber) different from the first reinforcing fiber and having a second linear expansion coefficient different from the first linear expansion coefficient Consists of. Through the injection molding of the second fiber reinforced resin 33, the second fiber reinforced resin 33 and the first fiber reinforced resin 32 are integrally joined and molded, and the fiber reinforced resin injection molding material 31 having a hybrid configuration is formed. It is configured. The second fiber reinforced resin 33 is made of discontinuous fibers in addition to the second reinforcing fibers, and contains the same type of reinforcing fibers (for example, carbon fibers) as the first reinforcing fibers. As the linear expansion coefficient, the linear expansion coefficient between the first linear expansion coefficient and the third linear expansion coefficient when the second fiber reinforced resin 33 contains only the second reinforcing fiber as the reinforcing fiber. have.

  In such an embodiment, the difference in linear expansion coefficient between the second fiber reinforced resin 33 and the first fiber reinforced resin 32 to be injection molded is reduced, and the first fiber reinforced resin 32 and the second fiber reinforced resin 32 The mechanical properties of the joint portion with the fiber reinforced resin 33 are ensured to be high, and peeling between the two fiber reinforced resins 32 and 33 at the joint portion is prevented, and excellent properties at the joint portion are ensured. .

  FIG. 6 shows a fiber-reinforced resin injection molded body according to another embodiment of the present invention. In this embodiment, the fiber reinforced resin injection molded body 41 is provided with two flat or sheet-like first fiber reinforced resins 42 and 43 on the upper and lower sides of the figure, and both the first fiber reinforced resins 42 and 43. A second fiber reinforced resin 46 formed in a flat web portion 45 having a rib-like portion 44 is interposed between the first fiber reinforced resins 42 and 43 and the second fiber reinforced resin 46. The second fiber reinforced resin 46 is integrally joined and molded through injection molding. As in the previous embodiment, the first fiber reinforced resins 42 and 43 are made of a fiber reinforced resin containing a first reinforced fiber (for example, carbon fiber) made of continuous fibers and having a first linear expansion coefficient, The second fiber reinforced resin 46 is made of discontinuous fibers, contains a second reinforcing fiber (for example, glass fiber) that is different from the first reinforcing fiber, and is different from the first linear expansion coefficient. It consists of fiber reinforced resin which has the linear expansion coefficient of. The second fiber reinforced resin 46 is made of discontinuous fibers in addition to the second reinforced fibers and contains the same type of reinforced fibers (for example, carbon fibers) as the first reinforced fibers. As the expansion coefficient, a linear expansion coefficient between the first linear expansion coefficient and the third linear expansion coefficient when the second fiber reinforced resin 46 contains only the second reinforcing fiber as the reinforcing fiber is Have.

  In such an embodiment, the rib-like portion 44 is provided with respect to the flat-plate-like web portion 45, so that the second fiber reinforced resin 46 is joined to the first fiber reinforced resins 42 and 43. In addition, there is a change portion of the cross-sectional shape and a thickness change portion where the thickness of the second fiber reinforced resin 46 changes. Due to the presence of the change part of the cross-sectional shape and the change part of the thickness, the heat which shows the heat shrinkage behavior different from other parts in the vicinity of the joint surface of the second fiber reinforced resin 46 with the first fiber reinforced resin 42, 43. A contraction behavior changing portion is generated. However, in this embodiment, since the difference in the linear expansion coefficient between the second fiber reinforced resin 46 and the first fiber reinforced resin 42 and 43 to be injection-molded is reduced, the heat shrinkage caused by this difference. The change in behavior is also suppressed to a small extent, and the possibility that separation between the two fiber reinforced resins at the joint portion or a locally low portion in the mechanical properties of the joint portion is reliably eliminated. Other actions and effects are the same as in the above-described embodiment.

  FIG. 7 shows a fiber-reinforced resin injection molded body according to still another embodiment of the present invention. In this embodiment, the fiber reinforced resin injection molded body 51 is provided with two flat or sheet-like first fiber reinforced resins 52 and 53 on the upper and lower sides of the figure, and both the first fiber reinforced resins 52 and 53 are provided. A second fiber reinforced resin 56 formed on a flat web portion 55 having a rib-like portion 54 extending in a corrugated or zigzag manner is interposed between the first fiber reinforced resins 52 and 53. And the second fiber reinforced resin 56 are integrally joined and molded through injection molding of the second fiber reinforced resin 56. Similar to the above-described embodiment, the first fiber reinforced resins 52 and 53 are made of a fiber reinforced resin containing a first reinforcing fiber (for example, carbon fiber) made of continuous fibers and having a first linear expansion coefficient, The second fiber reinforced resin 56 is made of discontinuous fibers, contains second reinforced fibers (for example, glass fibers) that are different from the first reinforced fibers, and is different from the first linear expansion coefficient. It consists of fiber reinforced resin which has the linear expansion coefficient of. The second fiber reinforced resin 56 is made of discontinuous fibers in addition to the second reinforcing fibers, and contains the same type of reinforcing fibers (for example, carbon fibers) as the first reinforcing fibers. As the expansion coefficient, a linear expansion coefficient between the first linear expansion coefficient and the third linear expansion coefficient when the second fiber reinforced resin 56 contains only the second reinforcing fiber as the reinforcing fiber is Have.

  In such an embodiment, as in the above-described embodiment, the second fiber is provided by providing the rib-like portion 54 extending in a corrugated or zigzag manner with respect to the flat web portion 55. That the reinforced resin 56 is joined to the first fiber reinforced resins 52 and 53, the cross-sectional shape changing portion exists, and the second fiber reinforced resin 56 has a thickness changing portion where the thickness changes. Become. Due to the presence of the change part of the cross-sectional shape and the change part of the thickness, the heat which shows the heat shrinkage behavior different from other parts in the vicinity of the joint surface of the second fiber reinforced resin 56 with the first fiber reinforced resin 52, 53. A contraction behavior changing portion is generated. However, in this embodiment, since the difference in the linear expansion coefficient between the second fiber reinforced resin 56 and the first fiber reinforced resin 52, 53 to be injection-molded is reduced, the heat shrinkage caused by this difference. The change in behavior is also suppressed to a small extent, and the possibility that separation between the two fiber reinforced resins at the joint portion or a locally low portion in the mechanical properties of the joint portion is reliably eliminated. Other actions and effects are the same as in the above-described embodiment.

  Thus, various forms can be taken about each form of 1st fiber reinforced resin and 2nd fiber reinforced resin, and the joining form of both.

Example 1
A component having a reactive functional group made of acid anhydride-modified polypropylene (acid anhydride-modified PP) on the surface of a sheet-like molded product reinforced with carbon fiber, using polyamide (PA) as a matrix resin as the thermoplastic resin A Adhesive material (injection molded product) using resin C made of polypropylene (PP) as a matrix is bonded via the adhesive layer B contained, and the bonding strength is measured by the shear test shown in FIG. 3 to evaluate the adhesive performance. did. As a result, as shown in Table 1, a high bonding strength of 10 MPa was obtained, and the fracture mode in the shear test was a matrix fracture (destruction of a portion other than the adhesive layer B containing a component having a reactive functional group). It was confirmed that they were joined with sufficiently high strength.

Example 2
Adhesion containing polyphenylene sulfide (PPS) as a thermoplastic resin A as a matrix resin and a component having a reactive functional group made of imide-modified polyamide (imide-modified PA) on the surface of a sheet-like molded product reinforced with carbon fiber Through the layer B, an injection material (injection molded product) having a resin C made of polyamide (PA) as a matrix was bonded, and the bonding strength was measured by a shear test shown in FIG. 3 to evaluate the bonding performance. As a result, as shown in Table 1, a high bonding strength of 8 MPa was obtained, and the fracture mode in the shear test was a matrix fracture (destruction of a portion other than the adhesive layer B containing a component having a reactive functional group). It was confirmed that they were joined with sufficiently high strength.

Comparative Example 1
As a thermoplastic resin A, polyamide (PA) is used as a matrix resin, and a sheet-like molded product reinforced with carbon fiber and an injection material (injection molded product) using a resin C made of polypropylene (PP) as a matrix are used as an injection material. Were bonded through an adhesive layer B containing a component having a reactive functional group made of the same or the same type of polypropylene (PP), and the bonding strength was measured by a shear test shown in FIG. 3 to evaluate the bonding performance. As a result, as shown in Table 1, only a low bonding strength of 1 MPa was obtained, and the fracture mode in the shear test was an interfacial fracture in the adhesive layer B portion containing a component having a reactive functional group, and a sufficiently high bond It was confirmed that the strength was not obtained.

Comparative Example 2
A sheet-shaped molded product reinforced with carbon fibers and polyphenylene sulfide (PPS) as a thermoplastic resin A and an injection material (injected molded product) using a resin C made of polyamide (PA) as a matrix. Adhesion performance is measured by using a shear test shown in FIG. 3 and bonding strength is measured through an adhesive layer B containing a component having a reactive functional group composed of the same or the same type of polyphenylene sulfide (PPS) as the molded article. Evaluated. As a result, as shown in Table 1, only a low bonding strength of 1 MPa was obtained, and the fracture mode in the shear test was an interfacial fracture in the adhesive layer B portion containing a component having a reactive functional group, and a sufficiently high bond It was confirmed that the strength was not obtained.

Example 3
A component having a reactive functional group made of acid anhydride-modified polypropylene (acid anhydride-modified PP) on the surface of a sheet-like molded product reinforced with carbon fiber, using polyamide (PA) as a matrix resin as the thermoplastic resin A A press material (press-molded product) having a resin C made of polypropylene (PP) as a matrix is bonded via the adhesive layer B contained, and the bonding strength is measured by the shear test shown in FIG. 3 to evaluate the adhesive performance. did. As a result, as shown in Table 2, a high bonding strength of 9 MPa was obtained, and the fracture mode in the shear test was a base material fracture (fracture of a portion other than the adhesive layer B containing a component having a reactive functional group). It was confirmed that they were joined with sufficiently high strength.

Example 4
Adhesion containing polyphenylene sulfide (PPS) as a thermoplastic resin A as a matrix resin and a component having a reactive functional group made of imide-modified polyamide (imide-modified PA) on the surface of a sheet-like molded product reinforced with carbon fiber A press material (press-molded product) using a resin C made of polyamide (PA) as a matrix was bonded via the layer B, and the bonding strength was measured by a shear test shown in FIG. 3 to evaluate the bonding performance. As a result, as shown in Table 2, a high bonding strength of 7 MPa was obtained, and the fracture mode in the shear test was a matrix fracture (destruction of a portion other than the adhesive layer B containing a component having a reactive functional group). It was confirmed that they were joined with sufficiently high strength.

Comparative Example 3
As a thermoplastic resin A, polyamide (PA) is used as a matrix resin, a sheet-like molded product reinforced with carbon fibers, and a press material (press-molded product) using a resin C made of polypropylene (PP) as a matrix is used as an injection material. Were bonded through an adhesive layer B containing a component having a reactive functional group made of the same or the same type of polypropylene (PP), and the bonding strength was measured by a shear test shown in FIG. 3 to evaluate the bonding performance. As a result, as shown in Table 2, only a low bonding strength of 1 MPa was obtained, and the fracture mode in the shear test was an interface fracture in the adhesive layer B portion containing the component having a reactive functional group, and a sufficiently high bond It was confirmed that the strength was not obtained.

Comparative Example 4
A sheet-shaped molded product reinforced with carbon fiber and polyphenylene sulfide (PPS) as a thermoplastic resin A and a press material (press-molded product) using a resin C made of polyamide (PA) as a matrix. Adhesion performance is measured by using a shear test shown in FIG. 3 and bonding strength is measured through an adhesive layer B containing a component having a reactive functional group composed of the same or the same type of polyphenylene sulfide (PPS) as the molded article. Evaluated. As a result, as shown in Table 2, only a low bonding strength of 1 MPa was obtained, and the fracture mode in the shear test was an interface fracture in the adhesive layer B portion containing the component having a reactive functional group, and a sufficiently high bond It was confirmed that the strength was not obtained.

  The molded body according to the present invention is particularly excellent in all uses where it is desired to produce a molded body having high mechanical properties and high bonding strength with excellent moldability, and having high mechanical properties. It can be deployed in any application where it is desired to develop energy absorption performance.

DESCRIPTION OF SYMBOLS 1,11 Molded body 2 Sheet-shaped molded article 3 Adhesive layer 4 Injection material or press material 22 Sheet-shaped molded article 23 Injection material 25 Molded body 26 according to embodiments of the present invention Thermoplastic sheets 31, 41, 51 Fiber-reinforced resin injection Molding materials 32, 42, 43, 52, 53 First fiber reinforced resin 33, 46, 56 Second fiber reinforced resin 44, 54 Rib-shaped portion 45, 55 Web portion

Claims (6)

A molded body formed by integrally molding an injection material or a press material with a resin C different from the resin A as a matrix, on the surface of a fiber-reinforced sheet-like molded product using the resin A as a matrix resin. A molded article in which the resin A, the adhesive layer B, and the resin C are formed of any combination of the following (1) and (2).
(1) Resin A: polyamide, adhesive layer B: acid anhydride-modified polypropylene having a reactive functional group that reacts with resin A , resin C: polypropylene (2) resin A: polyphenylene sulfide, adhesive layer B: reacts with resin A Modified polyamide having a reactive functional group , resin C: polyamide The fibers in the sheet-shaped molded article is continuous, molded product according to claim 1. The molded object of Claim 1 or 2 containing a carbon fiber as a fiber in the said sheet-like molded product. The adhesive layer B is made of a thermoplastic sheet, and the elastic modulus (a) of the sheet-like molded product, the elastic modulus (c) of the injection material or press material, and the elastic modulus (b) of the thermoplastic sheet are as follows. The molded article according to any one of claims 1 to 3 .
a>c> b The thermoplastic sheet satisfies E (V1)> E (V2) when V1 <V2 when the tensile elastic modulus is E (V1) and E (V2) at the tensile speeds V1 and V2 in the tensile test. The molded product according to claim 4 . The molded article according to any one of claims 1 to 5, which has the following shape (A) or (B).
(A) The sheet-like molded product is composed of two flat or sheet-like first fiber reinforced resins arranged to face each other with a gap therebetween, and the resin C is different from the first fiber reinforced resin. A second fiber reinforced resin, comprising a flat web portion and a rib-like portion extending in a direction perpendicular to the web portion, interposed between the two first fiber reinforced resins. A shape made of a fiber reinforced resin, in which the first fiber reinforced resin and the second fiber reinforced resin are integrally formed through injection molding of the second fiber reinforced resin .
(B) The sheet-like molded product is composed of two flat or sheet-like first fiber reinforced resins that are arranged to face each other with a gap therebetween, and the resin C is different from the first fiber reinforced resin. A second fiber reinforced resin, which is interposed between two sheets of the first fiber reinforced resin and extends in a corrugated or zigzag manner between the flat web portion and the two sheets of the first fiber reinforced resin. A second fiber reinforced resin having a rib-shaped portion formed, and the first fiber reinforced resin and the second fiber reinforced resin are integrally formed through injection molding of the second fiber reinforced resin. Shape.

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