WO2014112501A1 - Corps moulé - Google Patents

Corps moulé Download PDF

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Publication number
WO2014112501A1
WO2014112501A1 PCT/JP2014/050526 JP2014050526W WO2014112501A1 WO 2014112501 A1 WO2014112501 A1 WO 2014112501A1 JP 2014050526 W JP2014050526 W JP 2014050526W WO 2014112501 A1 WO2014112501 A1 WO 2014112501A1
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WO
WIPO (PCT)
Prior art keywords
resin
fiber
thermoplastic
sheet
molded
Prior art date
Application number
PCT/JP2014/050526
Other languages
English (en)
Japanese (ja)
Inventor
山口晃司
松岡英夫
清水信彦
Original Assignee
東レ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to JP2014557471A priority Critical patent/JP6395050B2/ja
Publication of WO2014112501A1 publication Critical patent/WO2014112501A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14778—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the article consisting of a material with particular properties, e.g. porous, brittle
    • B29C45/14811—Multilayered articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14778—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the article consisting of a material with particular properties, e.g. porous, brittle
    • B29C45/14786—Fibrous material or fibre containing material, e.g. fibre mats or fibre reinforced material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2715/00—Condition, form or state of preformed parts, e.g. inserts
    • B29K2715/006—Glues or adhesives, e.g. hot melts or thermofusible adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic

Definitions

  • 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.
  • 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 enclosing a resin film in carbon fiber reinforced plastic (CFRP).
  • CFRP carbon fiber reinforced plastic
  • 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.
  • 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.
  • thermoplastic resin A is molded in advance, and the other thermoplastic resin is molded.
  • 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.
  • various reinforcing fibers such as carbon fiber, glass fiber and aramid fiber are known as the reinforcing fiber of the fiber reinforced resin.
  • 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.
  • 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.
  • a molded body having a laminated integrated structure 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.
  • 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.
  • 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.
  • An 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.
  • 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.
  • 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. It is formed by integrally molding with an injection material or a press material.
  • the adhesive layer B has a composition different from both the resin A and the resin C.
  • a molded body according to the present invention when a layer having a resin A as a matrix resin and a resin C different from the resin A as a matrix is bonded to the surface of the fiber-reinforced sheet-like molded product, while the adhesive layer B is interposed, 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. 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.
  • the layer of resin C is shape
  • the layer part of resin C is shape
  • the resin C layer is joined to the sheet-like molded product made of the fiber reinforced resin layer together with the resin C layer by injection molding or press molding through the adhesive layer B, the joining itself is extremely easy. 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.
  • the adhesive layer B is preferably a thermoplastic resin having a reactive functional group that reacts with the resin A.
  • the adhesive layer B is made of such a specific thermoplastic resin, higher bonding strength with a sheet-like molded product made of the resin A is obtained, and higher bonding strength is obtained for the entire molded body.
  • reactive functional group that reacts with the resin A various reactive functional groups can be employed. From the viewpoint of high bonding strength, for example, amino groups, carboxyl groups, carboxyl metal salts, epoxy groups, among others. And at least one selected from an acid anhydride group and an oxazoline group.
  • thermoplastic resin constituting the adhesive layer B various thermoplastic resins can be used. Particularly, polyamide resin, polyester resin, polyphenylene sulfide resin, styrene resin, polyphenylene oxide resin, polycarbonate resin, It is preferably at least one selected from polylactic acid resins, polypropylene resins, and modified resins thereof.
  • 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 preferable to consist of a thermoplastic resin composition formed by blending resin D.
  • 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.
  • 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.
  • 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.
  • An epoxy group, an acid anhydride group, and an oxazoline group are preferable.
  • 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.
  • 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.
  • the fibers in the sheet-shaped molded article are continuous reinforcing fibers.
  • 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.
  • 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.
  • 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.
  • the adhesive layer B is made of a thermoplastic sheet, and the elastic modulus (a) of the sheet-like molded product and the elastic modulus (c) of the injection material or press material are bonded.
  • a molded body in which the elastic modulus (b) of the thermoplastic sheet as the layer B is in the following relationship can be exemplified. a>c> b
  • 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.
  • 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.
  • the thermoplastic sheet in order to express the excellent energy absorption performance more reliably, 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.
  • a preferred fiber reinforced resin injection-molded body comprises a first fiber reinforced resin having a first linear expansion coefficient containing a first reinforced fiber composed of continuous fibers, and a discontinuous fiber.
  • a second fiber reinforced resin containing a second reinforced fiber different from the first reinforced fiber and having a second linear expansion coefficient different from the first linear expansion coefficient.
  • a fiber reinforced resin injection molding material having a hybrid structure integrally joined and molded through injection molding of the above, wherein the second fiber reinforced resin comprises discontinuous fibers in addition to the second reinforced fibers. It contains the same type of reinforcing fiber as the first reinforcing fiber, the first linear expansion coefficient as the second linear expansion coefficient, and the second reinforcing fiber as the second fiber reinforced resin as the reinforcing fiber. Between the third linear expansion coefficient when containing only Also it provides for a fiber-reinforced resin injection molded article characterized by having a few.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • an inexpensive fiber-reinforced resin injection molded body is realized.
  • 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.
  • 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 changing part is generated as follows, for example.
  • a cross-sectional shape changing portion on the joint surface of the second fiber reinforced resin with the first fiber reinforced resin 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.
  • 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.
  • a form in which the heat shrinkage behavior changing portion is generated due to the presence of the thickness changing portion is exemplified.
  • 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.
  • 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.
  • the first reinforcing fiber oriented in one direction 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.
  • the resin A is a matrix resin.
  • the adhesive layer B is interposed therebetween, 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. Bonding and integration can be performed with injection molding or press molding, and it is possible to easily realize a molded body made of a laminate having high bonding strength and taking advantage of the high mechanical properties of the sheet-like molded product layer with good moldability.
  • thermoplastic resin having a reactive functional group that reacts with the resin A as the thermoplastic resin constituting the adhesive layer B, a molded body having higher bonding strength can be obtained.
  • a material in which the resin A is a matrix resin and the fiber-reinforced sheet-like molded product is a resin C as a matrix through a specific thermoplastic sheet.
  • thermoplastic sheet having an elastic modulus (b) lower than the elastic modulus (a) of the sheet-shaped molded article and the elastic modulus (c) of the injection material or the press material between the press materials, As a whole, excellent energy absorption performance can be exhibited.
  • the second fiber reinforced resin to be injection-molded is also made of discontinuous fibers.
  • 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.
  • the second fiber reinforced resin to be injection-molded and the first fiber reinforced resin 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 risk of peeling between the resins, Keru excellent characteristics can be ensured. Thereby, it is possible to realize preferable excellent characteristics over the entire molded product integrated by injection molding of the second fiber reinforced resin.
  • the molded body according to the present invention is configured, for example, as shown in FIG.
  • the molded body 1 according to an embodiment of the present invention includes a resin C different from the resin A via the adhesive layer B (3) on the surface of the fiber-reinforced sheet-shaped molded product 2 using the resin A as a matrix resin. It is integrally formed with an injection material or a press material 4 as a matrix.
  • the adhesive layer B (3) is preferably made of a thermoplastic resin having a reactive functional group that reacts with the resin A. 1 shows a molded body 1 having a three-layer structure of a sheet-shaped molded article 2, an adhesive layer B (3), an injection material or a press material 4, but other laminated structures such as FIG.
  • the sheet-shaped molded product 2 the adhesive layer B (3), the injection material or press material 4
  • the adhesive layer B (3) the five-layered sheet-shaped molded product 2, etc. It is also possible to do.
  • 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.
  • the resin A is a matrix resin
  • a resin different from the resin A is formed on a part of the surface of the test piece of the fiber-reinforced sheet-like molded product 2 via the adhesive layer B (3).
  • a test sample is manufactured by integrally molding with an injection material (injection molding product) using C as a matrix or a test piece of press material 4, and an end portion on the sheet-like molding product 2 side and an injection material or press material 4 side are prepared.
  • the end part is gripped by the chuck parts 5 and 6 of the tensile tester, and the sheet-like molded product 2 and the injection material or press material 4 are applied so that a shear load is applied to the joint by the adhesive layer B (3) by the tensile tester.
  • the joint strength is quantitatively measured by pulling in a direction opposite to each other and measuring a tensile load when the joint portion caused by the adhesive layer B (3) breaks or deforms more than a predetermined amount (for example, interface fracture).
  • a predetermined amount for example, interface fracture
  • the resin C constituting the injection material or the press material is not particularly limited.
  • 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.
  • resin A which comprises the fiber-reinforced sheet-like molded product
  • the thermoplastic resin similar to resin C can be used. These resin layers only need to be bonded via the adhesive layer B.
  • Such an adhesive layer B is particularly preferably made of a thermoplastic resin having a reactive functional group that reacts with the resin A.
  • the thermoplastic resin constituting the adhesive layer B is at least one selected from polyamide resin, polyester resin, polyphenylene sulfide resin, styrene resin, polyphenylene oxide resin, polycarbonate resin, polylactic acid resin, polypropylene resin, and modified resins thereof. It is preferable to use seeds, and polyamide resins, polyester resins, polyphenylene oxide resins, and modified resins thereof are more preferably used because of their high end group reactivity.
  • the polyamide resin is a resin composed of a polymer having an amide bond, and is mainly composed of amino acid, lactam or diamine and dicarboxylic acid.
  • the raw materials include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, lactams such as ⁇ -caprolactam and ⁇ -laurolactam, tetramethylenediamine, penta Methylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, undecameethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylene Diamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,
  • polyamide resin particularly useful for the adhesive layer B examples include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polypentamethylene adipamide (nylon). 56), polytetramethylene adipamide (nylon 46), polyhexamethylene sebamide (nylon 610), polypentamethylene sebacamide (nylon 510), polyhexamethylene dodecamide (nylon 612), polyundecanamide ( Nylon 11), polydodecanamide (nylon 12), polycaproamide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66 / 6T), polyhexamethyle Adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (n
  • 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.
  • 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.
  • 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.
  • 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.
  • dicarboxylic acid examples 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.
  • aromatic dicarboxylic acids such as 5-sodiumsulfoisophthalic acid
  • aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc.
  • alicyclic dicarboxylic acids and ester-forming derivatives thereof are examples of aromatic dicarboxylic acids and ester-forming derivatives thereof.
  • the diol component includes aliphatic glycols 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 Examples include naphthalate and polycyclohexanedimethylene terephthalate.
  • polyester compositions To polybutylene terephthalate, polybutylene (terephthalate / adipate), polybutylene (terephthalate / decanedicarboxylate), 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.
  • polybutylene terephthalate resins having different intrinsic viscosities may be used in combination, and the intrinsic viscosity is preferably in the range of 0.35 to 2.00.
  • polybutylene terephthalate resins having a COOH end group amount determined by potentiometric titration of an m-cresol solution with an alkaline solution in the range of 1 to 50 eq / t (end group amount per ton of polymer) are durable. From the point of anisotropy suppressing effect, it can be preferably used.
  • polyphenylene oxide resin examples 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), etc.
  • a copolymer such as a copolymer of 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol) can be mentioned.
  • 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 known methods 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.
  • polypropylene resin examples include a homopolymer of propylene or a copolymer of propylene and at least one ⁇ -olefin, conjugated diene, non-conjugated diene, or the like.
  • Examples of the monomer repeating unit constituting the ⁇ -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, 1-dodecene, etc.
  • propylene such as 1-hexene, 4,4 dimethyl-1-hexene, 1-nonene, 1-octene, 1-heptene, 1-hexene, 1-decene, 1-undecene, 1-dodecene, etc.
  • Examples of the monomer repeating unit constituting the ⁇ -olefin, conjugated diene, and non-conjugated diene include butadiene, ethylidene norbornene, dicyclopentadiene, 1,5-hexadiene, and the other monomer repeating units. 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.
  • polypropylene, ethylene / propylene copolymer, propylene / 1-butene copolymer, ethylene / propylene / 1-butene copolymer, and the like are preferable.
  • 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.
  • 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 resin A, but preferably an amino group, a carboxyl group, a carboxyl metal salt, Examples include at least one selected from 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. .
  • numerator which does not have a functional group at all may be contained, it is so preferable that the ratio is small.
  • thermoplastic resin in the adhesive layer B in the molded body of the present invention various components may be added as necessary within the range not impairing the characteristics.
  • components that can be added include fillers, other thermoplastic resins, rubbers, and various additives.
  • a filler may be used as necessary to improve strength and dimensional stability.
  • the filler may be fibrous or non-fibrous, or a combination of fibrous filler and non-fibrous filler may be used.
  • the filler examples 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 Glass beads, 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
  • 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.
  • a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, an epoxy compound
  • 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.
  • thermoplastic resins to be blended as necessary within the range not impairing the properties of the adhesive layer B include, 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, Polyethylene resin, Polypropylene Examples thereof include resins, styrene resins such as polystyrene resin and ABS resin, 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 it is preferable to blend 1 to 400 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition.
  • rubbers and various additives can be blended as necessary within the range not impairing the properties of the adhesive layer B.
  • Such rubbers include, for example, polybutadiene, polyisoprene, styrene-butadiene random copolymers and block copolymers, hydrogenated products of the block copolymers, acrylonitrile-butadiene copolymers, butadiene-isoprene copolymers, and the like.
  • ethylene-propylene random copolymer and block copolymer ethylene-butene random copolymer and block copolymer, ethylene and ⁇ -olefin copolymer
  • ethylene-acrylic acid ethylene -Ethylene-unsaturated carboxylic acid copolymers such as methacrylic acid, ethylene-acrylic acid esters, ethylene-unsaturated carboxylic acid ester copolymers such as ethylene-methacrylic acid esters, and some unsaturated carboxylic acids are metal salts.
  • ethylene-acrylic acid-gold acrylate Salt 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 ternary copolymer such as ethylene-propylene-ethylidene norbornene copolymer, ethylene-propylene-hexadiene copolymer, ethylene-propylene copolymer such as ethylene-vinyl acetate
  • Preferred examples include polymers, butylene-isoprene copolymers, thermoplastic elastomers such as 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,
  • antioxidants such as crystal nucleating agents, anti-coloring agents, hindered phenols, hindered amines, etc.
  • Agents, mold release agents such as ethylene bisstearylamide and higher fatty acid esters, plasticizers, heat stabilizers, lubricants, UV inhibitors, colorants, flame retardants, foaming agents and the like.
  • thermoplastic resin composition in the adhesive layer B in the molded article of the present invention.
  • a method of adding the resin at the same time a method of adding the resin by a method such as side feed during melt kneading, a method of adding the resin after melt kneading in advance, First, a method of adding the remaining resin to one resin constituting the thermoplastic resin composition, melt-kneading, and the like can be mentioned.
  • Any method can be used as a method for forming the adhesive layer B itself in the present invention.
  • a molding method for example, extrusion molding, calendar molding, or the like is possible.
  • the fiber-reinforced sheet-like molded product 2 may be simultaneously formed in the manufacturing process of the fiber-reinforced sheet-like molded product 2. Specifically, extrusion molding, calendar molding, and the like are possible.
  • the adhesive layer B is made of a thermoplastic sheet, and the elastic modulus (a) of the sheet-like molded product and the elastic modulus (c) of the injection material or the press material
  • the elastic modulus (b) of the thermoplastic sheet as the adhesive layer B is in a relationship of a> c> b. That is, a specific thermoplastic sheet layer is interposed between a sheet-like molded product made of 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.
  • 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.
  • 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.
  • 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.
  • the energy absorption performance excellent as the whole body 25 can be expressed.
  • thermoplastic sheet is particularly preferably made of a thermoplastic resin composition containing a thermoplastic resin and a resin D having a reactive functional group.
  • 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.
  • polyamide resin 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • ethylene-propylene random copolymer and block copolymer ethylene-butene random copolymer and block copolymer, ethylene and ⁇ -olefin copolymer
  • ethylene-acrylic acid ethylene -Ethylene-unsaturated carboxylic acid copolymers such as methacrylic acid, ethylene-acrylic acid esters, ethylene-unsaturated carboxylic acid ester copolymers such as ethylene-methacrylic acid esters, and some unsaturated carboxylic acids are metal salts.
  • An 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.
  • thermoplastic resin of the thermoplastic sheet 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 the unsaturated carboxylic acid ester include (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and 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.
  • the unsaturated carboxylic acid in the ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid metal salt copolymer include (meth) acrylic acid.
  • unsaturated carboxylic acid metal salts include (meth) acrylic acid metal salts.
  • 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, A range of 90/10 to 10/90 is more preferable.
  • 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.
  • 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 mentioned.
  • 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 method can be carried out by a generally known technique and is not particularly limited.
  • maleic anhydride, itaconic anhydride, endic acid anhydride A method of copolymerizing an acid anhydride such as citraconic anhydride or 1-butene-3,4-dicarboxylic acid anhydride and a monomer as a raw material of the rubber polymer, grafting the acid anhydride onto the rubber polymer Or the like can be used.
  • the method can be carried out by a generally known technique and is not particularly limited.
  • 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 ⁇ , ⁇ -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.
  • the method can be carried out by a generally known technique, and is not particularly limited.
  • 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 that 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.
  • numerator which does not have a functional group at all may be contained, it is so preferable that the ratio is small.
  • the weight Aw of the thermoplastic resin and the weight of the resin D which has a reactive functional group in the thermoplastic sheet in the said molded object 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.
  • 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.
  • 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.
  • 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.
  • V tensile elastic modulus
  • E (V1)> E (V2) tensile speed
  • V2 is preferably established.
  • V1 and V2 when the tensile breaking elongation at the tensile speeds V1 and V2 is ⁇ (V1) and ⁇ (V2), it is preferable that ⁇ (V1) ⁇ (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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the value of L / D0 is preferably 50 or more, more preferably 60 to 200, particularly 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.
  • 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.
  • 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.
  • 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.
  • 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
  • the kneading zone is composed of one or more kneading discs.
  • the maximum kneading zone resin pressure is Pkmax (MPa)
  • Pfmin the minimum resin pressure in the full flight zone
  • 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.
  • the kneading zone 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.
  • 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.
  • 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.
  • a method of introducing a seal ring zone having a gap can be 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.
  • 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.
  • a filler may be used as necessary to improve strength and dimensional stability.
  • the filler may be fibrous or non-fibrous, or a combination of fibrous filler and non-fibrous filler may be used.
  • Fibrous fillers such as stone fiber, metal fiber, wollastonite, zeolite, sericite, kaolin, mica
  • 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.
  • a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, an epoxy compound
  • 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.
  • thermoplastic resin composition in the thermoplastic sheet in the molded article of the present invention other thermoplastic resins can be blended as necessary within the range not impairing the characteristics.
  • thermoplastic resins examples 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 it is preferable to blend 1 to 400 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition.
  • 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.
  • thermoplastic resin composition in the thermoplastic sheet in the molded body examples include those exemplified for the adhesive layer B described above.
  • 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.
  • 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.
  • a supercritical fluid is introduced from the viewpoint of improving the reactivity when melt kneading with the twin screw extruder.
  • 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.
  • 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. .
  • the molding method of the thermoplastic sheet in the molded body of the present invention can be any method.
  • a molding method for example, extrusion molding, calendar molding, or the like is possible.
  • 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.
  • the resin composition constituting a portion having a higher elastic modulus (rigidity) than the thermoplastic sheet in the molded article of the present invention preferably contains a filler for the purpose of increasing the 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.
  • the filler examples 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 Glass beads, 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
  • 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.
  • 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.
  • a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, an epoxy compound
  • 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.
  • thermoplastic sheet in the molded body of the present invention has a feature that the peak value of loss tangent (tan ⁇ ) is large, 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.
  • FIG. 5 shows a fiber-reinforced resin injection molded body according to one embodiment of the present invention.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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. These are integrally joined and molded through injection molding of the second fiber reinforced resin 46.
  • the first fiber reinforced resins 42 and 43 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 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 composed 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.
  • the 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.
  • 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.
  • FIG. 7 shows a fiber-reinforced resin injection molded body according to still another embodiment of the present invention.
  • 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.
  • the second fiber reinforced resin 56 are integrally joined and molded through injection molding of the second fiber reinforced resin 56.
  • 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.
  • 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.
  • 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.
  • Example 1 Polyamide (PA) is used as the resin A as a matrix resin, and the surface of a sheet-shaped molded product reinforced with carbon fibers is bonded with polypropylene (PP) via an adhesive layer B made of acid anhydride-modified polypropylene (acid anhydride-modified PP).
  • An injection material (injection molded product) having a resin C as a matrix was bonded, and the bonding strength was measured by a shear test shown in FIG. 3 to evaluate the bonding performance.
  • Table 1 a high bonding strength of 10 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), which was joined with sufficiently high strength. I was able to confirm.
  • Example 2 Polyphenylene sulfide (PPS) is used as the resin A as a matrix resin, and the surface of a sheet-like molded product reinforced with carbon fiber is made of polyamide (PA) through an adhesive layer B made of imide-modified polyamide (imide-modified PA).
  • PA polyamide
  • An injection material (injection-molded product) having the resin C as a matrix was adhered, and the bonding strength was measured by a shear test shown in FIG. 3 to evaluate the adhesion performance.
  • Table 1 a high bonding strength of 8 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), which was joined with sufficiently high strength. I was able to confirm.
  • the resin A is made of polyamide (PA) as a matrix resin, and a sheet-like molded product reinforced with carbon fiber and an injection material (injection molded product) in which a resin C made of polypropylene (PP) is used as a matrix are the same as the injection material.
  • a resin C made of polypropylene (PP) is used as a matrix are the same as the injection material.
  • the adhesive layer B which consists of the same kind of polypropylene (PP)
  • measured the joint strength by the shear test shown in FIG. 3 measured the joint strength by the shear test shown in FIG. 3, and evaluated the adhesive performance.
  • Table 1 only a low bonding strength of 1 MPa was obtained, and it was confirmed that the fracture mode in the shear test was interface fracture at the adhesive layer B portion, and a sufficiently high bonding strength was not obtained. It was.
  • Example 3 Polyamide (PA) is used as the resin A as a matrix resin, and the surface of a sheet-shaped molded product reinforced with carbon fibers is bonded with polypropylene (PP) via an adhesive layer B made of acid anhydride-modified polypropylene (acid anhydride-modified PP).
  • a press material (press-molded product) composed of a resin C made of) was bonded, and the bonding strength was measured by the shear test shown in FIG. 3 to evaluate the bonding performance.
  • 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), which was joined with sufficiently high strength. I was able to confirm.
  • Example 4 Polyphenylene sulfide (PPS) is used as the resin A as a matrix resin, and the surface of a sheet-like molded product reinforced with carbon fiber is made of polyamide (PA) through an adhesive layer B made of imide-modified polyamide (imide-modified PA).
  • PA polyamide
  • PA imide-modified polyamide
  • FIG. 3 A press material (press-molded product) using the resin C as a matrix was bonded, and the bonding strength was measured by a shear test shown in FIG. 3 to evaluate the bonding performance.
  • Table 2 a high bonding strength of 7 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), which was joined with sufficiently high strength. I was able to confirm.
  • the resin A is made of polyamide (PA) 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 the same as the injection material.
  • PP polypropylene
  • the adhesive layer B which consists of the same kind of polypropylene (PP)
  • Table 2 only a low bonding strength of 1 MPa was obtained, and it was confirmed that the fracture mode in the shear test was interface fracture at the adhesive layer B portion, and a sufficiently high bonding strength was not obtained. It was.
  • Comparative Example 4 Sheet-shaped molding of sheet-shaped molded product reinforced with carbon fiber and resin material C made of polyamide (PA) (press-molded product) with polyphenylene sulfide (PPS) as matrix resin as resin A
  • PA polyamide
  • PPS polyphenylene sulfide
  • the adhesive was bonded through an adhesive layer B made of the same or the same kind of polyphenylene sulfide (PPS) as the product, the bonding strength was measured by the shear test shown in FIG. 3, and the adhesive performance was evaluated.
  • Table 2 only a low bonding strength of 1 MPa was obtained, and it was confirmed that the fracture mode in the shear test was interface fracture at the adhesive layer B portion, and a sufficiently high bonding strength was not obtained. It was.
  • 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.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention se rapporte à un corps moulé qui est obtenu en moulant d'une seule pièce un matériau de moulage par injection ou à la presse et qui comprend une résine (C) en tant que matrice sur la surface d'un article moulé en forme de feuille renforcée par des fibres qui comprend une résine (A) en tant que résine de matrice, une couche adhésive (B) étant intercalée entre ces éléments, lesdites résines (A) et (C) étant différentes l'une de l'autre. Il est préférable que la couche adhésive (B) comprenne une résine thermoplastique qui comporte un groupe fonctionnel qui est réactif avec la résine (A). Ainsi, un corps moulé qui présente une résistance d'adhérence élevée et qui est composé d'un stratifié permettant de mettre en valeur les importantes caractéristiques mécaniques de la couche d'article moulé en forme de feuille, peut être facilement obtenu avec une excellente aptitude au moulage. Lorsqu'une feuille thermoplastique qui présente un module d'élasticité spécifique, est utilisée comme couche adhésive (B), le corps moulé présente également, dans son ensemble, une excellente performance d'absorption d'énergie.
PCT/JP2014/050526 2013-01-15 2014-01-15 Corps moulé WO2014112501A1 (fr)

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