JP2006044264A - Decorative molded article and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative molded article having a light weight and excellent dynamic characteristics and also having a good design by making the 1st material composed of an FRP and a decorating material as the 2nd material into a strongly adhered homogenous structure. <P>SOLUTION: In the decorative molded article, a decorative surface is formed by making at least the 1st material and the decorative material as the 2nd material into a homogenous structure, and at least the 1st material comprises mainly a thermosetting resin reinforced by continuous reinforced fibers and also a thermoplastic resin layer at the joint part with the decorative material, wherein the thermoplastic resin layer incorporates a part of the reinforced fibers. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a decorative molded body in which a decorative material is integrated with a first member to form a decorative surface, and a method for manufacturing the same, and more specifically, reinforced with a group of reinforcing fibers composed of continuous reinforcing fibers. A decorative molded body that is excellent in lightness and mechanical properties, has both moldability and productivity, and has design characteristics by firmly integrating a decorative material with fiber reinforced resin (FRP), and its manufacture Regarding the method.

  Currently, fiber reinforced resin (FRP) reinforced with a group of reinforced fibers consisting of many continuous reinforcing fibers is used for transportation equipment such as aircraft, automobiles, motorcycles and bicycles, sports applications such as tennis, golf and fishing rods, and earthquake resistance. It is frequently used as a construction material such as a reinforcing material, a structure requiring lightness and mechanical properties such as electrical and electronic equipment, and a material for industrial use such as a robot arm. Furthermore, in recent years, applications have been expanded to parts and members such as consumer robots and toys from the viewpoints of balance between mechanical properties and weight as materials and design. In addition to its excellent performance, the product can further increase the commercial value by having a design on the surface.

  For example, it is generally performed to apply a molded product made of FRP, but the coating process is disadvantageous in terms of cost and environmental load, and a molded product whose surface shape is not necessarily smooth like FRP. Coating is not easy, and it is a problem in terms of productivity and quality control.

  In addition, a method of polishing the surface resin of FRP is generally performed, but this method also requires man-hours and lead time, and does not solve the above problems. In addition, there is a method of performing gel coating on the mold in advance, but this method also does not solve the above-mentioned problems because it takes time for the gel coating layer to cure and quality control is difficult.

  Furthermore, in consumer robots and toys, painting, artificial leather, and artificial skin are applied from the viewpoints of design and touch. In the known bonding process, the FRP material and the decorative material are bonded. Since the technology was not mature, it was impossible to obtain a molded product having both a design surface and mechanical strength.

Therefore, as a method for easily imparting design properties, Patent Document 1 discloses a method in which a thermoplastic resin film is pressure-bonded to both surfaces of a carbon fiber reinforced thermosetting resin sheet at a temperature lower than the melting temperature of the film. However, this method improves the quality stability of the design surface and the production efficiency, but the adhesion strength between the design film and the thermosetting resin sheet is poor, so that the decorative surface easily peels off. .
JP 10-138354 A

  In view of the prior art, the problem of the present invention is that the first member made of FRP and the decorating material as the second member are firmly integrated, so that it is lightweight and excellent in mechanical properties, and further has a design property. An object of the present invention is to provide a decorative molded body having both of the above. Furthermore, it is providing the manufacturing method of the decorative molded object which can manufacture the decorative molded object excellent in adhesive strength simply and efficiently.

  In order to solve the above problems, a decorative molded body according to the present invention is a decorative molded body in which a decorative surface is formed by integrating at least two members of a first member and a decorative material. The at least first member of the members is mainly composed of a thermosetting resin reinforced with a continuous reinforcing fiber group, and has a thermoplastic resin layer at a joint portion with a decorating material. The resin layer includes a part of reinforcing fibers of the reinforcing fiber group.

  The decorative molded body according to the present invention is a decorative molded body in which a decorative surface is formed by integrating at least two members of the first member and the decorative material, and at least of the members. The first member is mainly composed of a thermosetting resin reinforced with a group of continuous reinforcing fibers, and the decorating material is characterized in that the image clarity on the decorating surface is 50% or more. .

  Furthermore, the decorative molded body according to the present invention is a decorative molded body in which a decorative surface is formed by integrating at least the first member and the two members of the decorative material. At least the first member is composed mainly of a thermosetting resin reinforced with a group of continuous reinforcing fibers, and the decorative material is artificial skin imitating a skin shape.

  Moreover, when the manufacturing method of the decorative molded body which concerns on this invention manufactures the above decorative molded bodies, a 1st member and a 2nd decorative material are heat-welded, vibration welding, and an ultrasonic wave. It consists of a method of integrating by at least one method selected from welding, laser welding, insert injection molding, outsert injection molding, resin transfer molding, hot press molding, autoclave molding, and vacuum pressure molding.

  According to the decorative molded body and the method for manufacturing the same according to the present invention, the first member made of the FRP molded body can be firmly integrated with the decorative material. A decorative molded body having design characteristics can be realized. Moreover, it is excellent in adhesive strength and can provide a decorative surface simply and efficiently. The decorative molded body according to the present invention is an electrical / electronic device application, sports equipment, automobile application, industrial use such as a robot arm, amusement, toy application, etc., by appropriately selecting a decorative surface according to the intended characteristics. It can use suitably for.

Below, the decorative molded object and its manufacturing method of this invention are demonstrated in detail with desirable embodiment.
The first aspect of the decorative molded body is a decorative molded body in which a decorative portion is formed by integrating at least two members, and at least the first member of the members is The thermoplastic resin layer is composed mainly of a thermosetting resin reinforced with a group of reinforcing fibers composed of continuous reinforcing fibers, and has a thermoplastic resin layer at a joint portion with a decorating material to be a decorative portion. Is a decorative molded body comprising a part of the reinforcing fibers of the reinforcing fiber group.

  As specific forms of reinforcing fiber groups, reinforcing fibers, cloth, UD (unidirectional) cloth, UD (unidirectional fiber bundle), blades, multi-reinforced fibers and spun yarn are drawn in one direction with drum wind. Although the form of the reinforced fiber of the aligned form can be illustrated, from the viewpoint of productivity in terms of the manufacturing process, cloth and UD can be preferably used. Moreover, these strengthening forms may be used independently or may use 2 or more types of strengthening forms together. Furthermore, it is good also as a sandwich form which laminated | stacked another base material between the lamination | stacking of the continuous reinforcing fiber group as needed.

  Further, in order to control the mechanical characteristics, a form in which the direction of the reinforcing fiber is changed and laminated is preferably used. In particular, it is preferable to use UD in the form of a plurality of layers in order to efficiently increase the elastic modulus and strength of the laminated body. When the number of laminated layers is limited, the longitudinal direction of the molded product is set to 0 degree. It is more preferable to arrange the angle of the outermost laminated reinforcing fibers at about 45 degrees.

  In order to give the decorative molded body a cloth appearance, it is preferable to use a cloth such as a satin weave or a twill weave for the outermost layer. In particular, the number of reinforcing fibers in the reinforcing fiber group is preferably in the range of 300 to 6000 from the viewpoint of obtaining a beautiful cloth appearance.

  As a 2nd form of the decoration molded object of this invention, in the decoration molded object which formed the decoration surface by integrating at least 2 member of a 1st member and a decorating material, at least said 1st The member is a decorative molded body whose main component is a thermosetting resin reinforced with a group of continuous reinforcing fibers, and in which the decorative material has a projected image quality of 50% or more on the decorative surface.

  Considering that the decorating material is used for, for example, an automobile outer plate, it is preferable from the viewpoint of design that the image clarity is 50% or more.

  Here, the image clarity (S) is described in ASTM D5767, and two numerical values NSIC * (A) using a commercially available tester (for example, S89-A manufactured by Suga Test Instruments Co., Ltd.). NSIC (B) is measured according to ASTM D5767. A corresponds to “spider or rainbow” and B corresponds to “Yugami or avatar”.

  In the present invention, a value calculated by a calculation formula of S = {0.75 × A + 0.25 × B} × 100/100 is defined as image clarity (S). Within this range, the decorative molded body becomes extremely practical and is a preferable member for an automobile outer plate.

  Here, A being high does not mean that there is no blur and there is merchandise, but it can reflect more light and suppress deterioration and temperature rise due to light. Furthermore, it becomes easy for a third party to easily recognize by visual observation or the like, which is preferable from the viewpoint of safety.

  Another B corresponds to unevenness (scratches) on the order of microns. The stress concentration at the tip of the scratch increases according to the size of the scratch, and the destruction from the tip of the scratch progresses. Therefore, the durability of the outer plate is improved when the scratch is small. The larger the value of B obtained with the image sharpness measuring machine, the smaller the size of the scratches, which is preferable as the outer plate. Further, the outer plate having a large roughness easily adheres to the dirt, and the dirt accumulates, thereby reducing the surface smoothness and increasing the fluid resistance. Furthermore, it corresponds to the limit of the size of a wound that can be detected by a human. It is more preferable that the value of image clarity is 70% or more, since a high-class feeling comes out.

  Furthermore, as a 3rd form of the decorative molded body of this invention, it is the decorative molded body which formed the decoration surface by integrating at least the 1st member and the two members of the decorating material, The at least first member of the members is a decorative molded body mainly composed of a thermosetting resin reinforced with a group of continuous reinforcing fibers, and the decorating material is artificial skin imitating a skin shape. .

  Here, the artificial skin is a skin-like molded article that artificially mimics the skin of an animal typified by a human, and is composed of a thermoplastic resin or elastomer as a main component, which is formed into a film, and its surface. The non-skin groove portion is provided with unevenness in view of the actual surface structure of the skin.

  Means for providing such a concavo-convex structure is not particularly limited, and examples thereof include treatment with chemicals, treatment with files, blast treatment, embossing with a mold, etc., but they are always the same. Blasting and embossing are preferable because it is easy to manufacture.

  Furthermore, in the artificial skin which is the decorative material of the present invention, the main component is selected from the group of polyamide, polyurethane, polyester, polyolefin, polybutadiene, silicone, fluorine, polyvinyl chloride, Any one thermoplastic resin or elastomer is preferable, and copolymers, modified products, and resins obtained by blending at least two of them can be used. This is preferable because it has a stretchable property that can withstand the expansion and contraction of the working part, in view of the skin feel and design surface required for artificial skin, and also for robot applications, and in addition to the above properties, In consideration of economy and moldability, it is preferable to use polyurethane-based, polyester-based, polyolefin-based, polybutadiene-based, or silicone-based thermoplastic resins or elastomers.

  Furthermore, the decorative molded body according to the second and third embodiments is a decorative molded body in which a decorative surface is formed by integrating at least two members of the first member and the decorative material. The at least first member of the members is mainly composed of a thermosetting resin reinforced with a group of continuous reinforcing fibers, and has a thermoplastic resin layer at a joint portion with the decorating material. It is preferable from the viewpoint of the adhesive strength between the first member and the decorating material that the thermoplastic resin layer includes a group of reinforcing fibers of the reinforcing fiber group.

  In the decorative molded body of the present invention, the thermoplastic resin layer is integrated with a thermosetting resin reinforced with a group of reinforcing fibers composed of continuous reinforcing fibers and has an uneven shape at the interface. It is preferable.

  The uneven shape is effective for an excellent integration method with a decorative material. When the resin of the thermosetting resin layer and the resin of the thermoplastic resin layer approach a substantially linear shape (substantially linear shape) at the interface, the adhesive strength after joining may not be sufficiently secured. Further, if the reinforcing fibers of the reinforcing fiber group are not in contact with the resin of the thermoplastic resin layer, the adhesive strength may be insufficient, such as peeling after integration. Furthermore, when the thermoplastic resin layer is not located on the surface of the molded product, it is not preferable because easy integration such as thermal bonding cannot be applied.

  Further, in the integration, the adhesive state between the members is such that the layer made of the thermosetting resin that is the matrix resin of the first member and the thermoplastic resin layer have an uneven shape at the interface between these layers. And a group of continuous reinforcing fibers included in the thermoplastic resin layer is in contact with at least the matrix resin of the first member, and the reinforcing fibers of the remaining group of the reinforcing fibers are at least thermoplastic. It is preferable to take the structure contained in the resin layer.

  Here, the decorative molded body of the present invention will be described with reference to FIG. The decorative molded body is composed of a first member 1 and a decorative material 2 as a second member.

  FIG. 2 shows an enlarged cross-sectional view of an example of a joint portion between the first member 3 and the decorating material 4. FIG. 2 is a diagram created based on a photograph obtained by using a scanning electron micrograph. In FIG. 2, the first member 3 is mainly composed of a large number of continuous reinforcing fibers 5 a and 5 b and a thermosetting resin 6. And it has the thermoplastic resin layer 7 in the junction part with the decorating material 4, and this thermoplastic resin layer 7 includes a group (part) reinforcement fiber 5b. Here, it is preferable that the thermoplastic resin layer 7 has an uneven shape at the interface with the thermosetting resin 6 and is integrated.

  In addition, the structure of such a 1st member is the prepreg or prepreg laminated body by which the reinforced fiber group 8 which consists of many continuous reinforcement fibers 5a and 5b is impregnated with the thermosetting resin before hardening. Formed by placing a base material obtained by processing a thermoplastic resin and impregnating the reinforcing fiber group 8 with the thermoplastic resin of the base material during the curing reaction of the thermosetting resin or during preheating before the curing reaction. can do. Further, the thermosetting resin 6 forms a thermosetting resin layer, and the thermoplastic resin forms a thermoplastic resin layer 7. The thermosetting resin 6 and the thermoplastic resin layer are impregnated into the reinforcing fiber group 8 of the thermoplastic resin, that is, by penetration of the thermoplastic resin between the multiple reinforcing fibers 5b forming the reinforcing fiber group 8. 7 is formed.

  As the prepreg, a prepreg composed of a plurality of reinforcing fiber groups 8 as necessary and arranged in the width direction of the prepreg or laminated in the thickness direction of the prepreg is used. In FIG. 2, the reinforcing fiber group 8 that is located in the outermost layer in the prepreg and is closest to the joint surface with the decorating material 4 is shown.

  Here, the reinforcing fiber group is composed of a large number of reinforcing fibers continuous in a length of 10 mm or more in at least one direction. The reinforcing fiber group does not need to be continuous over the entire length in the length direction of the first member or over the entire width in the width direction of the first member, and may be divided in the middle.

  The reinforcing fiber group includes a reinforcing fiber bundle composed of a large number of reinforcing fibers, a cloth composed of the fiber bundle, a reinforcing fiber bundle in which a large number of reinforcing fibers are arranged in one direction (unidirectional fiber bundle), A unidirectional cloth composed of directional fiber bundles. Among these, from the viewpoint of prepreg and member productivity, a cloth and a unidirectional fiber bundle are preferable. The reinforcing fiber group may be composed of a plurality of fiber bundles having the same form or may be composed of a plurality of fiber bundles having different forms. The number of reinforcing fibers constituting one reinforcing fiber group is usually 300 to 48,000, but in consideration of the production of prepreg and the production of cloth, it is preferably 300 to 24,000, more preferably 1,000 to 12,000.

  Moreover, as a preferable aspect of a 1st member, it is the laminated body by which the fiber bundle was laminated | stacked in layers. By changing the orientation direction of the reinforcing fiber group and laminating, the mechanical properties of the entire member can be controlled.

  The said structure of the 1st member in the decorative molded body of this invention can be verified with the following method, for example. First, the first test method is based on observation of a partial cross section of a surface layer of a member joint by a scanning electron microscope (SEM) or a transmission electron microscope (TEM). The observation of the cross section may be performed based on the taken cross-sectional photograph, if necessary. The test piece to be observed is a thin slice created using the surface layer portion cut out from the member. In making this, some of the reinforcing fibers of the reinforcing fiber group may fall off, but there is no problem as long as the observation is not affected. The test piece may be stained as necessary to adjust the contrast of observation.

  The reinforcing fibers constituting the reinforcing fiber group are usually observed as a circular cross section. When the reinforcing fiber is dropped, it is usually observed as a circular drop mark. In the portion other than the portion where the reinforcing fibers constituting the reinforcing fiber group are located, the thermosetting resin layer and the thermoplastic resin layer are observed as two regions having different contrasts.

  An example of the observation result by the first method is shown in FIG. FIG. 3 is an enlarged view of the cross section of the joint portion of the decorative molded body formed by integrating the first member 11 and the decorative material 12. The state in which the resin of the thermoplastic resin layer 13 penetrates into the gaps between the multiple reinforcing fibers 15a and 15b constituting the reinforcing fiber group 14 is shown. Further, the thermosetting resin 16 and the thermoplastic resin are shown. The state where the interface 17 with the layer 13 has an uneven shape is shown.

  The second test method is based on observation with a scanning electron microscope (SEM) or a transmission electron microscope (TEM) of a cross section in which the thermoplastic resin in the surface layer portion of the member joint is extracted and removed with a solvent. The observation of the cross section may be performed based on a cross-sectional photograph as necessary. The member is cut to a length of about 10 mm and a width of about 10 mm to obtain a test piece. In this test piece, the thermoplastic resin layer is sufficiently washed with a good solvent for the resin constituting the test piece, and the thermoplastic resin is removed to prepare a test piece for observation. The cross section of the prepared test piece is observed using SEM (or TEM).

  An example of the observation result by the second method is shown in FIG. FIG. 4 shows an enlarged cross section of the joint portion in a state where the decorative material and the thermoplastic resin layer are removed from the decorative molded body in which the first member 18 and the decorative material 19 are integrated. Is. In FIG. 4, the thermosetting resin 20 exists with the reinforcing fibers 22 a constituting the reinforcing fiber group 21, but the thermoplastic that has existed with the thermosetting resin 20 and the uneven interface 23. The resin layer does not exist because it is removed by the solvent when the test piece is prepared. While the uneven shape of the interface 23 is observed, the reinforcing fiber 22b constituting the reinforcing fiber group 21 is observed at the position where the thermoplastic resin layer was present, and the void 24 is observed between these reinforcing fibers. The This proves that the reinforcing fiber 22b constituting the reinforcing fiber group 21 was included in the thermoplastic resin layer.

  In the first method and the second method, when observing the member joint from the integrated decorative molded body, whether the joint is peeled by heating to a temperature at which the resin of the thermoplastic resin layer is plasticized The decorative material may be removed by a method such as mechanical removal.

  The third test method is based on observation of a state obtained when the other is forcibly peeled from one to the other in an integrated molded product. This test method is performed by forcibly peeling the integrally molded product at room temperature so as to break between the first member and the decorating material. A part of the first member surface layer may adhere to the peeled decorating material as a residue. This residue is observed with a microscope.

  An example of the state of the test piece obtained by implementing the third test method is shown in FIG. In FIG. 5, a joining portion 26 where the surface of the first member is joined is shown on the decorative material 25, and a part of the first member surface layer portion is used as a residue 27 in a part of the joining portion 26. Observed. In this residue 27, it is observed that there are a plurality of reinforcing fibers dropped from the reinforcing fiber group located on the surface layer of the first member.

  The structural characteristics of the decorative molded body of the present invention can be verified by at least one test method among the above test methods.

  The first member in the decorative molded body of the present invention is a region in which the continuous reinforcing fibers 5b are present in the thermoplastic resin layer 7 shown in FIG. 2 for the purpose of increasing the adhesive strength with the decorative material. The maximum thickness Tpf-max is preferably 10 μm or more, more preferably 20 μm or more, and further preferably 40 μm or more. This maximum thickness Tpf-max is the outermost (bonding side) reinforcing fiber 5b-out in contact with the resin of the thermoplastic resin layer 7 in the thickness direction of the thermoplastic resin layer 7, and the thermoplastic resin layer 7 Is defined as a distance (Tpf-max) between the innermost reinforcing fiber 5b-in-max in contact with the resin of the thermoplastic resin layer 7 at the portion where the penetration depth from the surface of the resin is the largest. The The maximum thickness Tpf-max can be measured in the SEM or TEM photograph obtained by the first test method or the second test method. If the maximum thickness Tpf-max is 1,000 μm at the maximum, the effect of the present invention is sufficiently achieved.

  The minimum thickness Tpf-min is the outermost (surface side) reinforcing fiber 5a-out in contact with the resin of the thermoplastic resin layer 7 in the thickness direction of the thermoplastic resin layer 7, and the thermoplastic resin layer 7 It is defined as the distance (Tpf-min) between the innermost reinforcing fiber 5b-in-min in contact with the resin of the thermoplastic resin layer 7 at the portion where the penetration depth from the resin surface is the smallest. .

  In the first member, as shown in FIG. 2, the interface 9 between the thermosetting resin 6 and the thermoplastic resin layer 7 is a reinforcing fiber composed of a large number of reinforcing fibers 5a and 5b aligned in one direction. It is preferably present in group 13. In the first member, in the case where a plurality of reinforcing fiber groups 13 are laminated in the thickness direction, it is more preferable that the interface 9 exists only in the outermost reinforcing fiber group.

  Further, the thickness of the coating is preferably 0.01 to 1000 μm, more preferably 1 to 200 μm, and more preferably 10 to 50 μm from the viewpoint of adhesiveness.

  Furthermore, the first member constituting the decorative molded body is preferably a laminated body in which the fiber groups are arranged in layers from the viewpoints of mechanical properties and moldability. Here, the laminate means a molded product having a form in which continuous reinforcing fiber groups are laminated in the thickness direction.

  Examples of the reinforcing fibers that are constituent elements of the first member include metal fibers such as aluminum fibers, brass fibers, and stainless fibers, polyacrylonitrile-based, rayon-based, lignin-based, pitch-based carbon fibers, and graphite fibers. In addition to fibers that exhibit conductivity alone, insulating fibers such as glass fibers, organic fibers such as aramid fibers, PBO fibers, polyphenylene sulfide fibers, polyester fibers, acrylic fibers, nylon fibers, polyethylene fibers, and silicon carbide Examples thereof include inorganic fibers such as fibers and silicon nitride fibers, and fibers obtained by coating these fibers with a conductor. As a method for coating the conductor, for example, at least a metal such as nickel, ytterbium, gold, silver, copper, or aluminum is plated (electrolytic or electroless), CVD, PVD, ion plating, vapor deposition, or the like. A known method for coating one or more layers can be exemplified.

  These reinforcing fibers may be used alone or in combination of two or more. Among them, carbon fiber, particularly polyacrylonitrile-based carbon fiber is preferably used from the viewpoint of the balance of specific strength, specific rigidity, and light weight, and in particular, at a low cost.

  The carbon fiber used in the present invention will be described. The carbon fiber means a fibrous material having a carbon content in the range of 85 to 100% by weight and at least partially having a graphite structure. Specific examples of such fibrous materials include polyacrylonitrile-based carbon fiber, rayon-based carbon fiber, lignin-based carbon fiber, pitch-based carbon fiber, vapor-grown carbon fiber, and carbon nanotube. Among them, polyacrylonitrile-based carbon fibers are preferably used in that satisfactory lightness of the molded product is satisfied and low cost can be realized.

  The carbon fiber is preferably within the range of 15,000 to 500,000, more preferably 30,000, from the viewpoint of the economic efficiency of the thermoplastic resin composition reinforced with carbon fiber and the handleability of the carbon fiber. In the range of ˜250,000, particularly those bundled with 60,000 to 120,000 can be used.

  As the matrix resin which is a constituent element of the first member, a thermosetting resin can be preferably used from the viewpoint of excellent rigidity and strength of the decorative molded body.

  Examples of such thermosetting resins include unsaturated polyesters, vinyl esters, epoxies, phenols (resol type), urea melamines, polyimides, copolymers thereof, modified products, and resins obtained by blending two or more types. Etc. can be used. Furthermore, an elastomer or a rubber component may be added to the thermosetting resin in order to improve impact resistance. Among these, an epoxy resin is particularly preferable from the viewpoint of rigidity and strength of a molded product.

  Examples of the thermoplastic resin that can achieve the solubility parameter δ include amide bonds, ester bonds, urethane bonds, ether bonds, amino groups, hydroxyl groups, carboxyl groups, acid anhydride groups, sulfonic acid groups, aromatic rings, imide rings, and the like. And those having a bond, functional group or structure having a polarity higher than that of the hydrocarbon skeleton.

  Moreover, as a weight average molecular weight of a thermoplastic resin, 2,000-200,000 are preferable, 5,000-150,000 are more preferable, 10,000-100,000 are still more preferable. By making it within the above range, intermolecular forces and entanglement of molecular chains increase, and the strength of the thermoplastic resin itself increases, making it difficult for the thermoplastic resin itself to be easily broken, and further strengthening the thermoplastic resin. Impregnation into the fiber group, it becomes easy to include the fiber group, and a strong adhesive force can be expressed.

Furthermore, in the decorative molded body of the present invention, the thermoplastic resin forming the thermoplastic resin layer used for the first member is selected from a carboxyl group, an acid anhydride group, an amino group, an epoxy group, and a hydroxyl group. By containing at least one kind of functional group, the reactivity of the thermoplastic resin is increased, which is effective in increasing the adhesive strength, which is one of the objects of the present invention. Among these, an acid anhydride group, an amino group, and an epoxy group are more preferably selected. Here, the functional group amount of the thermoplastic resin is preferably 1 × 10 ⁻⁵ mol / g or more, more preferably 1 × 10 ⁻⁴ mol / g or more, and further preferably 1 × 10 ⁻³ mol / g or more. The amount of the functional group is not particularly limited and can be measured by a general chemical analysis method. For example, the components are identified by IR (infrared absorption spectrum measurement), the molecular structure is identified by NMR (nuclear magnetic resonance spectrum measurement), and the molecular weight is identified by GPC (gel permeation chromatography). From the obtained result, the number of moles of the functional group per unit weight of the polymer chain can be calculated.

  From the above, in the decorative molded body of the present invention, as the thermoplastic resin composition used for the first member, for example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene Polyester such as naphthalate (PEN), liquid crystal polyester, modified polyethylene (PE), modified polypropylene (PP), modified polyolefin such as polybutylene, styrene resin, polyoxymethylene (POM), polyamide (PA) , Polycarbonate (PC), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polyphenylene sulfide (PPS), polyphenylene ether (PPE), modified PPE, polyimide (PI), polyamideimide (PAI) Polyetherimide (PEI), Polysulfone (PSU), Modified PSU, Polyethersulfone, Polyketone (PK), Polyetherketone (PEK), Polyetheretherketone (PEEK), Polyetherketoneketone (PEKK), Polyarylate ( PAR), polyether nitrile (PEN), phenolic resin, phenoxy resin, polytetrafluoroethylene and other fluorine resins, polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene, polyisoprene, Fluorine-based thermoplastic elastomers and the like, copolymers, modified products, and resins obtained by blending at least two of them can be used. Among these, polyester resins, polyamide resins, and modified polyolefin resins are preferably used from the viewpoints of productivity and economy.

  Here, the specific method for producing the resin composition reinforced with the continuous reinforcing fibers is not particularly limited, and is a hand lay-up molding method, a spray-up molding method, a vacuum back molding method, a pressurization method. Examples thereof include a method using a thermosetting resin such as a molding method, an autoclave molding method, a press molding method and a transfer molding method, and a method using a thermoplastic resin such as a press molding and a stamping molding method. In particular, vacuum back molding, press molding, transfer molding, and the like are preferably used from the viewpoint of processability and mechanical properties.

  The decorating material, which is a component of the decorative molded body of the present invention, preferably has a film shape from the viewpoint of ease of handling and shaping into a complex shape.

  The film-like decorating material preferably has a thickness in the range of 1 to 500 μm, more preferably 10 to 400 μm. When the thickness is 10 μm or less, it is not preferable because the film is wrinkled or torn during molding of the decorative molded body. When the thickness exceeds 500 μm, the drape property peculiar to the film is lost, and the handling property and shaping at the time of molding. This is not preferable because the properties are lowered.

  Moreover, it is preferable that the shape of the said decorating material is a sheet form from a viewpoint of economical efficiency and handling property.

  The sheet-shaped decorating material preferably has a thickness in the range of 5 mm or less, more preferably 0.5 to 4 mm. When the thickness is less than 0.5 mm, it is not preferable because processing of the sheet becomes difficult and economical efficiency is lost. On the other hand, if the thickness is greater than 5 mm, the weight of the sheet is increased, and handling properties are deteriorated.

  Furthermore, it is preferable that the said decorating material is plate shape from a viewpoint of intensity | strength and rigidity.

  The plate-shaped decorating material may have substantially the same configuration as the first member, and having substantially the same configuration as the first member means adhesion in integration, and It is preferable from the viewpoint of the mechanical properties of the decorative molded body after integration.

  Moreover, it is preferable that the said plate-shaped decorating material exists in the range whose thickness is 5 mm or more, More preferably, it is 7-20 mm. Such a thickness of less than 5 mm is not preferable because it leads to a decrease in strength and rigidity. Moreover, when it has thickness exceeding 20 mm, when integrated with a 1st member, since the weight of a decoration molded object will increase, it is unpreferable from a lightweight viewpoint.

  The plate-like decorating material preferably has at least one shape selected from a laminated board and a decorative board, and is preferable from the viewpoint of imparting high strength, high rigidity, and designability, and has high strength and high rigidity. A laminated board is preferable from the viewpoint that it can be applied, and a decorative board is preferable from the viewpoint that it can provide designability.

  Furthermore, the decorating material preferably has a light transmittance of 60% or more from the viewpoint of design. Here, the light transmittance refers to the total light average transmittance at 380 to 780 nm measured according to JIS K7105, and the decorative material of the present invention preferably has a total light average transmittance of 60% or more, more preferably 70. % Or more. The total light average transmittance is obtained by measuring the transmittance from 380 nm to 780 nm at intervals of 40 nm using a D65 light source according to JIS K7105, and obtaining the average value of the total transmittance obtained. When the average transmittance is less than the above value, the visible light transparency is inferior and the design property is lowered. In addition to the predetermined transmittance, it is preferable that there is no turbidity, spots, irregularities, and the like.

  Moreover, it is preferable that the shape of the said decorating material is a cloth form from a viewpoint of lightweight property and design property.

  Such a fabric-like decorating material preferably has at least one shape selected from woven fabric, cloth, non-woven fabric, and leather, and more specifically, plain structure, twill structure, satin structure, warpile weave, cloth, meltblown web Card web, air lay web, wet papermaking web, spunbond web, natural leather, artificial leather, synthetic leather, artificial leather, etc. These fabrics include stitch yarn, knot yarn, resin (discontinuous film, non-woven fabric, binder) Etc.) may be integrated by a plurality of joining means. From the viewpoint of high strength and high rigidity, a woven fabric and cloth are preferable. From the viewpoint of high strength and design, cloth and leather are preferable, and from the viewpoint of light weight, a nonwoven fabric is preferable.

Moreover, it is preferable that the said fabric-like decorating material exists in the range of 10-2000 g / m < ² > or less, More preferably, it is 30-1800 g / m < ² >. When the basis weight is less than 10 g / m ^2, the distance between the fibers constituting the fabric is widened, and the first member is exposed, so that the design characteristic of the fabric is deteriorated. On the other hand, if the basis weight is larger than 2000 g / m ² , the weight increases, which is not preferable from the viewpoint of light weight.

  The fiber material constituting the cloth-like decorating material is preferably at least one fiber material selected from carbon fiber, glass fiber, thermoplastic resin fiber, natural fiber, and metal fiber, and has high strength and high elasticity. Carbon fiber is preferable from the viewpoint of rate, lightness, conductivity, and thermal conductivity, glass fiber, natural fiber, and thermoplastic resin fiber are preferable from the viewpoint of economy, and metal from the viewpoint of conductivity and thermal conductivity. Fiber is preferred.

  Moreover, it is preferable that the said fabric-like decorating material contains the thermoplastic resin from a viewpoint of appearance quality, heat resistance, chemical resistance, and mechanical characteristics. Examples of such thermoplastic resins include polycarbonate resins, styrene resins, polyamide resins, polyester resins, polyphenylene sulfide resins (PPS resins), modified polyphenylene ether resins (modified PPE resins), polyacetal resins (POM resins) and polyetherimide resins. It is at least one selected from polyolefin resins such as (PEI resin), polypropylene resin (PP resin), and polyethylene resin (PE resin).

  The viewpoint that the decorating material can select and impart various properties such as strength, rigidity, gas barrier properties, flame retardancy, heat resistance, chemical resistance, conductivity, thermal conductivity, transparency, and surface properties. Therefore, a multilayer structure is preferable.

  The decorating material is preferably at least one shape selected from a film shape, a sheet shape, a plate shape, and a fabric shape, but it is also a decorative molding that contains a thermoplastic resin as a main component. It is preferable from the viewpoint of body dimensional stability, design properties, economy, productivity, molded product quality, heat resistance, chemical resistance, and mechanical properties.

  Examples of the thermoplastic resin used as the main component of the decorating material include polycarbonate resin, styrene resin, polyamide resin, polyester resin, polyphenylene sulfide resin (PPS resin), modified polyphenylene ether resin (modified PPE resin), and polyacetal. It is at least one selected from polyolefin resins such as resin (POM resin), polyetherimide resin (PEI resin), polypropylene resin (PP resin), and polyethylene resin (PE resin).

  For the thermoplastic resin, for example, when priority is given to dimensional stability, design, economy, productivity, and molded product quality, a polycarbonate resin, a styrene resin, a polyolefin resin, or the like is preferably selected. In the case of giving priority to chemical resistance, polyamide resin, polyester resin, polyphenylene sulfide resin, modified polyphenylene ether resin, polyacetal resin, and polyetherimide resin are preferably selected. Or 2 or more types can be used. Furthermore, a thermoplastic resin may be previously melt-kneaded and used as a polymer alloy.

  Furthermore, the decorating material is preferably a metal material from the viewpoint of imparting strength, rigidity, conductivity, thermal conductivity, and design properties. Such a metal material is not particularly limited as long as it has thermal adhesiveness, and in order to improve thermal adhesiveness to aluminum, iron, magnesium, titanium, nickel, gold, silver, copper and alloys thereof. Primer treatment may be applied. As a primer, an organic primer containing an epoxy resin, a urethane resin, a phenol resin, a rubber polymer (eg, polybutadiene), an inorganic primer containing magnesium, manganese, silicon, etc. These mixed primers can also be used. Furthermore, the decorating material preferably has a geometric or non-geometric pattern from the viewpoint of design. The geometric pattern is composed of characters, figures, symbols, or a combination thereof, and may be any pattern that forms a pattern. A non-geometric pattern is an amorphous one having no specific pattern.

  Furthermore, the decorating material may contain a filler or an additive in a range that does not impair the object of the present invention, depending on required characteristics. For example, inorganic fillers, flame retardants, conductivity imparting agents, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insect repellents, deodorants, anti-coloring agents, heat stabilizers, release agents , Antistatic agents, plasticizers, lubricants, colorants, pigments, dyes, foaming agents, antifoaming agents, coupling agents and the like. Examples of the conductivity-imparting agent include carbon black, amorphous carbon powder, natural graphite powder, artificial graphite powder, expanded graphite powder, pitch microbeads, vapor grown carbon fiber, and carbon nanotube.

  Furthermore, it is preferable that the said decorating material is a metal material from a viewpoint of intensity | strength, rigidity, electroconductivity, thermal conductivity, and design property. Such a metal material is not particularly limited as long as it has thermal adhesiveness, and in order to improve thermal adhesiveness to aluminum, iron, magnesium, titanium, nickel, gold, silver, copper and alloys thereof. Primer treatment may be applied. As a primer, an organic primer containing an epoxy resin, a urethane resin, a phenol resin, a rubber polymer (eg, polybutadiene), an inorganic primer containing magnesium, manganese, silicon, etc. These mixed primers can also be used.

  Further, the decorating material is preferably a carbon fiber reinforced carbon composite material from the viewpoint of heat resistance and light weight. Carbon fiber reinforced carbon composite materials are manufactured by impregnation method using thermoplastic resin represented by furan resin, phenol resin, pitch as matrix raw material, or by CVD method using methane, propane, argon, etc. It may be a thing.

In the present invention, the decorative molded body obtained by integrating the first member and the decorating material obtains good quality by suppressing the decrease in dimensional stability and the occurrence of warpage due to the shrinkage difference peculiar to each member. From the viewpoint, in the substantially flat portion of the decorative molded body in which the first member and the decorating material are integrated, C _IID that is the absolute value of the linear expansion coefficient of the decorating material with respect to an arbitrary direction D, The absolute value of the value C _IID / C _ID divided by C _ID which is the absolute value of the linear expansion coefficient of the first member with respect to the same direction D is preferably 3 to 50. More preferably, it is 5-50.

  The linear expansion coefficients of the first member and the decorating material can be evaluated and determined based on ISO 11359-2. When a 1st member and a decorating material can be evaluated separately previously, it evaluates in advance. When evaluating from the integrated decorative molded product, the first member and the substantially flat surface portion of the decorative material of the decorative molded product are used as the reference in the longitudinal direction of the first member and the decorative material. Four test pieces cut out at different angles of 45 degrees, 90 degrees, and 135 degrees are prepared. As for the cutout position of the test piece, portions where shapes such as ribs, hinges, and concavo-convex portions are intentionally avoided should be avoided as much as possible. The average value of the linear expansion coefficients obtained from these test pieces is adopted as the linear expansion coefficient here.

Moreover, in the decorative molded body of the present invention, the decorative molded body in which the first member and the decorative material are integrated suppresses the decrease in dimensional stability and the occurrence of warpage due to the difference in rigidity of each member. From the viewpoint of obtaining good quality, the value t _II / t _{I obtained} by dividing the average thickness t _II of the second member by the average thickness t _I of the first member is in the range of 0.01 to 2. It is preferable to be within. More preferably, it is the range of 0.05-1.

The average thicknesses t _I and t _II of the first member and the decorating material are as much as possible avoiding the portions where the shapes such as the concavo-convex portions are intentionally attached as much as possible. The thickness was measured using a micrometer, and the average value was taken as the representative value.

  Moreover, it is preferable that the said decorating material has image clarity 50% or more, considering using it, for example for a motor vehicle outer plate use.

  Moreover, the decorative molded body according to the present invention may have a curved surface shape. Furthermore, it only needs to have at least one curved surface shape, and may be a two-dimensional, three-dimensional curved surface or a wavy shape.

  Moreover, the decorative molded body according to the present invention may have a substantially planar shape. Here, examples of the substantially flat surface include a surface having the maximum projected area of the flat surface portion in the decorative molded body.

  The decorative molded body of the present invention is a casing or part of an electric / electronic device, a sports article or a member such as an automobile, a motorcycle, a building material, a structural member such as a skin or panel, a robot arm, a toy, an amusement robot, etc. It can be suitably used for members such as parts, members and artificial limbs.

  As the above electronic / electrical devices, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards, tuners, Speaker, microphone, headphones, small motor, magnetic head base, power module, semiconductor, display, FDD carriage, chassis, HDD, MO, motor brush holder, parabolic antenna, laptop computer, mobile phone, digital still camera, PDA, portable MD , Parts of electrical or electronic equipment such as plasma displays, parts and casings, pachinko, slot machines, gaming or entertainment product parts such as game machines, parts and casings, microscopes, binoculars, cameras, watches, etc. Optical equipment, precision machinery related parts, and the like member and the housing.

The above-mentioned automobiles, two-wheeled vehicle members, outer plates, and fittings include motor parts, alternator terminals, alternator connectors, IC regulators, light-depot potentiometer bases, suspension parts, exhaust gas valves and other valves, fuel-related, exhaust systems or Various intake pipes, air intake nozzle snorkel, intake manifold, various arms, various frames, various hinges, various bearings, fuel pump, gasoline tank, CNG tank, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, Cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, blur Kibat wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, distributor, starter switch, starter relay, wire harness for transmission, Window washer nozzle, air conditioner panel switch board, coil for fuel related electromagnetic valve, connector for fuse, battery tray, AT bracket, headlamp support, pedal housing, handle, door beam, protector, chassis, frame, armrest, horn terminal, step motor Rotor, lamp socket, lamp reflector, lamp housing, brake piston, noise Shield, Radiator support, Spare tire cover, Seat shell, Solenoid bobbin, Engine oil filter, Ignition case, Under cover, Scuff plate, Pillar trim, Propeller shaft, Wheel, Fender, Faisher, Bumper, Bumper beam, Bonnet, Molded ceiling, Door trims, aero parts, platforms, cowl louvers, roofs, instrument panels, spoilers and various modules.
Furthermore, sports equipment includes rackets such as tennis and badminton, shafts such as golf and gateball, bats such as baseball, soccer, handball goal posts, net posts such as volleyball, etc. , Structural members such as skins or panels, robot arms, parts and members such as toys and amusement robots, medical applications such as artificial limbs and X-ray cassettes, telephones, facsimiles, VTRs, copiers, televisions, irons, hair dryers, Household or office product parts and parts represented by rice cookers, microwave ovens, audio equipment, vacuum cleaners, toiletries, laser discs, compact discs, lighting, refrigerators, air conditioners, typewriters, word processors, bags, shelves, desks, etc. And housing, and also ship It can be suitably used in aircraft applications and the like.

  As a method for producing the decorative molded body of the present invention, the decorating material is bonded at a process temperature equal to or higher than the melting point of the thermoplastic resin constituting the thermoplastic resin layer in the first member, and then cooled. The method of integrating 1 member and decorating material is mentioned. Examples of techniques for melting and adhering thermoplastic resins include thermal welding, vibration welding, ultrasonic welding, laser welding, insert injection molding, outsert injection molding, resin transfer molding, hot press molding, autoclave molding, and vacuum pressure molding. Can be mentioned.

Furthermore, in the process of integrating the first member and the decorative material in the method for producing a decorative molded body of the present invention, the first member and the decorative material are at least the first member and The decorative material is placed on a heated hot plate at a heat deformation temperature (t _m −10) ° C. or lower of the decorative material, or placed in an atmosphere and heated, and then the temperature is increased. The first member and the decorating material are preferably heat-bonded by pressurizing them with a surface pressure of 0.01 to 10 MPa. When the molding temperature during such integration is (t _m -10) ° C. or higher, the surface properties and mechanical properties of the decorative material are lost due to heat, and the quality of the decorative molded body is significantly reduced. Therefore, it is not preferable. In addition, performing the integrated molding under a pressure outside the range of 0.01 to 10 MPa for the molding pressure (surface pressure) at the time of such integration is, for example, when the integration is performed under a pressure of less than 0.01 MPa. The adhesion between the first decorating member and the decorating material is lowered, and this reduces the adhesion between the first member of the molded decorating product and the decorating material, which is not preferable. . In addition, if the integration is performed under a pressure exceeding 10 MPa, the decorative material may be crushed and the decorative effect may be lost, whereby the designability of the molded decorative molded body Is unfavorable because it decreases. As a method of making the surface pressure 0.01 MPa or more during the above integration, the laminate is bagged with a film of nylon or the like and pressed by applying a vacuum, or directly using a press. And a method of applying pressure by an autoclave method.

  EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the following examples are not intended to limit the present invention, and all modifications may be made without departing from the scope of the present invention. It is included in the technical scope.

(1) Linear expansion coefficient The 1st member and decorating material which were used in each Example were evaluated based on ISO 11359-2. When a 1st member and a decorating material can be evaluated separately previously, it evaluates in advance. When evaluating from the integrated decorative molded product, the first member and the substantially flat surface portion of the decorative material of the decorative molded product are used as the reference in the longitudinal direction of the first member and the decorative material. Four test pieces cut out at different angles of 45 degrees, 90 degrees, and 135 degrees are prepared. As for the cutout position of the test piece, portions where shapes such as ribs, hinges, and concavo-convex portions are intentionally avoided should be avoided as much as possible. The average value of the linear expansion coefficients obtained from these test pieces is adopted as the linear expansion coefficient here. Of these, the maximum is the maximum linear expansion coefficient, and the minimum is the minimum linear expansion coefficient. In this example, the first member and the decorating material were evaluated in advance.

(2) Thickness ratio of the members The average thicknesses t _I and t _II of the first member and the decorating material are respectively avoided as much as possible in the portions where the shapes such as the concavo-convex portions are intentionally attached. Then, arbitrarily measure the thickness at 10 locations using a micrometer, take the average value as a representative value, and divide the average thickness t _II of the second member by the average thickness t _I of the first member. The obtained value t _II / t _I was determined.

Example 1
(Laminate)
As a prepreg constituting the laminate, carbon fiber manufactured by Toray Industries, Inc. ("Treka (registered trademark)" T300B (tensile strength 3500 MPa, tensile modulus 230 GPa, number of filaments 3000, fiber basis weight 0.2 g / m) as a reinforced fiber ) As a warp and weft, and a carbon fiber woven fabric having a plain weave so that the warp and weft are 5 pieces / cm, and a carbon fiber basis weight is 198 g / m ² using a 130 ° C. curing type epoxy resin as a matrix resin. A cross prepreg having a resin content (Wr) of 40% ("Torayca (registered trademark)" prepreg F6343B-05 manufactured by Toray Industries, Inc.) was used. This was cut into a size of 1000 mm × 700 mm to produce a planar laminate. First, six prepregs were laminated on a flat plate female mold. Two pieces of the thermoplastic resin produced by the method described later, cut to the same size as the laminate, were stacked on top of the last laminated prepreg to form a thermoplastic resin layer.

  Next, a flat plate male mold was set and press molding was performed. After preheating with a press molding machine at 160 ° C. for 5 minutes to melt the adhesive, it was cured by heating at 150 ° C. for 30 minutes while applying a pressure of 6 MPa. After completion of curing, the mixture was cooled at room temperature and demolded to obtain a laminate having an average thickness of 1.5 mm.

(Thermoplastic resin layer)
A pellet of crystalline polyester resin (made by Toyobo Co., Ltd., crystalline polyester resin, Byron GA-5300, melting point 114 ° C., solubility parameter δ (SP value) 10.7) is formed into a nonwoven fabric having a width of 1000 mm by a melt blow method. A base material was used. The basis weight of the adhesive thermoplastic resin was 30 g / m ² .

(Decorated molding)
The laminate is set in a press molding machine (using a flat plate mold), and as a decorative material, a surface design class A sheet (1000 mm × 700 mm × 1.4 mm) (product; Lexan SLX12A32-Solid Colors, manufactured by GE Plastics, Inc.) ) To form a decorative molded body. At this time, the decorating material formed by the press molding machine is in contact with the portion where the adhesive layer of the laminate is laminated. Moreover, the press molding machine heated only the hot plate which contacts a 1st member, and did not apply temperature directly to a decorating material. Integration with the decorating material was performed by heating at a hot plate temperature of 160 ° C. for 5 minutes. After the press, the product was cooled at room temperature and demolded to obtain a decorative molded body. In the obtained decorative molded body, the decorating material and the laminate were firmly bonded. Moreover, by the decoration of the surface design class A sheet, good transparency was obtained, whereby the cross place of the cross prepreg was reflected and high design properties could be obtained. In addition, by decorating the surface design class A sheet, it was possible to obtain a decorative molded body that did not require painting, thereby reducing the cost due to the absence of painting in addition to the design properties.

  A cross section of the obtained decorative molded body was cut out from a portion where a thermoplastic resin was laminated, and a 10 mm square test piece was cut out and subjected to ultrasonic cleaning with methyl alcohol for 30 minutes to remove the thermoplastic resin as an adhesive layer, and then SEM. Observations were made. As a result, fiber bundles are barely observed on the surface, and in the cross section, a fiber group layer having voids in the surface direction of the molded body and a fiber group layer having no voids in the inner direction of the molded body. A two-layer structure was observed. The interface of these layers has an uneven shape, and the layer of the fiber group having voids is a region where the continuous reinforcing fibers of the thermoplastic resin layer were contained, and the maximum thickness Tpf and the minimum When the thickness Tpf-min was measured, the minimum thickness Tpf-min was 30 μm, and the maximum thickness Tpf-max was 60 μm.

  When the cross section of the joint portion of the decorative molded body was observed with an SEM, the thermoplastic resin was melted and adhered to the surface in the form of a film, and the film thickness was 10 μm. Further, the ratio of the thickness of the first member to the thickness of the decorating material was 0.9.

Example 2
(Laminate)
It was obtained in the same manner as in Example 1 except that a hemispherical mold was used for the production.
(Thermoplastic resin layer)
Obtained in the same manner as in Example 1.

(Decorated molding)
The laminate is set in a press molding machine (using a hemispherical mold), and as a decorating material, a surface design class A sheet (1000 mm × 700 mm × 1.4 mm) (product; Lexan SLX12A32-red, manufactured by GE Plastics) ) To form a decorative molded body. At this time, the decorating material formed by the press molding machine is in contact with the portion where the adhesive layer of the laminate is laminated. Moreover, the press molding machine heated up only the hot plate which contacts a laminated body, and did not apply temperature directly to a decorating material. Moreover, the decorating material was arrange | positioned on the convex surface of the hemispherical metal mold | die, and it was made to decorate a decorating material inside a hemispherical surface after integration of a laminated body and a decorating material. Integration with the decorating material was performed by heating at a hot plate temperature of 160 ° C. for 5 minutes. After the press, the product was cooled at room temperature and demolded to obtain a decorative molded body. In the obtained decorative molded body, the decorating material and the laminate were firmly bonded. Moreover, favorable surface property was obtained by decorating the surface design class A sheet. Moreover, by decorating the surface design class A sheet, it was possible to obtain a decorative molded body that did not require coating, thereby reducing the cost without painting. Furthermore, by decorating the surface design class A sheet, it was possible to obtain a decorative molded body with good surface properties with few surface irregularities, and a decorated molded body excellent in radio wave reflectivity.

  Similarly to Example 1, it was recognized that the interface between the thermosetting resin reinforced with the continuous reinforcing fiber group and the thermoplastic resin layer had an uneven shape. When the maximum thickness Tpf and the minimum thickness Tpf-min were measured, the minimum thickness Tpf-min was 30 μm, and the maximum thickness Tpf-max was 60 μm. When the cross section of the joint portion of the decorative molded body was observed with an SEM, the thermoplastic resin was melted and adhered to the surface in the form of a film, and the film thickness was 10 μm. Further, the ratio of the thickness of the first member to the thickness of the decorating material was 0.9.

Example 3
(Laminate)
As a prepreg constituting the laminate to be the first member 3, carbon fiber manufactured by Toray Industries, Inc. (“Treka (registered trademark)” M46J (tensile strength 4200 MPa, tensile elastic modulus 436 GPa, filament number 6000, fiber) A basis weight of 0.2 g / m)), a 130 ° C. type epoxy resin as a matrix resin, a carbon fiber basis weight of 116 g / m ² , and a resin content (Wr) of 30% unidirectional (UD) prepreg (Toray "Torayca (registered trademark)" prepreg P6053-12 manufactured by Co., Ltd. was used. This was cut into a size of 1000 mm × 700 mm to produce a planar laminate. First, six prepregs are laminated on a female mold so that the longitudinal direction of the rectangular bottom is 0 ° and the fiber direction is 45 °, −45 °, 90 °, 90 °, −45 °, 45 ° from the top. To do. Two pieces of the thermoplastic resin produced by the method described later, cut to the same size as the laminate, were stacked on top of the last laminated prepreg to form a thermoplastic resin layer. Next, a male mold was set and press molding was performed. After preheating with a press molding machine at 160 ° C. for 5 minutes to melt the adhesive, it was cured by heating at 150 ° C. for 30 minutes while applying a pressure of 6 MPa. After completion of curing, it was cooled at room temperature and demolded to obtain a laminate having an average thickness of 0.7 mm.

(Thermoplastic resin layer)
Pellets of ternary copolymer polyamide resin (manufactured by Toray Industries, Inc., ternary copolymer polyamide resin CM4000, polyamide 6/66/610, melting point 150 ° C., solubility parameter δ (SP value) 13.3), A non-woven substrate having a width of 1000 mm was obtained by a melt blow method. The basis weight of the adhesive thermoplastic resin was 30 g / m ² .

(Decorated molding)
The laminate 1 is set in a press molding machine (using the same mold as in Example 1), and as a decorating material, a transparent polyester film (1000 mm × 700 mm × 125 μm) (product; Emblet S, Unitika Ltd.) )) And integrated with one of the cross prepregs used in Example 1 to obtain a decorative molded body. At this time, the decorating material formed by the press molding machine is in contact with the portion where the adhesive layer of the laminate is laminated. Moreover, the press molding machine heated up only the hot plate which contacts a laminated body, and did not apply temperature directly to a decorating material. The press molding machine was heated at a hot plate temperature of 160 ° C. for 5 minutes and integrated with the decorating material. After the press, the product was cooled at room temperature and demolded to obtain a decorative molded body. In the obtained decorative molded body, the decorative material and the laminate 1 were firmly bonded. Furthermore, due to the transparency of the transparent polyester film of the decorating material, the cross prepreg sandwiched between the laminate and the decorating material could be clearly confirmed, and a product having high designability was obtained.

  Similarly to Example 1, it was recognized that the interface between the thermosetting resin reinforced with the continuous reinforcing fiber group and the thermoplastic resin layer had an uneven shape. When the maximum thickness Tpf and the minimum thickness Tpf-min were measured, the minimum thickness Tpf-min was 30 μm, and the maximum thickness Tpf-max was 60 μm. When the cross section of the joint portion of the decorative molded body was observed with an SEM, the thermoplastic resin was melted and adhered to the surface in the form of a film, and the film thickness was 10 μm. Moreover, the ratio of the thickness of the 1st member and the thickness of a decorating material was 0.2.

Example 4
(Laminate) and (Thermoplastic resin layer)
The same one as in Example 3 was used.

(Decorated molding)
The laminate was set in a press molding machine, and an aluminum plate (1000 mm × 700 mm × 4 mm) was used as a decorating material. A primer composition (trade name; Ruby Coat E, manufactured by Toyo Polymer Co., Ltd.) was applied to the aluminum plate with a brush, air-dried at room temperature for 15 minutes, and heat-treated at 120 ° C. for 15 minutes. A primer-treated aluminum plate was integrated into a decorative molded body. At this time, the decorating material formed by the press molding machine is in contact with the portion where the adhesive layer of the laminate is laminated. Moreover, the press molding machine heated up only the hot plate which contacts a laminated body, and did not apply temperature directly to a decorating material. The press molding machine was heated at a hot plate temperature of 160 ° C. for 5 minutes and integrated with the decorating material. After the press, the product was cooled at room temperature and demolded to obtain a decorative molded body. In the obtained decorative molded body, the decorative material and the aluminum plate were firmly bonded. Furthermore, high designability was obtained due to the metallic luster of the decorating material. Similarly to Example 1, it was recognized that the interface between the thermosetting resin reinforced with the continuous reinforcing fiber group and the thermoplastic resin layer had an uneven shape. When the maximum thickness Tpf and the minimum thickness Tpf-min were measured, the minimum thickness Tpf-min was 30 μm, and the maximum thickness Tpf-max was 60 μm. When the cross section of the joint portion of the decorative molded body was observed with an SEM, the thermoplastic resin was melted and adhered to the surface in the form of a film, and the film thickness was 10 μm. The linear expansion coefficient C _ID of the first member was 3.3 × 10 ⁻⁶ , and the linear expansion coefficient C _IID of the decorating material was 2.4 × 10 ⁻⁵ . Among these, the absolute value of the value C _b / C _{s obtained} by dividing the larger value C _b by the smaller value C _s was 7.

Example 5
(Laminate) and (Thermoplastic resin layer)
The same one as in Example 1 was used.

(Decorated molding)
The laminate is set in a press molding machine, and is used as a decorative material, using artificial leather (1000 mm × 700 mm, basis weight 220 g / m ² ) (trade name; EXEN 100E, manufactured by Toray Industries, Inc.), and integrated. A decorative molded body was obtained. At this time, the parts and members formed by the press molding machine are in contact with the portion of the laminated body where the adhesive layers are laminated. Moreover, the press molding machine heated up only the hot plate which contacts a laminated body, and did not apply temperature directly to a decorating material. The press molding machine was heated at a hot plate temperature of 160 ° C. for 5 minutes and integrated with the decorating material. After the press, the product was cooled at room temperature and demolded to obtain a decorative molded body. In the obtained decorative molded body, the decorative material and the laminate 1 were firmly bonded. Furthermore, the design texture of the soft texture that cannot be obtained only by the laminated body was able to be obtained by the decorative material EXSEINE. Similarly to Example 1, it was recognized that the interface between the thermosetting resin reinforced with the continuous reinforcing fiber group and the thermoplastic resin layer had an uneven shape. When the maximum thickness Tpf and the minimum thickness Tpf-min were measured, the minimum thickness Tpf-min was 30 μm, and the maximum thickness Tpf-max was 60 μm. Moreover, when the joint part cross section of the said decoration molded object was observed by SEM, the thermoplastic resin melt | dissolved and adhered to the surface at the surface, and the film thickness was 10 micrometers.

Example 6
(Laminate) and (Thermoplastic resin layer)
The same one as in Example 1 was used.

(Decorated molding)
The laminated body is set in a flat sheet metal mold, and a surface design class A sheet (1000 mm × 700 mm × 1.4 mm) (product; Lexan SLX12A32-Solid Colors, manufactured by GE Plastics) is used as a decorating material. Then, a decorative molded body is obtained by integrating them by vacuum pressure molding. At this time, the decoration material to be formed is in contact with the portion where the adhesive layer of the laminate is laminated.

  In vacuum pressure molding, the molding process will be described. First, the laminate is placed so that the portion where the adhesive layer is not placed is in contact with the mold. Next, a decorating material is arrange | positioned so that the part which laminated | stacked the contact bonding layer of the laminated body, and bagging is performed from the upper part with the film made from nylon. At that time, after reducing the pressure to [atmospheric pressure 0.1 (MPa)] using a vacuum pump, only the flat sheet metal mold is heated to 120 ° C. so that the decorative material is not directly heated. The flat plate mold was held at 120 ° C. for 5 minutes as it was, and heat bonding was performed. After completion of holding for 5 minutes, it was cooled at room temperature, demolded, and a decorative molded body was obtained. In the obtained decorative molded body, the decorative material and the laminate were firmly bonded. Moreover, by the decoration of the surface design class A sheet, good transparency was obtained, whereby the cross place of the cross prepreg was reflected and high design properties could be obtained. In addition, by decorating the surface design class A sheet, it was possible to obtain a decorative molded body that did not require painting, thereby realizing a cost reduction without painting in addition to the design properties.

  Similarly to Example 1, it was recognized that the interface between the thermosetting resin reinforced with the continuous reinforcing fiber group and the thermoplastic resin layer had an uneven shape. When the maximum thickness Tpf and the minimum thickness Tpf-min were measured, the minimum thickness Tpf-min was 30 μm, and the maximum thickness Tpf-max was 60 μm. When the cross section of the joint portion of the decorative molded body was observed with an SEM, the thermoplastic resin was melted and adhered to the surface in the form of a film, and the film thickness was 10 μm. Further, the ratio of the thickness of the first member to the thickness of the decorating material was 0.9.

Example 7
(Laminate)
A prepreg similar to that in Example 1 was arranged in the same laminated configuration as in Example 1, and a thermoplastic resin layer was used in the same manner as in Example 1. Next, unlike Example 1, it is used in the state of a laminate comprising an uncured prepreg and a thermoplastic resin layer 1 without performing a curing reaction of the prepreg by hot press molding.

(Thermoplastic resin layer)
The same one as in Example 1 was used.

(Decorated molding)
The laminated body is set in a flat sheet metal mold, and a surface design class A sheet (1000 mm × 700 mm × 1.4 mm) (product; Lexan SLX12A32-Solid Colors, manufactured by GE Plastics) is used as a decorating material. Then, a decorative molded body is obtained by integrating them by vacuum pressure molding. At this time, the decoration material to be formed is in contact with the portion where the adhesive layer of the laminate is laminated.

  In vacuum pressure molding, the molding process will be described. First, the laminate is placed so that the portion where the adhesive layer is not placed is in contact with the mold. Next, a decorating material is arrange | positioned so that the part which laminated | stacked the contact bonding layer of the laminated body, and bagging is performed from the upper part with the film made from nylon. At that time, after reducing the pressure to [atmospheric pressure 0.1 (MPa)] using a vacuum pump, the temperature of only the flat sheet metal mold is raised to 100 ° C. so that the decorative material is not directly heated. The flat plate mold was held at 100 ° C. for 120 minutes as it was, and the prepreg of the laminate was subjected to a curing reaction to form a first member, and the first member and the decorating material were simultaneously bonded by heating. After completion of holding for 150 minutes, the mixture was cooled at room temperature and demolded to obtain a decorative molded body. In the obtained decorative molded body, the decorating material and the first member were firmly bonded. Moreover, by the decoration of the surface design class A sheet, good transparency was obtained, whereby the cross place of the cross prepreg was reflected and high design properties could be obtained. In addition, by decorating the surface design class A sheet, it was possible to obtain a decorative molded body that did not require painting, thereby realizing a cost reduction without painting in addition to the design properties.

  Similarly to Example 1, it was recognized that the interface between the thermosetting resin reinforced with the continuous reinforcing fiber group and the thermoplastic resin layer had an uneven shape. When the maximum thickness Tpf and the minimum thickness Tpf-min were measured, the minimum thickness Tpf-min was 30 μm, and the maximum thickness Tpf-max was 60 μm. Moreover, when the joint part cross section of the said decoration molded object was observed by SEM, the thermoplastic resin melt | dissolved and adhered to the surface at the surface, and the film thickness was 10 micrometers. Furthermore, the ratio of the thickness of the first member to the thickness of the decorating material was 0.9.

Example 8
(Laminate)
A prepreg similar to that in Example 1 was arranged in the same laminated configuration as in Example 1, and a thermoplastic resin layer was used in the same manner as in Example 1. Next, unlike Example 1, it is used in the state of a laminate comprising an uncured prepreg and a thermoplastic resin layer 1 without performing a curing reaction of the prepreg by hot press molding.

(Thermoplastic resin layer 1)
The same one as in Example 1 was used.

(Decorated molding)
The laminate is set in a flat sheet metal mold, and an olefin elastomer (commercial product: Sumitomo TPE820, manufactured by Sumitomo Chemical Co., Ltd.) is used as a decoration material in a sheet form (1000 mm × 700 mm × 1.0 mm), and the surface is textured to form a concavo-convex shape, which is used as artificial skin and integrated by vacuum pressure molding to obtain a decorative molded body. At this time, the decoration material to be formed is in contact with the portion where the adhesive layer of the laminate is laminated.

  In vacuum pressure molding, the molding process will be described. First, the laminate is placed so that the portion where the adhesive layer is not placed is in contact with the mold. Next, a decorating material is arrange | positioned so that the part which laminated | stacked the contact bonding layer of the laminated body, and bagging is performed from the upper part with the film made from nylon. At that time, after reducing the pressure to [atmospheric pressure 0.1 (MPa)] using a vacuum pump, only the flat sheet metal mold is heated to 120 ° C. so that the decorative material is not directly heated. The flat sheet metal mold was held at 120 ° C. for 120 minutes as it was, and the prepreg of the laminate was subjected to a curing reaction to form a first member, and the first member and the decorating material were simultaneously bonded by heating. After completion of holding for 120 minutes, the mixture was cooled at room temperature and demolded to obtain a decorative molded body. In the obtained decorative molded body, the decorating material and the first member were firmly bonded. In addition, a good skin feel was obtained by decorating the artificial skin sheet, thereby achieving high design properties.

  Similarly to Example 1, it was recognized that the interface between the thermosetting resin reinforced with the continuous reinforcing fiber group and the thermoplastic resin layer had an uneven shape. When the maximum thickness Tpf and the minimum thickness Tpf-min were measured, the minimum thickness Tpf-min was 30 μm, and the maximum thickness Tpf-max was 60 μm. When the cross section of the joint portion of the decorative molded body was observed with an SEM, the thermoplastic resin was melted and adhered to the surface in the form of a film, and the film thickness was 8 μm. Moreover, the ratio of the thickness of the 1st member and the thickness of a decorating material was 0.7.

  The decorative molded body according to the present invention can be suitably applied particularly to electrical / electronic devices, automotive applications, and the like, but is not limited thereto, depending on the selection of decorative materials, home appliances, civil engineering / architecture, ships, aircraft applications, etc. It can be applied to various uses, and the application range is not particularly limited.

It is a perspective view of the decorative molded body which concerns on one embodiment of this invention. It is an expanded sectional view of a joined part in a decoration fabrication object of the present invention. It is sectional drawing which shows the result of having observed the decorating molded object of this invention by the 1st test method. It is sectional drawing which shows the result of having observed the decorative molded body of this invention with the 2nd test method. It is sectional drawing which shows the result of having observed the decorating molded object of this invention with the 3rd test method.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 1st member 2 Decorating material 3 1st member 4 Decorating material 5a, 5b Reinforcing fiber 6 Thermosetting resin 7 Thermoplastic resin layer 8 Reinforcing fiber group 9 Interface between thermosetting resin and thermoplastic resin layer DESCRIPTION OF SYMBOLS 10 Interface of 1st member and 2nd decorating material 2nd decorating material 2nd decorating material 11 1st member 12 Decorating material 13 Thermoplastic resin layer 14 Reinforcing fiber group 15a, 15b Reinforcing fiber 16 Thermosetting resin 17 Interface between thermosetting resin and thermoplastic resin layer 18 First member 19 Decorating material 20 Thermosetting resin 21 Reinforcing fiber group 22a, 22b Reinforcing fiber 23 Thermosetting resin and thermoplastic resin Interface with layer 24 Void where thermoplastic resin layer was present 25 Decorating material 26 Joining portion with first member 27 Residue

Claims (20)

  A decorative molded body in which a decorative surface is formed by integrating at least two members of a first member and a decorative material, and at least the first member of the members is reinforced with a continuous reinforcing fiber group. The thermoplastic resin layer has a thermoplastic resin layer at the joint portion with the decorative material, and the thermoplastic resin layer includes a part of the reinforcing fibers of the reinforcing fiber group. A decorative molded body characterized by that.   A decorative molded body in which a decorative surface is formed by integrating at least two members of a first member and a decorative material, and at least the first member of the members is reinforced with a continuous reinforcing fiber group. A decorative molded body comprising the thermosetting resin as a main component, wherein the decorating material has a projected image quality of 50% or more on a decorative surface.   It is a decorative molded body in which a decorative surface is formed by integrating at least a first member and two members of a decorative material, and at least the first member of the members is a continuous reinforcing fiber group. A decorative molded body comprising a reinforced thermosetting resin as a main component, and the decorative material is artificial skin imitating a skin shape.   In the artificial skin as a decorating material, the main component is any one selected from the group consisting of polyamide, polyurethane, polyester, polyolefin, polybutadiene, silicone, fluorine, and polyvinyl chloride. The decorative molded body according to claim 3, which is a plastic resin or an elastomer.   It has a thermoplastic resin layer in the joined part of the first member and the decorating material, and the thermoplastic resin layer includes a group of reinforcing fibers in the reinforcing fiber group. 4. The decorative molded body according to any one of 4.   The thermoplastic resin layer is integrated with a thermosetting resin layer reinforced with a group of reinforcing fibers composed of continuous reinforcing fibers, and has an uneven shape at the interface thereof. The decorative molded body as described.   The decorative molded body according to claim 1, wherein the thermoplastic resin layer has a maximum thickness of 10 μm or more in a region where the reinforcing fibers are included.   The decorative molded body according to claim 7, wherein the maximum thickness is 1000 μm or less.   The decorative molded body according to any one of claims 1 to 5, wherein the resin of the thermoplastic resin layer is interposed in a film shape at a joint portion with a decorating material.   The decorative molded body according to claim 9, wherein the minimum thickness of the coating film is in the range of 0.01 to 1000 µm.   The decorative molded body according to any one of claims 1 to 10, wherein the first member is a laminate.   The decorative molded body according to any one of claims 1 to 11, wherein the reinforcing fibers are made of carbon fibers.   The decorative molded body according to any one of claims 1 to 12, wherein the thermosetting resin is a resin mainly composed of an epoxy resin.   The decorative molded body according to any one of claims 1 and 5 to 13, wherein a solubility parameter δ (SP value) of a thermoplastic resin constituting the thermoplastic resin layer is in a range of 9 to 16.   The decorative molded body according to any one of claims 1 to 14, wherein the decorative material has any one form selected from the group consisting of a film form, a sheet form, a plate form, and a fabric form. .   The decorative molded body according to claim 15, wherein the decorative material comprises a multilayer structure.   The decorative molded body according to claim 15 or 16, wherein the decorating material contains a thermoplastic resin as a main component.   Cases and parts of electrical and electronic equipment, sporting goods or members of automobiles, motorcycles, building materials, outer plates or panels, structural members such as robot arms, parts such as toys and amusement robots, members, members of artificial limbs, etc. The decorative molded body according to any one of claims 1 to 17.   The first member and the decorating material are selected from heat welding, vibration welding, ultrasonic welding, laser welding, insert injection molding, outsert injection molding, resin transfer molding, hot press molding, autoclave molding, and vacuum pressure molding. The manufacturing method of the decorative molded object in any one of Claims 1-18 integrated by the at least 1 integration method performed. In the step of integrating the first member and the decorating material, at least the first member and the decorating material are heated to a heat deformation temperature (t _m −10) ° C. or less of the decorating material. After placing on a hot plate or putting in an atmosphere and heating, pressurize the heated first member and the decorating material at a surface pressure of 0.01 to 10 MPa. The manufacturing method of the decorative molded object in any one of Claims 2-5 which heat-bonds by.

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