WO1997039869A1 - Materiau composite de type plaque et procede de fabrication - Google Patents
Materiau composite de type plaque et procede de fabrication Download PDFInfo
- Publication number
- WO1997039869A1 WO1997039869A1 PCT/JP1997/001190 JP9701190W WO9739869A1 WO 1997039869 A1 WO1997039869 A1 WO 1997039869A1 JP 9701190 W JP9701190 W JP 9701190W WO 9739869 A1 WO9739869 A1 WO 9739869A1
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- WO
- WIPO (PCT)
- Prior art keywords
- plate
- resin
- glass
- resin material
- layer
- Prior art date
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Classifications
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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
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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
- B29C45/14311—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 using means for bonding the coating to the articles
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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
- B29C45/14467—Joining articles or parts of a single article
-
- 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
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/46—Means for plasticising or homogenising the moulding material or forcing it into the mould
- B29C45/56—Means for plasticising or homogenising the moulding material or forcing it into the mould using mould parts movable during or after injection, e.g. injection-compression moulding
- B29C45/561—Injection-compression moulding
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- 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
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10018—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet
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- 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
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
-
- 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
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
- B32B17/10816—Making laminated safety glass or glazing; Apparatus therefor by pressing
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- 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
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
- B32B17/10899—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin
- B32B17/10908—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin in liquid form
- B32B17/10917—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin in liquid form between two pre-positioned glass layers
-
- 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
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/58—Measuring, controlling or regulating
- B29C2043/5833—Measuring, controlling or regulating movement of moulds or mould parts, e.g. opening or closing, actuating
-
- 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
- B29C45/14467—Joining articles or parts of a single article
- B29C2045/14532—Joining articles or parts of a single article injecting between two sheets
-
- 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
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/46—Means for plasticising or homogenising the moulding material or forcing it into the mould
- B29C45/56—Means for plasticising or homogenising the moulding material or forcing it into the mould using mould parts movable during or after injection, e.g. injection-compression moulding
- B29C45/561—Injection-compression moulding
- B29C2045/5615—Compression stroke, e.g. length thereof
- B29C2045/562—Velocity profiles of the compression stroke
-
- 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
- B29K2709/00—Use of inorganic materials not provided for in groups B29K2703/00 - B29K2707/00, for preformed parts, e.g. for inserts
- B29K2709/08—Glass
Definitions
- a glass layer located on one side and a resin layer located on the other side with respect to this glass layer are provided in a laminated state, and are used, for example, for a so-called front glass of a vehicle.
- the present invention relates to a suitable plate-like composite and a method for producing the same. Background art
- a plate-like composite having such a weight reduction has been provided, and further, a plate-like composite having a glass layer located on one surface thereof has been provided so as not to be damaged on the surface.
- a sheet of glass has been laminated in a laminated manner on one surface that is the front surface of an already molded resin plate. Further, there is a type in which each plate-shaped glass is adhered on both sides of the front and rear surfaces of the formed resin plate such that the resin plate is sandwiched in a sandwich shape.
- the present invention has been made in order to solve such a problem, and is intended to prevent the surface from being damaged, and to provide a bonding method in which a glass layer is disposed on at least one surface. It is desirable to provide a plate-shaped composite which can be easily manufactured without defects and which does not generate stress and strain, and a method for manufacturing the same. Disclosure of the invention The plate-shaped composite according to the present invention has the following objects.
- the molten resin material is positioned on the other surface side of the glass layer and stretched along the glass layer by uniformly applying pressure to the entire molten resin material to form the molten resin material. And a glass layer and a resin layer are provided in a laminated state.
- first glass layer, the resin layer, and the second glass layer are provided in a stacked manner in that order.
- the molten resin material is spread along the glass layer and the first resin layer by uniformly applying pressure to the entire molten resin material.
- Second resin layer formed by molding Wherein the glass layer, the second resin layer, and the first resin layer are provided in a stacked manner in that order.
- the resin layer is formed by expanding the molten resin material along the glass layer formed by the plate-like glass by uniformly applying pressure to the entire molten resin material and molding the molten resin material.
- the glass layer is positioned on at least one surface so that the surface is not easily damaged, and there is no adhesion failure between the glass layer and the resin layer.
- stress is uniformly applied to the entire molten resin material to expand and form the resin layer, no stress distortion occurs.
- the pressure applied to the entire molten resin material is a pressure sufficient to suppress the growth of gas contained in the molten resin material as bubbles, the resin layer becomes cloudy due to the bubbles. There is no.
- the surface of the plate-like glass forming the glass layer, which is in contact with the resin layer, is subjected to a pretreatment of applying a silane coupling agent or a borane, or at least the glass layer A difference in shrinkage between the plate-shaped glass and the formed molten resin material during the molding of the molten resin material while being adhered to the plate-shaped glass and the molded resin material between the joining surfaces with the resin layer. and if the thermal expansion buffer for example, a thermoplastic resin material as the c correct preferred is a this intermediate layer is provided consisting of a, thereby the strength of adhesion between the glass layer and the resin layer.
- the intermediate layer may be formed by subjecting the plate-shaped glass to a bonding treatment with the resin layer on the bonding surface with the resin material before forming the resin layer, or may be made of the resin material. It is good to provide by attaching a resin film to be used.
- the plate-shaped glass is transparent, and the molten resin material is a polycarbonate resin, an atalyl resin, a polystyrene resin, an amorph.
- Aspiro olefin resin polyethylene phthalate resin, ethylene vinyl acetate copolymer (EVA), thermoplastic polyurethan (TPU), ethylene acrylate '' It is a maleic anhydride terpolymer, hydrogenated styrene butadiene rubber (glazed SBR), polyvinyl butyrate (PVB), or a polyolefin-based elastomer.
- the pressure uniformly applied is 15 kg Z cm 2 or more, which is a pressure sufficient to suppress the gas contained in the molten resin material from growing as bubbles. In this way, a plate-like composite having no transparent cloudiness and no stress distortion can be obtained.
- the thermoplastic resin material constituting the intermediate layer may be made of a polycarbonate resin, an acrylic resin, or the like which has transparency after molding the resin layer.
- a resin plate When a resin plate is used, a polycarbonate resin, an acrylic resin, a polystyrene resin, an amorphous sulfur resin, a polyethylene resin which becomes a transparent resin plate.
- Intermediate resin ethylene butyl acetate copolymer (EVA), thermoplastic polyurethane (TPU), ethylene ⁇ acrylate ester 'maleic anhydride terpolymer, It is better than the molded resinous resin material of hydrogenated styrene butadiene rubber (hydrogenated SBR), polybutyrate (PVB) and polyolefin elastomer. It is preferable to select a hard resin material with a high melting point. In addition, the thinner the plate-like glass, the lighter it can be.Next, the method for producing a plate-like composite according to the present invention,
- At least one of the two dies of the compression molding machine is placed inside the at least one of the dies so that the glass is in contact with and adheres to the mold.
- the molten resin material to be supplied is stretched by applying pressure uniformly to the whole of the molten resin material along the plate-like glass so that both molds are clamped and compression molded.
- the glass layer formed of the plate-like glass and the molten resin material are spread and molded by uniformly applying pressure to the entire molten resin material.
- the present invention is characterized in that a plate-like composite having a resin layer formed in a laminated shape is manufactured.
- a bonding surface of the plate-like glass with a resin layer formed by molding the molten resin material is adhered to the plate-like glass and the molten resin material to be molded and formed of the molten resin material.
- the plate-like glass is made transparent and the molten resin material is made of polycarbonate resin.
- the molten resin material is made of polycarbonate resin.
- Acryl resin Polystyrene resin, Amorphous polypropylene resin, Polyethylene terephthalate resin, Ethylene acetate butyl copolymer (EVA), Heat Plastic polyurethane (TPU), ethylene / acrylic acid ester, maleic anhydride terpolymer, hydrogenated styrene butadiene rubber (hydrogenated SBR), polyvinyl butyrate (PVB) Or polyolefin
- the pressure applied uniformly to the entire molten resin material is a pressure sufficient to suppress the gas contained in the molten resin material from growing as air bubbles.
- the resin material for the primer treatment and the resin material constituting the resin film are, as described above, a transparent polycarbonate resin and an acrylic resin having transparency after the molding of the resin material.
- a transparent polycarbonate resin and an acrylic resin having transparency after the molding of the resin material are, as described above, a transparent polycarbonate resin and an acrylic resin having transparency after the molding of the resin material.
- thermoplastic resin materials such as maleic anhydride terpolymer, hydrogenated styrene butadiene rubber (hydrogenated SBR), polyvinyl butyrate (PVB), or polyolefin elastomer. Good.
- the plate-like composite after being expanded and molded by uniformly applying pressure to the entire molten resin material is used. Is mounted between a first plate located on one surface and having a heating device and a second plate located on the other surface and arranged parallel to the first plate and having a heating device.
- the molten resin material is formed by uniformly applying heat and pressure to the entire molten resin material so that it is further reflowed and expanded, and then compression-molded again. .
- the molding temperature required to further reflow the solidified molten resin material and expand it is set to 200 t or less, and the molten resin material is further reflowed. It is preferred that the pressure required for stretching be less than 20 kg / cm 2 .
- FIG. 1 is an overall schematic view of an injection compression molding machine used for explaining an embodiment of a plate-shaped composite according to the present invention and a method for producing the same.
- FIGS. 2 (a) to 2 (e) are schematic views showing steps of manufacturing the plate composite according to the present invention using the injection compression molding machine shown in FIG. 1, and FIG. FIG. 1 is a sequence diagram of a movable mold and a screw when a plate-shaped composite according to the present invention is manufactured by an injection compression molding machine.
- FIG. 4 is a cross-sectional view of the plate composite manufactured by the process shown in FIG. 2,
- FIG. 5 shows a plate composite in another embodiment in which the intermediate layer is omitted and a pretreatment for applying a silane cutting agent or a borane to the bonding surface of the plate glass is performed.
- FIG. 6 is a process schematic diagram corresponding to FIG. 2 (b) showing a process of manufacturing a plate-like composite having glass layers on both sides according to another embodiment
- FIG. 7 is a diagram shown in FIG. It is sectional drawing of the plate-shaped composite body manufactured by the process currently performed.
- the injection compression molding machine 1 includes a compression molding unit 10 and an injection unit. And a controller A for controlling the compression molding unit 10 and the injection unit 30.
- a mold opening / closing cylinder 13 is provided on the left side of a frame 12 fixed to the table 11 and provided so as to extend to the left.
- a movable plate 15 in a frame 12 is engaged with a piston rod 14 of the mold opening / closing cylinder 13.
- the movable plate 15 is provided with an electromagnetic force generated by the controller A.
- a movable mold 18 is mounted on the right side of the movable die 15 and a fixed mold 19 is mounted on the left side of the table 11 so as to face the movable mold 18. Installed.
- An injection port 20 is formed in the fixed mold 19, and the molten resin material is supplied to the mold cavity 21 formed between the molds 18 and 19 through the injection port 20. Supplied.
- the movable die plate 15 is driven rightward by the mold opening / closing cylinder 13 to move the movable die 15 attached to the movable die plate 15.
- 1 8 is the predetermined interval for the fixed mold 1 9 1!
- the movable die plate 15 is locked when it becomes, and the locked movable die plate 15 is further moved so that the molds 18 and 19 are closed.
- a mold clamping device 22 for moving the die plate 15 to the right is provided.
- the mold clamping device 22 is configured by providing the following mechanisms above and below the movable plate 15 respectively.
- the mold clamping device 22 is fixed to the table 11 by a high adjuster 22 a and the high adjuster 22 a through the rod 22 b via the rod 22 b.
- a cylinder frame 22c which is moved and adjusted according to the thickness, the predetermined interval 1, etc., and a pin 22d, which is rotatable with respect to the cylinder frame 22c in the direction of the arrow a shown in the figure.
- a link 22g having a mold clamping cylinder 22f at the tip end supported via 22e and the link 22g are moved in the direction of the arrow a in the direction of the arrow in the perspective direction with respect to the movable plate 15 It consists of a lock cylinder 22 h that rotates.
- the controller A controls the electromagnetic switching valves 23 and 25 for the excitation switching control and the flow control for the flow control valve 24 by controlling the flow from the hydraulic power source 17 to the mold closing cylinder.
- the controller A controls the electromagnetic switching valves 23 and 25 for the excitation switching control and the flow control for the flow control valve 24 by controlling the flow from the hydraulic power source 17 to the mold closing cylinder.
- the nozzle part 31 is joined to the injection port 20 of the fixed mold 19 in the compression molding unit 10, and the inside of the cylinder 32 is also connected.
- the heated cylinder 32 the molten resin material is weighed while melting and kneading the pelletized or powdered resin material of the plasticized synthetic resin supplied from the material hopper 33 in the heated cylinder 32.
- a flow passage 34 formed in the nozzle portion 31 and a screw 35 to be injected and supplied to the mold cavity 21 through the injection port 20 in the fixed mold 19 are internally provided. Have been.
- the screw 35 is rotated by a screw rotating motor 36 for melting and kneading the resin material.
- the screw 35 and the screw rotation motor 36 are
- the base 37 In addition to being mounted on 37, the base 37 must be controlled by the controller A to control the flow of the flow control valve 38 and the control of the pressure value setting to the electromagnetic relief valve 39.
- the pressure oil discharged from the hydraulic pressure source 40 to the hydraulic piston 41 By controlling the pressure oil discharged from the hydraulic pressure source 40 to the hydraulic piston 41, it is driven to move left and right.
- Application of a predetermined pressing force to the screw 35 for setting the resin material to a predetermined injection pressure is performed via the base 37 by supplying and discharging pressurized oil to and from the hydraulic screw 41.
- the controller A is provided with a screw position value actually measured by the screw position detector 42 engaged with the base plate 37, and this measured screw position value is compared with the screw position value actually measured. Based on the result of comparison with the set stroke value, each of the aforementioned solenoid-operated directional control valves 16, 23, 25, as well as the flow control valves 24, 38, and the electromagnetic relief according to a predetermined program The control operation of the valve 3 9 and the control of the rotation or stop of the screw rotation motor 36 are also performed. In addition, the servo motor 4 of the open / close valve 4 3 provided in the flow path 34 of the nozzle section 31 The opening / closing control via 4 is also performed in connection with the advance / retreat of the screw 35 by the control port A.
- the movable mold 18 in a state where the movable mold 18 is in an open state exceeding a predetermined interval 1 t with respect to the fixed mold 19, the movable mold 18 is formed in a predetermined shape inside the movable mold 18.
- the thin 50 mm glass plate 50 is placed in contact with the glass plate, and installed so as to be in close contact with no gap.
- a resin film 51 made of a resin material to be described later is previously adhered to a surface of the plate-shaped glass 50 opposite to a surface in contact with the movable mold 18.
- the movable mold 18 with the plate-shaped glass 50 installed inside is fixed.
- the movable die plate 15 is moved rightward by the mold opening / closing cylinder 13 by performing the control operation of the excitation switching control on the electromagnetic switching valve 16 until the predetermined interval 1 is reached with respect to the fixed mold 19.
- Movable mold locking process (Fig. 2 (a))
- the control operation of the excitation switching control for the electromagnetic switching valve 25 is performed, and the lock cylinder 22 h is operated.
- the link 22 g is rotated to the movable plate 15 side, and then the control operation of the excitation switching control for the electromagnetic switching valve 23 and the flow control for the flow control valve 24 is performed to perform the mold clamping cylinder.
- the mold clamping cylinder 22 f is driven so that the right end of 22 f contacts the left side of the movable die plate 15, and the movable die plate 15, in other words, the movable mold 18 is locked. .
- the arc clamping Siri Sunda 2 2 f movable die 1 8 Ri by the moves driving the movable Daipure sheet 1 5 until 1 second intervals white compression for stationary die 1 9 rightward To move forward.
- Off valve 4 3 at Roh nozzle portion 3 1 of the movable mold 1 8 drives the mono Bomota 4 4 in the presence of the 1 second interval white compression for the stationary die 1 9 injection Yuni' DOO 3 0
- the flow rate control valve 38 is controlled to flow and the solenoid relief valve 39 is controlled to set the pressure value, and the hydraulic screw 41 moves the screw 35 forward.
- the molten resin material 52 is introduced into the mold cavity 21 via the flow path 34 and the injection port 20, and in this embodiment, the gas contained in the molten resin material 52 grows as bubbles.
- the injection supply is performed at 150 kg / cm 2 , which is not less than 15 kg Z cm 2, which is a pressure sufficient to suppress.
- the servo motor 44 is driven while the molten resin material 52 required for molding is injected and supplied to the mold cavity 21 to close the on-off valve 43. At this time, by closing the open / close valve 43, the resin material 52 can be prevented from flowing back to the injection unit 30 by the pressure of the press. ⁇ Also, the open / close valve 43 is connected to the resin passage of the mold. Even so, the same effect can be obtained.
- the mold switching cylinder 22 f is driven by controlling the excitation switching control of the electromagnetic switching valve 23 to move the movable mold.
- the plate-shaped glass 50 a thin glass of 0.1 mm was used, but it is preferable that the glass be in the range of 0.1 to 3 mm. Further, the thickness of the resin layer 57 is formed to be 3 mm, but it is preferable that the thickness of the resin layer 57 is in the range of 3 mm to 6 mm. It is needless to say that the thickness of the plate-like glass 50 and the resin layer 57 may be out of the range depending on the use.
- the resin material constituting the above-mentioned resin film 51 includes a plate-like glass 50 and a molded resin material 52 which are adhered to and molded at the time of molding the molten resin material 52. If a material that reduces the difference in contraction and difference in thermal expansion between the plate-like glass 50 and the molded resin material 52 is selected, the adhesion between the glass layer 55 and the resin layer 57 can be reduced. Strength can be improved.
- the resin material for example, in producing a transparent plate-like composite 58, not only the plate-like glass 50 is transparent but also a transparent molten resin material 52.
- thermoplastic resin materials for example, polycarbonate resin, acrylic resin, polystyrene resin, amorphous porphyrin refin resin, polyethylene terephthalate resin, and ethylene butyl acetate Polymer (EVA), thermoplastic polyurethane (TPU), ethylene ⁇ acrylic acid ester 'maleic anhydride terpolymer, hydrogenated styrene butadiene rubber (hydrogenated SBR), Polybutyrate (PVB) or a polyolefin elastomer is recommended.
- TPU thermoplastic polyurethane
- SBR hydrogenated styrene butadiene rubber
- PVB Polybutyrate
- a polyolefin elastomer is recommended.
- the pressure required to expand and mold the molten resin material 52 along the plate-like glass 50 is required. At a pressure of 15 kg / cm 2 or more, the molten resin material 52 is sufficient to prevent the gas contained in the molten resin material 52 from growing as bubbles.
- the intermediate layer 56 is formed by adhering the resin film 51 composed of the above-described resin material, but such a resin material is formed of a plate-like glass 50.
- a primer treatment to be applied to the joint surface may be performed in advance.
- the intermediate layer 56 may be omitted altogether, and furthermore, as shown in FIG. 5, the intermediate layer may be omitted to form the glass layer 55 ′, at the joining surface of the plate-like glass 50 ′.
- the plate-like composite 58 ' may be manufactured by performing a pretreatment of applying a silane coupling agent or a borane in order to increase the bonding strength.
- the resin film 51 is adhered to or adhered to a plate-like glass 50 to which a primer treatment has been applied.
- Print processing can be performed.
- a mirror surface treatment, and further a transparent conductive film such as an indium tin oxide film can be applied to the bonding surface of the plate-like glass 50 with the intermediate layer 56 by sputtering. .
- the glass layer 55 was provided on one surface of the plate-like composite 58, but as shown in FIG. 6, the molten resin material 52 "was injected into the mold cavities 21.
- the supply port 20 ′ for supplying is provided on the side, the thin plate-shaped glass 50 ′′, 50 ′′ ′′ formed in a predetermined shape can be connected to the movable mold 18 ′ and the fixed mold 19 ′.
- a plate as shown in Fig. 7 is installed by contacting the inside with each other so that they are tightly attached without any gap.
- a plate-like composite 58 having glass layers 55 ", 55 on both sides of the fibrous composite can be manufactured. Note that reference numerals 5 6 ', 5 6" in the figure denote intermediate layers.
- the intermediate layers 56 ′ and 56 ′′ may be omitted altogether, or the intermediate layers 56 ′ and 56 ′′ may be replaced with a pretreatment of applying a silane coupling agent or a borane as described above. It goes without saying that it is good.
- the same polycarbonate resin, acrylic resin, polystyrene resin, and amorphous polyethylene as described above are used instead of the plate-like glass 50 "" constituting the glass layer 55 "".
- Ethylene resin polyethylene terephthalate resin, ethylene vinyl acetate copolymer (EVA), thermoplastic polyurethane (TPU), ethylene acrylate, ice-free male Transparent resin made of resin materials such as acid terpolymer, hydrogenated styrene butadiene rubber (hydrogenated SBR), polybutyrate (PVB), and polyolefin elastomer A plate may be used.
- resin material having a higher melting point than the resin material of the resin layer 57 and a hard resin material for the resin plate may be used.
- an intermediate layer may be formed between the resin plate and the resin layer 57 "by applying a resin film or by performing a primer treatment.
- the resin film may be applied.
- the printed surface may be printed on the bonded surface of the attached or primed plate-like glass, and the surface of the resin plate bonded to the intermediate layer is mirror-finished, and furthermore, transparent conductive material.
- a film may be applied ⁇ Needless to say, the intermediate layer may be omitted.
- the glass layer 55 has a thickness of 0.1 mm, and the intermediate layer 56 and the intermediate layer 56 formed of a 0.4 mm-thick resin film 51 made of a thermoplastic polyurethane resin material.
- the glass layer 55 is on the upper surface and the height is 2 m from the upper lm.
- the plate-like composite may be a layered plate-like composite in which a plurality of resin layers of the molten resin material to be molded are interposed.
- a glass layer formed of plate-like glass, a resin layer formed of a molten resin material, a resin layer formed of a resin plate, a resin layer formed of a molten resin material, a resin plate In the case where the resin layers formed in step (a) are sequentially arranged in layers, a glass layer formed of plate-like glass, a resin layer formed of a molten resin material, and a resin layer formed of a resin plate. This is the case where a resin layer, a resin layer molded and formed of a molten resin material, and a glass layer formed of plate-like glass are sequentially arranged in layers.
- the compression molding unit 10 instead of the compression molding unit 10 in this embodiment, the compression molding unit disclosed in Japanese Patent Application Laid-Open Nos. 5-22049 and 5-285595 is used. Can be used.
- Japanese Patent Application Laid-Open Nos. Hei 4-3161034 and Hei 4-3339646 disclose.
- a hot plate press method disclosed in Japanese Patent Application Laid-Open No. HEI 8-189896 describes a plate-like composite that has been injected and then cooled to room temperature in order to easily and thinly reduce the thickness.
- the resin was solidified by applying a pressure of 5 kg Z cm 2 at a plate temperature of 150 ° for 10 seconds using a hot press apparatus as disclosed in Layer 57 can be heated, cured and compressed to a thickness of lmm to 0.6mm.
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/171,093 US6296799B1 (en) | 1996-04-22 | 1997-04-07 | Plate-like composite material and method of producing the same |
EP97914625A EP0908287A4 (en) | 1996-04-22 | 1997-04-07 | PLATFORM MATERIAL AND METHOD FOR THE PRODUCTION THEREOF |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8100569A JPH09286039A (ja) | 1996-04-22 | 1996-04-22 | 板状複合体およびその製造法 |
JP8/100569 | 1996-04-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997039869A1 true WO1997039869A1 (fr) | 1997-10-30 |
Family
ID=14277549
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1997/001190 WO1997039869A1 (fr) | 1996-04-22 | 1997-04-07 | Materiau composite de type plaque et procede de fabrication |
Country Status (4)
Country | Link |
---|---|
US (1) | US6296799B1 (ja) |
EP (1) | EP0908287A4 (ja) |
JP (1) | JPH09286039A (ja) |
WO (1) | WO1997039869A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US6379771B1 (en) | 1997-11-12 | 2002-04-30 | Komatsu Ltd. | Sheet-like structure material and manufacturing method |
CN112874073A (zh) * | 2021-01-20 | 2021-06-01 | 浙江水墨江南新材料科技有限公司 | 树脂装饰板及制造方法 |
Families Citing this family (21)
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---|---|---|---|---|
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DE102009021938A1 (de) * | 2009-05-19 | 2010-11-25 | Nyssen, Siegfried, Dr. | Verbundglasscheibe und Verfahren zu ihrer Herstellung |
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EP3085510A4 (en) | 2013-12-16 | 2017-07-26 | Asahi Glass Company, Limited | Glass-resin laminate and method for producing same |
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CN108025474A (zh) * | 2015-09-25 | 2018-05-11 | 沙特基础工业全球技术有限公司 | 使用模具插入件进行模塑的方法及用于其的装置 |
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CN110587910A (zh) * | 2019-09-12 | 2019-12-20 | 中国航发北京航空材料研究院 | 一种复合结构透明件的注射成型方法 |
KR102363856B1 (ko) * | 2019-09-24 | 2022-02-17 | 주식회사 서연이화 | 차량용 폴리카보네이트 글레이징 제조방법 |
CN113443841B (zh) * | 2021-08-02 | 2022-04-19 | 南京宣汉玻璃有限公司 | 一种抵御太阳和电磁辐射的玻璃新材料的粘合装置及该玻璃新材料的生产方法 |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5328475B1 (ja) * | 1969-10-21 | 1978-08-15 | ||
JPS63262241A (ja) * | 1987-04-21 | 1988-10-28 | 旭化成株式会社 | 積層体 |
JPH0180418U (ja) * | 1987-11-18 | 1989-05-30 | ||
JPH04364910A (ja) * | 1991-06-12 | 1992-12-17 | Sumitomo Chem Co Ltd | 多層成形品の成形方法 |
JPH0584867A (ja) * | 1991-09-27 | 1993-04-06 | Sekisui Chem Co Ltd | 積層安全ガラス |
JPH0596235A (ja) * | 1991-10-09 | 1993-04-20 | Sumitomo Electric Ind Ltd | 弗素樹脂被覆物 |
JPH05208467A (ja) * | 1991-10-23 | 1993-08-20 | Sumitomo Chem Co Ltd | 多層成形体及びその製造方法 |
JPH0623910A (ja) * | 1992-05-14 | 1994-02-01 | Saint Gobain Vitrage Internatl | 断面材とガラスの接着方法及びその方法で得られたガラス |
JPH07205374A (ja) * | 1993-07-28 | 1995-08-08 | Asahi Glass Co Ltd | 積層ガラスおよび積層ガラスの製造方法 |
WO1996012604A1 (fr) * | 1994-10-20 | 1996-05-02 | Komatsu Ltd. | Plaque composite et son procede de fabrication |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2084113A (en) * | 1935-03-23 | 1937-06-15 | Duplate Corp | Process and apparatus for making safety glass |
US3382137A (en) * | 1964-09-18 | 1968-05-07 | Corning Glass Works | Laminated structures and method for preparing such structures |
DE1629350A1 (de) * | 1966-02-16 | 1971-05-19 | Deutsche Spiegelglas Ag | Mit UEberzug versehene,kratzfeste,chemisch und mechanisch widerstandsfaehige Kunststoffscheibe |
US3666614A (en) | 1969-06-24 | 1972-05-30 | Union Carbide Corp | Glass-polycarbonate resin laminates |
JPS5936800B2 (ja) | 1976-08-30 | 1984-09-05 | 沖エンジニアリング株式会社 | 車輌分離識別装置 |
CA1114115A (en) * | 1977-11-04 | 1981-12-15 | Corning Glass Works | Direct casting method for producing low-stress glass/plastic composites |
ZA824094B (en) | 1981-06-19 | 1983-07-27 | Ici Plc | A process for the manufacture of cephalosporin derivative |
US4724023A (en) * | 1985-04-09 | 1988-02-09 | E M Partners Ag | Method of making laminated glass |
JPH07166B2 (ja) | 1987-09-24 | 1995-01-11 | 三菱重工業株式会社 | Co吸着分離方法 |
FR2634753B1 (fr) * | 1988-07-27 | 1992-08-21 | Saint Gobain Vitrage | Vitrage a couche electro-conductrice obtenue par pyrolyse de composes en poudre, utilisable en tant que pare-brise pour automobile |
GB9009066D0 (en) | 1990-04-23 | 1990-06-20 | Hickman James A A | Method of laminating glass |
ATE179652T1 (de) * | 1990-12-11 | 1999-05-15 | Pilkington Uk Ltd | Verfahren zur verbindung von glasscheiben und danach hergestellte artikel |
US5264160A (en) * | 1991-04-30 | 1993-11-23 | Canon Kabushiki Kaisha | Method of molding optical elements |
JPH05514A (ja) | 1991-06-24 | 1993-01-08 | Ricoh Co Ltd | インク吐出用ノズルの目詰まり防止機能をもつ保存装置 |
DE4212944A1 (de) * | 1992-04-18 | 1993-10-21 | Docter Optic Wetzlar Gmbh | Verfahren zur Herstellung einer Glasfläche |
GB9313830D0 (en) * | 1993-07-01 | 1993-08-18 | Aho Michael S | Improvements in and relating to strengthened glass products |
DE4406097A1 (de) * | 1994-02-25 | 1995-08-31 | Dornier Gmbh | Verglasung |
US5545277A (en) | 1994-10-03 | 1996-08-13 | Ford Motor Company | Plate glass edge strength |
US5593786A (en) | 1994-11-09 | 1997-01-14 | Libbey-Owens-Ford Company | Self-adhering polyvinyl chloride safety glass interlayer |
FR2743802B1 (fr) * | 1996-01-19 | 1998-03-20 | Saint Gobain Vitrage | Vitrage feuillete et primaire utilise pour sa realisation |
-
1996
- 1996-04-22 JP JP8100569A patent/JPH09286039A/ja active Pending
-
1997
- 1997-04-07 WO PCT/JP1997/001190 patent/WO1997039869A1/ja not_active Application Discontinuation
- 1997-04-07 US US09/171,093 patent/US6296799B1/en not_active Expired - Fee Related
- 1997-04-07 EP EP97914625A patent/EP0908287A4/en not_active Withdrawn
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5328475B1 (ja) * | 1969-10-21 | 1978-08-15 | ||
JPS63262241A (ja) * | 1987-04-21 | 1988-10-28 | 旭化成株式会社 | 積層体 |
JPH0180418U (ja) * | 1987-11-18 | 1989-05-30 | ||
JPH04364910A (ja) * | 1991-06-12 | 1992-12-17 | Sumitomo Chem Co Ltd | 多層成形品の成形方法 |
JPH0584867A (ja) * | 1991-09-27 | 1993-04-06 | Sekisui Chem Co Ltd | 積層安全ガラス |
JPH0596235A (ja) * | 1991-10-09 | 1993-04-20 | Sumitomo Electric Ind Ltd | 弗素樹脂被覆物 |
JPH05208467A (ja) * | 1991-10-23 | 1993-08-20 | Sumitomo Chem Co Ltd | 多層成形体及びその製造方法 |
JPH0623910A (ja) * | 1992-05-14 | 1994-02-01 | Saint Gobain Vitrage Internatl | 断面材とガラスの接着方法及びその方法で得られたガラス |
JPH07205374A (ja) * | 1993-07-28 | 1995-08-08 | Asahi Glass Co Ltd | 積層ガラスおよび積層ガラスの製造方法 |
WO1996012604A1 (fr) * | 1994-10-20 | 1996-05-02 | Komatsu Ltd. | Plaque composite et son procede de fabrication |
Non-Patent Citations (1)
Title |
---|
See also references of EP0908287A4 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6379771B1 (en) | 1997-11-12 | 2002-04-30 | Komatsu Ltd. | Sheet-like structure material and manufacturing method |
US6669890B1 (en) | 1997-11-12 | 2003-12-30 | Komatsu, Ltd. | Sheet-like structure material and manufacturing method |
CN112874073A (zh) * | 2021-01-20 | 2021-06-01 | 浙江水墨江南新材料科技有限公司 | 树脂装饰板及制造方法 |
Also Published As
Publication number | Publication date |
---|---|
JPH09286039A (ja) | 1997-11-04 |
EP0908287A1 (en) | 1999-04-14 |
EP0908287A4 (en) | 1999-08-11 |
US6296799B1 (en) | 2001-10-02 |
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