WO2009101822A1 - Process for producing composite molding - Google Patents
Process for producing composite molding Download PDFInfo
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- WO2009101822A1 WO2009101822A1 PCT/JP2009/000583 JP2009000583W WO2009101822A1 WO 2009101822 A1 WO2009101822 A1 WO 2009101822A1 JP 2009000583 W JP2009000583 W JP 2009000583W WO 2009101822 A1 WO2009101822 A1 WO 2009101822A1
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- Prior art keywords
- mold
- resin
- temperature
- molding
- thermoplastic resin
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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
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/72—Heating or cooling
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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
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/76—Measuring, controlling or regulating
- B29C45/78—Measuring, controlling or regulating of temperature
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- 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
- B29K2705/00—Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts
Definitions
- the present invention relates to a method for producing a composite molded product of at least one thermoplastic resin selected from polyarylene sulfide resin and polyamide resin and a metal part, and in particular, ensures excellent adhesion between the resin and the metal part.
- the present invention relates to a method for manufacturing a composite molded article having an improved molding cycle.
- Composite molded products composed of resin and metal typified by insert molded products are used in the manufacture of electrical / electronic parts, automobile parts and the like.
- the close contact between the metal insert and the resin interface is not sufficient by a normal molding method, and it causes dropout or gas / liquid leakage from the interface.
- a method is known in which irregularities are formed by surface treatment of a metal and a molten resin is injected there. According to this method, a resin-metal composite molded product with excellent interface adhesion can be obtained.
- chemicals are used for surface treatment, it is costly to introduce such as equipment installation and chemical management. There are many difficult points from up.
- JP 2001-1382 by performing the control of pouring the molten resin into the system heated above the melting point by the insert heating method, maintaining the pressure, further lowering the temperature and raising the load pressure, Although a technique for improving the adhesion between the resin and the metal has been proposed, it is required to strictly control the temperature and pressure, and the incidental facilities tend to increase, so it cannot be said that it is highly practical.
- JP 2001-1382 assumes low density polyethylene resin, polypropylene, polystyrene, and the like. In the case of polyarylene sulfide resin and polyamide resin, the method disclosed in JP 2001-1382 A A composite molded article with good metal adhesion cannot be obtained.
- Japanese Patent Application Laid-Open No. 2005-342922 proposes to improve the adhesion strength between metal and resin by using a die surface-treated with a diamond-like carbon coating. There was a problem that molding could not be performed in cycle time. Disclosure of the invention
- the object of the present invention is to solve the above-mentioned problems of the prior art, to shorten the molding cycle time, and to provide a composite molded product of resin and metal having stable and good adhesion.
- the present inventors have performed molding by controlling the temperature of the molding die to a specific condition, and for that purpose, using a molding die having a specific structure. It has been found that it is extremely effective, and the present invention has been completed.
- the present invention is a method for producing a composite molded product of at least one thermoplastic resin selected from polyarylene sulfide resin and polyamide resin and a metal part,
- the molding die has a main mold for controlling the interlocking with the molding machine, and a portion where a thermoplastic resin having a heating circuit and a cooling circuit for temperature control and a metal part are in contact with each other. Divided into pieces that are included in (2) The portion where resin flows in and comes into contact with the mold during molding is surface-treated with a 10-point average roughness (Rz) of 0.5 ⁇ m or less, and the volume of the piece mold is 60 cm 3 or less.
- Rz 10-point average roughness
- thermoplastic resin in a state where the die mold temperature is heated to 200 ° C to the melting point of the thermoplastic resin.
- the piece-shaped heating circuit is immediately shut off, and the piece-shaped cooling circuit is rapidly cooled at a cooling rate of 7 ° C./second or more. It is a manufacturing method.
- thermoplastic resin metals it has become possible to produce a composite molded article having improved adhesion between a thermoplastic resin and a metal, which has been insufficient with the conventional method.
- excellent adhesion between thermoplastic resin metals can be ensured in a shorter molding cycle by temperature control simpler than the conventional method.
- FIG. 1 is a view showing an example of a piece shape used in the present invention.
- (A) is a top view of a piece shape on the metal component set side
- (b) is a side sectional view
- (c) is a metal component opposite set.
- (d) is a side cross-sectional view.
- FIG. 2 is a view showing an example of a metal part used in the present invention.
- FIG. 3 is a view showing an example of a composite molded product obtained by the present invention, in which (a) is a top view, (b) is a bottom view, (c) is a side view, and (d) is a side cross-sectional view.
- FIG. 4A and 4B are schematic views showing the state of airtightness evaluation, where FIG. 4A is a schematic cross-sectional view, and FIG. 4B is a schematic perspective view.
- FIG. 1 is a view showing another example of a piece shape used in the present invention.
- (A) is a top view of a piece shape on the metal component set side
- (b) is a side sectional view
- (c) is a metal component.
- (d) is a side cross-sectional view.
- FIG. 6 is a view showing another example of the composite molded product obtained by the present invention, in which (a) is a top view and (b) is a side view.
- FIG. 7 is a schematic diagram showing the situation of adhesion strength evaluation.
- (A) is a schematic side view
- (b) is a schematic front view.
- the metal parts used in the present invention are not particularly limited in materials, and examples thereof include metals such as copper, aluminum and iron, alloys such as phosphor bronze and stainless steel, bonded bodies of different metals, and plated products thereof. .
- Examples of stainless steel include martensite and austenite.
- the metal part used in the present invention is a shape processed into a predetermined shape, and the shape is not particularly limited.
- the metal part is an insert part, there is no particular limitation on the shape thereof, and one end part of the insert part is exposed or protrudes outside the molded product, for example, terminals of electric / electronic parts. Can be mentioned.
- Metal parts generally have fine irregularities on rolled plates, etc., and can be adhered without special roughening treatment, but further adhesion can be achieved by roughening the surface. It is more preferable to perform surface treatment for improving the property.
- Examples of the roughening treatment include a method of forming a porous shape by surface polishing, plating, etching, or the like.
- thermoplastic resin and the metal In order to improve the adhesion between the thermoplastic resin and the metal, it is important to control the temperature of the metal part where the thermoplastic resin and the metal part are in contact with each other. It is necessary to design the frame shape so as to include the part where the metal part and the metal part are in contact.
- the molding cycle can be shortened.
- the target molding cycle cannot be shortened, the volume of the piece mold must be 60 cm 3 or less, and the outer peripheral portion in contact with the main mold of the piece mold needs to be heat-insulated.
- a method such as providing a heat insulation layer is simple. When the volume of the piece shape exceeds 60 cm 3 , the molding cycle becomes long in normal equipment, which is not preferable.
- the piece mold is molded with the piece mold embedded in the main mold, if the heat insulating layer is not provided, the instantaneous temperature change of the piece mold is impossible and the molding cycle cannot be shortened.
- a heat insulating plate is used as the heat insulating layer, but it may be a heat insulating layer such as an air cap and is not particularly limited to this method.
- the heat insulating plate include glass reinforced polyester, glass epoxy laminated plate, phenol resin and the like.
- the portion where the resin flows in and comes into contact with the main mold and the piece mold is surface-treated so that the ten-point average roughness (Rz) is 0.5 ⁇ m or less. is necessary. If the ten-point average roughness (Rz) is greater than 0.5 ⁇ m, the resin will be in close contact with the mold (piece mold), and a good composite molded product cannot be obtained due to mold release failure.
- any surface treatment may be used as long as the surface roughness is within the above range, but specifically, a surface treatment such as diamond-like carbon coating (DLC), CrN, Cr plating, etc. Surface treatment with a diamond-like carbon coating is preferred from the standpoint of corrosion resistance and abrasion resistance.
- thermoplastic resin is injected and filled while being heated to a temperature range of 230 ° C. to the melting point of the thermoplastic resin.
- the die temperature of the piece is lower than 200 ° C, the adhesion between the thermoplastic resin and the metal parts is reduced, and if the melting point of the thermoplastic resin is exceeded, the resin is difficult to solidify in the mold, causing problems in the molding process. May occur, which is not preferable.
- thermoplastic resin is filled around the metal part and the thermoplastic resin is sufficiently pressed against the heated metal part by the injection pressure, and before that, if the temperature of the metal part falls below the above temperature, There arises a problem that the adhesion between the plastic resin and the metal part is insufficient. Therefore, after the thermoplastic resin is injected and filled, and the thermoplastic resin is completely filled in the molding die, the piece-shaped heating circuit is immediately shut off for release, and the piece-shaped cooling circuit is used. It is necessary to rapidly cool at a cooling rate of more than a second. As a result, the thermoplastic resin and the metal part can be brought into close contact with each other in a short time.
- Both the main mold for controlling the interlocking with the molding machine and the block mold having a heating circuit and a cooling circuit for temperature control are heated by a heating element which is a method for heating a normal mold. And a method of heating with a heat medium.
- a method of heating with a heating element a method of heating with a heater electrically insulated from a mold, an electromagnetic induction heater or a heat medium can be mentioned.
- Examples of the method of heating with a heater electrically insulated from the mold include a method of embedding a sheath wire heater or the like in the mold, or a method of attaching a heating plate embedded with a heater to the mold surface.
- a method for heating with a heat medium there is a method in which a heat medium flow path is provided in a mold, and a heat medium having a predetermined temperature is supplied from the outside and discharged.
- a heat medium Fluids, such as oil, water, air, nitrogen, a combustion gas, are mentioned, In the case of a vapor
- the main mold that maintains a constant temperature is not particularly limited, but as a piece-shaped heating method that requires instantaneous temperature control, a heating method using a heating element such as a heater is preferably used.
- a heating method using a heating element such as a heater is preferably used.
- the piece heating circuit is immediately shut off and rapidly cooled at a cooling rate of 7 ° C./second or more by the piece cooling circuit.
- the heat medium is not particularly limited, and examples thereof include fluids such as oil, water, air, nitrogen, and combustion gas.
- a cooling flow path is provided in the block shape as a cooling circuit, and the flow path is in the air.
- Examples include a method in which low-temperature air in which moisture is condensed or solidified and frozen is allowed to pass, and the piece in contact with the metal part is cooled by heat of melting ice or heat of vaporization of moisture.
- FIG. 1 is a view showing an example of a piece shape for holding a metal part in order to manufacture a composite molded product by the method of the present invention.
- FIG. 1 has a piece shape that includes the entire metal part, it is not necessary to include the entire metal part, and the portion where the thermoplastic resin and the metal part are in contact is included in the interior to provide good adhesion.
- the composite molded product can be obtained.
- FIG. 1 is provided with a heat insulating plate 4 as shown in FIG. 1, embedded in the main mold (not shown), and used as a molding die.
- the heating component (bar heater) 3 is a heater that raises the piece shape to a predetermined temperature as a heating circuit.
- the flow path 2 allows low-temperature air to pass through low-temperature air in which moisture in the air is dewed or solidified and frozen, and cools the block shape by heat of melting ice or heat of vaporization of water. It becomes the flow path.
- thermoplastic resin used in the present invention is at least one selected from polyarylene sulfide resins and polyamide resins.
- the polyarylene sulfide resin is mainly composed of-(Ar-S)-(where Ar is an arylene group) as a repeating unit.
- the arylene group include p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group, p, p′-diphenylene sulfone group, p, p′-biphenylene group, and p, p′-di.
- a phenylene ether group, p, p′-diphenylenecarbonyl group, naphthalene group, and the like can be used.
- a copolymer containing different types of repeating units is used from the viewpoint of processability of the composition. It may be preferable.
- polyphenylene sulfide using p-phenylene group as an arylene group and p-phenylene sulfide group as a repeating unit is preferably used.
- the copolymer among the arylene sulfide groups comprising the above-mentioned arylene groups, two or more different combinations can be used, and among them, a combination containing a p-phenylene sulfide group and an m-phenylene sulfide group is particularly preferably used. It is done.
- those containing p-phenylene sulfide groups of 70 mol% or more, preferably 80 mol% or more are suitable from the viewpoint of physical properties such as heat resistance, moldability and mechanical properties.
- polyarylene sulfide resins a high molecular weight polymer having a substantially linear structure obtained by condensation polymerization from a monomer mainly composed of a bifunctional halogen aromatic compound can be preferably used.
- a low molecular weight linear structure polymer that can be used and heated at a high temperature in the presence of oxygen or an oxidant to increase the melt viscosity by oxidative crosslinking or thermal crosslinking to improve molding processability, or a mixture thereof Can also be used.
- the polyarylene sulfide resin is mainly composed of the linear polyarylene sulfide resin, and a part of the polyarylene sulfide resin (1 to 30% by weight, preferably 2 to 25% by weight) has a relatively high viscosity (resin temperature 310 ° C.,
- a mixed system with a branched or crosslinked polyarylene sulfide resin having a melt viscosity of 300 to 3000 Pa ⁇ s, preferably 500 to 2000 Pa ⁇ s at a shear rate of 1200 sec ⁇ 1 is also suitable.
- the polyarylene sulfide resin used in the present invention is preferably a polyarylene sulfide resin that has been subjected to acid cleaning, hot water cleaning, organic solvent cleaning (or a combination thereof) and the like to remove by-product impurities and the like after polymerization.
- examples of the polyamide resin include various known polyamide resins.
- dicarboxylic acids such as oxalic acid, adipic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, 1,4-cyclohexyl dicarboxylic acid and ethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine, 1,4- Polyamide resins obtained by polycondensation with diamines such as cyclohexyldiamine and m-xylylenediamine; Polyamide resins obtained by polymerizing cyclic lactams such as caprolactam and laurin lactam; or salts of cyclic lactam and diamine Examples thereof include a polyamide resin obtained by copolymerization. Among these polyamide-based resins, 6 nylon, 66 nylon, 12 nylon, 46 nylon, MXD6 nylon, and copolymers thereof are preferable.
- a polyamide elastomer resin can also be used as the polyamide resin.
- the polyamide elastomer resin is a polyamide block copolymer having a flexural modulus of 10,000 kgf / cm 2 or less (50% relative humidity, 23 ° C.) in which a polyamide hard segment and other soft segments are bonded.
- a typical example of such an elastomer soft segment is polyalkylene oxide (alkylene group having 2 to 6 carbon atoms).
- examples of the polyamide component of the hard segment include polyamides such as polyamide 6, polyamide 66, polyamide 6,12, polyamide 11, and polyamide 12.
- Polyether components as the soft segment include polyoxyethylene glycol, polyoxy Examples include propylene glycol and polyoxytetramethylene glycol.
- thermoplastic resin used in the present invention may be either a polyarylene sulfide resin or a polyamide resin, or both may be used in combination.
- two or more polyarylene sulfide resins can be used in combination or two or more polyamide resins can be used in combination in order to adjust the target physical property value.
- thermoplastic resin used in the present invention can also be used as a resin composition containing an elastomer, and a polyphenylene sulfide resin composition containing an elastomer is particularly preferred because the effect of the present invention is remarkable.
- Any elastomer can be included as long as it has heat resistance that does not cause significant decomposition during the melt processing of the thermoplastic resin. From the viewpoint of heat resistance, an ethylene copolymer is preferred. .
- Examples of the ethylene copolymer include an ethylene copolymer mainly composed of ethylene and a glycidyl ester of ⁇ , ⁇ -unsaturated acid, an ethylene copolymer mainly composed of ethylene and an alkyl ester of ⁇ , ⁇ -unsaturated acid, ethylene And ethylene copolymers of ⁇ -olefins having 5 or more carbon atoms.
- a graft copolymer in which a third component such as acrylic acid, methyl acrylate, methacrylic acid, acrylonitrile, styrene or the like is branched or crosslinked chemically bonded to these ethylene ethylene copolymers may be used.
- the elastomer content is preferably 1 to 15% by weight of the entire composition.
- the resin may contain various resin additives and fillers.
- [Usage] The composite molded article obtained by the present invention can be widely used for electric / electronic parts, automobile parts and the like.
- A Polyphenylene sulfide (PPS) resin, manufactured by Kureha Co., Ltd., Fortron KPS (melting viscosity 30 Pa ⁇ s at a resin temperature of 310 ° C. and a shear rate of 1200 sec ⁇ 1 )
- B Elastomer ⁇ (B-1) Copolymer obtained by grafting 30 parts by weight of methyl methacrylate / butyl acrylate copolymer (9/21) to 70 parts by weight of ethylene / ethyl acrylate copolymer (Nippon Yushi Co., Ltd.) Manufactured by Modiper A5300) ⁇ (B-2) Ethylene / octene copolymer (DuPont Dow Elastomers LLC, Engage 8440) (B-3) A copolymer obtained by grafting 30 parts by weight of a methyl methacrylate / butyl acrylate copolymer (9/21) to 70 parts by weight of an
- Example 1 Using a molding die composed of a main mold for controlling the interlocking between the heating circuit and the molding machine having the cooling mold shown in FIG. 1 and maintaining the temperature of the main mold at 150 ° C.
- the metal part shown in FIG. 2 was set in a piece shape, and immediately the temperature of the piece shape was raised from 150 ° C. to a predetermined temperature (245 ° C.). It took 9.5 seconds to reach 245 ° C.
- the molding die was closed, and then a PPS resin was injection molded under the following conditions to obtain a composite molded product as shown in FIG.
- the material 1 shown in Table 1 was used as the PPS resin.
- Piece-shaped surface treatment A steel film SUS420J2 was coated with a diamond-like carbon coating (DLC) to a thickness of 1.0 ⁇ m.
- the surface roughness is the resin flow direction; ten-point average roughness (Rz) of 0.45 ⁇ m and arithmetic average roughness (Ra) of 0.1 ⁇ m.
- Test product shape for airtightness evaluation width 10 mm x length 10 mm x height 3 mm (see Fig. 3) Molding machine: TR40VR manufactured by Sodick Plustech Co., Ltd.
- the molding cycle time refers to the time from the time when the metal part is set in the piece shape to the time when the composite molded product is taken out.
- Example 2 The PPS resin was molded and evaluated in the same manner as in Example 1 except that the material 2 shown in Table 1 was used.
- Example 3 Molding and evaluation were performed in the same manner as in Example 1 except that the piece temperature at the time of injection molding was 200 ° C.
- Examples 4-5 The PPS resin was molded and evaluated in the same manner as in Example 3 except that the materials 3 and 4 in Table 1 were used.
- Comparative Example 1 It was molded and evaluated in the same manner as in Example 1 except that a heat insulating plate was not used between the main mold and the piece mold. It took 10 minutes or more to raise the temperature to 245 ° C.
- Comparative Example 2 Molding and evaluation were performed in the same manner as in Example 1 except that the volume of the piece was 250 cm 3 . It took 10 minutes or more to raise the temperature to 245 ° C.
- Comparative Example 3 It was molded in the same manner as in Example 1 except that the piece shape was not subjected to the surface treatment and the 10-point average roughness (Rz) of 3.0 ⁇ m was used. I could't.
- Comparative Example 4 Molding and evaluation were performed in the same manner as in Example 1 except that the piece temperature during injection molding was set to 170 ° C.
- Example 6 Using a molding die comprising a main mold for controlling the interlocking between the heating circuit and the molding machine having the cooling mold shown in FIG. 5 and maintaining the temperature of the main mold at 150 ° C.
- a metal plate having a thickness of 1 mm and 50 mm ⁇ 50 mm was set in a piece shape, and immediately the temperature of the piece shape was raised from 150 ° C. to a predetermined temperature (200 ° C.). It took 7 seconds to reach 200 ° C.
- the molding die was closed, and then a PPS resin was injection molded under the following conditions to obtain a composite molded product as shown in FIG.
- the material 1 shown in Table 1 was used as the PPS resin.
- Piece-shaped surface treatment A steel film SUS420J2 was coated with a diamond-like carbon coating (DLC) to a thickness of 1.0 ⁇ m.
- the surface roughness is the resin flow direction; ten-point average roughness (Rz) of 0.35 ⁇ m and arithmetic average roughness (Ra) of 0.09 ⁇ m.
- Test article shape for adhesion strength evaluation see FIG. 6 Molding machine; TR40VR manufactured by Sodick Plustech Co., Ltd.
- Thermal insulation plate Glass epoxy laminate Mold temperature; Main mold is 150 ° C Piece volume; 50cm 3 Cylinder temperature: 320 ° C Piece temperature during injection molding; 200 ° C Injection time (including pressure holding time); 5 seconds Injection speed; 200 mm / second Pressure holding; 100 MPa Cooling rate: 8 ° C / sec Cooling method at the time of cooling: Immediately after the thermoplastic resin is completely filled in the molding die, the heating rod heater is turned off and the moisture in the air is in a dew condensation state. Low-temperature compressed air—30 ° C., 0.6 MPa is passed through the flow path 2.
- peel strength evaluation The peel strength was measured by the method shown in FIG. 7 by using the Tensilon RTC-1325A manufactured by Orientec Co., Ltd. and the indentation speed of 1 mm / min.
- Examples 7-9 The PPS resin was molded and evaluated in the same manner as in Example 6 except that the materials 2, 3, and 4 shown in Table 1 were used.
- Example 10 Molding and evaluation were performed in the same manner as in Example 6 except that the piece mold temperature at the time of injection molding was 220 ° C.
- Examples 11-13 The PPS resin was molded and evaluated in the same manner as in Example 10 except that the materials 2, 3, and 4 in Table 1 were used.
- Example 14 Nylon resin (manufactured by Mitsubishi Engineer Plastics Co., Ltd., polyamide MXD6 resin Reny 1025) was used as the resin, and molding was carried out in the same manner as in Example 6 except that the cylinder temperature of the injection molding machine was changed to 280 ° C.
- Example 15 Molding and evaluation were performed in the same manner as in Example 14 except that the piece mold temperature at the time of injection molding was 220 ° C.
- Comparative Example 5 Molding and evaluation were performed in the same manner as in Example 6 except that the piece mold temperature at the time of injection molding was set to 170 ° C.
- Comparative Examples 6-7 It was molded and evaluated in the same manner as in Example 6 except that the piece-shaped temperature at the time of injection molding was 170 ° C., and the materials 3 and 4 in Table 1 were used as the PPS resin. Comparative Example 8 Molding and evaluation were performed in the same manner as in Example 14 except that the piece mold temperature at the time of injection molding was set to 170 ° C.
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Abstract
Description
背景技術 The present invention relates to a method for producing a composite molded product of at least one thermoplastic resin selected from polyarylene sulfide resin and polyamide resin and a metal part, and in particular, ensures excellent adhesion between the resin and the metal part. In addition, the present invention relates to a method for manufacturing a composite molded article having an improved molding cycle.
Background art
発明の開示 On the other hand, Japanese Patent Application Laid-Open No. 2005-342922 proposes to improve the adhesion strength between metal and resin by using a die surface-treated with a diamond-like carbon coating. There was a problem that molding could not be performed in cycle time.
Disclosure of the invention
(1)成形用金型が、成形機との連動性を制御するための主型と、温度制御のための加熱用回路と冷却用回路を有する熱可塑性樹脂と金属部品とが接する部分を内部に包含する駒型に分割され、
(2)成形用金型の成形時に樹脂が流入して接する部分が十点平均粗さ(Rz)が0.5μm以下に表面処理され、駒型の容積を60cm3以下にし、駒型の主型に接する外周部が断熱処理された状態で主型に駒型が埋め込まれた成形用金型を用い、
(3)成形用金型内に金属部品を設置し、駒型の金型温度を200℃~熱可塑性樹脂の融点の温度範囲に加熱した状態で熱可塑性樹脂を射出充填し、成形用金型内に熱可塑性樹脂が充填完了した後、直ちに駒型の加熱用回路を遮断すると共に駒型の冷却用回路により7℃/秒以上の冷却速度で急速冷却する
ことを特徴とする複合成形品の製造方法である。 That is, the present invention is a method for producing a composite molded product of at least one thermoplastic resin selected from polyarylene sulfide resin and polyamide resin and a metal part,
(1) The molding die has a main mold for controlling the interlocking with the molding machine, and a portion where a thermoplastic resin having a heating circuit and a cooling circuit for temperature control and a metal part are in contact with each other. Divided into pieces that are included in
(2) The portion where resin flows in and comes into contact with the mold during molding is surface-treated with a 10-point average roughness (Rz) of 0.5 μm or less, and the volume of the piece mold is 60 cm 3 or less. Using a molding die in which a piece mold is embedded in the main mold in a state where the outer peripheral portion in contact with the mold is thermally insulated,
(3) A metal part is placed in the mold, and the mold is injected and filled with the thermoplastic resin in a state where the die mold temperature is heated to 200 ° C to the melting point of the thermoplastic resin. Immediately after the filling of the thermoplastic resin inside, the piece-shaped heating circuit is immediately shut off, and the piece-shaped cooling circuit is rapidly cooled at a cooling rate of 7 ° C./second or more. It is a manufacturing method.
2 冷却エアー流路
3 棒ヒータ
4 断熱板
5 金属部品保持ピン
6 複合成形品
7 圧縮エアー挿入孔
8 エアー漏れ測定箇所
9 金属板セット部
10 ボス
11 試験品固定部分
12 金属部品
13 金属板
発明の詳細な説明 DESCRIPTION OF
本発明で使用する金属部品は、材質には特に制限はなく、銅、アルミ、鉄などの金属、燐青銅、ステンレスなどの合金、異種金属の貼合わせ体、これらのメッキ処理品などが挙げられる。ステンレスは、マルテンサイト系、オーステナイト系などが挙げられる。 [Metal parts]
The metal parts used in the present invention are not particularly limited in materials, and examples thereof include metals such as copper, aluminum and iron, alloys such as phosphor bronze and stainless steel, bonded bodies of different metals, and plated products thereof. . Examples of stainless steel include martensite and austenite.
[金型]
本発明では、成形用金型として、成形機との連動性を制御するための主型と、温度制御のための加熱用回路と冷却用回路を有する熱可塑性樹脂と金属部品とが接する部分を内部に包含する駒型に分割して構成されたものを用いる。 Metal parts generally have fine irregularities on rolled plates, etc., and can be adhered without special roughening treatment, but further adhesion can be achieved by roughening the surface. It is more preferable to perform surface treatment for improving the property. Examples of the roughening treatment include a method of forming a porous shape by surface polishing, plating, etching, or the like.
[Mold]
In the present invention, as a molding die, a main mold for controlling the interlocking with the molding machine, a portion where a thermoplastic resin having a heating circuit and a cooling circuit for temperature control and a metal part are in contact with each other are provided. A piece divided into pieces contained inside is used.
[金属部品の加熱]
本発明では、成形用金型内に金属部品を設置し、熱可塑性樹脂と金属部品とが接する部分を内部に包含する駒型の金型温度を200℃~熱可塑性樹脂の融点、より好ましくは230℃~熱可塑性樹脂の融点の温度範囲に加熱した状態で熱可塑性樹脂を射出充填する。駒型の金型温度を200℃~熱可塑性樹脂の融点の温度範囲にすることにより、十分な熱可塑性樹脂-金属間の密着性を得ることができる。駒型の金型温度が200℃より低いと熱可塑性樹脂と金属部品の密着性が低下し、熱可塑性樹脂の融点を超える場合は、金型内で樹脂が固化しにくくなり、成形工程上問題が生じる場合があり好ましくない。 Further, in the molding die used in the present invention, the portion where the resin flows in and comes into contact with the main mold and the piece mold is surface-treated so that the ten-point average roughness (Rz) is 0.5 μm or less. is necessary. If the ten-point average roughness (Rz) is greater than 0.5 μm, the resin will be in close contact with the mold (piece mold), and a good composite molded product cannot be obtained due to mold release failure. As the surface treatment method, any surface treatment may be used as long as the surface roughness is within the above range, but specifically, a surface treatment such as diamond-like carbon coating (DLC), CrN, Cr plating, etc. Surface treatment with a diamond-like carbon coating is preferred from the standpoint of corrosion resistance and abrasion resistance.
[Heating metal parts]
In the present invention, a metal part is placed in a molding die, and a piece mold temperature including a portion where the thermoplastic resin and the metal part are in contact is set to 200 ° C. to the melting point of the thermoplastic resin, more preferably The thermoplastic resin is injected and filled while being heated to a temperature range of 230 ° C. to the melting point of the thermoplastic resin. By setting the piece mold temperature in the temperature range of 200 ° C. to the melting point of the thermoplastic resin, sufficient adhesion between the thermoplastic resin and the metal can be obtained. If the die temperature of the piece is lower than 200 ° C, the adhesion between the thermoplastic resin and the metal parts is reduced, and if the melting point of the thermoplastic resin is exceeded, the resin is difficult to solidify in the mold, causing problems in the molding process. May occur, which is not preferable.
[成形用金型の加熱方法]
成形機との連動性を制御するための主型、温度制御のための加熱用回路と冷却用回路を有する駒型とも、加熱方法としては、通常金型を加熱する方法である発熱体により加熱する方法、熱媒体により加熱する方法等が挙げられる。 In addition, it is necessary that the thermoplastic resin is filled around the metal part and the thermoplastic resin is sufficiently pressed against the heated metal part by the injection pressure, and before that, if the temperature of the metal part falls below the above temperature, There arises a problem that the adhesion between the plastic resin and the metal part is insufficient. Therefore, after the thermoplastic resin is injected and filled, and the thermoplastic resin is completely filled in the molding die, the piece-shaped heating circuit is immediately shut off for release, and the piece-shaped cooling circuit is used. It is necessary to rapidly cool at a cooling rate of more than a second. As a result, the thermoplastic resin and the metal part can be brought into close contact with each other in a short time.
[Method of heating molding die]
Both the main mold for controlling the interlocking with the molding machine and the block mold having a heating circuit and a cooling circuit for temperature control are heated by a heating element which is a method for heating a normal mold. And a method of heating with a heat medium.
[駒型の冷却方法]
本発明では、成形用金型内に熱可塑性樹脂が充填完了した後、直ちに駒型の加熱用回路を遮断すると共に駒型の冷却用回路により7℃/秒以上の冷却速度で急速冷却する。主型と駒型を分割し、駒型のみを温度制御することによって、以上の範囲での急速冷却が可能となるであり、駒型の冷却方法としては、瞬時に冷却可能な方法であれば、通常の冷却方法を用いてもよい。熱媒体として特に制限はなく、油、水、空気、窒素、燃焼ガス等の流体が挙げられるが、好ましくは、冷却回路として駒型内に冷却用流路を設け、その流路に空気中の水分が結露状態あるいは水分が固化し氷結状態にある低温空気を通過させ、氷分の融解熱あるいは水分の気化熱によって金属部品が接する駒型を冷却する方法等が挙げられる。
[成形品及び成形用金型]
本発明で用いられる金属部品及び複合成形品の形状の一例を、図2及び3に示す。 The main mold that maintains a constant temperature is not particularly limited, but as a piece-shaped heating method that requires instantaneous temperature control, a heating method using a heating element such as a heater is preferably used.
[Cool type cooling method]
In the present invention, after the thermoplastic resin is completely filled in the molding die, the piece heating circuit is immediately shut off and rapidly cooled at a cooling rate of 7 ° C./second or more by the piece cooling circuit. By dividing the main mold and the piece mold, and controlling the temperature of only the piece mold, rapid cooling in the above range is possible. Ordinary cooling methods may be used. The heat medium is not particularly limited, and examples thereof include fluids such as oil, water, air, nitrogen, and combustion gas. Preferably, a cooling flow path is provided in the block shape as a cooling circuit, and the flow path is in the air. Examples include a method in which low-temperature air in which moisture is condensed or solidified and frozen is allowed to pass, and the piece in contact with the metal part is cooled by heat of melting ice or heat of vaporization of moisture.
[Molded products and molds]
An example of the shape of the metal part and composite molded product used in the present invention is shown in FIGS.
[樹脂]
本発明に用いられる熱可塑性樹脂は、ポリアリーレンサルファイド樹脂及びポリアミド樹脂より選ばれる1種以上である。 From the outlet of the
[resin]
The thermoplastic resin used in the present invention is at least one selected from polyarylene sulfide resins and polyamide resins.
挙げられる。 Next, examples of the polyamide resin include various known polyamide resins. For example, dicarboxylic acids such as oxalic acid, adipic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, 1,4-cyclohexyl dicarboxylic acid and ethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine, 1,4- Polyamide resins obtained by polycondensation with diamines such as cyclohexyldiamine and m-xylylenediamine; Polyamide resins obtained by polymerizing cyclic lactams such as caprolactam and laurin lactam; or salts of cyclic lactam and diamine Examples thereof include a polyamide resin obtained by copolymerization. Among these polyamide-based resins, 6 nylon, 66 nylon, 12 nylon, 46 nylon, MXD6 nylon, and copolymers thereof are preferable.
[用途]
本発明により得られた複合成形品は、電機・電子部品、自動車部品等に広く使用することができる。 The resin may contain various resin additives and fillers.
[Usage]
The composite molded article obtained by the present invention can be widely used for electric / electronic parts, automobile parts and the like.
(樹脂材料の調製)
表1に示す(A)、(B)、(D)成分をヘンシェルミキサーで5分間混合し、次いでこれをシ
リンダー温度320℃の二軸押出機に投入後、(C)成分は押出機のサイドフィード部より別添加し、二軸押出機内の樹脂温度350℃にて溶融混練を行い、樹脂組成物をペレット状に調製した。(A)~(D)成分の詳細は以下の通りである。
(A)ポリフェニレンサルファイド(PPS)樹脂
・(株)クレハ製、フォートロンKPS(樹脂温度310℃、剪断速度1200sec-1における溶融粘度30Pa・s)
(B)エラストマー
・(B-1)エチレン/エチルアクリレート共重合体70重量部にメチルメタクリレート/ブチルアクリレート共重合体(9/21)を30重量部グラフトさせた共重合体(日本油脂(株)製、モディパーA5300)
・(B-2)エチレン/オクテン共重合体(DuPont Dow Elastomers L.L.C製、エンゲージ8440)
・(B-3)エチレン/グリシジルメタクリレート共重合体70重量部にメチルメタクリレート/ブチルアクリレート共重合体(9/21)を30重量部グラフトさせた共重合体(日本油脂(株)製、モディパーA4300)
(C)無機充填剤
・(C-1)ガラス繊維(10μmφのチョップドストランド(ファイバーグラスジャパン(株)製、CS03JA-FT636))
・(C-2)ガラスフレーク(日本板ガラス(株)製ガラスフレーク、Eガラス平均粒径600μmφ)
・(C-3)炭酸カルシウム(東洋ファインケミカル(株)製ホワイトンP)
(D)離型剤
・日本油脂(株)製、ユニスターH-476 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
(Preparation of resin material)
Components (A), (B), and (D) shown in Table 1 were mixed with a Henschel mixer for 5 minutes, then charged into a twin-screw extruder with a cylinder temperature of 320 ° C, and then component (C) was the side of the extruder. Separately added from the feed section, melt kneading was performed at a resin temperature of 350 ° C. in the twin-screw extruder to prepare a resin composition in the form of pellets. Details of the components (A) to (D) are as follows.
(A) Polyphenylene sulfide (PPS) resin, manufactured by Kureha Co., Ltd., Fortron KPS (melting viscosity 30 Pa · s at a resin temperature of 310 ° C. and a shear rate of 1200 sec −1 )
(B) Elastomer ・ (B-1) Copolymer obtained by grafting 30 parts by weight of methyl methacrylate / butyl acrylate copolymer (9/21) to 70 parts by weight of ethylene / ethyl acrylate copolymer (Nippon Yushi Co., Ltd.) Manufactured by Modiper A5300)
・ (B-2) Ethylene / octene copolymer (DuPont Dow Elastomers LLC, Engage 8440)
(B-3) A copolymer obtained by grafting 30 parts by weight of a methyl methacrylate / butyl acrylate copolymer (9/21) to 70 parts by weight of an ethylene / glycidyl methacrylate copolymer (manufactured by NOF Corporation, Modiper A4300 )
(C) Inorganic filler (C-1) Glass fiber (10μmφ chopped strand (manufactured by Fiberglass Japan Co., Ltd., CS03JA-FT636))
・ (C-2) Glass flakes (Nippon Sheet Glass Co., Ltd. glass flakes, E glass average particle size 600μmφ)
・ (C-3) Calcium carbonate (Whiteon P manufactured by Toyo Fine Chemical Co., Ltd.)
(D) Mold release agent, manufactured by NOF Corporation, Unistar H-476
図1に示す加熱用回路と冷却用回路を有する駒型が埋め込まれた成形機との連動性を制御するための主型からなる成形用金型を用い、主型の温度を150℃に保った状態で、図2に示す金属部品を駒型にセット後、直ちに駒型の温度を150℃から所定温度(245℃)まで昇温した。245℃まで9.5秒かかった。同時に成形用金型を閉めた後、下記条件でPPS樹脂を射出成形することにより図3のような複合成形品を得た。 Example 1
Using a molding die composed of a main mold for controlling the interlocking between the heating circuit and the molding machine having the cooling mold shown in FIG. 1 and maintaining the temperature of the main mold at 150 ° C. In this state, the metal part shown in FIG. 2 was set in a piece shape, and immediately the temperature of the piece shape was raised from 150 ° C. to a predetermined temperature (245 ° C.). It took 9.5 seconds to reach 245 ° C. At the same time, the molding die was closed, and then a PPS resin was injection molded under the following conditions to obtain a composite molded product as shown in FIG.
駒型の表面処理;鋼材SUS420J2上に、ダイヤモンド状炭素被膜(DLC)を厚み1.0μmにコーティング処理した。表面粗さは、樹脂流動方向;十点平均粗さ(Rz)0.45μm、算術平均粗さ(Ra)0.1μmである。
気密性評価用試験品形状;幅10mm×長さ10mm×高さ3mm(図3参照)
成形機;ソディックプラステック(株)製TR40VR
金属部品;銅製リードフレーム(詳細については図2参照)
断熱板;ガラスエポキシ積層板
金型温度;主型は150℃
駒型容積;15cm3
射出成形時の駒型温度;245℃
射出時間(保圧時間を含む);3秒
射出速度;200mm/秒
保圧;100MPa
冷却速度;10℃/秒
冷却時の駒型冷却方法;成形用金型内に熱可塑性樹脂が充填完了後、直ちに加熱用棒ヒータの電源をオフにし、空気中の水分が結露状態にある極低温圧縮空気-30℃、0.6MPaを流路2に流す。 [Molding condition]
Piece-shaped surface treatment: A steel film SUS420J2 was coated with a diamond-like carbon coating (DLC) to a thickness of 1.0 μm. The surface roughness is the resin flow direction; ten-point average roughness (Rz) of 0.45 μm and arithmetic average roughness (Ra) of 0.1 μm.
Test product shape for airtightness evaluation:
Molding machine: TR40VR manufactured by Sodick Plustech Co., Ltd.
Metal parts; copper lead frame (see Figure 2 for details)
Insulation plate; Glass epoxy laminate Mold temperature; Main mold is 150 ° C
Piece volume; 15cm 3
Piece temperature during injection molding; 245 ° C
Injection time (including pressure holding time); 3 seconds Injection speed; 200 mm / second Pressure holding; 100 MPa
Cooling rate: 10 ° C / sec Cooling method when cooling: The pole where the heating rod heater is turned off immediately after the thermoplastic resin is completely filled in the molding die, and moisture in the air is in a dew condensation state Low-temperature compressed air—30 ° C., 0.6 MPa is passed through the
複合成形品を図4に示す装置にセットし、評価装置全体を水の中に入れた後、配管によりエアー加圧を行い、複合成形品の金属部品と樹脂の界面からのエアー(気泡)の漏れが発生する最大のエアー圧力を測定した。エアー圧力の数値が大きいほど、気密性が高いことになる。 [Airtight evaluation]
After the composite molded product is set in the apparatus shown in FIG. 4 and the entire evaluation apparatus is placed in water, air pressure is applied by piping, and air (bubbles) from the interface between the metal part of the composite molded product and the resin The maximum air pressure at which leakage occurred was measured. The larger the air pressure value, the higher the airtightness.
PPS樹脂として、表1の材料2を使用した以外は実施例1と同様にして成形し、評価した。 Example 2
The PPS resin was molded and evaluated in the same manner as in Example 1 except that the
射出成形時の駒型温度を200℃とした以外は実施例1と同様にして成形し、評価した。 Example 3
Molding and evaluation were performed in the same manner as in Example 1 except that the piece temperature at the time of injection molding was 200 ° C.
PPS樹脂として、表1の材料3、材料4を使用した以外は実施例3と同様にして成形し、評価した。 Examples 4-5
The PPS resin was molded and evaluated in the same manner as in Example 3 except that the
主型と駒型の間に断熱板を使用しない以外は実施例1と同様にして成形し、評価した。245℃まで昇温するのに10分以上を要した。 Comparative Example 1
It was molded and evaluated in the same manner as in Example 1 except that a heat insulating plate was not used between the main mold and the piece mold. It took 10 minutes or more to raise the temperature to 245 ° C.
駒型の容積を250cm3とした以外は実施例1と同様にして成形し、評価した。245℃まで昇温するのに10分以上を要した。 Comparative Example 2
Molding and evaluation were performed in the same manner as in Example 1 except that the volume of the piece was 250 cm 3 . It took 10 minutes or more to raise the temperature to 245 ° C.
駒型の表面処理をせず、十点平均粗さ(Rz)3.0μmのままの駒型を用いた以外は実施例1と同様にして成形したが、離型不良のため試験品を得ることができなかった。 Comparative Example 3
It was molded in the same manner as in Example 1 except that the piece shape was not subjected to the surface treatment and the 10-point average roughness (Rz) of 3.0 μm was used. I couldn't.
射出成形時の駒型温度を170℃とした以外は実施例1と同様にして成形し、評価した。 Comparative Example 4
Molding and evaluation were performed in the same manner as in Example 1 except that the piece temperature during injection molding was set to 170 ° C.
図5に示す加熱用回路と冷却用回路を有する駒型が埋め込まれた成形機との連動性を制御するための主型からなる成形用金型を用い、主型の温度を150℃に保った状態で、厚さ1mm、50mm×50mmの金属板を駒型にセット後、直ちに駒型の温度を150℃から所定温度(200℃)まで昇温した。200℃まで7秒かかった。同時に成形用金型を閉めた後、下記条件でPPS樹脂を射出成形することにより図6のような複合成形品を得た。 Example 6
Using a molding die comprising a main mold for controlling the interlocking between the heating circuit and the molding machine having the cooling mold shown in FIG. 5 and maintaining the temperature of the main mold at 150 ° C. In this state, a metal plate having a thickness of 1 mm and 50 mm × 50 mm was set in a piece shape, and immediately the temperature of the piece shape was raised from 150 ° C. to a predetermined temperature (200 ° C.). It took 7 seconds to reach 200 ° C. At the same time, the molding die was closed, and then a PPS resin was injection molded under the following conditions to obtain a composite molded product as shown in FIG.
駒型の表面処理;鋼材SUS420J2上に、ダイヤモンド状炭素被膜(DLC)を厚み1.0μmにコーティング処理した。表面粗さは、樹脂流動方向;十点平均粗さ(Rz)0.35μm、算術平均粗さ(Ra)0.09μmである。
密着強度評価用試験品形状;図6参照
成形機;ソディックプラステック(株)製TR40VR
金属部品;厚さ1mm、50mm×50mmの金属板
断熱板;ガラスエポキシ積層板
金型温度;主型は150℃
駒型容積;50cm3
シリンダー温度;320℃
射出成形時の駒型温度;200℃
射出時間(保圧時間を含む);5秒
射出速度;200mm/秒
保圧;100MPa
冷却速度;8℃/秒
冷却時の駒型冷却方法;成形用金型内に熱可塑性樹脂が充填完了後、直ちに加熱用棒ヒータの電源をオフにし、空気中の水分が結露状態にある極低温圧縮空気-30℃、0.6MPaを流路2に流す。 [Molding condition]
Piece-shaped surface treatment: A steel film SUS420J2 was coated with a diamond-like carbon coating (DLC) to a thickness of 1.0 μm. The surface roughness is the resin flow direction; ten-point average roughness (Rz) of 0.35 μm and arithmetic average roughness (Ra) of 0.09 μm.
Test article shape for adhesion strength evaluation; see FIG. 6 Molding machine; TR40VR manufactured by Sodick Plustech Co., Ltd.
Metal parts: 1mm thick, 50mm x 50mm metal plate Thermal insulation plate: Glass epoxy laminate Mold temperature; Main mold is 150 ° C
Piece volume; 50cm 3
Cylinder temperature: 320 ° C
Piece temperature during injection molding; 200 ° C
Injection time (including pressure holding time); 5 seconds Injection speed; 200 mm / second Pressure holding; 100 MPa
Cooling rate: 8 ° C / sec Cooling method at the time of cooling: Immediately after the thermoplastic resin is completely filled in the molding die, the heating rod heater is turned off and the moisture in the air is in a dew condensation state. Low-temperature compressed air—30 ° C., 0.6 MPa is passed through the
図6の密着強度評価用試験品を、オリエンテック製テンシロンRTC-1325Aを用いて、押し込む速度を1mm/minとして、図7に示す方法で剥離強度を測定した。 [Adhesion strength evaluation]
The peel strength was measured by the method shown in FIG. 7 by using the Tensilon RTC-1325A manufactured by Orientec Co., Ltd. and the indentation speed of 1 mm / min.
PPS樹脂として、表1の材料2、材料3、材料4を使用した以外は実施例6と同様にして成形し、評価した。 Examples 7-9
The PPS resin was molded and evaluated in the same manner as in Example 6 except that the
射出成形時の駒型温度を220℃とした以外は実施例6と同様にして成形し、評価した。 Example 10
Molding and evaluation were performed in the same manner as in Example 6 except that the piece mold temperature at the time of injection molding was 220 ° C.
PPS樹脂として、表1の材料2、材料3、材料4を使用した以外は実施例10と同様にして成形し、評価した。 Examples 11-13
The PPS resin was molded and evaluated in the same manner as in Example 10 except that the
樹脂としてナイロン樹脂(三菱エンジニアプラスチックス(株)製、ポリアミドMXD6樹脂レニー1025)を用い、射出成形機のシリンダー温度を280℃にした以外は実施例6と同様にして成形し、評価した。 Example 14
Nylon resin (manufactured by Mitsubishi Engineer Plastics Co., Ltd., polyamide MXD6 resin Reny 1025) was used as the resin, and molding was carried out in the same manner as in Example 6 except that the cylinder temperature of the injection molding machine was changed to 280 ° C.
射出成形時の駒型温度を220℃とした以外は実施例14と同様にして成形し、評価した。 Example 15
Molding and evaluation were performed in the same manner as in Example 14 except that the piece mold temperature at the time of injection molding was 220 ° C.
射出成形時の駒型の温度を170℃とした以外は実施例6と同様にして成形し、評価した。 Comparative Example 5
Molding and evaluation were performed in the same manner as in Example 6 except that the piece mold temperature at the time of injection molding was set to 170 ° C.
射出成形時の駒型の温度を170℃とし、PPS樹脂として、表1の材料3、材料4を使用した以外は実施例6と同様にして成形し、評価した。
比較例8
射出成形時の駒型の温度を170℃とした以外は実施例14と同様にして成形し、評価した。 Comparative Examples 6-7
It was molded and evaluated in the same manner as in Example 6 except that the piece-shaped temperature at the time of injection molding was 170 ° C., and the
Comparative Example 8
Molding and evaluation were performed in the same manner as in Example 14 except that the piece mold temperature at the time of injection molding was set to 170 ° C.
Claims (4)
- ポリアリーレンサルファイド樹脂及びポリアミド樹脂より選ばれる1種以上の熱可塑性樹脂と金属部品との複合成形品の製造方法であって、
(1)成形用金型が、成形機との連動性を制御するための主型と、温度制御のための加熱用回路と冷却用回路を有する熱可塑性樹脂と金属部品とが接する部分を内部に包含する駒型に分割され、
(2)成形用金型の成形時に樹脂が流入して接する部分が十点平均粗さ(Rz)が0.5μm以下に表面処理され、駒型の容積を60cm3以下にし、駒型の主型に接する外周部が断熱処理された状態で主型に駒型が埋め込まれた成形用金型を用い、
(3)成形用金型内に金属部品を設置し、駒型の金型温度を200℃~熱可塑性樹脂の融点の温度範囲に加熱した状態で熱可塑性樹脂を射出充填し、成形用金型内に熱可塑性樹脂が充填完了した後、直ちに駒型の加熱用回路を遮断すると共に駒型の冷却用回路により7℃/秒以上の冷却速度で急速冷却する
ことを特徴とする複合成形品の製造方法。 A method for producing a composite molded product of at least one thermoplastic resin selected from polyarylene sulfide resin and polyamide resin and a metal part,
(1) The molding die has a main mold for controlling the interlocking with the molding machine, and a portion where a thermoplastic resin having a heating circuit and a cooling circuit for temperature control and a metal part are in contact with each other. Divided into pieces that are included in
(2) The portion where resin flows in and comes into contact with the mold during molding is surface-treated with a 10-point average roughness (Rz) of 0.5 μm or less, and the volume of the piece mold is 60 cm 3 or less. Using a molding die in which a piece mold is embedded in the main mold in a state where the outer peripheral portion in contact with the mold is thermally insulated,
(3) A metal part is placed in a molding die, and a thermoplastic resin is injected and filled in a state where the die mold temperature is heated to a temperature range of 200 ° C to the melting point of the thermoplastic resin. Immediately after the thermoplastic resin is filled in, the piece-shaped heating circuit is immediately shut off, and the piece-shaped cooling circuit is rapidly cooled at a cooling rate of 7 ° C./second or more. Production method. - 熱可塑性樹脂がエラストマーを含有する熱可塑性樹脂組成物である請求項1記載の複合成形品の製造方法。 The method for producing a composite molded article according to claim 1, wherein the thermoplastic resin is a thermoplastic resin composition containing an elastomer.
- 成形用金型の駒型の成形時に樹脂が流入して接する部分が、ダイヤモンド状炭素被膜により表面処理されたものである請求項1又は2記載の複合成形品の製造方法。 The method for producing a composite molded article according to claim 1 or 2, wherein a portion where the resin flows in and comes into contact with the molding die is molded with a diamond-like carbon coating.
- 急速冷却が、空気中の水分が結露状態あるいは水分が固化し氷結状態にある低温空気を用いるものである請求項1~3の何れか1項記載の複合成形品の製造方法。 The method for producing a composite molded article according to any one of claims 1 to 3, wherein the rapid cooling uses low-temperature air in which moisture in the air is in a condensed state or in which the moisture is solidified and frozen.
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CN2009801049845A CN102089134A (en) | 2008-02-15 | 2009-02-16 | Process for producing composite molding |
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JP2008-034016 | 2008-02-15 | ||
JP2008034016A JP5128306B2 (en) | 2008-02-15 | 2008-02-15 | Manufacturing method of composite molded product |
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JP (1) | JP5128306B2 (en) |
KR (1) | KR20100112167A (en) |
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JP6471975B2 (en) * | 2015-07-31 | 2019-02-20 | パナソニックIpマネジメント株式会社 | Manufacturing method of three-dimensional shaped object and three-dimensional shaped object |
JP6885096B2 (en) * | 2016-02-26 | 2021-06-09 | 東レ株式会社 | Polyphenylene sulfide resin composition and molded article |
KR101890406B1 (en) * | 2016-05-12 | 2018-08-24 | 한국엔지니어링플라스틱 주식회사 | Method of metal-resin bonded body |
KR102275118B1 (en) | 2017-09-28 | 2021-07-07 | 코오롱플라스틱 주식회사 | High Temperature Blow Asistied Fabrication Method For Fiber Reinforced Thermoplastic Composites and That Apparatus |
JP7217233B2 (en) | 2017-10-30 | 2023-02-02 | 株式会社クラレ | WATERPROOF COMPONENT, ELECTRONIC DEVICE INCLUDING THE SAME, WATERPROOF METHOD FOR INSERT MOLDED PRODUCT, AND WATERPROOF METHOD FOR ELECTRONIC DEVICE |
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- 2008-02-15 JP JP2008034016A patent/JP5128306B2/en not_active Expired - Fee Related
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2009
- 2009-02-16 WO PCT/JP2009/000583 patent/WO2009101822A1/en active Application Filing
- 2009-02-16 KR KR1020107018052A patent/KR20100112167A/en not_active Application Discontinuation
- 2009-02-16 CN CN2009801049845A patent/CN102089134A/en active Pending
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JP5128306B2 (en) | 2013-01-23 |
JP2009190294A (en) | 2009-08-27 |
CN102089134A (en) | 2011-06-08 |
KR20100112167A (en) | 2010-10-18 |
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