WO2009101822A1 - Process for producing composite molding - Google Patents

Process for producing composite molding Download PDF

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Publication number
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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WO
WIPO (PCT)
Prior art keywords
mold
resin
temperature
molding
thermoplastic resin
Prior art date
Application number
PCT/JP2009/000583
Other languages
French (fr)
Japanese (ja)
Inventor
Yasumitsu Miyamoto
Akihiro Mochizuki
Tatsuya Kanezuka
Original Assignee
Polyplastics Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to JP2008-034016 priority Critical
Priority to JP2008034016A priority patent/JP5128306B2/en
Application filed by Polyplastics Co., Ltd. filed Critical Polyplastics Co., Ltd.
Publication of WO2009101822A1 publication Critical patent/WO2009101822A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14Injection 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
    • B29C45/14778Injection 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14Injection 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
    • B29C45/14311Injection 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17Component parts, details or accessories; Auxiliary operations
    • B29C45/72Heating or cooling
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17Component parts, details or accessories; Auxiliary operations
    • B29C45/76Measuring, controlling or regulating
    • B29C45/78Measuring, controlling or regulating of temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING 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
    • B29K2705/00Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts

Abstract

A process for producing a composite molding comprising one or more thermoplastic resins selected between a polyarylene sulfide resin and a polyamide resin and a metallic part and stably having satisfactory adhesion. A reduction in molding cycle time can be attained in the process. The process is characterized in that (1) a mold is used which is divided into a main mold for controlling linkage with a molding machine and a core which has a circuit for heating and a circuit for cooling and involves inside an area where the one or more resins come into contact with a metallic part. The process is further characterized in that (2) that part of the mold which comes into contact with the resin(s) flowing in during molding has been surface-treated so as to have a ten-point average roughness (Rz) of 0.5 µm or less, and the core has a capacity of 60 cm3 or less and has been embedded in the main mold, with that peripheral part of the core which is in contact with the main mold having been heat-insulated. The process is furthermore characterized by (3) setting the metallic part in the mold, heating the core to a temperature in a specific range, injecting the resin(s) to fill the cavity therewith while keeping that temperature of the core, and immediately after completion of the filling of the mold cavity with the resin(s), blocking the heating circuit of the core and rapidly cooling the core with the cooling circuit of the core at a cooling rate of 7 °C/sec or higher.

Description

Manufacturing method of composite molded product

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

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. However, 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. In order to improve such a defect, 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. However, since 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.

In addition, as a technique for improving adhesion by heating the insert, 1) pre-heated metal is placed in a mold and then injection molding is performed. 2) heating means such as an electric heater or electromagnetic induction is used in the mold. The insert metal is heated to perform injection molding, and 3) a molding method that maintains the mold temperature at a high temperature and switches to cooling after injection molding has been proposed. The temperature of the insert metal is apt to be lowered depending on the time until injection, and it is difficult to obtain the effect particularly in small and thin inserts. As for 3), in heating and cooling, it is necessary to control the temperature of the entire mold, and a heater and a cooling system having a large heat capacity are required, and the molding becomes very long.

Furthermore, in Japanese Patent Laid-Open No. 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.

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

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.

As a result of intensive studies to achieve the above object, 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.

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.

According to the present invention, 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. In addition, 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, and (c) is a metal component opposite set. A top view of the side piece shape, (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. 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, and (c) is a metal component. The top view of the piece type on the side opposite to the set, (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, and (b) is a schematic front view.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Metal component positioning pin 2 Cooling air flow path 3 Bar heater 4 Heat insulation board 5 Metal component holding pin 6 Composite molded product 7 Compressed air insertion hole 8 Air leak measurement location 9 Metal plate set part 10 Boss 11 Test article fixing part 12 Metal part 13 Detailed description of the metal plate invention

[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.

The metal part used in the present invention is a shape processed into a predetermined shape, and the shape is not particularly limited. In addition, when 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.
[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.

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.

By dividing the main mold and the piece mold, keeping the main mold at a certain temperature, and controlling the temperature of only the piece mold, an instantaneous temperature change is possible and the molding cycle can be shortened. . Here, by simply dividing the main mold and the piece mold, 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. . As the heat insulation treatment, 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.

Also, although 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.

Usually, 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. Examples of the heat insulating plate include glass reinforced polyester, glass epoxy laminated plate, phenol resin and the like.

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.

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.

As 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.

As 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. There is no restriction | limiting in particular as a heat medium, Fluids, such as oil, water, air, nitrogen, a combustion gas, are mentioned, In the case of a vapor | steam, the condensation heat transfer to a liquid may be sufficient.

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.

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. Although 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.

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.

As the cooling 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.

From the outlet of the flow path 2, the moisture in the low-temperature air is discharged in the form of steam that has evaporated the piece-shaped heat and evaporated. The discharge may be a discharge to the atmosphere or a discharge pipe.
[resin]
The 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. Examples of 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.

In this case, in addition to the polymer using the same repeating unit in the arylene sulfide group composed of the arylene group, that is, a homopolymer, a copolymer containing different types of repeating units is used from the viewpoint of processability of the composition. It may be preferable.

As the homopolymer, polyphenylene sulfide using p-phenylene group as an arylene group and p-phenylene sulfide group as a repeating unit is preferably used. As 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. Among these, 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.

Further, among these 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. In addition to the polyarylene sulfide resin having a structure, a polymer in which a branched structure or a crosslinked structure is partially formed by using a small amount of a monomer such as a polyhaloaromatic compound having three or more halogen functional groups at the time of condensation polymerization. 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.

In addition, 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.

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.

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). There are many reports on the synthesis method of such a polyamide elastomer, but it is usually carried out in two stages, namely, the formation of a nylon oligomer and the high molecular weight by esterification. Here, 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.

The 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. In addition, 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.

The 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 α, β-unsaturated acid, an ethylene copolymer mainly composed of ethylene and an alkyl ester of α, β-unsaturated acid, ethylene And ethylene copolymers of α-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.

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

Figure JPOXMLDOC01-appb-T000001

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.

As the PPS resin, the material 1 shown in Table 1 was used.

[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: width 10 mm x length 10 mm x height 3 mm (see Fig. 3)
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 flow path 2.

When taking out the molded product from the molding die, the shortest molding cycle time at which the composite molded product does not deform or break was 24.5 seconds. The molded composite product thus obtained was left at room temperature for 48 hours or more after molding, and then the following airtightness test was performed to evaluate the airtightness between the resin and the metal. Incidentally, 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.

[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.

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 μm was used. I couldn'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.

These results are shown in Table 2.

Figure JPOXMLDOC01-appb-T000002

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.

As the PPS resin, the material 1 shown in Table 1 was used.

[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 flow path 2.

[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.

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.

These results are shown in Table 3.

Figure JPOXMLDOC01-appb-T000003

Claims (4)

  1. 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.
  2. The method for producing a composite molded article according to claim 1, wherein the thermoplastic resin is a thermoplastic resin composition containing an elastomer.
  3. 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.
  4. 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.
PCT/JP2009/000583 2008-02-15 2009-02-16 Process for producing composite molding WO2009101822A1 (en)

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