CN102089134A

CN102089134A - Process for producing composite molding

Info

Publication number: CN102089134A
Application number: CN2009801049845A
Authority: CN
Inventors: 宫本康满; 望月章弘; 金塚竜也
Original assignee: Polyplastics Co Ltd
Current assignee: Polyplastics Co Ltd
Priority date: 2008-02-15
Filing date: 2009-02-16
Publication date: 2011-06-08
Also published as: WO2009101822A1; JP5128306B2; JP2009190294A; KR20100112167A

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 [mu]m 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 DEG C/sec or higher.

Description

The manufacture method of combined shaping product

Technical field

The manufacture method of the thermoplastic resin more than a kind that the present invention relates to from polyarylene sulfide resin and polyamide, select and the combined shaping product of metal parts, specifically, relate to the combining closely property of guaranteeing the excellence between the resin-metal part and improve the manufacture method of the combined shaping product of forming period.

Background technology

To embed formed products is that the combined shaping product that are made of resin and metal of representative are used in the manufacturings such as motor-electronic component, auto parts.But, utilize common forming process that metal insert and resin boundary surface are fully combined closely, thus become come off, gas, liquid is from the reason of boundary leakage.In order to improve such shortcoming, known have form concavo-convexly by metal being carried out surface treatment, inject the method for molten resin at concavo-convex place.According to this method, can access the resin of combining closely property excellence at interface and the combined shaping product of metal, but because in surface treatment, use medicine, so when reality is introduced this method, at the aspects such as management of equipment introduction, soup, consider that from aspects such as cost increases difficulty is more.

In addition,, propose to have following manufacturing process, 1 as improving the method for combining closely property by the heating insert) in advance warmed-up metal be accommodated in the mould, afterwards, implement injection molded; 2) in mould, utilize heater means heating such as electric heater, electromagnetic induction to embed metal, implement injection molded; 3) mold temperature is remained high temperature, cooling etc. again behind injection molded, yet 1), 2) in owing to finish the asynchronism(-nization) of back till the injection moulding from heating, reduce easily so embed the temperature of metal, insert particularly little, that approach is difficult to obtain this effect.In addition, about 3), when the heating cooling, need control the temperature of mold integral, need big heater of thermal capacity and cooling system, and exist to be shaped and need the problem of very long time.

In addition, in TOHKEMY 2001-1382 communique, proposition has following method, promptly, utilize the embedding heating that molten resin is flowed into and be heated in the above system of fusing point, keep-up pressure, further, improve the combining closely property of resin and metal by implementing to reduce temperature and the such control of raising load pressure.But, control temperature, pressure in the method strictly, and the tendency that increases auxiliary device is also arranged, not talkative have a practicality.In addition, in TOHKEMY 2001-1382 communique, be assumed to ldpe resin, polypropylene, polystyrene etc., under the situation that is polyarylene sulfide resin and polyamide, utilize the method for TOHKEMY 2001-1382 communique can't obtain the good combined shaping product of combining closely property of resin and metal.

On the other hand, in TOHKEMY 2005-342922 communique, proposition has by use and utilizes diamond-like carbon film to implement the surface-treated mould, improve the scheme of the intensity of combining closely between the metal-resin, yet, exist in this scheme and can't form such problem with the forming period time of practicality.

Summary of the invention

The object of the present invention is to provide a kind of can solve above-mentioned in the past technical task, shorten the forming period time, have the resin of stable and good combining closely property and the combined shaping product of metal.

The inventor has carried out deep research to achieve these goals, and it found that, the temperature of molding die etc. is controlled to be specified conditions form and therefore adopt the molding die of particular configuration very effective, thereby has finished the present invention.

That is, the manufacture method of combined shaping product of the present invention is manufacture methods of the combined shaping product of the thermoplastic resin more than a kind selected from polyarylene sulfide resin and polyamide and metal parts, it is characterized in that,

(1) molding die is divided into main mould and core, and this main mould is used to control the linkage with former; This core mold is useful on temperature controlled heating and uses the loop with loop and cooling, and this core inside comprises the part that thermoplastic resin contacts with metal parts;

(2) use following molding die: when being shaped resin flow into and the part that contacts with this molding die become 10 mean roughness (Rz) by surface treatment be below the 0.5 μ m, the volume of core is 60cm ³Below, in main mould, imbed core at the peripheral part that contacts with main mould of core under by the state of insulation;

(3) metal parts is set in molding die, be heated in mold temperature under the state of temperature range of fusing point of 200 ℃～thermoplastic resin core, the injection filling thermoplastic resin, filled in molding die after the thermoplastic resin, the heating of cutting off core at once is with the loop and utilize the cooling of core to cool off rapidly with the cooling velocity more than 7 ℃/second with the loop.

According to the present invention, can be manufactured on the sufficient inadequately improved combined shaping product of problem of the combining closely property between thermoplastic resin-metal in the previous methods.In addition, by the temperature control easier, can guarantee combining closely property excellent between thermoplastic resin-metal with shorter forming period than previous methods.

Description of drawings

Fig. 1 is the figure of 1 example of the core that uses of expression the present invention, (a) be the vertical view of the core of metal parts configuration side, (b) be the side sectional view of the core of this metal parts configuration side, (c) being the vertical view of core of the opposition side of metal parts configuration side, (d) is the side sectional view of core of the opposition side of this metal parts configuration side.

Fig. 2 is the figure of 1 example of the metal parts that uses of expression the present invention.

Fig. 3 is the figure that expression utilizes 1 example of the resulting combined shaping product of the present invention, is that vertical view, (b) are that upward view, (c) are that side view, (d) are side sectional views (a).

Fig. 4 is the schematic diagram of the situation of expression air-tightness evaluation, (a) is general profile chart, (b) is approximate three-dimensional map.

Fig. 5 is the figure of 1 example in addition of the core of expression the present invention use, (a) be the vertical view of the core of metal parts configuration side, (b) be the side sectional view of the core of this metal parts configuration side, (c) being the vertical view of core of the opposition side of metal parts configuration side, (d) is the side sectional view of core of the opposition side of this metal parts configuration side.

Fig. 6 is the figure of 1 example in addition that expression utilizes the resulting combined shaping product of the present invention, (a) is vertical view, (b) is side view.

Fig. 7 is the combine closely schematic diagram of situation of intensity evaluation of expression, (a) is summary side elevation, (b) is general principal view.

Description of reference numerals

1, metal parts alignment pin; 2, cooling air flow circuit; 3, bar type heater; 4, heat-insulating shield; 5, metal parts keeps pin; 6, combined shaping product; 7, compressed air patchhole; 8, air leakage measuring instrumentation position; 9, metallic plate installation portion; 10, boss; 11, trial target standing part; 12, metal parts; 13, metallic plate.

The specific embodiment

Metal parts

The metal parts that the present invention uses is not particularly limited on material, can enumerate the convered structure of alloys such as metals such as copper, aluminium, iron, phosphor bronze, stainless steel, dissimilar metals and the electroplating processes part of above-mentioned material etc.Stainless steel can list martensite, austenitic type etc.

The metal parts that the present invention uses is the shape thing that is processed to the regulation shape, and its shape is not particularly limited.In addition, metal parts is to embed under the situation of part, and its shape also is not particularly limited, and can list two ends that embed part and expose or protrude in the shape of the outside of formed products, the terminal etc. of electric-electronic component for example.

Metal parts is generally by acquisitions such as milled sheets, milled sheet itself just has tiny concavo-convex, and do not carry out special roughening and handle and can realize combining closely yet, yet, be more preferably the enforcement Surface Machining, make combining closely property better by the surface being carried out roughening processing etc.Handle as roughening, can list by carrying out surface grinding, plating, etch processes etc. and make the surface become the processing method of porous matter shape.

Mould

In the present invention, as molding die, use the mould be divided into main mould and core and constitute, this main mould is used to control the linkage with former; This core mold is useful on carries out temperature controlled heating and use the loop with loop and cooling, and inside comprises the part that thermoplastic resin contacts with metal parts.

In order to improve the combining closely property between thermoplastic resin-metal, importantly control the temperature of the metal parts of the part that thermoplastic resin contacts with metal parts, because carry out this temperature control by core, so core need be designed to the part that inside comprises that thermoplastic resin contacts with metal parts.

By being divided into main mould and core, main mould keeps certain steady temperature, only core is carried out temperature control, thereby can realize the variations in temperature of moment, can shorten forming period., only by being divided into main mould and core, can't seek the shortening forming period that will realize here, the volume that need make core is 60cm ³Below, and the peripheral part that contacts with main mould of core carried out insulation.As insulation, the method that heat insulation layer etc. is set is easier.If the volume of core is greater than 60cm ³, then utilize common equipment can make forming period longer, so not preferred.

In addition,,, then the variations in temperature of the moment of core can not be realized, forming period can't be sought to shorten still if heat insulation layer is not set in main mould, to imbed the state shaping core of core.

Usually, with heat-insulating shield as heat insulation layer, but also can be with gas cap etc. as heat insulation layer, this method is not defined especially.As heat-insulating shield, can list glass reinforced polyester, glass epoxy resin plywood, phenolic resins etc.

In addition, the molding die that the present invention uses need will be when the shaping of main mould and core resin flow into and the part that contacts is carried out surface treatment, making 10 mean roughness (Rz) is below the 0.5 μ m.If 10 mean roughness (Rz) are greater than 0.5 μ m, then resin can be combined closely with mould (core), can't obtain good combined shaping product because the demoulding is bad.As the surface-treated method, as long as surface roughness is in above-mentioned scope, any surface treatment all can, but specifically enumerated diamond-like carbon film (DLC), plating CrN, surface treatments such as plating Cr etc., preferably carry out surface treatment from viewpoints such as corrosion-proof wears by diamond-like carbon film.

The heating of metal parts

In the present invention, metal parts is set in molding die, be heated to the fusing point of 200 ℃～thermoplastic resin, more preferably be heated under the state of temperature range of fusing point of 230 ℃～thermoplastic resin the injection filling thermoplastic resin in the mold temperature that inside is comprised the core of the part that thermoplastic resin contacts with metal parts.By the mold temperature that makes core is the temperature range of the fusing point of 200 ℃～thermoplastic resin, can obtain the combining closely property between sufficient thermoplastic resin-metal.If the mold temperature of core is lower than 200 ℃, then the combining closely property reduction of thermoplastic resin and metal parts is if under the situation greater than the fusing point of thermoplastic resin, resin is difficult to solidify in mould, has problems on forming process sometimes, so not preferred.

In addition, need thermoplastic resin be filled in metal parts around, with injection pressure to around the metal parts that has been heated of thermoplastic resin fully push, before this, if the temperature of metal parts is lower than said temperature, then can produce the inadequate problem of the power of combining closely between thermoplastic resin and the metal parts.Therefore, the injection filling thermoplastic resin, in molding die, filled thermoplastic resin after, for the demoulding, need cut off the heating of core at once and use the loop, and utilize the cooling of core to cool off rapidly with the cooling velocity more than 7 ℃/second with the loop.Thus, can be so that chien shih thermoplastic resin and metal parts are combined closely in short-term.

The heating means of molding die

As to be used to control with the main mould of the linkage of former and have be used to carry out temperature controlled heating with loop and cooling with the method that the core in loop heats, can list the utilizing method that heater heats, utilize method that thermal medium heats etc. of method of the common heating mould of conduct.

As the method for utilizing heater to heat, can list the method for utilizing heater, electromagnetic induction heater or thermal medium with the mould electric insulation to heat.As the method that the heater that utilizes with the mould electric insulation heats, illustration has to be imbedded the heating plate that in the mould, maybe will imbed having heaters with armouring (sheath) line style heater etc. and is installed in method on the die surface etc.

As the method for utilizing thermal medium to heat, can list the method that the thermal medium stream is set, supplies with the thermal medium of set point of temperature and it is discharged to the outside in mould from the outside.As thermal medium, be not particularly limited, can enumerate fluids such as fuel-displaced, water, air, nitrogen, burning gases, under the situation that is steam, also can utilize to condense into liquid (liquefaction) and come transfer of heat.

Be not particularly limited for the main mould that keeps steady temperature, yet, carry out the heating means of the temperature controlled core of moment, the preferred method that heats by heaters such as heaters of using as needs.

The cooling means of core

In the present invention, in molding die, filled thermoplastic resin after, cut off the heating of core at once and use the loop, and utilize the cooling of core to cool off rapidly with the cooling velocity more than 7 ℃/second with the loop.By being divided into main mould and core, only core is carried out temperature control, can in above scope, cool off rapidly, as the cooling means of core, so long as can instantaneously cooled method get final product, also can be with common cooling means.As thermal medium, be not particularly limited, can enumerate fluids such as fuel-displaced, water, air, nitrogen, burning gases, but preferably list: cooling is set in core uses the loop as cooling with stream as inferior method, the Cryogenic air that makes airborne moisture form the dewfall state or make airborne moisture-curing form the state of freezing is passed through this stream, the core that the heat of solution of utilization ice part or the heat of gasification cooling of moisture contact with metal parts.

Formed products and molding die

An example of the metal parts that Fig. 2 and 3 expression the present invention are used and the shape of combined shaping product.

Fig. 1 is the figure of an example of the expression core that is used to keep metal parts in order to utilize method of the present invention to make the combined shaping product.Fig. 1 is the core shape that comprises metal parts integral body, but need not to comprise metal parts integral body, as long as the inner part that thermoplastic resin contacts with metal parts, the combined shaping product that just can obtain having good combining closely property of comprising.

As shown in Figure 1, be provided with heat-insulating shield 4 on main mould, the core of Fig. 1 is imbedded main mould (omitting diagram), uses as molding die.

Use the loop as heating, heated components (bar type heater) the 3rd makes core be warmed up to the heater of set point of temperature.

Use loop, stream 2 as cooling is to make airborne moisture form the dewfall state or make airborne moisture-curing and the Cryogenic air that forms the state of freezing is passed through, by ice partly heat of solution or the heat of gasification of moisture come the stream of the Cryogenic air of cooling plugs.

The heat of the moisture absorption core in the Cryogenic air, and the form of the steam that has gasified with evaporation is discharged from from the outlet of stream 2.Both can in atmosphere, discharge also and can discharge to discharge line.

Resin

The thermoplastic resin that the present invention uses be from polyarylene sulfide resin and polyamide select more than a kind.

Polyarylene sulfide resin with-(Ar-S)-(wherein Ar is an arlydene) serve as that main repetitive constitutes.As arlydene, for example can use to phenylene, metaphenylene, adjacent phenylene, substituted phenylene, p p '-diphenylene sulfo group, p, p '-biphenylene, p, p '-diphenylene ether, p, p '-diphenylene carbonyl, naphthylene etc.

Under this situation, the identical repetitive in using the arylene sulfide ether that constitutes by aforementioned arlydene and the polymer that obtains, be the homopolymers, consider that from the processability this point of composition comprising not sometimes, the copolymer of repetitive of the same race is preferred.

As homopolymers, preferred use with to phenylene as arlydene use, with to the polyphenylene sulfide of poly (phenylene sulfide) ether as repetitive.In addition, as copolymer, can use the different combination more than 2 kinds in the arylene sulfide ether that is made of aforementioned arlydene, wherein, preferred especially use comprises the combination to poly (phenylene sulfide) ether and metaphenylene thioether group.Wherein, consider that it is suitable comprising above phenylene is vulcanized the thing base, is preferably 80 moles of materials more than the % of 70 moles of % from the viewpoint of rerum naturas such as hear resistance, formability, mechanical property.

In addition, in these polyarylene sulfide resins, can preferably use the heavy polymer that is essentially straight chain structure that obtains by polycondensation as the monomer of main body by with two functionality halogen aromatic compounds, except that the polyarylene sulfide resin of straight chain structure, also can use following polymer: when polycondensation, use monomer such as the poly-halogenated aromatic compound have the halogen functional group more than 3 on a small quantity and part forms the polymer of branched structure or cross-linked structure, also can use low-molecular-weight straight chain structure polymer is come oxidation cross-linked or heat cross-linking with the high temperature heating in the presence of oxygen or oxidant, thereby melt viscosity is risen, the polymer of shaping processability improvement, or their mixture.

In addition, as polyarylene sulfide resin, with aforementioned linear shape polyarylene sulfide resin as main body, its part (1～30 weight %, be preferably 2～25 weight %) for viscosity higher (at 310 ℃ of resin temperatures, shear rate 1200sec ^-1Under melt viscosity be 300～3000Pas, be preferably 500～2000Pas) side chain or the mixed system of crosslinked polyarylene sulfide resin also suits.

In addition, for the used polyarylene sulfide resin of the present invention, preferably after polymerization, carry out acid elution, hot wash, organic solvent washing (or their combination) etc. with by-product impurity etc. remove, purifying and obtaining.

Then, as polyamide, can list known various polyamide-based resin.For example can list oxalic acid, adipic acid, suberic acid, decanedioic acid, phthalic acid, M-phthalic acid, 1, the dicarboxylic acids that the 4-cyclohexyl dicarboxylic acid is such, with ethylenediamine, five methylene diamine, hexamethylene diamine, decamethylene diamine, 1,4-cyclohexanediamine, the such diamines polycondensation of m-xylene diamine (m-Xylylenediamine) and obtain polyamide; Caprolactam, the such cyclic lactames of lauric lactam are carried out polymerization and the polyamide that obtains; Or the salt of cyclic lactames and diamines carried out copolymerization and polyamide of obtaining etc.In these polyamide-based resins, can preferably list 6 nylon, 66 nylon, 12 nylon, 46 nylon, MXD6 nylon and their copolymer etc.

In addition, the polyamide elastomer resin also can be used as polyamide-based resin use.The polyamide elastomer resin be polyamide hard segment and other soft chain segment bondings and obtain, bending modulus is at 10000kgf/cm ²Below the polyamide-based block copolymer of (50% relative humidity, 23 ℃).As described elastomeric soft chain segment, polyalkylene oxides (polyalkylene oxide) (carbon number 2～6 of alkylidene) is representational example.Synthetic method for described polyamide elastomer has a lot of reports, carries out but be divided into the generation of nylon oligomer usually and quantize these 2 stages based on the macromolecule of esterification.At this, polyamide composition as hard segment can list polyamide 6, polyamide 66,

polyamide

6, and 12, polyamide such as polyamide 11, polyamide 12, as the polyether components of soft chain segment, can list polyoxyethylene glycol, polyoxy propane diols, polyoxy tetramethylene glycol etc.

The used thermoplastic resin of the present invention can be any one of polyarylene sulfide resin, polyamide, also can be used in combination the two.In addition, in order to regulate the physics value of target, use also capable of being combined more than 2 kinds polyarylene sulfide resin or be used in combination polyamide more than 2 kinds.

In addition, the used thermoplastic resin of the present invention can use and comprise elastomeric resin combination, and especially for containing elastomeric polyphenyl thioether resin composition, effect of the present invention is remarkable, so preferably use.

As elastomer,, consider that from stable on heating aspect ethylene copolymer is preferred as long as, then can contain arbitrary substance for having the stable on heating material that when the melt-processed of thermoplastic resin, can not cause significant decomposition etc.

As ethylene copolymer, can list with ethene and α, the ethylene oxidic ester of beta-unsaturated acid is as the ethylene copolymer of main body, with ethene and α, and the Arrcostab of beta-unsaturated acid is as ethylene copolymer of ethylene copolymer, ethene and the alpha-olefin of carbon number more than 5 of main body etc.Also can be to make these ethylene copolymers and acrylic acid, methyl acrylate, methacrylic acid, acrylonitrile, the synthetic side chain of styrene grade in an imperial examination three composition chemical bonds or cross-linked structure and the graft copolymer that obtains.

As elastomeric content, preferably account for 1～15 all weight % of composition.

In above-mentioned resin, also can contain various resin additives, filler.

Purposes

By the resulting combined shaping product of the present invention, can be used in motor-electronic component, auto parts etc. widely.

Embodiment

Below, specifically describe the present invention according to embodiment, but the present invention is not limited to embodiment.

The modulation of resin material

With Henschel mixer (A) shown in the table 1, (B), (D) composition were mixed 5 minutes, then, it is put into start cylinder temperature is in 320 ℃ the double screw extruder, utilize the side feeder of extruder to add (C) composition in addition, in double screw extruder, carry out fusion-mixing for 350 ℃, resin combination is modulated into graininess with resin temperature.(A)～(D) composition is specific as follows.

(A) polyphenylene sulfide (PPS) resin

. (Co., Ltd.) KUREHA (Network レ Ha) system, FORTRON KPS (310 ℃ of resin temperatures, shear rate 1200sec ^-1Melt viscosity be 30Pas)

(B) elastomer

. (B-1) methyl methacrylate/butyl acrylate copolymer (9/21) 30 weight portion is grafted on the copolymer (the MODIPER A5300 of Japanese grease (Co., Ltd.) system) that forms in ethylene/ethyl acrylate copolymer 70 weight portions

. (B-2) ethylene/octene (Engage 8440 of DuPont Dow Elastomers L.L.C system)

. (B-3) methyl methacrylate/butyl acrylate copolymer (9/21) 30 weight portion is grafted on the copolymer (the MODIPER A4300 of Japanese grease (Co., Ltd.) system) that forms in ethylene/methacrylic acid glycidyl ester copolymer 70 weight portions

(C) inorganic filler

. (C-1) glass fibre (chopped strand of 10 μ m φ (CS03JA-FT636 of Japanese Asahi Glass fiber (Co., Ltd.) system))

. (C-2) sheet glass (Japanese plate glass (Co., Ltd.) system sheet glass, E glass average grain diameter are 600 μ m φ)

. (C-3) calcium carbonate (Japan's precision chemical (Co., Ltd.) system HOWAITON (ホワイト Application, trade name) P)

(D) releasing agent

. the Unistar H-476 of Japanese grease (Co., Ltd.) system

Table 1

	Material 1	Material 2	Material 3	Material 4
					(A) PPS resin (weight portion)	100	100	100	100
(B) elastomer (B-1) (weight portion)	9		6	5
					(B) elastomer (B-2) (weight portion)			10
(B) elastomer (B-3) (weight portion)	5
					(C) inorganic filler (C-1) (weight portion)	80	77	60	80
(C) inorganic filler (C-2) (weight portion)			60
					(C) inorganic filler (C-3) (weight portion)		77
(D) releasing agent (weight portion)	2	1	2	2

Embodiment 1

Use shown in Figure 1 has heating with the loop with cool off the molding die that the main mould with the core in loop constitutes by imbedding, this main mould is used to control the linkage with former, the temperature of main mould remained under 150 ℃ the state, after being disposed at metal parts shown in Figure 2 in the core, at once the temperature of core is warmed up to set point of temperature (245 ℃) from 150 ℃, arrives 245 ℃ with 9.5 seconds.Simultaneously, close after the molding die,, obtained combined shaping product as shown in Figure 3 under the following conditions by the PPS resin is carried out injection molded.

As the PPS resin, used the material 1 of table 1.

Molding condition

The surface treatment of core: carried out the face coat processing on steel SUS420J2, applied thickness is the diamond-like carbon film (DLC) of 1.0 μ m.Surface roughness is as described below: 10 mean roughness (Rz) on the resin flows direction are 0.45 μ m, and arithmetic average roughness (Ra) is 0.1 μ m.

Air-tightness evaluation trial target shape: width 10mm * length 10mm * height 3mm (with reference to Fig. 3)

Former: Sodick Plustech (Co., Ltd.) makes TR40VR

Metal parts: copper lead frame (specifically with reference to Fig. 2)

Heat-insulating shield: glass epoxy resin plywood

Mold temperature: main mould is 150 ℃

Core volume: 15cm ³

Core temperature during injection molded: 245 ℃

Inject time (comprising the dwell time): 3 seconds

Injection speed: 200mm/ second

Pressurize: 100MPa

Cooling velocity: 10 ℃/second

Core cooling means during cooling: after in molding die, having filled thermoplastic resin, turn off the power supply of heating at once, make airborne moisture form-30 ℃ and the utmost point low temperature compressed air inflow stream 2 of 0.6MPa of dewfall state with the bar type heater.

From molding die taking-up formed products the time, the shortest forming period time that does not produce distortion of combined shaping product or destruction is 24.5 seconds.Combined shaping product resulting, that be shaped are being placed after the shaping more than 48 hours at normal temperatures, afterwards, carried out following air seal test, estimating the air-tightness between the resin-metal.In addition, the forming period time be meant from finish with metal parts be disposed at the core the time be carved into time in the moment of taking out the combined shaping product.

Air-tightness is estimated

The combined shaping product are configured in the device shown in Figure 4, and after putting into evaluating apparatus integral body in the water, utilize pipe arrangement to carry out air pressurized, measured air (bubble) produces the maximum of leaking from the interface of the metal parts of combined shaping product and resin air pressure.The big more air-tightness of the numerical value of air pressure is high more.

Embodiment 2

As the PPS resin, use the material 2 of table 1, carried out shaping, evaluation in the same manner with embodiment 1 in addition.

Embodiment 3

Core temperature during except injection molded is 200 ℃ and embodiment 1 has carried out shaping, evaluation in the same manner.

Embodiment 4～5

As the PPS resin, use material 3, the material 4 of table 1, carried out shaping, evaluation in the same manner with embodiment 3 in addition.

Comparative example 1

Except not using heat-insulating shield between main mould and the core, not carried out shaping, evaluation in the same manner with embodiment 1.Be warmed up to 245 ℃ of needs more than 10 minutes.

Comparative example 2

Except the volume of core is 250cm ³Shaping, evaluation have been carried out in the same manner with embodiment 1 in addition.Be warmed up to 245 ℃ of needs more than 10 minutes.

Comparative example 3

Core is not carried out surface treatment,,, can not access trial target because the demoulding is bad except to use 10 mean roughness (Rz) be the core of 3.0 μ m and embodiment 1 is shaped in the same manner.

Comparative example 4

Core temperature during except injection molded is 170 ℃ and embodiment 1 has carried out shaping, evaluation in the same manner.

The above results is shown in table 2.

Table 2

Embodiment 6

Use shown in Figure 5 has heating with the loop with cool off the molding die that the main mould with the core in loop constitutes by imbedding, this main mould is used to control the linkage with former, the temperature of main mould remained under 150 ℃ the state, after being disposed at the metallic plate of thickness 1mm, 50mm * 50mm in the core, at once the temperature of core is warmed up to set point of temperature (200 ℃) from 150 ℃, arrives 200 ℃ with 7 seconds.Simultaneously, close after the molding die,, obtained combined shaping product as shown in Figure 6 under the following conditions by the PPS resin is carried out injection molded.

As the PPS resin, used the material 1 of table 1.

Molding condition

The surface treatment of core: carried out the face coat processing on steel SUS420J2, applied thickness is the diamond-like carbon film (DLC) of 1.0 μ m.Surface roughness is as described below: 10 mean roughness (Rz) on the resin flows direction are that 0.35 μ m, arithmetic average roughness (Ra) are 0.09 μ m.

The intensity evaluation of combining closely trial target shape: with reference to Fig. 6

Former: Sodick Plustech (Co., Ltd.) makes TR40VR

Metal parts: the metallic plate of thickness 1mm, 50mm * 50mm

Heat-insulating shield: glass epoxy resin plywood

Mold temperature: main mould is 150 ℃

Core volume: 50cm ³

Start cylinder temperature: 320 ℃

Core temperature during injection molded: 200 ℃

Inject time (comprising the dwell time): 5 seconds

Injection speed: 200mm/ second

Pressurize: 100MPa

Cooling velocity: 8 ℃/second

Core cooling means during cooling: after in molding die, having filled thermoplastic resin, turn off the power supply of heating at once, make airborne moisture form-30 ℃ of the dewfall state, the utmost point low temperature compressed air of 0.6mPa and flow into stream 2 with the bar type heater.

The intensity evaluation of combining closely

Use ORIENTEC system TENSILON RTC-1325A, the speed of pushing is as 1mm/min and utilizes method shown in Figure 7 to measure the peel strength of intensity evaluation of combining closely of Fig. 6 with trial target.

Embodiment 7～9

As the PPS resin, use material 2, material 3, the material 4 of table 1, carried out shaping, evaluation in the same manner with embodiment 6 in addition.

Embodiment 10

The temperature of the core during except injection molded is 220 ℃ and embodiment 6 has carried out shaping, evaluation in the same manner.

Embodiment 11～13

As the PPS resin, use material 2, material 3, the material 4 of table 1, carried out shaping, evaluation in the same manner with embodiment 10 in addition.

Embodiment 14

As resin, use nylon resin (the polyamide MXD 6 resin RENY-1025 of Mitsubishi's engineering plastics (Co., Ltd.) system), the start cylinder temperature of injection molded equipment is 280 ℃, has carried out shaping, evaluation in the same manner with embodiment 6 in addition.

Embodiment 15

The temperature of the core during except injection molded is 220 ℃ and embodiment 14 has carried out shaping, evaluation in the same manner.

Comparative example 5

The temperature of the core during except injection molded is 170 ℃ and embodiment 6 has carried out shaping, evaluation in the same manner.

Comparative example 6～7

The temperature of the core during except injection molded is 170 ℃, as the PPS resin, beyond the material 3 of use table 1, the material 4 and embodiment 6 carried out shaping, evaluation in the same manner.

Comparative example 8

The temperature of the core during except injection molded is 170 ℃ and embodiment 14 has carried out shaping, evaluation in the same manner.

The above results is shown in table 3.

Table 3

* the interface between thermoplastic resin-metal does not produce and peels off, and the base portion of boss produces and destroys.

Claims

1. the manufacture method of combined shaping product, it is the manufacture method of the combined shaping product of the thermoplastic resin more than a kind selected from polyarylene sulfide resin and polyamide and metal parts, it is characterized in that,

(1) molding die is divided into main mould and core, and this main mould is used to control the linkage with former; This core mold is useful on carries out temperature controlled heating and uses the loop with loop and cooling, and this core inside comprises the part that thermoplastic resin contacts with metal parts,

(2) use following molding die: the resin when being shaped of molding die flow into and the part that contacts with this molding die become 10 mean roughness (Rz) by surface treatment be below the 0.5 μ m, the volume of core is 60cm ³Below, in main mould, imbed core at the peripheral part that contacts with main mould of core under by the state of insulation,

2. the manufacture method of combined shaping product according to claim 1, wherein,

Above-mentioned thermoplastic resin is to contain elastomeric thermoplastic resin composition.

3. the manufacture method of combined shaping product according to claim 1 and 2, wherein,

The part of utilizing diamond-like carbon film that the resin when being shaped of the core of above-mentioned molding die is flowed into and contacting with this core is carried out surface treatment.

4. according to the manufacture method of each described combined shaping product in the claim 1～3, wherein,

The Cryogenic air of using airborne moisture to form dewfall state or moisture-curing and forming the state of freezing is cooled off rapidly.