WO2011158700A1 - 金型の製造方法 - Google Patents
金型の製造方法 Download PDFInfo
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- WO2011158700A1 WO2011158700A1 PCT/JP2011/063072 JP2011063072W WO2011158700A1 WO 2011158700 A1 WO2011158700 A1 WO 2011158700A1 JP 2011063072 W JP2011063072 W JP 2011063072W WO 2011158700 A1 WO2011158700 A1 WO 2011158700A1
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- mold
- temperature
- insulating layer
- heat insulating
- resin
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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
- 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
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
- B29C33/3842—Manufacturing moulds, e.g. shaping the mould surface by machining
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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
- B29C45/0025—Preventing defects on the moulded article, e.g. weld lines, shrinkage marks
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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
- B29C45/73—Heating or cooling of the mould
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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
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/02—Moulds or cores; Details thereof or accessories therefor with incorporated heating or cooling means
- B29C2033/023—Thermal insulation of moulds or mould parts
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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
- B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
- B29C2945/76—Measuring, controlling or regulating
- B29C2945/76003—Measured parameter
- B29C2945/7604—Temperature
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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
- B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
- B29C2945/76—Measuring, controlling or regulating
- B29C2945/76494—Controlled parameter
- B29C2945/76618—Crystallinity
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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
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0041—Crystalline
Definitions
- the present invention relates to a mold manufacturing method.
- Crystalline thermoplastic resins tend to be superior in physical properties such as mechanical strength compared to amorphous thermoplastic resins, and are used in a wide range of fields such as home appliance exterior panels, automotive exteriors, and interior parts. It has been.
- the crystalline thermoplastic resin is excellent in physical properties, but has a low crystallization rate and a high glass transition temperature. For this reason, it tends to be a locally non-uniform crystal structure. For this reason, the surface of the molded product is likely to be uneven in appearance and structure.
- a molded product made of a crystalline thermoplastic resin As a raw material with stable quality, it is necessary to promote crystallization.
- a molded product is manufactured under conditions of a high mold temperature exceeding 100 ° C.
- the mold temperature is high, a large amount of burrs are generated on the mold mating surface, which is a problem.
- a low mold temperature for example, 100 ° C. or less
- the temperature can be controlled with water without using the temperature with oil, and the complexity is eliminated. .
- the present invention has been made in order to solve the above-described problems.
- the object of the present invention is to generate burrs by setting the mold temperature at the time of molding a crystalline thermoplastic resin to T c2 -100 ° C. or lower.
- Another object of the present invention is to provide a mold manufacturing method for manufacturing a molded article that suppresses the crystallization and sufficiently promotes the crystallization of the surface.
- the inventors of the present invention have made extensive studies to solve the above problems.
- the crystalline thermoplastic resin filled in the mold has a desired crystallinity within the desired range.
- the mold temperature is T It has been found that the above-mentioned problem can be solved if a mold is provided with a heat insulating layer so that the time at which the temperature near the mold cavity surface is not less than the derived temperature at c2 -100 ° C. or lower satisfies the derived retention time,
- the present invention has been completed. More specifically, the present invention provides the following.
- a method for producing a mold for molding a molded article comprising a resin composition containing a crystalline thermoplastic resin, based on the relationship between the crystallization speed of the crystalline thermoplastic resin and the resin temperature, A temperature at which the crystallization speed of the crystalline thermoplastic resin filled in the mold is sufficiently high in the vicinity of the mold cavity surface so that the crystallinity of the surface of the molded product is in a desired range, and the crystalline thermoplasticity
- the holding time for holding the resin at a temperature at which the crystallization speed is sufficiently high in the mold is derived, and the mold temperature is T c2 -100 ° C. or less, and the mold cavity surface temperature is maintained at the derived temperature or more.
- the mold temperature is 100 ° C. or less, and when the crystalline thermoplastic resin is a polyarylene sulfide-based resin, the temperature near the cavity surface is 150 ° C. or more, and the holding time is The manufacturing method of the metal mold
- the heat insulating layer derives the relationship between the temperature near the cavity surface and the holding time by heat conduction analysis, and the material, installation position, and shape of the heat insulating layer are determined based on the relationship, and the heat conduction
- the analysis is performed using a mold in which a heat insulating layer is formed on the surface of the cavity, and using the specific gravity, specific heat, thermal conductivity, and thermal diffusivity of the material constituting the mold and the crystalline thermoplastic resin as parameters ( The manufacturing method of the metal mold
- thermoforming layer includes at least one resin selected from polybenzimidazole, polyimide, and polyetheretherketone.
- the mold temperature when molding the crystalline thermoplastic resin can be set to T c2 -100 ° C. or lower, and the occurrence of burrs can be suppressed, and the molded product It is also possible to sufficiently promote surface crystallization.
- the mold manufacturing method of the present invention is based on the relationship between the crystallization speed of the crystalline thermoplastic resin and the resin temperature, and the mold is filled so that the crystallinity of the surface of the molded product is within a desired range.
- the temperature at which the crystallizing rate of the crystalline thermoplastic resin near the mold cavity surface is sufficiently high and the holding time at which the crystalline thermoplastic resin maintains a temperature at which the crystallizing rate is sufficiently high in the mold are derived.
- the mold temperature is T c2 ⁇ 100 ° C. or lower, more preferably T c1 or lower, and the mold cavity surface is insulated so that the time for holding the temperature near the mold cavity surface is higher than the derived temperature satisfies the derived holding time. Is to provide a layer.
- T c2 is a crystallization temperature when solidifying by cooling from a molten state
- T c1 is a temperature at which crystallization occurs when a resin molded with insufficient crystals is heated. Point to.
- the crystallinity of the surface of the molded product can be increased to a desired value even if the mold temperature is set to T c2 -100 ° C. or lower.
- the temperature near the mold cavity surface of the crystalline thermoplastic resin filled in the mold for obtaining the above-described effect This is because the crystalline thermoplastic resin can derive the holding time at which the temperature at which the crystallization rate is sufficiently high in the mold is maintained.
- the resin material is not particularly limited as long as it is a crystalline thermoplastic resin, and conventionally known ones can be selected.
- crystalline thermoplastic resins polyarylene sulfide resins (particularly polyphenylene sulfide resins) are particularly problematic in terms of burrs and low crystallinity of the surface of the molded product. In other words, it is difficult to mold the polyarylene sulfide resin by setting the mold temperature to 100 ° C. or less so that the crystallinity of the surface of the molded product is sufficiently increased.
- the mold obtained by the method of the present invention is used, even if polyarylene sulfide resin is used as the resin material, the mold temperature is set to 100 ° C. or less, and the crystallinity of the surface of the molded article is sufficiently obtained. Can be increased.
- the polyarylene sulfide resin include polyarylene sulfide resins and modified products of polyarylene sulfide resins described in JP-A-2009-178967.
- polyether ether ketone resins In addition to polyarylene sulfide resins, polyether ether ketone resins, polyether ketone resins, polyphenylene ether resins, aromatic polyamide resins, and the like are also slow in crystallization, and it is difficult to increase the degree of crystallinity on the surface of the molded product. If the mold obtained by this method is used, the mold temperature of T c2 ⁇ 100 ° C. or lower can be set to sufficiently increase the crystallinity of the surface of the molded product.
- the crystallinity of the surface of the molded product can be sufficiently increased by setting the mold temperature to T c2 -100 ° C. or lower.
- the crystallinity of the surface of the molded product can be sufficiently increased by setting the mold temperature to T c2 -100 ° C. or lower.
- a resin composition containing a crystalline thermoplastic resin in which a conventionally known additive such as another resin, an antioxidant, an inorganic filler, or a stabilizer is blended with the crystalline thermoplastic resin may be used as a raw material. .
- the desired crystallinity of the molded product surface is determined.
- a preferable value can be arbitrarily determined according to, for example, the use of the molded product.
- the heat insulating layer is first installed based on the relationship between the crystallization speed of the crystalline thermoplastic resin and the resin temperature, and the crystallinity filled in the mold so that the crystallinity of the molded product satisfies the desired range. Deriving a temperature at which the crystallization rate of the thermoplastic resin near the mold cavity surface is sufficiently high and a holding time during which the crystalline thermoplastic resin maintains a temperature at which the crystallization rate is sufficiently high in the mold (No. 1) One step). Next, a heat insulating layer is provided on the mold such that the mold temperature is T c2 ⁇ 100 ° C. or lower and the time for holding the derived temperature or higher satisfies the derived holding time (second step).
- die of this invention is demonstrated, dividing into a 1st process and a 2nd process.
- First step> based on the relationship between the crystallization rate of the crystalline thermoplastic resin and the resin temperature, a temperature at which the crystallization rate in the vicinity of the cavity surface is sufficiently high so as to satisfy a specific condition, and the mold
- the derivation method is not particularly limited as long as the retention time for maintaining the temperature at a sufficiently high crystallization speed can be derived. For example, it can be derived by the following method.
- the temperature at which the crystallization speed is sufficiently high is determined from the relationship between the crystallization speed of the crystalline thermoplastic resin and the resin temperature.
- the temperature at which the crystallization rate is sufficiently fast refers to the lowest resin temperature that is faster than 1/1000 of the fastest crystallization rate, and preferably the lowest resin temperature that is faster than 1/100. If the relationship between the crystallization speed of the crystalline thermoplastic resin and the resin temperature is unknown, it must be derived by a conventionally known method.
- the holding time can be determined by the following method, for example. First, by setting the mold temperature to a temperature (e.g., T c2 -90 ° C.) close to T c2 -100 ° C. greater than the T c2 -100 ° C., holding time within the resin temperature and the die in the vicinity of the cavity surface and The degree of crystallinity is confirmed.
- FIG. 1 shows the relationship between the resin temperature near the cavity surface and the holding time during which the resin is held in the mold (solid line P). Here, it is assumed that the crystallinity of the surface of the molded product does not reach the desired range.
- FIG. 1 shows the relationship between the resin temperature near the cavity surface and the holding time during which the resin is held in the mold (solid line Q).
- solid line Q the crystallinity of the surface of the molded product has reached a desired range.
- the crystallization rate was fast enough temperature T 1, as shown in FIG.
- the time during which the resin temperature in the vicinity of the cavity surface is maintained at T 1 or more is increased by changing the mold temperature to a higher temperature or forming a heat insulating layer on the mold ( ⁇ t 2 > ⁇ t 1 ).
- This ⁇ t 2 can be adopted as the holding time. That is, when the holding time is ⁇ t 2 or more, the crystallinity of the surface of the molded product satisfies a desired range.
- the threshold value of the holding time for determining whether the crystallinity falls within a desired range is between ⁇ t 1 and ⁇ t 2 .
- ⁇ Second step> placing a heat insulating layer that satisfies the hold time the resin temperature of the cavity surface near the is maintained by T 1 or the mold.
- the material, shape, arrangement location, etc. of the heat insulating layer may be determined in any way, but can be determined by the following method, for example.
- the material, installation position, and shape of the heat insulating layer can be derived based on the relationship between the temperature of the resin near the cavity surface and the retention time by heat conduction analysis.
- the heat conduction analysis uses a mold in which a heat insulating layer is formed on the surface of the cavity, and the specific gravity, specific heat, thermal conductivity, and thermal diffusivity of the material constituting the mold and the crystalline thermoplastic resin are parameters. As done.
- the heat insulating layer is used to suppress a decrease in the resin temperature in the vicinity of the cavity surface.
- the thermal conductivity and heat capacity of the heat insulating layer and the like it is necessary to consider the thermal conductivity and heat capacity of the heat insulating layer and the like. Therefore, it is necessary to use the thermophysical properties of specific gravity, specific heat, thermal conductivity, and thermal diffusivity of the material constituting the mold and the crystalline thermoplastic resin as parameters. These parameters are input when conducting heat conduction analysis.
- FIG. 2A shows a schematic diagram of a cross section of a split mold in which the heat insulating layer is formed on the entire surface of the cavity.
- the thickness L S of the heat insulating layer (direction perpendicular to the combined surface of the divided molds), the mold in the thickness direction of the heat insulating layer Thickness L M and the thickness L P of the cavity in the thickness direction of the heat insulating layer are determined. These values are also input during the heat conduction analysis.
- FIG. 3 shows the positions of L S , L M , and L P.
- the heat insulating layer is formed on the entire surface of the cavity. However, as shown in FIG. 2 (b), the heat insulating layer may be formed on a part of the cavity surface.
- FIG.2 The schematic diagram of the cross section of the split mold in which the metal layer was formed is shown.
- the thickness L S of the heat insulation layer (direction perpendicular to the combined surface of the split molds), the metal in the thickness direction of the heat insulation layer
- the thickness L M of the mold, the thickness L P of the cavity in the thickness direction of the heat insulating layer, and the thickness L HI of the metal layer in the thickness direction of the heat insulating layer are determined. These values are input during the heat conduction analysis.
- the heat conduction analysis is performed using the input conditions such as the parameters determined as described above. While changing molding conditions such as resin temperature, mold temperature, injection speed, etc., the relationship between the resin temperature near the cavity surface and the holding time is derived for each molding condition. If the time during which the resin temperature in the vicinity of the cavity surface is maintained above the temperature at which the crystallization speed is sufficiently high is at least ⁇ t 2 above, the surface of the molded article has a desired crystallinity. In this way, it is possible to determine a heat insulating layer that satisfies a specific condition.
- the heat insulating layer preferably has a thermal conductivity of 0.3 W / m ⁇ K or less and a thickness of 60 ⁇ m or more. If the heat insulating layer satisfies these conditions, the time that the resin is held in the mold is likely to be equal to or greater than the above ⁇ t 2 at a temperature at which the crystallization speed is increased.
- Examples of the material having a heat conductivity of 0.3 W / m ⁇ K or less and heat resistance sufficient to withstand the high temperature during molding include epoxy, polyimide, polybenzimidazole, polyimide, and polyether ether. Ketones.
- a metal layer can be disposed on the heat insulating layer.
- a plate made of aluminum, SUS or the like is preferably used.
- a method for forming the metal layer on the heat insulating layer a conventionally known laminating method or the like can be employed.
- the thickness of a metal layer is based also on the kind of metal contained in a metal layer, it is preferable that it is 0.1 mm or less.
- it is necessary to make a heat insulation layer thick as above-mentioned For example, it sets to 10 mm or more, More preferably, it is set to 20 mm or more.
- a thin metal layer can be formed on the heat insulating layer by using a conventionally known plating film forming method such as a sputtering method or an ion plating method. Since the plating film is very thin, unlike the case where a metal plate is used, it is preferable that the thickness of the heat insulating layer is 60 ⁇ m or more.
- the method for forming the heat insulating layer on the inner surface of the metal part of the mold is not particularly limited.
- a polyimide film by applying a solution of a polymer precursor such as a polyimide precursor capable of forming a polymer heat insulating layer to the inner surface of a metal part of a mold, evaporating the solvent by heating, and further polymerizing by heating.
- a method of forming a heat insulation layer such as, a method of vapor-deposition polymerization of a heat-resistant polymer monomer such as pyromellitic anhydride and 4,4-diaminodiphenyl ether, and creating a piece shape in which the portion corresponding to the cavity surface is made of a heat insulation plate
- the heat insulating layer may be formed by a method in which a resin for forming the heat insulating layer is electrodeposited on a mold.
- a metal layer can be formed in order to provide durability, such as damage prevention, to a heat insulation layer and a heat insulation board surface.
- a ceramic material can be used for the heat insulating layer. Since the surface of the ceramic is excellent in wear resistance, it is not necessary to dispose the metal layer as described above on the heat insulating layer made of ceramic.
- the ceramic is preferably porous zirconia or silicon dioxide containing bubbles inside.
- the heat insulating layer made of porous zirconia is mainly made of zirconia, it has high durability against pressure applied to the heat insulating layer during injection molding. Therefore, it becomes difficult to produce the malfunction of the heat insulation layer which generate
- Zirconia is not particularly limited, and may be any of stabilized zirconia, partially stabilized zirconia, and unstabilized zirconia.
- Stabilized zirconia is one in which cubic zirconia is stabilized even at room temperature, and is excellent in mechanical properties such as strength and toughness and wear resistance.
- Partially stabilized zirconia refers to a state in which tetragonal zirconia partially remains even at room temperature, and when subjected to external stress, a martensitic transformation from tetragonal to monoclinic crystal occurs, and is particularly advanced by the action of tensile stress. Suppresses crack growth and has high fracture toughness.
- Unstabilized zirconia refers to zirconia that is not stabilized by a stabilizer. In addition, you may use combining at least 2 or more types selected from stabilized zirconia, partially stabilized zirconia, and unstabilized zirconia.
- the stabilizer contained in the stabilized zirconia and the partially stabilized zirconia conventionally known general ones can be employed.
- yttria, ceria, magnesia and the like can be mentioned.
- the amount of the stabilizer used is not particularly limited, and the amount used can be appropriately set according to the application, the material used, and the like.
- the method for forming the heat insulating layer using the above raw materials is not particularly limited, but it is preferable to employ a thermal spraying method.
- the thermal spraying method By adopting the thermal spraying method, the thermal conductivity of porous zirconia can be easily adjusted to a desired range. Moreover, problems such as a significant decrease in the mechanical strength of the heat insulating layer due to excessive formation of bubbles inside the porous zirconia do not occur.
- the structure of a heat insulation layer becomes a thing suitable for the use of this invention.
- Formation of the heat insulation layer by thermal spraying can be performed as follows, for example. First, the raw material for the heat insulating layer is melted to form a liquid. This liquid is accelerated and collides with the inner surface of the cavity. Finally, the material that collides with and adheres to the inner surface of the cavity is solidified. By doing so, a very thin heat insulating layer is formed on the inner surface of the mold. The thickness of the heat insulating layer can be adjusted by causing the melted raw material to collide with the very thin heat insulating layer and solidify. As a method for solidifying the raw material, a conventionally known cooling means may be used, or the raw material may be solidified simply by leaving it to stand. The thermal spraying method is not particularly limited, and a preferable method can be appropriately selected from conventionally known methods such as arc spraying, plasma spraying, and flame spraying.
- the heat insulating layer having the above multilayer structure can be manufactured by adjusting the manufacturing conditions of the heat insulating layer. For example, when forming a heat insulation layer by a thermal spraying method, it can manufacture by adjusting the conditions etc. which make the fuse
- Example 1 In Example 1, the following materials were used.
- Crystalline resin Polyphenylene sulfide resin (PPS resin) (manufactured by Polyplastics Co., Ltd., “Fortron 1140A64” T c2 ; 225 ° C.)
- FIG. 4 shows the relationship between the crystallization rate (Log K, where K is the rate) of the crystalline resin and the resin temperature (° C.). The temperature at which the crystallization rate is sufficiently high is set to 150 ° C. or higher. The desired crystallinity was 30%.
- Thermal insulation layer Polyimide resin (Polyimide resin varnish (Fine Chemical Japan Co., Ltd.), thermal conductivity 0.2 W / m ⁇ K was sprayed and baked at 250 ° C.
- T c2 Method of measuring T c2: using a differential scanning calorimeter (Perkin Elmer DSC7), under nitrogen atmosphere, was held for 2 minutes at 340 ° C. The thermoplastic resin, the temperature was decreased at the 10 ° C. / minute rate, obtained It was T c2 by reading the temperature of the exothermic peak from DSC chart.
- L M 10 mm
- L P 0.7 mm
- L S 0.06 mm.
- the specific gravity, specific heat, thermal conductivity, and thermal diffusivity of the material constituting the mold and the crystalline resin were as follows.
- the thermal conductivity was calculated by measuring the thermal diffusivity by a laser flash method.
- Specific gravity was measured by Archimedes method, and specific heat was measured by DSC.
- Therm1 one-dimensional heat conduction analysis software
- Table 3 shows the time during which the resin temperature was maintained at 150 ° C. or higher for the mold temperatures of 140 ° C., 100 ° C., and 80 ° C. From the results of Tables 2 and 3, it was confirmed that the holding time capable of adjusting the crystallinity to 30% or more was 0.1 seconds even when the mold temperature condition was set to 100 ° C. or lower. It was also confirmed that if the heat insulating layer set in the heat conduction analysis is provided in the mold, the crystallinity of the surface of the molded product can be adjusted to a desired range even if the mold temperature is set to 100 ° C.
- the molding conditions of the derived relational expression are a mold temperature of 100 ° C. and a heat insulating layer (ceramic 1) of 2.5 mm, a mold temperature of 100 ° C. and a heat insulating layer (ceramic 1) of 5 mm.
- the specific gravity, specific heat, thermal conductivity, and thermal diffusivity of the ceramic 1 were as follows.
- the thermal conductivity was calculated by measuring the thermal diffusivity by a laser flash method. Specific gravity was measured by Archimedes method, and specific heat was measured by DSC. Specific gravity: 2520 (kg / m 3 ) Specific heat: 790 (J / (kg ⁇ K)) Thermal conductivity: 1.46 (W / (m ⁇ K)) Thermal diffusivity: 7.33 ⁇ 10 ⁇ 7 (m 2 ⁇ s)
- Example 3 By the said Example, it has confirmed that the resin which flowed into the metal mold
- Example 3 when the heat insulating layer is changed to a zirconia-sprayed porous zirconia layer (ceramic 2), the thickness of the heat insulating layer that keeps the resin flowing into the mold at 150 ° C. or higher for 0.1 second or longer is used. , Therm1 (one-dimensional heat conduction analysis software) was used. In addition, the metal mold
- Therm1 one-dimensional heat conduction analysis software
- the relationship between the temperature of the resin at a depth of 7 ⁇ m from the cavity surface and the holding time of the resin in the mold was changed by changing the thickness of the heat insulating layer.
- the thickness of the heat insulating layer was set to 500 ⁇ m for each thickness
- the formation method of a heat insulation layer is mentioned later.
- the thickness of the heat insulating layer that keeps the state at 150 ° C. or higher for 0.1 second or longer is determined by heat conduction analysis, and the metal mold for molding is manufactured by providing the heat insulating layer of this thickness in the mold.
- a mold is manufactured in this way and molded under set molding conditions (for example, a mold temperature of 80 ° C.), a molded product having a desired crystallinity can be obtained.
- ⁇ Formation of heat insulation layer> A raw material mainly composed of zirconia was sprayed on the inner surface of the mold by a thermal spraying method. The surface of the heat insulating layer was adjusted so as to increase the density, and a heat insulating layer having a multilayer structure was formed on the inner surface of the mold. Thermal spraying was continued until the thickness of the heat insulating layer reached 500 ⁇ m. As a result of actual measurement, the specific gravity, specific heat, thermal conductivity, and thermal diffusivity of the material constituting the mold and the crystalline resin were as shown in Table 5.
- the thermal conductivity ( ⁇ ) of the heat insulating layer having a multilayer structure is obtained by calculating the thermal conductivity of each of the low density layer and the high density layer, and the thermal conductivity ( ⁇ l) of the low density layer and the thermal conductivity of the high density layer.
- Example 2 From Example 2 and Example 3, if the heat insulating layer (ceramic) set in the heat conduction analysis is provided in the mold, the crystallinity of the surface of the molded product is desired even if the mold temperature is set to 100 ° C. It was confirmed that it can be in the range.
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Abstract
Description
以下、本発明の金型の製造方法についてさらに詳細に説明する。
先ず、成形する樹脂材料を選択する必要がある。樹脂材料は結晶性熱可塑性樹脂であれば特に限定されず、従来公知のものを選択することができる。
結晶性熱可塑性樹脂の中でもポリアリーレンサルファイド樹脂(特にポリフェニレンサルファイド樹脂)は、バリの問題、成形品表面の結晶化度が低い問題が特に大きい。つまり、100℃以下の金型温度に設定して、成形品表面の結晶化度が充分に高まるように、ポリアリーレンサルファイド樹脂を成形することは困難である。しかし、本発明の方法で得られる金型を用いれば、樹脂材料としてポリアリーレンサルファイド樹脂を使用しても、100℃以下の金型温度に設定して、成形品表面の結晶化度を充分に高めることができる。ここで、ポリアリーレンサルファイド樹脂としては、例えば、特開2009-178967号公報に記載のポリアリーレンサルファイド樹脂及びポリアリーレンサルファイド樹脂の変性物が挙げられる。
また、ポリアリーレンサルファイド樹脂以外では、ポリエーテルエーテルケトン樹脂、ポリエーテルケトン樹脂、ポリフェニレンエーテル樹脂、芳香族ポリアミド樹脂等も、結晶化が遅く、成形品表面の結晶化度が高まりにくいが、本発明の方法により得られる金型を用いれば、Tc2-100℃以下の金型温度に設定して、成形品表面の結晶化度を充分に高めることができる。
なお、結晶性熱可塑性樹脂に、その他の樹脂、酸化防止剤、無機充填剤、安定剤等の従来公知の添加剤を配合した結晶性熱可塑性樹脂を含む樹脂組成物を原料に用いてもよい。
断熱層の設置は、先ず、結晶性熱可塑性樹脂の結晶化速度と樹脂温度との関係に基づいて、成形品の結晶化度が所望の範囲を満たすような、金型に充填された結晶性熱可塑性樹脂の金型キャビティ表面近傍での結晶化速度が十分速い温度と、該結晶性熱可塑性樹脂が金型内で結晶化速度が十分速い温度以上を保持する保持時間とを導出する(第一工程)。
次いで、金型温度がTc2-100℃以下で、導出された温度以上を保持する時間が、導出した保持時間を満たすような断熱層を金型に設ける(第二工程)。
以下、第一工程と第二工程とに分けて、本発明の金型の製造方法について説明する。
第一工程では、結晶性熱可塑性樹脂の結晶化速度と樹脂温度との関係に基づいて、特定の条件を満たすような、上記キャビティ表面近傍での結晶化速度が十分速い温度と、上記金型内で結晶化速度が十分速い温度以上を保持する保持時間とを導出できれば、導出方法は特に限定されない。例えば、以下の方法で導出することができる。
先ず、Tc2-100℃を超えTc2-100℃に近い温度(例えばTc2-90℃)に金型温度を設定して、上記キャビティ表面近傍の樹脂温度と上記金型内で保持時間との関係を求め、結晶化度を確認する。図1に上記キャビティ表面近傍の樹脂温度と上記金型内で樹脂が保持される保持時間との関係を示した(実線P)。ここでは、成形品表面の結晶化度が所望の範囲まで達しなかったとする。
次いで、キャビティ表面近傍の樹脂温度の低下を抑えて、成形品表面の結晶化度を高めるために、金型温度をより高い温度に変更するか、又は断熱層を金型に形成する。そして、上記と同様にして、上記キャビティ表面近傍の樹脂温度と上記金型内での樹脂の保持時間との関係を求め、結晶化度を確認する。図1に上記キャビティ表面近傍の樹脂温度と上記金型内で樹脂が保持される保持時間との関係を示した(実線Q)。ここで、成形品表面の結晶化度が所望の範囲まで達したとする。
結晶性熱可塑性樹脂の結晶化速度と樹脂温度との関係から導出した、結晶化速度が十分速い温度をT1とし、図1に示した。このキャビティ表面近傍の樹脂温度がT1以上で保持される時間は、金型温度をより高い温度に変更するか、又は断熱層を金型に形成することで長くなる(Δt2>Δt1)。このΔt2を上記の保持時間として採用することができる。つまり、保持時間がΔt2以上であれば、成形品表面の結晶化度が所望の範囲を満たす。なお、結晶化度が所望の範囲になるか否かの、保持時間の閾値は、Δt1~Δt2との間にある。
第二工程では、上記のキャビティ表面近傍の樹脂温度がT1以上で保持される保持時間を満たすような断熱層を金型に配置する。断熱層の材料、形状、配置場所等はどのように決定してもよいが、例えば、以下の方法で決定することができる。
ここで、熱伝導解析は、キャビティの表面に断熱層が形成された金型を用い、金型を構成する材料及び結晶性熱可塑性樹脂の、比重、比熱、熱伝導率、熱拡散率をパラメータとして行われる。
例えば、キャビティの表面全体に断熱層が形成されている金型が挙げられ、図2(a)には断熱層がキャビティの表面全体に形成された分割金型の断面の模式図を示す。このようにキャビティ全体に断熱層を設けることで、成形品表面全体を所望の結晶化度にすることができる。また、分割金型の合わせ面において、断熱層と金型の金属とが接するようにすることで(図2(a)中で、下側の金型の断熱層が上側の金型の金属と接していることにあたる。)、金型の合わせ面に入り込んだ樹脂は、直ちに固まるため、バリが生じない。
断熱層上に金属層を形成することで、キャビティ表面の耐摩耗性が向上する。特に、ガラス繊維等の無機充填剤を配合した場合に、キャビティの表面が摩耗しやすくなる。したがって、ガラス繊維等を配合した樹脂組成物を用いる場合には、図2(c)に示すような金型を使用することが好ましい。
キャビティの表面全体に金属層が存在すると、金属層の熱伝導率が高いため、断熱層を厚くする等の必要が生じる。
上記のようにして、断熱層を決定することができるが、実際に断熱層を金型に形成する方法を説明する前に、上述の特定の条件を満たす断熱層等について簡単に説明する。
また、スパッタリング法、イオンプレーティング法等の従来公知のメッキ膜形成方法を用いて、断熱層上に薄膜状の金属層を形成することができる。メッキ膜は、非常に薄いため、金属板を用いる場合とは異なり、断熱層の厚みは60μm以上あれば好ましい。
実施例1では、以下の材料を使用した。
結晶性樹脂:ポリフェニレンサルファイド樹脂(PPS樹脂)(ポリプラスチックス株式会社製、「フォートロン1140A64」Tc2;225℃)
上記結晶性樹脂の結晶化速度(LogK、(Kは速度))と樹脂温度(℃)との関係を図4に示す。結晶化速度が十分速い温度を150℃以上とする。また、所望の結晶化度は30%とした。
断熱層:ポリイミド樹脂(ポリイミド樹脂ワニス(ファインケミカルジャパン社製)、熱伝導率0.2W/m・Kをスプレーし、250℃、1時間で焼付けした後、ポリイミド面を研摩した。)
Tc2の測定方法:示差走査熱量計(パーキンエルマー社製DSC7)を用い、窒素雰囲気下で、熱可塑性樹脂を340℃で2分間保持した後、10℃/分の速度で降温し、得られたDSCチャートから発熱ピークの温度を読み取りすることによりTc2とした。
また、それぞれの成形条件での結晶化度の測定も行った。結晶化度の測定は、断熱層が形成されている側と、断熱層が形成されていない側とに分けて行った。結晶化度の結果も表2に示した。
また、熱伝導解析で設定した断熱層を金型に設ければ、金型温度100℃の条件に設定しても、成形品表面の結晶化度を所望の範囲に調整できることが確認された。
断熱層の材料をポリイミドから二酸化ケイ素(セラミック1)に変更し、LS=2.5mm又は5mmである以外は、実施例1と同様にして、キャビティ表面から7μmの深さでの樹脂の温度と、樹脂の金型内での保持時間との関係を導出した。樹脂温度150℃以上を保持した時間と、それぞれの成形条件での、断熱層が形成されている側の結晶化度を表4に示した。なお、導出した関係式の成形条件は、金型温度が100℃、断熱層(セラミック1)2.5mmの条件、金型温度が100℃、断熱層(セラミック1)が5mmの条件である。
比重;2520(kg/m3)
比熱;790(J/(kg・K))
熱伝導率;1.46(W/(m・K))
熱拡散率;7.33×10-7(m2・s)
上記実施例により、金型に流れ込んだ樹脂が、150℃以上の状態を0.1秒以上保持することにより、結晶化度を30%以上に調整できることを確認できた。
主としてジルコニアから構成される原料を、溶射法にて上記金型の内表面に溶射した。断熱層の表面は密度が高くなるように調整し、多層構造の断熱層を金型内表面に形成した。断熱層の厚み500μmになるまで溶射を続けた。
実際に測定した結果、金型を構成する材料及び結晶性樹脂の、比重、比熱、熱伝導率、熱拡散率は、表5の通りであった。ジルコニア断熱層の熱伝導率はレーザーフラッシュ法にて熱拡散率、DSCにて比熱、水中置換法(JIS Z8807固体比重測定方法に準拠)にて比重を測定し、[熱伝導率]=[熱拡散率×比熱×比重]により算出した。
Claims (11)
- 結晶性熱可塑性樹脂を含む樹脂組成物からなる成形品を成形するための金型の製造方法であって、
結晶性熱可塑性樹脂の結晶化速度と樹脂温度との関係に基づいて、前記成形品表面の結晶化度が所望の範囲になるように、金型に充填された結晶性熱可塑性樹脂のキャビティ表面近傍での結晶化速度が十分速い温度と、該結晶性熱可塑性樹脂の金型内で結晶化速度が十分速い温度以上を保持する保持時間とを導出し、金型温度がTc2-100℃以下で、金型キャビティ表面近傍の温度が導出した温度以上を保持する時間が、導出した前記保持時間を満たすような断熱層を設ける金型の製造方法。 - 前記金型温度は、100℃以下であり、
前記結晶性熱可塑性樹脂が、ポリアリーレンサルファイド系樹脂の場合に、
前記キャビティ表面近傍の温度は、150℃以上であり、
前記保持時間は、0.1秒以上である請求項1に記載の金型の製造方法。 - 前記断熱層は、前記キャビティ表面近傍の温度と前記保持時間との関係を熱伝導解析により導出して、該関係に基づいて断熱層の材料、設置位置、形状が決定され、
前記熱伝導解析は、キャビティの表面に断熱層が形成された金型を用い、金型を構成する材料及びの前記結晶性熱可塑性樹脂の、比重、比熱、熱伝導率、熱拡散率をパラメータとして行う請求項1又は2に記載の金型の製造方法。 - 前記断熱層は、熱伝導率が0.3W/m・K以下、厚みが60μm以上である請求項1から3のいずれかに記載の金型の製造方法。
- 前記断熱層は、ポリベンゾイミダゾール、ポリイミド及びポリエーテルエーテルケトンから選ばれる少なくとも一種の樹脂を含む請求項1から4のいずれかに記載の金型の製造方法。
- 前記断熱層は、表面に金属層を有する請求項1から5のいずれかに記載の金型の製造方法。
- 前記断熱層は、セラミックを含む請求項1から6のいずれかに記載の金型の製造方法。
- 前記セラミックは、二酸化ケイ素である請求項7に記載の金型の製造方法。
- 前記セラミックは、多孔質ジルコニアから構成される請求項7に記載の金型の製造方法。
- 前記金型温度はTc1以下である請求項1から9のいずれかに記載の金型の製造方法。
- 請求項1から10のいずれかの方法で作成した金型を用いて得られる、結晶化度が30%以上である、ポリアリーレンサルファイド系樹脂の成形品。
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SG2012091336A SG186311A1 (en) | 2010-06-14 | 2011-06-07 | Method for manufacturing a mold |
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SG186311A1 (en) | 2013-02-28 |
JPWO2011158700A1 (ja) | 2013-08-19 |
CN103038037A (zh) | 2013-04-10 |
EP2581191A1 (en) | 2013-04-17 |
JP5730868B2 (ja) | 2015-06-10 |
US20130217855A1 (en) | 2013-08-22 |
TW201206678A (en) | 2012-02-16 |
CN103038037B (zh) | 2015-07-22 |
WO2011158700A9 (ja) | 2013-04-04 |
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