KR20100134522A - Resin molded article and its manufacturing method - Google Patents

Abstract

When molding the resin, the inorganic filler is mixed in the thermoplastic resin. Although an inorganic filler is excellent in heat dissipation, since the hardness is higher than a thermoplastic resin, it exists in the tendency to grind | polish a peripheral member. The inventors of the present application found that when the mold temperature is set to a high temperature, the arrangement direction of the inorganic filler made of a fibrous heat dissipating material becomes random, and the cooling efficiency is increased by the contact of the inorganic filler inside. In this method, even when the heat dissipation material in resin is not contained in the quantity large enough to polish a peripheral member, it can have sufficient thermal conductivity.

Description

RESIN FORMED BODY AND METHOD OF PRODUCING THE SAME

The present invention relates to a resin molded article having high thermal conductivity and a manufacturing method thereof.

Resin molded bodies are conventionally used in various industrial products. Since many electronic components are accompanied by heat generation, a resin molded article having high thermal conductivity is expected for the purpose of cooling it. For example, Patent Document 1 discloses a thermally conductive resin composition containing a fiber mainly composed of alumina having a number average fiber diameter of 1 to 50 µm, a carbon fiber having a number average fiber diameter of 1 to 50 µm, and a thermosetting resin. It is. Of course, when a large amount of heat dissipating material is mixed in the resin, its thermal conductivity increases.

Japanese Unexamined Patent Publication No. 2008-138157

However, if the amount of the heat dissipation material per unit volume is increased, there is a problem that the heat dissipation material is polished to molds or screws during resin molding, or the fluidity of the resin composition is lowered. For this reason, the electrical resistivity of a resin molded object becomes small and there is still room for improvement for use for the electronic component which requires insulation. When the content rate of the heat dissipation material is lowered, these problems are suppressed. In this case, the cooling efficiency is lowered.

This invention is made | formed in view of such a subject, and an object of this invention is to provide the resin molded object which has sufficient thermal conductivity, and its manufacturing method.

T1 (℃) - 140 ℃ 를 만족시키는 것을 특징으로 한다.MEANS TO SOLVE THE PROBLEM In order to solve the subject mentioned above, the manufacturing method of the resin molded object which concerns on this invention makes the resin composition obtained by mixing and granulating the thermoplastic resin which consists of a component (X), and the inorganic filler which consists of a component (Y). The manufacturing method of the resin molded object provided with the process of inject | pouring between heated metal molds, and the process of obtaining a resin molded object by cooling a metal mold and solidifying a resin composition, The component (X) of a thermoplastic resin flows at the time of injection of a resin composition. It consists of the material which has the orientation along a direction, and the thermal conductivity in 300K of the component (Y) of an inorganic filler is 10 W / mK or more, The flow start temperature of a resin composition is T1 (degreeC) and a resin composition is made to a metal mold | die. When the temperature of the mold at the time of injection is set to T2 (° C), the following relational expression: T2 (° C)

It is characterized by satisfy | filling T1 (degreeC)-140 degreeC.

In the method of this invention, when carrying out resin molding, an inorganic filler is mixed and granulated in a thermoplastic resin. As mentioned above, although the inorganic filler which consists of a heat radiating material is excellent in heat dissipation, since the hardness is higher than a thermoplastic resin, it exists in the tendency to grind | polish a peripheral member at the time of granulation or resin injection. When the mold temperature T2 is made into high temperature so that the said relation may be satisfied, the inventors of this application will randomize the arrangement direction of the inorganic filler which consists of a heat radiating material, and the effective heat capacity will increase by an inorganic filler contacting inside, and cooling efficiency (heat dissipation efficiency) ) Is found to be high. In this method, even when the heat dissipation material in resin is not contained in the quantity large enough to polish a peripheral member, it can have sufficient thermal conductivity. In addition, the glass which is not excellent in heat dissipation is not contained in the inorganic filler of component (Y).

Moreover, it is preferable that component (Y) is at least 1 sort (s) chosen from the group which consists of magnesium oxide, aluminum oxide, aluminum nitride, boron nitride, silicon nitride, silicon carbide, and carbon. Since the inorganic filler using these has high thermal conductivity, it becomes excellent in the thermal conductivity of a resin composition.

Moreover, it is preferable that component (Y) is fibrous. That is, when an inorganic filler consists of a fiber with a high aspect ratio, the probability that a plurality of inorganic fillers will contact internally by the random arrangement mentioned above. Therefore, according to the method mentioned above, the resin molding which was excellent in cooling efficiency can be manufactured by increasing the heat capacity by a substantially inorganic filler.

Moreover, the said inorganic filler can further contain components other than a component (Y). In other words, other properties such as rigidity can be improved by mixing inorganic fillers that contribute to resin reinforcement, although the thermal conductivity is poor. It is preferable that components other than this component (Y) are fibrous, For example, glass fiber can be mixed.

Moreover, it is preferable that component (X) is a liquid crystal polymer (liquid crystalline polyester). Since a liquid crystal polymer is excellent in the fluidity | liquidity in a metal mold | die, the precision of a resin molding can be made high. Moreover, when mixing an inorganic filler and a liquid crystal polymer, the resin molding which has very high rigidity is obtained. And although a liquid crystal polymer has the property of being oriented along a flow direction, when it inject | pours into a high temperature metal mold | die like the method of this invention, the orientation shows a tendency to randomize and an inorganic filler can be arranged at random.

Moreover, it is preferable that the heater which heats a metal mold | die is a high frequency induction heating heater (IH heater).

When heating with an IH heater, since a metal mold | die can be heated at high speed, productive efficiency improves.

The IH heater is characterized by comprising a metal top plate having a concave-convex pattern for resin molding constituting the metal mold, a metal pillar formed on the metal top plate, and a coil surrounding the axis of the pillar material.

When the coil is energized, the metal pillar is inductively heated, and this heat is transferred to the metal top plate. In the case of such a structure, a member contributing to the heating of the metal top plate having the uneven pattern for resin molding, that is, a pillar material having a relatively small volume is selectively induced and heated, and this heat is transferred to the metal top plate, so that the energy consumption in production This is suppressed and the production cost can be reduced.

Moreover, the resin molding which concerns on this invention is manufactured by the manufacturing method of the resin molding mentioned above, It is characterized by the above-mentioned. This resin molding becomes excellent in cooling efficiency.

The resin molded object which concerns on this invention is characterized by the electrical resistivity in 300K of 10 ¹² ohm * m or more. Increasing the addition amount of the heat dissipating material decreases the electrical resistivity of the resin molded body, but the resin molded body of the present invention has an effective heat capacity due to random arrangement of the inorganic filler and internal contact even if the content of the heat dissipating material is low, as described above. Since the cooling efficiency is increased, it can be used for electronic component applications requiring insulation.

According to the manufacturing method of the resin molded object of this invention, the resin molded object excellent in cooling efficiency can be obtained.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing of the resin molding which shows typically the internal structure of the resin molding which concerns on (A) comparative example and (B) embodiment.
It is a figure which shows typically the heat conduction mechanism which concerns on (A) comparative example and (B) embodiment.
3 is a longitudinal sectional view of a resin molding apparatus including a high frequency induction heating heater.

Hereinafter, the manufacturing method of the resin molding which concerns on embodiment is demonstrated. In addition, the same code | symbol is used about the same element, and the overlapping description is abbreviate | omitted.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing of the resin molding which shows typically the internal structure of the resin molding which concerns on (A) comparative example and (B) embodiment. 2 is a figure which shows typically the heat conduction mechanism which concerns on (A) comparative example and (B) embodiment. The component (X) of the thermoplastic resin (1) is made of a material having an orientation along the flow direction at the time of injection of the resin composition, and the thermal conductivity at 300 K of the component (Y) of the inorganic filler (2) is 10 W. / mK or more, made of a heat radiation material.

In the resin molded object which concerns on the comparative example shown to FIG. 1 (A), the fibrous inorganic filler 2 is aligned along the longitudinal direction of the molded object. In this state, even if the inorganic filler 2 is made of a heat dissipating material, since the insulating thermoplastic resin 1 is interposed between the inorganic fillers 2, the thermal conductivity performance is lowered.

That is, as shown in FIG. 2 (A), when the heat source T contacts the resin molded body, the heat propagates in the thermoplastic resin 1 and reaches the inorganic filler 2 present therein. In order for the heat propagated in the inorganic filler 2 to reach the adjacent inorganic filler 2, the thermoplastic resin 1 must be transferred again.

Since the thermoplastic resin is made of an organic insulator, that is, a material having low thermal conductivity, the heat generated from the heat source T is not so absorbed in the resin molded body, and the heat source T is hardly cooled.

On the other hand, in the resin molding which concerns on embodiment of FIG. 1 (B), the inorganic filler 2 is arrange | positioned at random in the thermoplastic resin 1. In order to manufacture such a resin molded body, before performing resin molding, an inorganic filler is mixed and granulated in a thermoplastic resin. And when the granulated resin composition is inject | poured and shape | molded between the metal mold | die heated at comparatively high temperature (T2), the arrangement direction of the inorganic filler 2 which consists of fibrous heat radiation material becomes random.

That is, as shown in FIG.2 (B), when the heat source T contacts the resin molding, the heat | fever propagates in the inorganic filler 2, and the heat which propagated in this inorganic filler 2, It is transmitted to the inorganic filler 2 which contacted internally. According to the resin molded body of this structure, an effective heat capacity increases by contacting the some inorganic filler 2 inside, and the cooling efficiency (heat dissipation efficiency) of a resin molded object becomes high. In addition, the glass which is not excellent in heat dissipation is not contained in the inorganic filler of component (Y).

Moreover, it is preferable that component (Y) is at least 1 sort (s) chosen from the group which consists of magnesium oxide, aluminum oxide, aluminum nitride, boron nitride, silicon nitride, silicon carbide, and carbon. Since the inorganic filler using these has high thermal conductivity, it becomes excellent in the thermal conductivity of a resin composition.

Moreover, it is preferable that component (Y) is fibrous. That is, when the inorganic filler 2 consists of a fiber with a high aspect ratio, the probability that a plurality of inorganic fillers will contact internally by the random arrangement mentioned above. Therefore, according to the method mentioned above, the resin molding which was excellent in cooling efficiency can be manufactured by increasing the heat capacity by a substantially inorganic filler. From such a viewpoint, 2 or more are preferable and, as for the aspect ratio of the inorganic filler 2, 10 or more are more preferable. The upper limit of this aspect ratio can be 40 or less in order to suppress that an inorganic filler fracture | ruptures at the process of assembling a thermoplastic resin and the inorganic filler 2.

Of course, the inorganic filler 2 can further contain components other than the component (Y). In other words, other properties such as rigidity can be improved by mixing inorganic fillers that contribute to resin reinforcement, although the thermal conductivity is poor. It is preferable that components other than this component (Y) are fibrous, For example, glass fiber can be mixed.

Moreover, it is preferable that component (X) is a liquid crystal polymer (liquid crystalline polyester). Since a liquid crystal polymer is excellent in the fluidity | liquidity in a metal mold | die, the precision of a resin molding can be made high. Moreover, when mixing the inorganic filler 2 and the liquid crystal polymer, the resin molded object which has very high rigidity is obtained. And although a liquid crystal polymer has the property orientated along a flow direction, when it inject | pours into a high temperature metal mold | die as mentioned above, the orientation shows the tendency to randomize and can arrange | position the inorganic filler 2 at random.

Next, the detail of the manufacturing method of the resin molding mentioned above is demonstrated below.

The manufacturing method of the resin molding which concerns on embodiment performs the following process (1)-(4) sequentially.

(1) Manufacturing Process of Liquid Crystalline Polyester (Liquid Crystal Polymer)

(2) Granulation step of resin composition containing liquid crystalline polyester and inorganic filler

(3) Resin injection process into mold

(4) mold cooling process

Hereinafter, each process is explained in full detail.

(1) Manufacturing process of liquid crystalline polyester

First, the following raw materials (X1) to (X4) are preferably prepared.

Raw material  (X1) Aromatic hydroxycarboxylic acid
(E.g. p-hydroxybenzoic acid)  (X2) Aromatic diols
(E.g. 4,4'-dihydroxybiphenyl)  (X3) Aromatic dicarboxylic acid
(E.g. terephthalic acid)
(E.g. isophthalic acid)  (X4) Fatty acid anhydride
(E.g. acetic anhydride)

As a preferable aromatic hydroxycarboxylic acid, although 1 type in the following table can be illustrated, it can also use combining two or more types of aromatic hydroxycarboxylic acid shown in the following table.

(X1) aromatic hydroxycarboxylic acid Parahydroxybenzoic acid
Methahydroxybenzoic acid
2-hydroxy-6-naphthoic acid
2-hydroxy-3-naphthoic acid
1-hydroxy-4-naphthoic acid
2,6-dichloro-parahydroxybenzoic acid
2-chloro-parahydroxybenzoic acid
2,6-difluoro-parahydroxybenzoic acid
4-hydroxy-4'-diphenylcarboxylic acid

As a preferable aromatic diol, although 1 type in the following table can be illustrated, it can also use combining two or more types of aromatic diol shown in the following table.

(X2) aromatic diols 4,4'-dihydroxybiphenyl
Hydroquinone
Resorcin
Methylhydroquinone
Chlorohydroquinone
Acetoxyhydroquinone
Nitrohydroquinone
1,4-dihydroxynaphthalene
ㆍ 1,5-dihydroxynaphthalene
1,6-dihydroxynaphthalene
2,6-dihydroxynaphthalene
2,7-dihydroxynaphthalene
2,2-bis (4-hydroxyphenyl) propane
2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane
2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane
2,2-bis (4-hydroxy-3-methylphenyl) propane
2,2-bis (4-hydroxy-3-chlorophenyl) propane
Bis- (4-hydroxyphenyl) methane Bis- (4-hydroxy-3,5-dimethylphenyl) methane
Bis- (4-hydroxy-3,5-dichlorophenyl) methane
Bis- (4-hydroxy-3,5-dibromophenyl) methane
Bis- (4-hydroxy-3-methylphenyl) methane
Bis- (4-hydroxy-3-chlorophenyl) methane
1,1-bis (4-hydroxyphenyl) cyclohexane
Bis- (4-hydroxyphenyl) ketone
Bis- (4-hydroxy-3,5-dimethylphenyl) ketone
Bis- (4-hydroxy-3,5-dichlorophenyl) ketone
Bis- (4-hydroxyphenyl) sulfide
Bis- (4-hydroxyphenyl) sulfone
Bis- (4-hydroxyphenyl) ether

As a preferable aromatic dicarboxylic acid, although 1 type in the following table can be illustrated, it can also use combining two or more types of aromatic dicarboxylic acids shown in the following table.

(X3) aromatic dicarboxylic acid ㆍ terephthalic acid
Isophthalic acid
2,6-naphthalenedicarboxylic acid
ㆍ 1,5-naphthalenedicarboxylic acid
4,4'-biphenyldicarboxylic acid
ㆍ Methyl terephthalic acid
ㆍ methylisophthalic acid

From the viewpoint of heat resistance, it is preferable to use two types of terephthalic acid or terephthalic acid and 2,6-naphthalenedicarboxylic acid, and from the viewpoint of low thermal expansion, it is preferable to use 2,6-naphthalenedicarboxylic acid. .

As a preferable fatty acid anhydride, although 1 type in the following table can be illustrated, it can also use combining two or more types of fatty acid anhydride shown in the following table | surface.

(X4) fatty acid anhydride ㆍ Acetic anhydride
ㆍ propionic anhydride
ㆍ butyric anhydride
ㆍ Isobutyric anhydride
ㆍ Valic anhydride
ㆍ anhydrous shedding
ㆍ 2 ethyl anhydride
ㆍ hexanoic acid
ㆍ Anhydrous monochloroacetic acid
ㆍ dichloroacetic anhydride
Trichloroacetic anhydride ㆍ monobromoacetic anhydride
ㆍ Dibromoacetic anhydride
ㆍ tribromoacetic anhydride
ㆍ monofluoroacetic anhydride
ㆍ difluoroacetic anhydride
ㆍ trifluoroacetic anhydride
ㆍ Anhydrous glutaric acid
Maleic Anhydride
ㆍ Non-Sook Shinsan
Anhydrous β-bromopropionic acid

Next, the said raw materials (X1)-(X4) are introduce | transduced into a reaction container, Next, the catalyst (X5) which promotes melt polymerization is introduce | transduced into a reaction container, and a reaction container is opened at predetermined melt polymerization temperature T (M). Heat. In addition, the content is stirred during the heating period.

As the catalyst (X5) to be added to the raw materials, various kinds are known. Preferably, an imidazole compound can be used.

(X5) catalyst Imidazole
1-methylimidazole
2-methylimidazole
4-methylimidazole
1-ethylimidazole
2-ethylimidazole
4-ethylimidazole
ㆍ 1,2-dimethylimidazole
ㆍ 1,4-dimethylimidazole
2,4-dimethylimidazole
1-methyl-2-ethylimidazole
1-methyl-4-ethylimidazole
1-ethyl-2-methylimidazole
1-Ethyl-2-ethylimidazole
1-ethyl-2-phenylimidazole
2-ethyl-4-methylimidazole
2-phenylimidazole
1-benzyl-2-methylimidazole
2-phenyl-4-methylimidazole 1-cyanoethyl-2-methylimidazole
1-cyanoethyl-2-phenylimidazole
4-cyanoethyl-2-ethyl-4-methylimidazole
1-aminoethyl-2-methylimidazole
2-alkyl-4-formylimidazole
2,4-dialkyl-5-formylimidazole
1-benzyl-2-phenylimidazole
1-aminoethyl-2-methylimidazole
1-aminoethyl-2-ethylimidazole
4-formylimidazole
2-methyl-4-formylimidazole
4-methyl-5-formylimidazole
2-ethyl-4-methyl-5-formylimidazole
2-phenyl-4-methyl-4-formylimidazole

Melt polymerization temperature T (M) is 180-320 degreeC in the initial stage of superposition | polymerization, and this is 0.3-5.0 degreeC / min. It is preferable to heat up at a ratio of and finally set it as 280-400 degreeC. Although fatty acid is by-produced by superposition | polymerization, it is preferable to superpose | polymerize, removing a fatty acid out of system. It is preferable to make the atmosphere of melt polymerization into inert gas atmosphere, such as nitrogen and argon, under normal pressure. Moreover, melt polymerization can also be performed under reduced pressure. Although the reaction time of melt polymerization is not specifically limited, Usually, it is about 0.3 to 10 hours.

The obtained solid content can be cooled to room temperature, and after grinding | pulverizing with a coarse grinder, a liquid crystalline polyester ((P)) can be obtained by heating up from the room temperature to the temperature T (degreeC) which advances a solid-state polymerization reaction in nitrogen atmosphere. Solid phase polymerization temperature T (degreeC) is about 200-350 degreeC normally, and processing time is about 1 to 20 hours normally. Although the weight average molecular weight of the liquid crystalline polyester obtained in this way is not specifically limited, It is preferable that it is 10000-500000. It can be confirmed by observing with a deflection microscope that the obtained polyester is liquid crystalline.

In addition, since liquid crystalline polyester is widely sold, it can also be obtained and the raw material structure can be used even if it does not mention above.

(2) Granulation step of resin composition containing liquid crystalline polyester and inorganic filler

A pellet-shaped thermoplastic resin composition ((Q) resin composition is obtained by mixing the above-mentioned (P) liquid crystalline polyester and the (X6) inorganic filler and granulating using a granulator (e.g., coaxial twin screw extruder)). Can be obtained.

As the inorganic filler (X6), one of the following may be used, but two or more may be used. Moreover, an appropriate inorganic filler can also be further mixed as needed. The following are the presently known preferred inorganic fillers.

In addition, among the following materials, materials other than the component (Y) which have heat dissipation characteristics of 10 W / mK or more of heat conductivity are glass, wollastonite, rock wool, aluminum silicate, potassium titanate, barium titanate, aluminum borate, titanium oxide, and calcium carbonate. And basic magnesium sulfate, zinc oxide, zonarite, talc and mica, which can be incorporated separately for purposes other than improving heat dissipation.

Moreover, the fiber diameter of a fibrous filler becomes like this. Preferably it is 0.001-50 micrometers, More preferably, it is 0.005-30 micrometers, More preferably, it is 0.01 micrometer-20 micrometers. If the fiber diameter is too large, the moldability deteriorates, and if the fiber diameter is too small, the fiber diameter is not easy to be folded at the time of molding, so that the effect of improving the thermal conductivity is inferior. Moreover, the fiber length of a fibrous filler becomes like this. Preferably it is 1-10000 micrometers, More preferably, it is 5-8000 micrometers, More preferably, it is 10-6000 micrometers. If the fiber length is the said range, since the moldability of a resin composition becomes favorable and the thermal conductivity which is the objective of this invention improves more, it is preferable.

(Q) The mixing ratio of (P) liquid crystalline polyester and (X6) inorganic filler for manufacturing a resin composition is set as follows.

(Q) resin composition  (P) liquid crystalline polyester (part by weight)  G (P)  (X6) weapon filler (X6A) fibrous filler
(Parts by weight)  G (X6A) (X6B) Plate Shape Filler
(Parts by weight)  G (X6B) (X6C) particulate filler
(Parts by weight)  G (X6C)

(P) When weight part G (P) = 100 of liquid crystalline polyester, the weight part G (X6) = G (X6A) + G (X6B) + G (X6C) of (X6) inorganic filler is 5 It is set to 250. (X6) When the weight part of an inorganic filler exists in the above-mentioned range, the effect of improving mechanical strength and improving the dimensionality of a resin molded object is acquired, maintaining fluidity, and when the weight part of an inorganic filler is higher than an upper limit, fluidity It is difficult to maintain, and when lower than the lower limit, the dimensional stability of the resin molded body is lowered and a resin molded body of a desired dimension is less likely to be obtained, and the anisotropy of the liquid crystalline polyester is strongly expressed, resulting in warpage or the like in the resin molded body. There is a possibility.

Moreover, when the inorganic filler mentioned above contains a plate-shaped filler, there exists an effect of reducing the anisotropy of liquid crystalline polyester and suppressing a curvature of a resin molding.

Moreover, it is preferable that this fibrous filler contains the fibrous filler in which the surface is not coated. In this case, since gas does not generate | occur | produce from an organic substance, the effect that a bubble does not generate | occur | produce in resin is acquired.

In addition, the inorganic filler may contain only a fibrous filler. Also in this case, when weight part G (P) = 100 of (P) liquid crystalline polyester is set, weight part G (X6) = G (X6A) of the (X6) inorganic filler is set to 5-250. (X6) When the weight part of an inorganic filler exists in the above-mentioned range, the effect of improving mechanical strength and improving the dimensionality of a resin molded object is acquired, maintaining fluidity, and when the weight part of an inorganic filler is higher than an upper limit, fluidity It is difficult to maintain, and when lower than the lower limit, the dimensional stability of the resin molded body is lowered and a resin molded body of a desired dimension is less likely to be obtained, and the anisotropy of the liquid crystalline polyester is strongly expressed, resulting in warpage or the like in the resin molded body. There is a possibility.

(3) Resin injection process into mold

In the space between the heated upper and lower molds, the granulated (Q) resin composition is melted and injected, and injection molding is performed. It is preferable to use a high frequency induction heating heater (IH heater) for heating.

(4) mold cooling process

(Q) After inject | pouring a resin composition in a metal mold | die, a resin molding can be obtained by solidifying a resin composition by cooling a metal mold | die, and after that, removing a metal mold | die.

As mentioned above, in this embodiment, the process of inject | pouring the (Q) resin composition obtained by mixing and granulating (P) thermoplastic resin and (X6) inorganic filler between heated molds, and cooling a metal mold (Q) It is a manufacturing method of the resin molded object provided with the process of obtaining a resin molded object by solidifying a resin composition.

T1 (℃) - 140 ℃) 를 만족시킨다.Here, when the flow start temperature of (Q) resin composition makes temperature T1 (degreeC) and the temperature of the metal mold | die at the time of injecting (Q) resin composition into a metal mold | die, T2 (degreeC), it is a relational formula (T2 (degreeC)).

T1 (° C)-140 ° C).

That is, the present inventors earnestly examined the manufacturing method of a resin molded object, and when it shapes with the (Q) resin composition which mixed (P) thermoplastic resin and mixed with (X6) inorganic filler, the rigidity of a resin molded object improves. In this case, when the above-described relation is satisfied, it was found that the cooling efficiency of the resin molded article was remarkably improved.

Furthermore, polybutylene terephthalate resin, polystyrene resin, acrylic resin, polycarbonate resin, polyester resin, polyamide resin, polyacetal resin, polyphenylene ether resin, fluorine resin, polyphenylene sulfide resin, polysulfone resin, Even when thermoplastic resins other than (P) liquid crystalline polyester, such as polyarylate resin, polyetherimide resin, polyether sulfone resin, polyether ketone resin, polyamideimide resin, and polyimide resin, are used, it flows at low temperature. In the case of resin which tends to be oriented in the direction and whose orientation is lowered at high temperatures, the above-described effects can be obtained. This is because the present invention is established due to the randomization of the arrangement of the inorganic fillers. Among the above-mentioned thermoplastic resins, polybutylene terephthalate resin, polystyrene resin, polyester resin, polyamide resin, polyacetal resin, fluororesin, polyphenylene sulfide resin, polyether ketone resin, polyamideimide resin, polyimide Mid resin is preferable and it is more preferable that it is liquid crystalline polyester (liquid crystal polymer). Since a liquid crystal polymer is excellent in the fluidity | liquidity in a metal mold | die, the precision of a resin molding can be made high. Moreover, when mixing an inorganic filler and a liquid crystal polymer, the resin molding which has very high rigidity is obtained.

Moreover, it is preferable that the heater which heats a metal mold | die is a high frequency induction heating heater (IH heater). When heating with an IH heater, since a metal mold | die can be heated at high speed, productive efficiency improves.

3 is a longitudinal cross-sectional view of a resin molding apparatus equipped with an IH heater. In the figure, two IH heaters are shown above and below.

The lower IH heater includes the metal top plate 21A having the uneven pattern MA for resin molding constituting the mold, the metal pillars 21A 'and 23A formed on the metal top plate 21A, and the pillar material 21A'. And 22A surrounding the shaft of 23A. The upper IH heater includes the metal top plate 21B having the uneven pattern MB for resin molding constituting the metal mold, the metal column members 21B 'and 23B formed on the metal top plate 21B, and the column material 21B'. And a coil 22B surrounding the shaft circumference of the 23B. Since the upper part uneven | corrugated pattern MB for resin molding moves to the arrow direction of the same figure, a metal mold | die opens or closes. In the state which closed the uneven | corrugated pattern (MA, MB) for resin molding heated, it injects while melt | dissolving (Q) resin composition (RGN) in the space between these uneven patterns (MA, MB) for resin molding, and performs injection molding. .

When energizing the coils 22A and 22B, the metal pillars (outer members 21A 'and 21B') are inductively heated, and this heat is applied to the metal top plates 21A and 21B through the inner members 23A and 23B. ) Is passed. Since the uneven patterns MA and MB for resin molding are formed in the metal top plates 21A and 21B, the uneven patterns MA and MB for resin molding are heated. In such a structure, a member contributing to the heating of the uneven patterns MA and MB for resin molding, that is, a pillar material having a relatively small volume is selectively induced and heated, and this heat is applied to the uneven patterns MA and MB for resin molding. Since it is transmitted, energy consumption at the time of production is suppressed and production cost can be reduced.

In addition, the inner members 23A and 23B are made of a material having a higher thermal conductivity than the materials (for example, stainless steel: Fe) of the outer members 21A 'and 21B' of the pillar material (e.g., Cu), so that the thermal conductivity can be improved with high efficiency. It can be carried out.

Moreover, the resin molding manufactured by the manufacturing method mentioned above is excellent in cooling efficiency, and can be applied to many electronic components etc. which are expected to suppress heat generation.

Example

Hereinafter, although the Example of this invention is described, this invention is not limited by the Example.

(Experimental conditions)

First, liquid crystalline polyester (P1, P2) was manufactured according to the following procedures, and the thermoplastic resin composition (Q1, Q2, Q3) was manufactured using these. Moreover, thermoplastic resin composition (Q4, Q5) was made using polybutylene terephthalate resin (Toray Corporation make, brand name Torecon (registered trademark): grade 1401x06), polyphenylene sulfide resin (made by DIC Corporation, T-4G). Was prepared. Then, thermoplastic resin composition (Q1, Q2, Q3, Q4, Q5) was injected into the heated metal mold | die, it cooled, and the resin molding was manufactured.

(I) Preparation of Liquid Crystalline Polyester (P1)

The reaction apparatus includes a stirring device having a blade rotating in the reaction vessel, a torque meter for measuring the rotational torque of the stirring apparatus blade, a nitrogen gas introduction tube for introducing nitrogen gas into the reaction vessel, and a thermometer for measuring the temperature in the reaction vessel. And a reflux condenser for cooling the gas flowing out of the reaction vessel.

The following starting materials (X1) to (X4) were introduced into the reaction vessel of this reaction apparatus.

Raw material weight  (X1)  p-hydroxybenzoic acid   994.5 g (7.2 mol)  (X2)  4,4'-dihydroxybiphenyl   446.9 g (2.4 mol)  (X3)  Terephthalic acid   299.0 g (1.8 mol)  Isophthalic acid    99.7 g (0.6 mol)  (X4)  Acetic anhydride  1347.6 g (13.2 mol)

First, nitrogen gas is introduced into the reaction vessel through a nitrogen gas introduction tube to sufficiently replace the gas inside the vessel with nitrogen gas. While nitrogen gas was flowing in the reaction vessel, the reaction vessel was heated to 150 ° C. over 30 minutes, and maintained at this temperature to reflux for 3 hours. Acetic acid is refluxed using a reflux condenser.

Thereafter, 2.4 g of the catalyst (X5) "1-methylimidazole" was added, and then the temperature was raised to 320 ° C. over 2 hours and 50 minutes while distilling off the by-product acetic acid and unreacted acetic anhydride, which were distilled off. The timing at which the increase in the torque measured by the reaction was observed was regarded as the completion of the reaction, and the contents in the reaction vessel were taken out.

The obtained solid was cooled to room temperature and pulverized by a coarse mill, and then heated up over 1 hour from room temperature to 250 ° C. under nitrogen atmosphere, heated up over 5 hours from 250 ° C. to 295 ° C., and maintained at 295 ° C. for 3 hours, The polymerization reaction was advanced to a solid phase to obtain liquid crystalline polyester (P1).

(II) Manufacturing process of liquid crystalline polyester (P2)

The following raw materials were introduce | transduced into the container of the reaction apparatus mentioned above.

Raw material weight  (X1)  p-hydroxybenzoic acid   994.5 g (7.2 mol)  (X2)  4,4'-dihydroxybiphenyl   446.9 g (2.4 mol)  (X3)  Terephthalic acid   239.0 g (1.44 mol)  Isophthalic acid   159.5 g (0.96 mol)  (X4)  Acetic anhydride  1347.6 g (13.2 mol)

After sufficiently replacing the inside of the reactor with nitrogen gas, the temperature was raised to 150 ° C. over 30 minutes under a nitrogen gas stream, and the temperature was maintained at reflux for 3 hours. Thereafter, 2.4 g of the catalyst (X5) "1-methylimidazole" was added, followed by distilling off the by-product acetic acid and unreacted acetic anhydride, which were distilled off, and the temperature was raised to 320 ° C. over 2 hours and 50 minutes, thereby increasing the torque. The observed time was regarded as the completion of the reaction, and the contents were taken out. The obtained solid was cooled to room temperature and pulverized by a coarse mill, and then heated up from room temperature to 220 ° C. over 1 hour in a nitrogen atmosphere, heated up over 220 hours from 220 ° C. to 240 ° C., and maintained at 240 ° C. for 10 hours, The polymerization reaction was advanced to a solid phase to obtain liquid crystalline polyester (P2).

(III) Process for producing thermoplastic resin composition (Q1, Q2, Q3, Q4, Q5)

First, what contains the following materials as inorganic filler (X6) was prepared.

(X6) weapon filler (X6A) fibrous filler (X6A1) carbon fiber
Part number: Diamond K223HG (manufactured by Mitsubishi Chemical Sanza Co., Ltd.)
Thermal Conductivity: 540 W / mK
Fiber diameter: 10 μm
Fiber Length: 6 mm

(X6A2) glass fiber
Part number: CS03JAPX-1 (made by Owens Corning)
Material: Glass (SiO ₂ )
Thermal Conductivity: 1.0 W / mK
Fiber diameter: 10 μm
Fiber Length: 3 mm

(X6A3) Alumina Fiber
Tenkaarusen (registered trademark): (manufactured by Denki Chemical Industries, Ltd.)
Material: 100% by weight of alumina
Fiber Diameter: 3.2 μm
Bulk Density: 0.28 g / cm 3 (X6B) Plate Shape Filler Part number: X-50 (manufactured by Nippon Talc Co., Ltd.)
Material: Talc
Thermal Conductivity: 0.12 W / mK
Dimension: particle size 14.5 ㎛ (X6C) particulate filler (X6C1) Alumina Fiber Particle Shape
The above-mentioned alumina fibers were stirred together (* 1).

(X6C2) Alumina Particles (Low Soda Alumina)
Part number: ALM-41 (manufactured by Sumitomo Chemical Co., Ltd.)
Thermal Conductivity: 36 W / mK
Average particle diameter: 1.5 μm
Alumina content: 99.9 wt%
Bulk Density: 0.28 g / cm 3

In addition, the (X6C1) alumina fiber particle (lump) shape object as described in (* 1) mentioned above is made to mix | blend (X6A3) alumina fiber in Henschel mixer (Kawata Co., Ltd. make, super mixer G100), and to carry out stirring granulation. In addition, the Henschel mixer is a kind of propeller mixer type high speed mixer, and is a machine mainly used for uniform mixing of powder, plastic raw materials, colorants and additives.

Next, the liquid crystalline polyester (P1, P2), polybutylene terephthalate resin, or polyphenylene sulfide resin obtained at the manufacturing process (I) and manufacturing process (II), and (X6) inorganic filler are mixed, It was granulated using an aromatic biaxial extruder (manufactured by Ikegai Steel Co., Ltd., PCM-30) to obtain a thermoplastic resin composition. These mixing ratios are as follows.

(Q1) thermoplastic
Resin composition (Q2) thermoplastic
Resin composition (Q3) thermoplastic
Resin composition (P1) liquid crystalline polyester
(Parts by weight)  32  15  20 (P2) liquid crystalline polyester
(Parts by weight)  0  12  16 (X6C1) Alumina Fiber Particle Shape (parts by weight)  61  65  0 (X6A1) carbon fiber
(Parts by weight)  7  0  0 (X6C2) Alumina Particles
(Parts by weight)  0  8  52 (X6B) talc
(Parts by weight)  0  0  6 (X6A2) glass fiber
(Parts by weight)  0  0  6 Flow start temperature T1
(℃)  336  310  306

(Q4)
Thermoplastic resin composition (Q5)
Thermoplastic resin composition Polybutylene terephthalate resin
(Parts by weight) 70 0 Polyphenylene sulfide resin
(Parts by weight) 0 70 (X6C1) Alumina Fiber Particle Shape (parts by weight) 30 30 Flow start temperature T1
(℃) 233 286

The flow start temperature of the obtained thermoplastic resin composition (Q1, Q2, Q3, Q4, Q5) was measured.

In addition, the flow start temperature is a temperature at which the resin starts flow, and in order to measure more precisely, in this example, the flow start temperature is 100 kg using a capillary rheometer having a nozzle having an internal diameter of 1 mm and a length of 10 mm. When the heating melt was extruded from the nozzle at a temperature rising temperature of 4 ° C / min under a load of / cm 2, the melt viscosity was set to a temperature at which 48000 poises were exhibited.

(Example 1)

Using thermoplastic resin composition Q1, the high frequency electric current was supplied to the IH heater of FIG. 3, and the top plate temperature was raised by high frequency induction heating, and injection molding was performed when the top plate temperature reached 227 degreeC. Moreover, resin was made to flow and inject along the longitudinal direction (longitudinal direction) of a molded article. The obtained molded article has a dimension of 20 mm in the resin flow direction (the longitudinal direction (MD)) and a dimension in the direction (the transverse direction (TD)) perpendicular to the resin flow direction of 7 mm, perpendicular to both the longitudinal and the transverse directions. It was a rectangular parallelepiped whose dimension of the thickness direction ZD is 1 mm, and made this the sample for thermal conductivity evaluation.

(Example 2)

The sample was produced like Example 1 except having made top plate temperature into 251 degreeC.

(Comparative Example 1)

The sample was produced like Example 1 except having made top plate temperature 130 degreeC.

(Example 3)

The sample was produced like Example 1 except having changed the thermoplastic resin composition into Q2.

(Example 4)

The sample was produced like Example 3 except having changed the top plate temperature to 251 degreeC.

(Comparative Example 2)

The sample was produced like Example 3 except having changed top plate temperature to 130 degreeC.

(Example 5)

The sample was produced like Example 1 except having changed the thermoplastic resin composition into Q3.

(Example 6)

The sample was produced like Example 5 except having changed the top plate temperature to 251 degreeC.

(Comparative Example 3)

The sample was produced like Example 5 except having changed top plate temperature to 130 degreeC.

(Example 7)

A sample was produced in the same manner as in Example 1 except that the thermoplastic resin composition was changed to Q4 and the top plate temperature was changed to 150 ° C.

(Comparative Example 4)

The sample was produced like Example 7 except having changed top plate temperature to 60 degreeC.

(Example 8)

A sample was prepared in the same manner as in Example 1 except that the thermoplastic resin composition was changed to Q5 and the top plate temperature was changed to 200 ° C.

(Comparative Example 5)

The sample was produced like Example 7 except having changed top plate temperature to 130 degreeC.

(Evaluation and results)

The thermal diffusion rate of resin in each Example and a comparative example was measured using the said sample. For this measurement, a thermal diffusivity and a thermal conductivity measuring device (manufactured by iphase Co., Ltd., iphase mobile (registered trademark)) were used. Specific heat was measured using DSC (manufactured by PERKIN ELMER, DSC7), and specific gravity using an automatic specific gravity measuring device (manufactured by Kanto Major Co., Ltd., model number ASG-320). The thermal conductivity of each direction (MD, TD, ZD) was computed from the product of a thermal diffusivity and specific gravity.

The electrical resistivity in the temperature of 300 K was measured using the test method of ASTM (American Materials Testing Association) -D257.

The above evaluation results are shown in the following table.

Example 1 Example 2 Comparative Example 1 Thermoplastic resin composition  Q1  Q1  Q1 Flow start temperature T1 (° C)  336  336  336 Mold temperature T2 (℃)  227  251  130 T1-140 (℃)  196  196  196 Thermal Conductivity (MD)
W / mK  7.6  7.7  7.5 Thermal conductivity (TD)
W / mK  8.8  9.3  8.3 Thermal Conductivity (ZD)
W / mK  1.8  1.8  1.6 Electrical resistivity (Ωm) 1 × 10 ¹³ 1 × 10 ¹³ 1 × 10 ¹³

Example 3 Example 4 Comparative Example 2 Thermoplastic resin composition  Q2  Q2  Q2 Flow start temperature T1 (° C)  310  310  310 Mold temperature T2 (℃)  227  251  130 T1-140 (℃)  170  170  170 Thermal Conductivity (MD)
W / mK  5.0  5.1  4.7 Thermal conductivity (TD)
W / mK  5.9  6.8  5.8 Thermal Conductivity (ZD)
W / mK  2.3  2.6  2.1 Electrical resistivity (Ωm) 1 × 10 ¹³ 1 × 10 ¹³ 1 × 10 ¹³

Example 5 Example 6 Comparative Example 3 Thermoplastic resin composition  Q3  Q3  Q3 Flow start temperature T1 (° C)  306  306  306 Mold temperature T2 (℃)  227  251  130 T1-140 (℃)  166  166  166 Thermal Conductivity (MD)
W / mK  3.1  3.2  2.8 Thermal conductivity (TD)
W / mK  2.4  3.9  2.1 Thermal Conductivity (ZD)
W / mK  1.1  1.3  0.8 Electrical resistivity (Ωm) 1 × 10 ¹³ 1 × 10 ¹³ 1 × 10 ¹³

Example 7 Comparative Example 4 Example 8 Comparative Example 5 Thermoplastic resin composition  Q4  Q4  Q5  Q5 Flow start temperature T1 (° C)  233  233  286  286 Mold temperature T2 (℃)  150  60  200  130 T1-140 (℃)  93  93  146  146 Thermal Conductivity (MD)
W / mK  0.5  0.4  0.5  0.4 Thermal conductivity (TD)
W / mK  0.9  0.5  0.4  0.3 Thermal Conductivity (ZD)
W / mK  0.3  0.2  0.3  0.2 Electrical resistivity (Ωm) 1 × 10 ¹³ 1 × 10 ¹³ 1 × 10 ¹³ 1 × 10 ¹³

T1 (℃) - 140 (℃) 인 경우에는, 열전도율을 향상시킬 수 있다는 것이 판명되었다. 특히, 단수 또는 복수의 액정성 폴리에스테르를 혼합함으로써 유동 개시 온도를 바꾼 열가소성 수지 조성물 (Q1, Q2, Q3, Q4, Q5) 중 어느 것을 사용해도 상기 관계식을 만족시킨 경우에는, 열전도율을 현저히 향상시킬 수 있다는 것이 판명되었다. 이와 같이, 금형 온도 T2 를 열가소성 수지 조성물의 유동 개시 온도 T1 에 대응시켜 소정값 이상의 고온으로 함으로써, 금형 내에서의 열가소성 수지 조성물의 고화가 느려지고, 열가소성 수지 조성물이 점탄성이 낮은 상태에서 유지되기 때문에, 그 동안에 무기 필러의 배향 방향이 랜덤해져, 성형체 내부에서 무기 필러가 접촉함으로써 열전도율을 향상시킬 수 있게 된다.From the above experimental result, T2 (degreeC)

In the case of T1 (degreeC)-140 (degreeC), it turned out that heat conductivity can be improved. In particular, even if any of the thermoplastic resin compositions (Q1, Q2, Q3, Q4, Q5) having changed the flow start temperature by mixing a single or a plurality of liquid crystalline polyesters is satisfied, the thermal conductivity can be significantly improved. It turned out that it could. Thus, since mold temperature T2 is made into the high temperature more than predetermined value corresponding to the flow start temperature T1 of a thermoplastic resin composition, solidification of the thermoplastic resin composition in a metal mold | die will become slow and a thermoplastic resin composition will be maintained in the state with low viscoelasticity, In the meantime, the orientation direction of an inorganic filler becomes random, and it becomes possible to improve thermal conductivity by making an inorganic filler contact in the inside of a molded object.

열가소성 수지의 분해 개시 온도인 것이 바람직하다.Moreover, T2 (degreeC) from a heat resistant viewpoint of a resin molded object.

It is preferable that it is the decomposition start temperature of a thermoplastic resin.

Moreover, even if the material of a thermoplastic resin or an inorganic filler is other than an experiment example, the improvement effect of thermal conductivity can be acquired similarly to the above because the random orientation raises the possibility that several inorganic filler will contact inside a thermoplastic resin. .

Claims (10)

And a step of injecting a resin composition obtained by mixing and granulating a thermoplastic resin composed of component X and an inorganic filler composed of component Y between heated molds, and cooling the mold to solidify the resin composition to obtain a resin molded body. As a method for producing a resin molded article,
The component X of the said thermoplastic resin consists of a material which has an orientation along the flow direction at the time of the said injection | pouring of the said resin composition,
The thermal conductivity in 300 K of component Y of the said inorganic filler is 10 W / mK or more,
The flow start temperature of the said resin composition is temperature T1 degreeC,
The temperature of the mold at the time of injecting the resin composition into the mold is T2 ° C,
In the following relation:
T2 ℃

The manufacturing method of the resin molded object characterized by satisfying T1 degreeC-140 degreeC. The method of claim 1,
The component Y is at least one member selected from the group consisting of magnesium oxide, aluminum oxide, aluminum nitride, boron nitride, silicon nitride, silicon carbide, and carbon. The method of claim 1,
The said component Y is fibrous form, The manufacturing method of the resin molded object characterized by the above-mentioned. The method of claim 1,
The said inorganic filler further contains components other than the component Y, The manufacturing method of the resin molded object characterized by the above-mentioned. The method of claim 4, wherein
Components other than the said component Y are fibrous, The manufacturing method of the resin molded object characterized by the above-mentioned. The method of claim 1,
The said component X is a liquid crystal polymer, The manufacturing method of the resin molded object characterized by the above-mentioned. The method of claim 1,
The heater which heats the said metal mold | die is a high frequency induction heating heater, The manufacturing method of the resin molded object characterized by the above-mentioned. The method of claim 7, wherein
The high frequency induction heating heater,
A metal top plate having an uneven pattern for resin molding constituting the mold;
A metal pillar formed on the metal top plate;
And a coil surrounding the axis of the pillar material. The resin molded object manufactured by the manufacturing method of the resin molded object in any one of Claims 1-8. The method of claim 9,
The electrical resistivity in 300K is 10 ¹² ohm * m or more, The resin molded object characterized by the above-mentioned.

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