KR20060003042A - Resin crystallization promoter and resin composition - Google Patents

Abstract

The present invention relates to a thermoplastic resin crystallization promoter comprising fine carbon fiber consisting of fiber filaments having a diameter of 0.001 mum to 5 mum and an aspect ratio of 5 to 15,000, a thermoplastic resin composition consisting of the fine carbon fiber and thermoplastic resin and comprising crystallized resin, and a production method thereof. The crystallization promoter comprising the fine carbon fiber of the present invention enables to crystallize even an amorphous resin, which has an irregular molecular structure and therefore is not crystallized, or which exhibits low crystallization degree and therefore is difficult to crystallize by means of a conventional crystallization promoter. The crystallization promoter provides a thermoplastic resin composition, which, when molded, exhibits improved strength and tribological characteristics and is further reinforced when mixed with a filler.

Description

Resin crystallization promoter and resin composition {RESIN CRYSTALLIZATION PROMOTER AND RESIN COMPOSITION}

The present invention relates to an agent for promoting crystallization of a resin (regular arrangement of polymers around the agent for promoting crystallization). More specifically, the present invention relates to an agent for promoting crystallization of a resin (hereinafter referred to as "resin crystallization accelerator"), and a resin composition containing the resin and the resin crystallization accelerator and a method for producing the same.

The resins are classified into crystalline resins and amorphous resins according to their crystallization characteristics. Simple, regularly arranged molecular structures are easily crystallized, and resins showing a high crystalline region ratio (high crystallinity) are classified as crystalline resins. On the other hand, resins containing a main chain composed of molecular units having different sizes are classified as amorphous resins because the degree of branching of the main chain is irregular and difficult to crystallize. The point of distinction between the crystalline resin and the amorphous resin is the presence or absence of a melting point resulting from crystallization in addition to the glass transition point. Specifically, when the crystalline resin is subjected to differential thermal analysis, a temperature range higher than the glass transition point of the resin in addition to the step including a peak or a step caused by heat absorption or heat generation at the glass transition point. In the endothermic / exothermic peak is observed. On the other hand, in the amorphous resin, no endothermic / exothermic peaks as described above are observed.

Crystalline resins exhibit unique properties such as high mechanical strength, good fatigue resistance, good chemical resistance and good tribological characteristic. In addition, among other properties, the crystalline resin is very hardened when mixed with the filler. On the other hand, the amorphous resin is characterized by transparency, excellent weather resistance and excellent impact resistance. In addition, the amorphous resin is characterized by being easily formed into a product having high dimensional accuracy and little warpage and shrinkage.

Among the crystalline resins, the degree of ease is different, and some crystalline resins exhibit low crystallization rates due to their molecular structure, so crystallization promoters (nucleating agents) are required for crystallization. In some cases, crystallization promoters are added to the easy-to-crystallize crystalline resin to control the rate of crystallization. For example, when a product is formed by melting the thermoplastic resin and then solidifying it under cooling, the thermal history of the rapidly cooled surface portion of the thus formed product is significantly different from that of the cooled central part. Specifically, the surface portion becomes amorphous due to insufficient crystal growth time, whereas the central portion tends to exhibit high crystallinity due to sufficient crystal growth time. That is, a skin-core structure is formed in the product. Thus, the mechanical properties from the surface portion to the center portion are changed. In such a case, the crystallization rate of the thermoplastic resin should be controlled so that the product exhibits uniform mechanical properties. For example, when a resin showing a low crystallization rate, such as polyamide-imide, is formed into a product, crystallization of the resin proceeds in the product thus formed, causing shrinkage of the resin, and causing low dimensional accuracy of the product. . Therefore, the crystallization rate of such a resin must be controlled.

Resin crystallization accelerators are roughly divided into inorganic crystallization accelerators and organic crystallization accelerators. Inorganic crystallization promoters are generally used in combination with organic crystallization promoters.

Examples of conventionally known inorganic crystallization accelerators include silica, talc, calcium carbonate, zinc fluoride, cadmium fluoride, titanium dioxide, kaolin, alumina and amorphous silica alumina particles.

Examples of conventionally known organic crystalline accelerators include fatty acid salts such as stearate (JP-A-47-23446), adipate, and sebacate (JP-A-50-6650); Organic phosphonates such as cyclohexylphosphonate and phenylsulfonate (Japanese Patent Laid-Open No. 50-32251); Aromatic salts such as benzoic acid (JP-A-53-50251); Oligomeric polyester (Japanese Patent Laid-Open No. 55-116751); And mixtures of a compound having a bisimide structure and a carbon powder (Japanese Patent Laid-Open No. 9-188812).

The resin is inherently difficult to crystallize; When a resin is used under ordinary cooling conditions, the crystallization temperature of the resin varies within a wide range. Therefore, in order to stabilize the morphology or physical properties of the resin product, the crystallization temperature or crystallization time of the resin must be controlled by the use of crystallization promoter. However, the crystallization promoter known in the prior art is insufficient enough to satisfy the requirements in terms of reducing the crystallization temperature, controlling the crystallization rate and controlling the crystallinity.

As described above, it is an object of the present invention to provide a crystallization promoter capable of crystallizing an amorphous resin that has an irregular molecular structure and thus is not crystallized or exhibits low crystallinity and which is difficult to crystallize by a conventional crystallization accelerator. As used herein, "crystallization" means not only a state in which molecules of the same configuration are regularly estimated in a three-dimensional periodic arrangement, such as when molecules are aligned in a crystal; It also includes a state in which the structure of the polymer around the agent for promoting crystallization is regularly arranged and a state in which irregularly arranged disordered molecules (amorphous states) are arranged to some degree. Another object of the present invention is to provide a thermoplastic resin composition comprising a crystallization promoter which, when molded, exhibits improved strength and frictional wear properties and which is further strengthened when mixed with the filler.

The inventors have found crystallization of amorphous resins (e.g. polycarbonates), which are presumed to be difficult to crystallize, from carbon fibers made of fine carbon fibers produced by vapor phase, in particular fiber filaments having a diameter of 0.001 µm to 5 µm and an aspect ratio of 5 to 15,000. It acts as an agent for promoting, and also, the fine carbon fiber can be crystallized, but promotes the crystallization (rate and degree of crystallization) of the crystalline resin showing a low crystallization rate and low crystallinity. The present invention has been accomplished based on this finding.

Therefore, this invention provides a resin crystallization promoter, its manufacturing method, the resin composition containing the said crystallization promoter, and its use, and is described below.

1. A resin crystallization accelerator comprising fine carbon fibers composed of respective fiber filaments having a diameter of 0.001 μm to 5 μm and an aspect ratio of 5 to 15,000.

2. The resin crystallization promoter according to 1 above, wherein the fine carbon fibers are vapor phase carbon fibers.

3. The resin crystallization accelerator according to the above 2, wherein the vapor phase carbon fiber contains boron in an amount of 0.001 to 5% by mass.

4. The resin composition characterized by including the resin crystallization promoter and resin in any one of said 1-3.

5. The resin composition according to 4 above, wherein the resin is a thermoplastic resin.

6. The resin composition according to the above 5, wherein the thermoplastic resin is an amorphous thermoplastic resin.

7. The resin composition according to 5 or 6, wherein the thermoplastic resin is a resin containing a polymer having a structural unit having an aromatic group as a repeating unit.

8. The thermoplastic resin according to the above 5, wherein the thermoplastic resin is polystyrene, polycarbonate, polyarylate, polysulfone, polyetherimide, polyethylene terephthalate, polyphenylene oxide, polyphenylene sulfide, polybutylene terephthalate, polyimide Any one selected from polyamide-imide and polyether-ether-ketone; Or a mixture thereof.

9. The endothermic / exothermic peak which is not related to the mass change at any temperature other than the glass transition point of the resin when the differential scanning calorimety (DSC) is performed according to any one of 4 to 8 above. Resin composition, characterized in that.

10. The heat generation / endothermic peak attributable to melting or crystallization of the composition, when the differential scanning calorimetry is carried out according to any one of 4 to 8, wherein the peak is any one of 1 to 3 above. The resin composition, characterized in that it is moved to a higher or higher temperature range than in the case of the resin composition containing no crystallization accelerator.

11. The resin composition according to any one of 4 to 8, wherein when the X-ray diffraction method is performed, a peak resulting from the resin and a peak resulting from a regular arrangement of the resin structure are shown.

12. The half width of the band of the diffraction angle 2θ corresponding to the peak resulting from the regular arrangement of the resin structure in the X-ray diffraction method is 5 ° or less according to any one of 4 to 8 above. Resin composition made into.

13. The resin composition according to any one of 4 to 12, wherein the content of the resin crystallization accelerator is 0.1 to 80% by mass.

14. Process of kneading resin and crystallization promoter of 1 or 2 above; And

Next, a method for producing a resin composition having a crystalline, regularly arranged structure, comprising the step of annealing the mixture obtained at a temperature equal to or higher than the glass transition point of the resin.

15. A conductive material comprising the resin composition according to any one of 4 to 13.

16. The heat conductive material containing the resin composition as described in any one of said 4-13.

17. A material characterized by exhibiting frictional wear characteristics comprising the resin composition according to any one of 4 to 13.

18. An appliance component comprising the resin composition according to any one of 4 to 13.

The crystallization promoter of the present invention contains fine carbon fibers composed of respective fiber filaments having a diameter of 0.001 μm to 5 μm and an aspect ratio of 5 to 15,000. Examples of such carbon fibers include vapor phase carbon fibers (Japanese Patent No. 2778434) produced by supplying an organic compound vaporized in a high temperature atmosphere together with iron acting as a catalyst. It is preferable that this invention uses such a vapor-phase carbon fiber.

The vapor phase carbon fibers used are, for example, carbon fibers as prepared; Carbon fibers obtained by heat-treating the prepared carbon fibers at 800 to 1,500 ° C; Or it may be a carbon fiber obtained by graphitizing the prepared carbon fiber at 2,000 ~ 3,000 ℃. Preferably graphitized carbon fibers are used at 1,500 ° C. or higher or 2,000-3,000 ° C.

The vapor-phase carbon fiber is composed of B, A1, Be or Si (preferably boron) such that a small amount of elements (0.001-5% by mass, preferably 0.01-2% by mass) is contained in the carbon crystal of the obtained vapor-phase carbon fiber. It may be a vapor phase carbon fiber graphitized in the presence of an element that promotes carbon crystallization (WO 00/585326).

The vapor-phase carbon fiber subjected to such high temperature treatment has an interlayer distance of 0.68 nm or less (that is, an index for evaluating carbon crystallization), and the vapor-phase carbon fiber compared to the case of the vapor-phase carbon fiber heat-treated at 800 to 1500 ° C. The surface structure of is closer to the graphite structure. Therefore, when the graphitized vapor-phase carbon fiber is added to the thermoplastic resin, it is speculated that an interaction between the carbon fiber and the surface of the resin may occur to promote crystallization of the resin.

The amount of fine carbon fibers added to the thermoplastic resin varies depending on the use of the obtained resin composition. As for the quantity of the said fine carbon fiber, 0.1-80 mass% is common with respect to the whole of the said thermoplastic resin, 1-80 mass% is preferable, and about 5-60 mass% is more preferable. If the amount of the fine carbon fiber is less than 0.1% by mass, the effect of the carbon fiber is not obtained, while if the amount of the carbon fiber exceeds 80% by mass, it becomes difficult in mixing the fine carbon fiber and the thermoplastic resin. .

It is preferable that the said vapor-phase carbon fiber is mixed uniformly with a thermoplastic resin. Thus, the vapor phase carbon fiber must be melt-mixed with the thermohydrophobic resin.

In the melt mixing method, there is no particular limitation, but the method may use, for example, a modified screw barrel such as a twin screw extruder, a planetary gear mixer or a kneader.

In the present invention, the thermoplastic resin in which the fine carbon fibers are combined to induce crystallization of the resin or to promote crystallization of the resin includes both crystalline resin and amorphous resin.

There is no particular limitation on the crystalline resin for promoting crystallization, but the resin is preferably a crystalline resin containing a polymer having a structural repeating unit having an aromatic group. Here, "aromatic group" means a group containing a heterocyclic ring, a benzene ring or a condensed ring such as naphthalene and anthracene. Examples of the aromatic group include monovalent groups such as pyridyl, quinazolinyl, anilino, phenyl, alkyl-substituted petyl, naphthyl and biphenylyl; And divalent groups such as pyridinediyl, phenylene, naphthylene, biphenylene and acenaphthylene. Phenyl, alkyl substituted phenyl, phenylene and biphenylene are preferred. Preferred examples of the crystalline thermoplastic resin include polyethylene terephthalate (PET), polyphenylene sulfide (PPS) and polybutylene terephthalate (PBT). The crystallization accelerator of the present invention containing the fine carbon fibers effectively promotes crystallization of resins, particularly polyethylene terephthalate, polyphenylene sulfide, and the like, which are difficult to crystallize under generally used conditions. By the crystallization promoter, the crystallization rate of the resin as described above is controlled, and therefore, the characteristics of the resin including mechanical strength, fatigue resistance, chemical resistance and frictional wear characteristics can be efficiently obtained.

Examples of the amorphous resin that can be crystallized by the crystallization promoter of the present invention containing the fine carbon fiber include polystyrene, polycarbonate (PC), polyarylate (PAR), polysulfone, polyetherimide, polyamide- Imides, modified polyphenylene oxides and polyimides. Generally, even when a crystallization promoter is added, such a resin is not crystallized. However, by using the vapor phase carbon fiber of the present invention, the resin can be crystallized due to the interaction between the resin and the vapor phase carbon fiber.

For example, polycarbonate is crystallized by the following procedure: vapor phase carbon fiber (fiber filament of carbon fiber having an average diameter of 0.15 μm and an aspect ratio of 70) (5% by mass) which is heat treated at 2,800 ° C. is added to the polycarbonate and melted Kneaded; The resulting mixture is molded into a product using a hot press; The product thus formed is subjected to annealing at 200 ° C., that is, 90 ° C. lower than 290 ° C. which is a generally used molding temperature; Immediately after the annealing, the obtained product is immersed in a water bath for quenching. The degree of crystallinity of the resin is chemical method; For example, (1) measurement of density, (2) X-ray diffraction intensity of crystalline and amorphous regions, (3) intensity of infrared absorption band of crystalline or amorphous region, (4) differential curve of broad nuclear magnetic resonance absorption spectrum , (5) measurement of heat of melting, and (6) adsorption or hydrolysis oxidation of water. However, the value of the crystallinity of the resin is a semi-crystalline region between the crystalline region and the amorphous region of the resin, which changes depending on the measurement method since it becomes difficult to measure one of the two. Crystallization of the resin can be confirmed, for example, by measuring the heat of melting using differential scanning calorimetry (DSC). The transition temperature of the said resin is the following method, for example, the method described by JIS K7121 in which the said resin is cooled after predetermined heat processing is performed, and then the said transition temperature is measured; Or by the method in which the resin (sample) is heated and melted. For example, when the transition temperature of the resin is measured by the use of DSC, the endothermic / exothermic peak attributable to the phase change not related to the mass change is near 200 ° C., which is higher than the glass transition point (Tg) at around 150 ° C. Observed in FIG. 2. Annealing (heat treatment) of the resin is mainly carried out to remove strain in the polymer, to promote crystallization of the resin, and to improve long-term stability of the resin.

This endothermic / exothermic peak corresponds to the melting point (Tm) of the crystalline thermoplastic resin. Therefore, it is assumed that the occurrence of the observed endothermic / exothermic peak is caused by the crystallization of the amorphous resin by the crystallization promoting action of the gas phase carbon fiber.

In the case of an amorphous methacryl resin that does not contain a polymer having a structural repeating unit having an aromatic group, even if the resin is annealed at a temperature lower than the molding temperature by the same method as described above, the glass transition point of the resin No peak is observed in the temperature region higher than (Tg).

Crystallization of the crystalline resin is promoted due to the crystallization promoting action of the gas phase carbon fiber. The crystallization promotion is a phenomenon that the endothermic or exothermic peak corresponding to the Tm of the resin obtained by DSC measurement is moved to a higher temperature region; Or it can be confirmed by the phenomenon that the peak corresponding to the Tm of the resin is further increased.

Crystallization of the resin composition of the present invention can be confirmed by X-ray diffraction performed at a temperature below the melting temperature of the composition. The peak resulting from the regular arrangement of the resin structure, which is sharper than the peak resulting from the disorderedly arranged resin structure, is obtained by X-ray diffraction, and the electron peak coexists with the latter peak. The half width of the band of the diffraction angle 2θ measured by the X-ray diffraction method of the peak resulting from the regular arrangement of the resin structure is 5 ° or less, preferably 0.5 to 5 °, and more preferably 0.5 to 4 °. .

It is assumed that the crystallization of the resin composition is facilitated by the interaction between the amorphous thermoplastic resin containing the polymer having a structural repeating unit having an aromatic group and the vapor phase carbon fiber surface. 1 shows a transmission electron micrograph of a fiber filament of vapor-phase carbon fiber having a heat treatment (graphitization) at 2,800 ° C. and having an average diameter of 0.15 μm and an aspect ratio of 70. FIG. As shown in FIG. 1, as a result of incomplete development of graphite crystals, the surface of the fiber filament contains short graphite crystals of non-uniform structure. It is presumed that the interaction between the disordered portion of the crystalline carbon and the amorphous thermoplastic resin causes the crystallization of the thermoplastic resin.

The crystallization showing an endothermic / exothermic peak at a temperature other than the glass transition point of the matrix resin, an increased endothermic / exothermic peak corresponding to the melting point of the resin, or a hot zone shifted endothermic / exothermic peak corresponding to the melting point of the resin The thermoplastic resin composition of the present invention containing a vapor phase carbon fiber acting as an accelerator can be used as a conductive material or a thermally conductive material by adjusting the amount of the vapor phase carbon fiber. When the amount of gaseous carbon fiber contained in the composition or the cooling rate of the composition is controlled, the degree or rate of crystallization of the composition can be controlled, thereby providing the mechanical strength, fatigue resistance and frictional wear characteristics of the composition. Features can be improved.

The resin composition of the present invention is a flame retardant, impact resistance improver, antistatic agent, slippery agent, antiblocking agent, lubricant, anti-fogging agent, natural oil, synthetic oil, waxy acid, so long as it does not interfere with the object of the present invention. And additives such as organic fillers and inorganic fillers.

The resin composition of this invention is an appliance part for electric devices, an electronic device, an optical device, an automobile, an OA apparatus, etc .; Materials exhibiting frictional wear characteristics; And to manufacture the housing.

1 is a transmission electron micrograph of a fiber filament of vapor-phase carbon fiber having a heat treatment at 2,800 ° C. and having an average diameter of 0.15 μm and an aspect ratio of 70.

FIG. 2 is a DSC curve of an experimental sample formed from the composition of Example 1 (annealing temperature: 180 ° C., 200 ° C., 220 ° C.) produced by kneading gas phase carbon fiber (VGCF) and polycarbonate (PC); FIG. And the DSC curve of the experimental sample formed from the composition of Comparative Example 1 (annealing temperature: 160 ° C, 240 ° C).

FIG. 3 shows the X-ray diffraction interference curves of the experimental samples formed from the compositions of Example 1 and Comparative Example 1 produced by kneading vapor phase carbon fiber (VGCF) and polycarbonate (PC).

FIG. 4 shows the DSC curve of an experimental sample formed from the composition of Example 4 prepared by kneading vapor phase carbon fiber (VGCF) and polycarbonate (PC).

FIG. 5 shows an X-ray diffraction interference curve of an experimental sample formed from the composition of Example 4 prepared by kneading a vapor phase carbon fiber (VGCF) and a polycarbonate (PC).

FIG. 6 shows the DSC curve of an experimental sample formed from polycarbonate (PC) used in Comparative Example 3. FIG.

FIG. 7 shows X-ray diffraction interference curves of experimental samples formed from polycarbonate (PC) used in Comparative Example 3. FIG.

Next, although this invention is demonstrated by the Example and the comparative example, this invention is not limited to the following Example.

Example 1:

Polycarbonate (PC; AD5503, Teijin Chemicals Ltd., average molecular weight: 20,000, mass molecular weight: 32,000) was dried under vacuum (20 Torr) at 120 ° C. for 24 hours. Gasoline carbon fiber (VGCF; Trademark, Showa Denko KK) obtained using Labo Plastomill, heat-treated at 2,800 ° C. (average diameter of fiber filament of the carbon island oil: 0.15 μm, Aspect ratio of the fiber filament: 70) and the mass ratio of 95: 5 to form a flat plate of 100mm x 100mm x 2mmt.

The flat plate thus formed was annealed for 2 hours at a temperature of 180 ° C, 200 ° C or 220 ° C. Immediately after annealing, the obtained plate was immersed in the water bath.

A specimen was prepared from the plate, and the specimen was subjected to differential thermal analysis using a differential scanning calorimeter (DSC; SSC5200, manufactured by Seiko Instruments Inc .; rate of temperature increase: 10 ° C / min). The results are shown in Table 2. Endothermic peaks attributable to Tg and Tm were observed at about 150 ° C. and 200-250 ° C., respectively.

The test piece was subjected to X-ray analysis using an X-ray diffraction apparatus (RAD-B, manufactured by Rigaku Corporation). 3 shows the interference curves obtained. The peak attributable to the disordered structure of the polycarbonate was confirmed at a diffraction angle (2θ) of 12 to 24 °, and the peak attributable to the polycarbonate structure regularly arranged by VGCF (registered trademark) is diffraction of 26 to 28 °. It was observed at an angle (2θ). It was confirmed that these peaks coexist with each other.

The test piece manufactured from the plate annealed at 200 degreeC was measured about thermal conductivity, flexural strength, flexural modulus, and dynamic friction coefficient by the following method. The results are shown in Table 1.

Thermal conductivity:

Measured by the method described by ASTM C-177 or by the hot wire method.

Flexural strength:

Measured by the method described by ASTM D-790.

Flexural modulus:

Measured by the method described by ASTM D-790.

Dynamic Friction Coefficient:

Measured by the continuous sliding wear test described by JIS K 7218 where the test piece is abraded by contact with the end face of the hollow cylinder (load: 2 kgf / cm ² , relative material: S45C steel).

Comparative Example 1:

The plate was produced in the same manner as in Example 1, and the plate was annealed for 2 hours at a temperature of 160 ° C or 240 ° C. In the same manner as in Example 1, the specimen prepared from the obtained plate was subjected to DSC measurement and X-ray diffraction analysis. The results are shown in FIGS. 2 and 3 (top and bottom curves in the shapes, respectively) along with the results of Example 1. FIG. No new peaks attributable to the crystallization of polycarbonates were identified.

Example 2 and Comparative Example 2:

A thermoplastic polyimide (PI; Aurum 400, manufactured by Mitsui Chemicals, Inc.) (95 mass%) was melt mixed with 5 mass% of VGCF (registered trademark) to prepare a sample. The sample was held in a DSC apparatus under nitrogen gas flow (50 ml / min) at 400 ° C. for 10 minutes, and then DSC measurements were performed under cooling conditions (cooling rate: 5 ° C./min). As a result, a peak attributable to crystallization (Tc) of the polyimide was observed at 358 ° C. After the sample was maintained at DSC at 370 ° C., when isothermal crystallization measurements were performed, it was confirmed that the elapsed time until the peak resulting from the crystallization was observed was 195 seconds.

In Comparative Example 2, the sample was made of only thermoplastic polyimide without adding VGCF (registered trademark), and DSC measurement was performed in the same manner as above. As a result, the peak resulting from the crystallization (Tc) of the said polyimide was observed at 356 degreeC, and it was confirmed that the elapsed time until the peak resulting from the said crystallization is observed is 256 second.

The basic properties (thermal conductivity, flexural strength, flexural modulus and dynamic friction coefficient) as the resin composition material of the produced sample were measured in the same manner as in Example 1. The results are shown in Table 1.

Example 3:

Samples were prepared using VGCF (registered trademark) containing 0.1 mass% boron instead of VGCF (registered trademark) used in Example 1, and the sample was annealed at 200 ° C. for 2 hours. In the same manner as in Example 1, the sample was subjected to DSC measurement and X-ray diffraction analysis. The same peak as observed in Example 1 was observed.

Example 4:

Samples were prepared using VGCF (registered trademark) heat-treated at 1200 ° C. instead of VGCF used in Example 1, which was subjected to annealing at 200 ° C. for 2 hours. In the same manner as in Example 1, the sample was subjected to DSC and X-ray diffraction analysis. The results are shown in FIGS. 4 and 5. For control purposes, the measurement results of the sample of Example 1 prepared using VGCF heat-treated at 2,800 ° C. and subjected to annealing are shown in FIGS. 4 and 5.

Comparative Example 3:

The procedure of Example 1 was repeated except that no VGCF (registered trademark) was used to prepare a plate sample. The flat sample was annealed for 2 hours at a temperature of 160 ° C, 180 ° C, 200 ° C, 220 ° C or 240 ° C. The obtained sample was subjected to DSC measurement and X-ray diffraction analysis in the same manner as in Example 1. The results are shown in FIGS. 6 and 7. No new peak attributable to the crystallization of the polycarbonate was observed.

Comparative Examples 4 and 5:

Polymethylmethacrylate (PMMA; 60N, manufactured by Asahi Kasei Corporation, number average molecular weight: 76,000, mass average molecular weight: 150,000) was dried under vacuum (20 Torr) at 80 ° C. for 24 hours. The polymethyl methacrylate obtained was subjected to a gas-treated carbon fiber (VCGF, registered trademark) (the diameter of the fiber filament of the carbon fiber: 0.15 mu m, the aspect ratio of the fiber filament of the fiber filament) where the obtained polymethyl methacrylate was heat treated at 2800 ° C. It was kneaded at a mass ratio of 95: 5 to form a flat plate of 100 mm x 100 mm x 2 mmt.

The plate thus formed was annealed at 150 ° C. for 2 hours. Immediately after the annealing, the obtained plate was immersed in the water bath.

A specimen was prepared from the plate, and the specimen was subjected to differential thermal analysis using a differential scanning calorimeter (DSC; SSC5200, manufactured by Seiko Instruments Inc .; temperature increase rate: 10 ° C / min) (Comparative Example 4). . In Comparative Example 5, the test piece was made only of polymethyl methacrylate without adding VGCF (registered trademark). The obtained test piece was subjected to DSC measurement in the same manner as above. As a result, in the DSC measurement, Tg was observed at about 100 ° C., but no endothermic peak was observed. In the same method as in Example 1, the test piece was measured with respect to thermal conductivity, flexural strength, flexural modulus, and dynamic friction coefficient. The results are shown in Table 1.

Composition Tg (℃) Tm or Tc (° C) Volume resistance (Ωcm) Thermal Conductivity (W / mk) Flexural strength (Mpa) Flexural Modulus (Gpa) Dynamic friction coefficient Example 1 PC + VGCF (5 mass%) 145 Tm = 232 10 ⁸ 0.39 91 2.2 0.30 Example 2 PI + VGCF (5 mass%) 251 Tc = 358 10 ⁸ 0.29 98 2.5 0.12 Comparative Example 2 PI 251 Tc = 356 > 10 ¹⁴ 0.28 96 2.4 0.12 Comparative Example 3 PC 145 Not detected > 10 ¹⁴ 0.25 90 1.0 0.33 Comparative Example 4 PMMA + VGCF (5 mass%) 97 Not detected 10 ⁸ 0.37 104 1.8 0.28 Comparative Example 5 PMMA 97 Not detected > 10 ¹⁴ 0.23 104 0.9 0.27

Fine carbon fibers; For example, vapor phase carbon fiber composed of fiber filaments having a diameter of 0.001 µm to 5 µm and an aspect ratio of 5 to 15,000 serves as a resin crystallization accelerator. When the crystallization promoter of the present invention is added to a resin (eg, a thermoplastic resin), the speed and degree of crystallization of the resin can be controlled, so that the properties of the resin can be changed. Therefore, it is suitable for the obtained resin composition to be used for a mechanical component or a material exhibiting frictional wear characteristics.

Claims (18)

A resin crystallization accelerator comprising fine carbon fibers each consisting of fiber filaments having a diameter of 0.001 μm to 5 μm and an aspect ratio of 5 to 15,000. The resin crystallization promoter according to claim 1, wherein the fine carbon fibers are vapor-phase carbon fibers. The resin crystallization accelerator according to claim 2, wherein the vapor-phase carbon fiber contains boron in an amount of 0.001 to 5 mass%. A resin composition comprising the resin crystallization promoter according to any one of claims 1 to 3 and a resin. The resin composition according to claim 4, wherein the resin is a thermoplastic resin. The resin composition according to claim 5, wherein the thermoplastic resin is an amorphous thermoplastic resin. The resin composition according to claim 5, wherein the thermoplastic resin is a resin containing a polymer having a structural unit having an aromatic group as a repeating unit. The method of claim 5, wherein the thermoplastic resin is polystyrene, polycarbonate, polyarylate, polysulfone, polyetherimide, polyethylene terephthalate, polyphenylene oxide, polyphenylene sulfide, polybutylene terephthalate, polyimide, Any one selected from polyamide-imide and polyether-ether-ketone; Or a mixture thereof. The endothermic / exothermic peak of any one of claims 4 to 8, wherein when differential scanning calorimety (DSC) is carried out, the endothermic / exothermic peak is not related to the mass change at a temperature other than the glass transition point of the resin. The resin composition characterized by the above-mentioned. The exotherm / endotherm peak attributable to melting or crystallization of the composition when the differential scanning calorimetry is performed, wherein the peak is in any one of the above 1 to 3. The resin composition characterized by being moved to a higher or higher temperature region than in the case of the resin composition which does not contain the resin crystallization promoter described. The resin composition according to any one of claims 4 to 8, wherein when the X-ray diffraction method is performed, a peak resulting from the resin and a peak resulting from a regular arrangement of the resin structure are shown. The X-ray diffraction method according to any one of claims 4 to 8, wherein the half width of the band of the band of the diffraction angle (2θ) corresponding to the peak resulting from the regular arrangement of the resin structure is 5 degrees or less. Resin composition, characterized in that. The resin composition according to any one of claims 4 to 8, wherein the content of the resin crystallization promoter is 0.1 to 80% by mass. A step of kneading the crystallization promoter and the resin according to claim 1 or 2; And Next, a method for producing a resin composition having a crystalline, regularly arranged structure, comprising the step of annealing the mixture obtained at a temperature equal to or higher than the glass transition point of the resin. The conductive material containing the resin composition of any one of Claims 4-13. The heat conductive material containing the resin composition as described in any one of Claims 4-13. A material comprising the resin composition according to any one of claims 4 to 13, which exhibits frictional wear characteristics. An apparatus component comprising the resin composition according to any one of claims 4 to 13.

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