JP3298988B2 - Manufacturing method of conductive resin masterbatch - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive resin masterbatch containing highly conductive carbon black, and in particular to an excellent surface smoothness for a conductive highly functional resin product finally produced by adding the masterbatch. The present invention relates to a conductive resin masterbatch capable of imparting properties, and a conductive high-performance resin product manufactured by adding the masterbatch.

[0002]

2. Description of the Related Art A conductive resin is a computer, a VT.
In recent years, demand has been remarkably growing mainly for applications such as antistatic and electromagnetic wave shielding of home electric appliances and the like. Conventionally,
As a method of imparting conductivity to a thermoplastic resin, there is known a method of filling carbon black (JP-A-60-65064 and JP-A-55-31103). In addition, the carbon black partially scatters and deteriorates the working environment. In addition, the heat generated by shearing of the carbon black causes a decrease in the molecular weight of the resin, resulting in a problem that the resin strength is reduced. The conductive thermoplastic resin containing carbon black is formed into various shapes depending on the application.
When formed into a film of less than mm, protrusions due to carbon black undispersed material appear on the surface, not only impairing the aesthetic appearance, but also using this as a transfer roll of a copying machine, the image becomes unclear. Problems have been pointed out.

[0003] Among these problems, a method using a carbon black-rich resin masterbatch has been proposed for the purpose of preventing carbon black from scattering, in particular (JP-A-54-58747). This resin masterbatch with a high carbon black content is obtained by adding a thermoplastic resin dissolved in an organic solvent to an aqueous solution in which carbon black is dispersed, and then removing water and the organic solvent. Applicable to the resin, when compared with the conventional method of manufacturing by kneading the thermoplastic resin and carbon black at or above the melting temperature of the resin, the resin that can be used due to the solubility of the resin in the organic solvent is limited,
Further, since a step of removing water and an organic solvent is required, it is not practical. On the other hand, even if the conductive carbon black is kneaded with a resin other than the polyolefin resin, particularly a high-performance resin using a Banbury mixer or the like to manufacture a master batch, the DBP oil absorption of the carbon black is 40%.
In the case of a highly conductive carbon black of 0 ml / 100 g or more, even if used in a small amount, it is extremely difficult to knead into the resin, and the final conductive highly functional resin product is manufactured using the master batch thus manufactured. Then, there was a problem that the smoothness of the surface of the obtained product was impaired.
Particularly, when the masterbatch resin is a high-performance resin other than the polyolefin resin, the problem is serious.

[0004]

SUMMARY OF THE INVENTION The present invention can improve the surface smoothness of a final conductive high-performance resin product containing and adding a highly conductive carbon black. And a conductive carbon black masterbatch. Another object of the present invention is to provide a conductive high-performance resin product manufactured by adding the master batch.

[0005]

The present invention is based on the finding that the above problems can be effectively solved by combining a predetermined amount of highly conductive carbon black with a high-performance resin having specific melt flow characteristics. It was done. That is, the present invention comprises (a) a thermoplastic resin other than the polyolefin resin and (b) conductive carbon black as essential components, and the thermoplastic resin of the component (a) has a melt flow rate (MFR) of 6 g / 10 min or more. And the DBP oil absorption of the conductive carbon black is 400 ml / 100.
g or more, and the content of the conductive carbon black is 8 to 20 parts by weight based on 100 parts by weight of the total amount of the components (a) and (b), and the volume resistivity is 0.1 Ω · cm. Provided is a conductive resin masterbatch characterized by having a resistivity of at least 10 Ω · cm.

[0006] The resin used in the conductive resin masterbatch of the present invention has strength and heat resistance corresponding to the use of the conductive thermoplastic resin obtained by using the masterbatch, and is 6 g / 10 min or more. Preferably 8g / 10min
~ 2000g / 10min, particularly preferably 8g / 1
It is a high-performance thermoplastic resin having a melt flow rate (MFR) of 0 min to 600 g / 10 min. Specifically, styrene resins such as polystyrene resin, ABS resin and AS resin, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin;
6-nylon resin, polyamide resin such as 6,6-nylon resin, polysulfone resin, modified polysulfone resin, polyallyl sulfone resin, polyketone resin, polyetherimide resin, polyarylate resin, polyphenylene sulfide resin, liquid crystal polymer, polyether Examples thereof include super engineering resins such as sulfone resins, polyether ether ketone resins, polyimide resins, polyamide imide resins, and fluororesins, polyvinyl chloride resins, thermoplastic urethane resins, polyacetal resins, polycarbonate resins, and modified polyphenylene ether resins. In recent years, as this conductive thermoplastic resin, a heat-resistant resin that has a high resin strength and can be used even under high temperature conditions has been required. A thermoplastic resin having a melting point of 200 ° C. or higher and a heat distortion temperature (ASTMD-648) of 130 ° C. or higher measured with a load of 18.6 Kg / cm ² for amorphous resin is preferable, and specifically, polycarbonate resin, polyethylene terephthalate Preferred are resin, polybutylene terephthalate resin, 6-nylon resin, 6,6-nylon resin, polyphenylene sulfide resin, and modified polyphenylene ether resin. Here, the melt flow rate (MFR) is measured in accordance with Japanese Industrial Standards for the resin for which the method for measuring the melt flow rate is specified, according to the measurement method, and for resins not specified, JIS K7210A. It is a value measured at the temperature and load shown in the table below using an apparatus described in the law. The following table shows the measurement conditions.

[0007]

[Table 1] Melt flow rate measurement conditions for resin ───────────────────────────────────Resin standard Temperature (° C) Load (Kgf) Polystyrene resin JIS K6871 200 5.00 Other than polystyrene resin JIS K6874 220 10.00 Styrene resin Polyester resin-275 2.16 6-nylon resin JIS K7210 230 2.16 6 Other than 6-nylon resin JISK7210 275 2.16 Polyamide resin Super engineering resin-316 5.00 Polyvinyl chloride resin-190 10.00 Thermoplastic urethane resin JISK7311 230 10.00 Polyacetal resin JISK7210 190 2.16 Polycarbonate resin JISK7210 300 1.20 Modified polyphenylene ether Resin-2 50 10.00 Other resins-230 10.00

The conductive carbon black used as the component (b) in the present invention has a DBP oil absorption of 400 ml / 10.
0 g or more, preferably 420 ml / 100 g or more. The upper limit of the DBP oil absorption is not particularly limited, but is preferably 700 ml / 100 g or less, particularly 6
It is appropriate that the amount is not more than 00 ml / 100 g. The conductive master batch of the present invention has a volume resistivity of 0.1 Ω · cm or more and 1
It is less than 0 Ω · cm, and the conductive carbon black is 8 to 20 parts by weight, preferably 8 to 15 parts by weight based on 100 parts by weight of the total amount of the polyolefin-based thermoplastic resin and the conductive carbon black.

In the present invention, it is only when the above-mentioned highly conductive carbon black, a specific resin and a specific compounding amount are employed that the high conductive carbon black, which is the object of the present invention, is contained and added. It has been possible to provide a conductive carbon black masterbatch capable of improving the surface smoothness of the final conductive high-performance resin product to be obtained. Further, the conductive masterbatch of the present invention includes mica, glass fiber in order to improve the heat resistance, dimensional stability, rigidity, and mechanical strength of the conductive thermoplastic resin obtained using this masterbatch. Inorganic fillers such as silica, talc, calcium carbonate, zinc oxide, barium sulfate, stainless steel, copper oxide, nickel, nickel oxide, and zirconia silicate can also be blended. These inorganic fillers, based on the total amount of 100 parts by weight of the thermoplastic resin and the conductive carbon black,
It is desirable to use it in a proportion of 5 to 300 parts by weight. Also,
For the purpose of improving the moldability and preventing deterioration during kneading of the thermoplastic resin and the conductive carbon black, a known phenol type,
Known flame retardants and plasticizers can be used depending on the molding aids and applications, such as phosphorus-based antioxidants, metal soaps, lubricants such as fatty acid amide derivatives, and the like.

The conductive masterbatch of the present invention is obtained by kneading conductive carbon black and a thermoplastic resin other than a polyolefin resin at a temperature not lower than the melting temperature of the resin, cooling, and then forming into an appropriate shape such as pellets, powders, and lumps. It is manufactured by molding. As a kneading device, a single-screw extruder, a twin-screw extruder, a two-roll mill, a Banbury mixer, an intermix,
A known device such as a pressure kneader can be used. The conductive masterbatch of the present invention is used as a raw material when producing a conductive thermoplastic resin, and the masterbatch is used as a diluent resin or a known inorganic filler depending on the application, an antioxidant, a lubricant, a flame retardant. By mixing with a plasticizer, a conductive thermoplastic resin is produced. The amount of the masterbatch of the present invention is usually 10 to 80 parts by weight, preferably 15 to 70 parts by weight, based on 100 parts by weight of the conductive thermoplastic resin.
Parts by weight. When the amount is less than 10 parts by weight, the thermoplastic resin obtained by using the master batch of the present invention cannot be provided with conductivity. There is a tendency for the strength to decrease.

A known method is used as a method for mixing the conductive masterbatch and the diluting resin to obtain the conductive thermoplastic resin. For example, a method of dry-blending the masterbatch and the diluted resin with a mixer such as a Henschel mixer or a tumbler, a method of kneading with the above-described kneading apparatus, and the like can be mentioned. In addition, by molding this mixture by a known molding method such as injection molding, vacuum molding, blow molding, inflation molding, etc., a conductive thermoplastic resin having a shape corresponding to the use such as a sheet shape, a film shape, a plate shape, and a different shape is used. The product is obtained. Thus, the obtained conductive thermoplastic resin has a volume resistivity of 10 ⁰
It has conductivity of ~ 10 ¹⁵ Ω · cm and is excellent in both strength and surface smoothness, so it is suitable for packaging materials for electronic devices, ICs, etc., tray carriers, surface heating elements, surface switches, electrodes, electromagnetic wave shielding materials. It can be used in a wide range of fields such as applications.

[0012]

Industrial Applicability According to the present invention, a conductive carbon which contains a high conductive carbon black and can be made to have excellent surface smoothness in a final conductive high-functional resin product produced by adding the conductive carbon black. A black masterbatch is provided. Also, by using the conductive masterbatch of the present invention, when manufacturing a conductive high-performance resin, there is no deterioration of the working environment due to scattering of carbon, and a small amount of the conductive masterbatch is blended to obtain a good conductive property. A conductive high-performance resin product having excellent properties and excellent resin strength can be obtained. Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0013]

【Example】

Example 1 A predetermined amount of carbon black and a thermoplastic resin were kneaded using a twin-screw extruder at a cylinder temperature of 280 to 350 ° C, and after cooling, a columnar conductive masterbatch was obtained using a pelletizer. This masterbatch is 280-35
By pressing at 0 ° C, 10cm × 10cm × 0.2c
A sample for physical property evaluation of m was prepared, and then the volume resistivity value of the sample for physical property evaluation was measured. Tables 1 and 2 show the composition, volume resistivity and moldability of the masterbatch.
Shown in

The following were used as carbon black and resin. Carbon black A: DBP oil absorption 499 ml / 100 g carbon black Carbon black B: DBP oil absorption 420 ml / 100 g carbon black Carbon black C: DBP oil absorption 370 ml / 100 g carbon black Polycarbonate resin A: Toughlon A-2200 (Idemitsu Oil (MFR: 12 g / 10 min, Measurement conditions: 300 ° C.)
1.2 kg) Polycarbonate resin B: Toughlon A-3000 (manufactured by Idemitsu Petrochemical) (MFR: 3 g / 10 min, measurement conditions: 300 ° C., 1.
2Kg) Polybutylene terephthalate resin: Toray PBT1401
X04 (manufactured by Toray) (MFR: 18 g / 10 min, measurement conditions: 275 ° C,
2.16Kg) Polyethylene terephthalate resin: Viropet EMC
307X04 (manufactured by Toyobo) (MFR: 120 g / 10 min, measurement condition: 275)
6 ° C., 2.16 Kg) 6-nylon resin: Novamide 1020 (manufactured by Mitsubishi Kasei) (MFR: 10 g / 10 min, measurement conditions: 230 ° C.)
2.16Kg) 6,6-nylon resin: Torayamiran CM3001-N
(Manufactured by Toray) (MFR: 70 g / 10 min, measurement conditions: 275 ° C.,
2.16 kg) Polyphenylene sulfide resin: M-2888 (manufactured by Toray Philippe Petroleum) (MFR: 600 g / 10 min, measurement condition: 316)
Modified polyphenylene ether resin: Noryl 115 (manufactured by Nippon GE Plastics) (MFR: 10 g / 10 min, measurement conditions: 250 ° C,
Glass fiber: CS03MA416 (manufactured by Asahi Fiberglass) Zinc oxide: Zinc flower No. 3 (manufactured by Hakusui Chemical Co., Ltd.) The moldability is as follows. The composition which was difficult to produce a masterbatch due to difficulty was evaluated as x. In addition, the volume specific resistance was measured according to the Japan Rubber Association SRIS-2301.

[0015]

[Table 2] Table 1 ──────────────────────────────────── Example of implementation No. AB C DEF GHI II Composition (parts by weight) Carbon black A 0 12 12 12 10 10 12 8 12 Carbon black B 15 0 0 0 0 0 0 0 0 Carbon black C 0 0 0 0 0 0 0 0 0 Polycarbonate 85 88 0 0 0 0 0 0 0 Resin A Polybutylene tele 0 0 88 0 0 0 0 92 0 Phthalate resin Polyethylene tele 0 0 0 88 0 0 0 0 0 Phthalate resin 6-nylon resin 0 0 0 0 90 0 0 0 0 6,6-Nylon resin 0 0 0 0 0 90 0 0 0 Polyphenylene 0 0 0 0 0 0 88 0 0 Sulfide resin Modified polyphenylene 0 0 0 0 0 0 0 0 88 Ether resin ──────────────────────── ──────────── Formability ○ ○ ○ ○ ○ ○ ○ ○ ──────────────────────────────────── Volume resistivity 4.0 2.1 9.0 1.4 4.6 5.2 8.0 7.5 2.1 (Ωcm) × 10 ⁰ × 10 ⁰ × 10 ^-1 × 10 ⁰ × 10 ⁰ × 10 ⁰ × 10 ^-1 × 10 ⁰ × 10 ⁰ ─────────── ─────────────────────────

[0016]

[Table 3] Table-2 {Comparative example No. JKLM}組成 Composition (parts by weight) Carbon black A 0 4 0 12 Carbon black B 3 0 0 0 Carbon black C 0 0 12 0 Polycarbonate 70 0 0 0 Resin A Polycarbonate 0 0 0 88 Resin B Polybutylene tele 0 0 0 0 Phthalate resin Polyethylene tele 0 0 0 0 Phthalate resin 6-Nylon resin 0 94 88 0 6,6-Nylon resin 0 0 0 0 Polyphenylene 0 0 0 0 Sulfide resin ──────────────────────────── Moldability × ○ ○ ○ ────────────体積 Volume specific resistance 3.0 2.5 5.0 (Ωcm)-× 10 ³ × 10 ¹ × 10 ⁰ ──────────── ─── ────────────

Example 2 The masterbatch, thermoplastic resin and inorganic filler described in Example 1 were used in a twin-screw extruder at a cylinder temperature of 280.
After kneading at ~ 350 ° C and cooling, columnar pellets were obtained using a pelletizer. For comparison, a predetermined amount of carbon black, a thermoplastic resin and an inorganic filler were kneaded at a cylinder temperature of 220 to 350 ° C. using a twin-screw extruder without using a masterbatch, and after cooling, a pelletizer was used. Was used to obtain a columnar pellet. The pellets were put into an injection molding machine, and injection-molded at a cylinder temperature of 220 to 350 ° C. using a predetermined mold to obtain a 7.5 cm × 7.5 cm × 0.3 cm sample for evaluating physical properties. Surface smoothness of physical property evaluation sample,
Izod impact strength and volume resistivity were measured.
Tables 3 and 4 show the compositions and measurement results.

[0018]

[Table 4] Table 3 ────────────────────────────────── Example No. 1 2 3 4 5 6 7 8 Composition (parts by weight) Example 1 B Composition 30 60 00 00 00 0 0 C Composition 0 0 30 0 0 0 00 0 D Composition 0 0 0 60 00 00 0 E Composition 0 0 0 0 60 0 0 0 F composition 0 0 0 0 0 60 0 0 G composition 0 0 0 0 0 0 60 0 I composition 0 0 0 0 0 0 0 30 Polycarbonate 70 40 0 0 0 0 0 0 Resin A Polybutylene tele 0 0 70 0 0 0 0 0 Phthalate resin Polyethylene tele 0 0 0 40 0 0 0 0 Phthalate resin 6-nylon resin 0 0 0 0 40 0 0 0 6, 6-Nylon resin 0 0 0 0 0 40 0 0 Polyphenylene 0 0 0 0 0 0 40 0 Sulfide resin Polyphenylene 0 0 0 0 0 0 0 70 Ether resin Zinc oxide 0 80 0 0 0 0 0 0 Glass fiber 0 0 0 60 60 60 40 0 Izod impact 7.5 4.6 4.2 6.3 6.4 6.1 5.2 6.3 Strength (kgfcm / cm ² ) (with 1/8 inch notch) Surface smoothness ○ ○ ○ ○ ○ ○ ○ ○ Volume resistivity 1.2 8.2 4.3 8.3 4.1 6.5 8.0 3.3 (Ωcm) × 10 ⁵ × 10 ³ × 10 ⁴ × 10 ³ × 10 ⁵ × 10 ⁵ × 10 ⁴ × 10 ⁵

[0019]

[Table 5] Table-4 ─────────────────────────────── Comparative Example No. 9 10 11 12 13 14 15 Composition (parts by weight) Example-1 K composition 0 0 0 0 6 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Carbon composition A 3.6 3.6 7.2 6 0 0 0 Polycarbonate 96.4 0 0 0 0 0 70 Resin A Polybutylene tele 0 96.4 0 0 0 0 0 Phthalate resin Polyethylene tele 0 0 92.8 0 0 0 0 Phthalate resin 6-Nylon resin 0 0 0 94 40 40 0 6,6-Nylon resin 0 0 0 0 0 0 0 Glass fiber 0 0 60 60 60 60 0 Izod impact 1.9 0.5 0.7 1.6 7.7 6.0 6.5 Strength (kgfcm / cm ² ) (with 1/8 inch notch) Surface smoothness × × × × ○ ○ × ─固有 Specific volume resistance value 4.3 1.2 6.4 8.9 10 ¹⁶ 10 ¹⁶ 8.2 (Ωcm) × 10 ⁵ × 10 ⁴ × 10 ⁴ × 10 ⁵ or more × 10 ⁹

The surface smoothness of the sample for evaluating physical properties was evaluated as × when the surface of the sample was dull, and as を when the sample was glossy. The Izod impact strength and volume specific resistance were measured according to JIS K-7110 and JIS K-7110, respectively. It measured according to the Japan Rubber Association SRIS-2301. Table-3, 4
No1 and No9, No3 and No10, No4 and No11, No5
And No12 have the same composition, respectively, and are data comparing the case where the master batch of the present invention was used and the case where the master batch of the present invention was not used. The volume resistivity of the resulting conductive resin was good, and the Izod impact strength was 4 to 10 times better. Also
No. 14 is a comparative example in which a masterbatch containing carbon black other than the present invention was used. The value becomes 10 ¹⁶ Ω · cm or more, and conductivity cannot be imparted (No. 5 and No. 1).
4). No. 15 is a comparative example in which a masterbatch containing a polycarbonate resin other than the present invention (MFR = 3 g / 10 min) was used, but an example in which a masterbatch containing the polycarbonate resin of the present invention was used was used. As compared with (No. 1), the conductivity shows a value about 10 ⁴ Ω · cm worse in volume resistivity.

Example 3 Pellets obtained by the same method as described in Example 2 were charged into an inflation molding machine, and a film having a thickness of 60 μm was prepared at a cylinder temperature of 220 to 300 ° C. The surface resistivity and the film strength were measured. The surface smoothness was evaluated by a surface roughness meter as ○ when the surface unevenness was less than 5 μm, and as X when more than 5 μm. The film strength was evaluated as ○ when the film was bent ten times and not cut from the fold, and as X when cut. The surface specific resistance value is ASTM D-
257 was measured. Table 5 shows the composition and measurement results.
Shown in

[0022]

[Table 6] Table 5 ──────────────────────────────────── Composition, etc. Example Comparison An example(Weight part) 16 17 18 19 20 21 22 23 24 25 Example-1 B composition 400 0 0 0 0 0 0 0 0 0 C composition 0 40 0 0 0 0 0 0 0 0 D composition 0 0 40 0 0 0 0 0 0 0 E composition 0 0 0 40 0 0 0 0 0 0 L composition 0 0 0 0 0 0 0 0 40 0 M composition 0 0 0 0 0 0 0 0 0 40 Carbon 0 0 0 0 4.8 4.8 4.8 4 0 0 Black B polycarbonate 60 0 0 0 95.2 0 0 0 0 60 Polyethylene resin 0 60 0 0 0 95.2 0 0 0 0 Terephthalate resin Polyethylene 0 0 60 0 0 0 95.2 0 0 0 Terephthalate resin 6-nylon 0 0 0 60 0 0 0 96 60 0resin Film strength ○ ○ ○ ○ × × × × ○ ○ Surface smoothness ○ ○ ○ ○ × × × × ○ × Surface specific 2.3 2.4 4.2 1.8 4.1 5.7 6.8 4.2 10¹⁶ 4.1 Resistance value (Ω) × 10 ⁶ × 10 ⁵ × 10 ⁵ × 10 ⁷ × 10 ⁶ × 10 ⁵ × 10 ⁵ × 10 ⁷ or more × 10 ¹⁰

According to Table-5, No. 16 and No. 20, No. 17 and No.
21, No. 18 and No. 22, and No. 19 and No. 23 have the same composition and are data comparing the case where the master batch of the present invention is used and the case where it is not used. As compared with the case where no batch was used, the result that the strength, surface smoothness, and surface resistivity of the obtained conductive film were good was obtained.
No. 24 is a comparative example in which a masterbatch blended with carbon black other than the present invention was used, but even if the same amount as the masterbatch of the present invention was used to obtain a conductive resin, the surface specific resistance was It becomes 10 ¹⁶ Ω · cm or more, so that conductivity cannot be imparted. (Comparison of No. 19 and No. 24) In addition, No. 25 is a comparative example using a masterbatch blended with a polycarbonate resin other than the present invention. As compared with the example (No. 16), the surface smoothness is poor, and the conductivity shows a value of about 10 ⁴ Ω · cm in terms of the surface specific resistance.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Hideo Komatsu 1-3-7 Honjo, Sumida-ku, Tokyo Inside Rion Co., Ltd. (56) References JP-A-62-20533 (JP, A) (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08 C08J 3/20-3/22

Claims (1)

(57) [Claims] 1. A thermoplastic resin other than a polyolefin resin, having a melt flow rate (MFR) of 6 g.
/ 10 min or more of a thermoplastic resin, and (b) DBP
A conductive carbon black having an oil absorption of 400 ml / 100 g or more is kneaded in an amount of 8 to 20 parts by weight based on 100 parts by weight of the total of components (a) and (b) at a melting temperature of the resin or higher, A method for producing a conductive resin masterbatch having a volume resistivity of 0.1 Ω · cm or more and less than 10 Ω · cm, characterized by cooling.