TWI613262B - Carbon black, conductive resin composition and composite material for electrode - Google Patents

Abstract

Carbon blacks of the present invention, BET specific surface area of ^{350m 2 / g ~ 650m 2 /} g, and a DBP oil absorption ^{270cm 3 / 100g ~ 340cm 3 /} 100g, the results of measurement described in JIS K6217-6 by aggregate diameters the method of the measured D90 diameter (D ₉₀₎ with respect to the mode diameter (D _mod) ratio D ₉₀ / D _mod from 1.90 to 2.20. The conductive resin composition of the present invention contains the carbon black of the present invention and a resin. The composite electrode material of the present invention contains the carbon black, the composite metal oxide, and the binder resin of the present invention.

Description

Carbon black, conductive resin composition and composite electrode material

The present invention relates to a carbon black, a conductive resin composition containing the carbon black, and a composite electrode material.

The present application claims priority based on Japanese Patent Application No. 2013-102327, Japanese Patent Application No. 2013-102328, and Japanese Patent Application No. 2013-102329, filed on Jan. The content is cited in this article.

In order to impart conductivity to a resin material or the like as an electrical insulator, carbon black is generally formulated. In addition, in various fields such as an electrode material, a conductive material for automobiles, and a semiconductor package, a conductive resin composition in which carbon black is blended to a thermoplastic resin as an electrical insulator to impart conductivity is widely used. In order to obtain a conductive article having excellent conductivity by the conductive resin composition, it is important that the conductivity of carbon black is high. Further, examples of the electrode material of the battery include an electrode material having a current collector and an active material layer formed on the current collector, and the active material layer is composed of a composite metal oxide, a conductive material, and a binder resin. The composite electrode material is formed. As the conductive material, carbon black is widely used. In order to obtain excellent battery performance, it is important that the carbon black has excellent conductivity imparting effect.

As carbon black which can obtain excellent conductivity, for example, carbon shown below is known. black.

(i) DBP (dibutyl phthalate, dibutyl phthalate) obtained by subjecting a liquid hydrocarbon (raw material oil) to a partial oxidation reaction in the presence of molecular oxygen and water vapor in a furnace to produce a synthesis gas The oil absorption is 290 cm ³ /100 g to 640 cm ³ /100 g of carbon black (for example, Patent Document 1 to Patent Document 4).

(ii) The DBP oil absorption amount obtained by subjecting the liquid hydrocarbon (raw material oil) to a partial oxidation reaction in the presence of molecular oxygen and water vapor in the furnace to produce a synthesis gas is 400 cm ³ /100 g or more and the specific surface area is Carbon black of 1000 m ² /g or more (for example, Patent Document 5).

However, the carbon black having a high DBP oil absorption amount and an excellent conductivity imparting effect is inferior in dispersibility in a dispersion medium such as a solvent, and it is difficult to uniformly impart a polymer material or the like. Further, when the carbon black is used for the conductive resin composition, the surface smoothness of the produced conductive article is liable to lower. Further, when the carbon black is used for a composite electrode material, an abnormality such as an internal short circuit is likely to occur.

On the other hand, acetylene black or the like is known as carbon black having a small specific surface area and excellent dispersibility in a dispersion medium. However, when acetylene black or the like is used, the conductivity imparting effect is low, and it is difficult to obtain a conductive material having excellent conductivity. Further, when acetylene black or the like is used for the conductive resin composition, it is difficult to obtain high mechanical strength of the produced conductive article. Further, in the case where acetylene black or the like is used for the composite electrode material, it is difficult to obtain sufficient battery performance.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1]

Japanese Patent Laid-Open No. 60-60912

[Patent Document 2]

Japanese Patent Laid-Open No. 60-67564

[Patent Document 3]

Japanese Patent Laid-Open No. 60-88073

[Patent Document 4]

Japanese Patent Laid-Open No. 60-152569

[Patent Document 5]

Japanese Patent Laid-Open No. 60-197763

The present invention provides a carbon black which simultaneously achieves good dispersibility and electrical conductivity. Further, the present invention provides a conductive resin composition capable of producing a conductive article having high mechanical strength, excellent surface smoothness, and electrical conductivity. Further, the present invention provides a composite electrode material which can produce an electrode material which is less likely to cause an abnormality such as an internal short circuit and which can attain excellent battery performance.

The carbon black of the present invention satisfies the following conditions (1) to (3).

(1) The BET (Brunauer-Emmett-Teller, Bouter) specific surface area is from 350 m ² /g to 650 m ² /g.

(2) DBP oil absorption ^{270cm 3 / 100g ~ 340cm 3 /} 100g.

(3) The ratio D ₉₀ /D _mod of the D90 diameter (D ₉₀ ) to the modal diameter (D _mod ) measured by the method for measuring the aggregate diameter described in JIS K6217-6 is 1.90. ~2.20.

The conductive resin composition of the present invention contains the above carbon black and a resin.

The composite electrode material of the present invention contains the above carbon black, a composite metal oxide, and Adhesive resin.

The carbon black of the present invention can achieve good dispersibility and electrical conductivity at the same time. Further, when the conductive resin composition of the present invention is used, a conductive article having high mechanical strength, excellent surface smoothness, and electrical conductivity can be produced. Further, when the composite electrode material of the present invention is used, it is possible to manufacture an electrode material which is less likely to cause an abnormality such as an internal short circuit and which can obtain excellent battery performance.

Fig. 1 is a view for explaining a method of obtaining a mode diameter (D _mod ) and a D90 diameter (D ₉₀ ).

[carbon black]

The carbon black of the present invention satisfies the following conditions (1) to (3). The carbon black satisfying the following conditions (1) to (3) simultaneously achieves good dispersibility into the dispersion medium and good conductivity. In addition, since the conductive resin composition of the present invention contains the carbon black, it is a conductive resin composition capable of producing a conductive article having high mechanical strength, excellent surface smoothness, and electrical conductivity. Further, since the composite electrode material of the present invention contains the carbon black, an electrode material which can obtain excellent battery performance can be produced.

(1) The BET specific surface area is from 350 m ² /g to 650 m ² /g.

(2) DBP oil absorption ^{270cm 3 / 100g ~ 340cm 3 /} 100g.

(3) The ratio D ₉₀ /D _mod of the D90 diameter (D ₉₀ ) to the mode diameter (D _mod ) measured by the method for measuring the aggregate diameter described in JIS K6217-6 is 1.90 to 2.20.

Carbon blacks of the present invention, BET specific surface area of ^{350m 2 / g ~ 650m 2 /} g, preferably from ^{350m 2 / g ~ 550m 2 /} g, more preferably ^{350m 2 / g ~ 500m 2 /} g. When the BET specific surface area of the carbon black is at least the lower limit value, good conductivity is easily obtained at the time of addition. In addition, when the carbon black is added to the conductive resin composition, the conductivity of the conductive resin composition is improved, and a conductive article having excellent conductivity can be produced. In addition, a conductive article having high mechanical strength can be manufactured. In addition, if the carbon black is added to the composite electrode material, excellent battery performance is obtained. When the BET specific surface area of the carbon black is at most the upper limit value, good dispersibility is easily obtained at the time of addition. In addition, when the carbon black is added to the conductive resin composition, the dispersibility of the carbon black in the resin is improved, and a conductive article having excellent surface smoothness can be produced. In addition, when the carbon black is added to the composite electrode material, the dispersibility of the carbon black in the composite electrode material becomes good, and it becomes difficult to cause an abnormality such as an internal short circuit in the electrode material.

Further, the BET specific surface area of carbon black was measured by a method in accordance with ASTM D 3037.

The carbon black of the present invention is a powder composed of secondary particles including a chain in which primary particles are linked into a grape-like chain. Since DBP (dibutyl phthalate) is absorbed into the void portion of the grape chain, etc., the DBP oil absorption is an important index value of carbon black.

DBP oil absorption amount of carbon black of the present invention is ^{270cm 3 / 100g ~ 340cm 3 /} 100g, preferably ^{270cm 3 / 100g ~ 320cm 3 /} 100g, more preferably ^{285cm 3 / 100g ~ 315cm 3 /} 100g. When the DBP oil absorption amount of carbon black is at least the lower limit value, good conductivity is easily obtained at the time of addition. Further, when carbon black is added to the conductive resin composition, the carbon black is efficiently formed into a network structure in the resin, and a conductive article having excellent conductivity can be produced. When the DBP oil absorption of carbon black is at most the upper limit value, carbon black having good dispersibility is easily obtained. In addition, when the carbon black is added to the conductive resin composition, the dispersibility in the resin is improved, and a conductive article having excellent surface smoothness can be produced.

Further, the DBP oil absorption of carbon black is a value obtained by measuring at a sample amount of 9 g in accordance with the conditions of ASTM D 2414.

Further, in the carbon black of the present invention, the ratio D90 diameter (D ₉₀ ) to the mode diameter (D _mod ) measured by the method for measuring the aggregate diameter described in JIS K6217-6 is D ₉₀ /D. _{The mod} is 1.90 to 2.20, preferably 2.00 to 2.20, more preferably 2.10 to 2.20. When the ratio D ₉₀ /D _mod is at least the lower limit value, a conductive resin composition having excellent dispersibility can be obtained. When the ratio D ₉₀ /D _mod is at most the upper limit value, a conductive resin composition having excellent conductivity can be obtained. In addition, by being in the above range, a conductive resin composition having high mechanical strength in addition to dispersibility and conductivity can be obtained. Further, when the above ratio D ₉₀ /D _mod is within the above range, stable electric conductivity is exhibited.

In addition, the D90 diameter (D ₉₀ ) means a particle diameter when the cumulative amount in the cumulative volume distribution curve in which the total volume of the particle size distribution obtained on the volume basis is 100% is 90%, that is, the volume reference accumulation 90 %diameter. In addition, the mode diameter (D _mod ) means the particle diameter in which the ratio of the largest particle size distribution occurs, that is, the particle diameter at the maximum value of the distribution.

The ratio D ₉₀ /D _mod is an indicator indicating a broad particle size distribution. If the increase ratio of D ₉₀ / D _mod, i.e. the particle size distribution is widened, it is to be easier to achieve good dispersibility when added to the resin or the like, but the electrical conductivity imparting effect is reduced. Therefore, in order to achieve both conductivity and dispersion performance, the control ratio D ₉₀ /D _mod becomes important.

The D _mod of the carbon black of the present invention is preferably from 0.110 μm to 0.140 μm, more preferably from 0.115 μm to 0.135 μm. When D _mod is in the above range, it becomes easy to achieve good dispersibility and conductivity at the same time. Further, when the above ratio D ₉₀ /D _mod is within the above range, stable electric conductivity is exhibited.

The D ₉₀ of the carbon black of the present invention is preferably from 0.230 μm to 0.300 μm, more preferably from 0.250 μm to 0.290 μm. When D ₉₀ is in the above range, it becomes easy to achieve good dispersibility and conductivity at the same time. Further, it is easy to obtain a conductive resin composition excellent in conductivity and surface smoothness.

In the present invention, it is easy to achieve good dispersibility to the dispersion medium at the same time, and in terms of good electrical conductivity, it is particularly preferable that the BET specific surface area is 350 m ² /g to 550 m ² /g, and the DBP oil absorption is 270cm ³ /100g~320cm ³ /100g, the above ratio D ₉₀ /D _mod is 1.90~2.20 carbon black.

The average primary particle diameter of the carbon black of the present invention is preferably from 30 nm to 55 nm, more preferably from 35 nm to 50 nm. When the average primary particle diameter of carbon black is at least the lower limit value, the dispersibility into the dispersion medium is further improved. When the average primary particle diameter of carbon black is at most the upper limit, good conductivity is easily obtained at the time of addition. Further, it is easy to obtain a good conductive resin composition and a composite electrode material having good conductivity.

Further, the average primary particle diameter of carbon black was measured by the method described in the examples.

The carbon black of the present invention preferably has a volatile content of 0.8% by mass or less, more preferably 0.5% by mass or less. When the volatilization of carbon black is less than or equal to the above upper limit value, good electrical conductivity can be easily obtained at the time of addition. Further, it is easy to obtain a good conductive resin composition and a composite electrode material having good conductivity.

Further, the volatile matter of carbon black was measured by the method described in the examples.

The ash content of the carbon black of the present invention is preferably 0.05% by mass or less, and more preferably 0.03% by mass or less. When the ash of the carbon black is equal to or less than the upper limit, stable conductivity can be easily obtained at the time of addition. In addition, it is easy to suppress the decrease in strength of the resin. In addition, an electrode material exhibiting stable electrical conductivity is easily obtained.

Further, the ash of carbon black was measured by a method in accordance with ASTM D 1506.

24M4DBP oil absorption of carbon black of the present invention (carbon black is compressed to 4 165MPa oil absorption amount of the resultant compression) is preferably ^{130cm 3 / 100g ~ 200cm 3 /} 100g, more preferably ^{140cm 3 / 100g ~ 180cm 3 /} 100g . When the oil absorption amount of 24M4DBP is at least the lower limit value, stable conductive properties are easily obtained at the time of addition. In addition, an electrode material having stable electrical conductivity is easily obtained. When the oil absorption amount of 24M4DBP is less than or equal to the upper limit value, good dispersibility is easily obtained at the time of addition. In addition, an electrode material having good dispersibility is easily obtained.

The oil absorption of 24M4DBP was measured using a sample amount of 20 g under the conditions described in JIS K 6217-4.

In the carbon black of the present invention, the iodine adsorption amount is preferably from 420 mg/g to 660 mg/g, and the pH of the 1% by mass aqueous solution is from 9 to 11. Thereby, stable conductivity is easily obtained at the time of addition. Further, it is easy to obtain a conductive resin composition excellent in conductivity and surface smoothness. In addition, it is easy to obtain an electrode material having stable conductivity.

The amount of iodine adsorption was measured by the method described in JIS K 6217-1.

The ratio of the CTAB (bromo cetyltrimethylammonium) adsorption specific surface area to the BET specific surface area (CTAB/BET) in the carbon black of the present invention is preferably from 0.3 to 0.8, more preferably from 0.6 to 0.8. When the above ratio (CTAB/BET) is within the above range, stable dispersion performance is easily obtained. In addition, easy to obtain conductivity and surface smoothness Excellent conductive resin composition.

The CTAB adsorption specific surface area was measured under the conditions described in JIS K 6217-3.

(Manufacturing method of carbon black)

As a method of producing the carbon black of the present invention, an oil-furnace method can be mentioned.

Specific examples of the oil furnace method include a method of producing carbon black by subjecting a raw material oil to a partial oxidation reaction in the presence of molecular oxygen and water vapor in a furnace to produce a synthesis gas.

Examples of the carbon production furnace include a GE (General Electric) furnace and an SG (Shell Gasification) furnace, and particularly preferably an SG furnace.

In order to obtain carbon black satisfying the above conditions (1) to (3), it is important to control the ratio (vapor ratio) of water vapor supplied to the furnace per ton of the feedstock oil, per ton of the feedstock oil. The ratio of the molecular oxygen supplied to the furnace (oxygen ratio) and the supply amount of the raw material oil supplied to the furnace per unit time are not emulsified. That is, it is important to control all of the manufacturing conditions corresponding to the above four items. In particular, in order to satisfy the condition (3), it is particularly important to control the supply amount of the feedstock oil and suppress the emulsification of the feedstock oil.

The steam ratio is preferably from 200 kg/t to 450 kg/t, more preferably from 250 kg/t to 300 kg/t, per 1 ton of the feedstock oil. When the vapor ratio is within the above range, carbon black satisfying the conditions (1) to (3) is easily obtained.

About oxygen ratio, preferably with respect to the feedstock oil per ton of 500Nm ³ ~ 650Nm ^3, more preferably 550Nm ³ ~ 600Nm ^3. When the oxygen ratio is within the above range, carbon black satisfying the conditions (1) to (3) is easily obtained.

The supply amount of the stock oil supplied to the furnace per unit time is preferably from 1,000 kg/hr to 1800 kg/hr, more preferably from 1200 kg/hr to 1600 kg/hr. When the supply amount of the raw material oil supplied to the furnace per unit time is within the above range, carbon black satisfying the conditions (1) to (3) is easily obtained.

The feedstock oil is preferably fed without emulsification. Thereby, carbon black which satisfies the conditions (1) to (3) is easily obtained.

The temperature in the furnace is preferably from 1250 ° C to 1350 ° C, more preferably from 1300 ° C to 1350 ° C.

The pressure in the furnace is preferably from 15 kg/cm ² to 45 kg/cm ² , more preferably from 25 kg/cm ² to 35 kg/cm ² .

Further, the obtained carbon black is preferably dried under a nitrogen atmosphere. The drying temperature is preferably from 300 ° C to 900 ° C, more preferably from 350 ° C to 700 ° C, and particularly preferably from 400 ° C to 600 ° C. When the drying temperature is 300 ° C or more, the volatile matter is reduced, and good electrical conductivity is easily obtained upon addition. When the drying temperature is 900 ° C or less, the degree of graphitization is reduced, and good dispersibility to a resin or a solvent is easily obtained.

As the raw material oil, a raw material oil which is usually used for the production of carbon black can be used, and a liquid hydrocarbon is preferable, and examples thereof include petroleum hydrocarbons such as creosote and petroleum oil such as ethylene bottom oil (EHE oil). Hydrocarbons, etc. Preferred among these are EHE oils.

The BMCI value (Bureau of Mines Correlation Index) of the stock oil is preferably from 100 to 200, more preferably from 120 to 180, and particularly preferably from 130 to 160. When the BMCI value is 100 or more, the yield is hard to be lowered, and it is preferable in terms of economy. When the BMCI value is 200 or less, it is easy to supply the raw material oil stably.

Further, the BMCI value of the stock oil was determined according to the following formula.

BMCI value = 48640 / K + 473.7S - 456.8

In the above formula, K is the average boiling point of the feedstock oil, and S is the specific gravity of the feedstock oil.

The C/H of the stock oil is preferably from 5 to 20, more preferably from 10 to 18. When the C/H ratio is 5 or more, the yield is hard to be lowered, and it is preferable in terms of economy. When the C/H ratio is 20 or less, it is easy to supply the raw material oil stably.

The impurity of the raw material oil is preferably 10 ppm by mass or less, more preferably 5 ppm by mass or less, and still more preferably 3 ppm by mass or less. When the sodium is divided into 10 ppm by mass or less, it is easy to suppress a large amount of metal such as iron remaining in the produced carbon.

The iron content of the stock oil is preferably 10 ppm by mass or less, more preferably 8 ppm by mass or less, and still more preferably 4 ppm by mass or less. When the iron content is 10 ppm by mass or less, it is easy to suppress the residual of the metal in the carbon and adversely affect the resin composition or the battery characteristics.

The content of nickel, copper and manganese in the stock oil is preferably 8 ppm by mass or less, more preferably 4 ppm by mass or less, and still more preferably 2 ppm by mass or less. When the content of nickel, copper, and manganese is 8 ppm by mass or less, it is easy to suppress the residual of metal in carbon and adversely affect the resin composition or battery characteristics.

The sulfur content of the stock oil is preferably 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.01% by mass or less. When the sulfur content is 1% by mass or less, it is easy to suppress the adverse effect on the resin composition or the battery characteristics.

The carbon black of the present invention described above satisfies the conditions (1) to (3), and therefore, good dispersibility and conductivity are simultaneously achieved. In addition, since the carbon black which satisfies the conditions (1) to (3) is used as the conductive resin composition of the present invention, it is possible to produce a conductive article having high mechanical strength, excellent surface smoothness, and electrical conductivity. another In addition, since the carbon black which satisfies the conditions (1) to (3) is used as the composite electrode material of the present invention, it is possible to manufacture an electrode material which is less likely to cause an abnormality such as an internal short circuit and which can obtain excellent battery performance. Further, since the ratio of the composite metal oxide can be increased in the composite electrode material of the present invention, it is easy to increase the energy density of the battery. Further, the electrode material produced by using the composite electrode material of the present invention is excellent in battery performance even when the amount of carbon black used is small.

Conventionally, as carbon black having good dispersibility, carbon black having a DBP oil absorption amount of less than 270 cm ³ /100 g and a BET specific surface area of less than 350 m ² /g (hereinafter referred to as "carbon black (a)")) is commercially available. However, the carbon black (a) has a low effect of imparting conductivity to a resin or the like. In addition, carbon black having a DBP oil absorption of more than 340 cm ³ /100 g and a BET specific surface area of more than 650 m ² /g (hereinafter referred to as "carbon black (b)") is commercially available as a carbon black having a high conductivity imparting effect. The carbon black (b) has low dispersibility. Although the reason is not clear, the carbon black of the present invention is more excellent even when compared with the intermediate property assumed based on the dispersibility and conductivity of carbon black (a) and the dispersibility and conductivity of carbon black (b). Dispersibility and conductivity.

The carbon black of the present invention can be suitably used in the fields of electrode materials, conductive materials for automobiles, semiconductor packages, and the like, and can be suitably applied to fields such as cables that require high dispersion properties in addition to conductivity.

[conductive resin composition]

The conductive resin composition of the present invention contains the carbon black of the present invention and a resin. Further, the conductive resin composition of the present invention may contain components other than carbon black and resin as needed.

The ratio of carbon black in the conductive resin composition (100% by mass) of the present invention is preferably 0.5% by mass to 40% by mass, more preferably 3.0% by mass to 30% by mass, When the ratio of the carbon black is at least the lower limit value, it is easy to obtain a conductive resin composition having excellent conductivity. When the ratio of the carbon black is at most the upper limit, it is easy to suppress the decrease in strength of the conductive resin composition.

[resin]

The resin is not particularly limited, and may be a thermoplastic resin or a thermosetting resin.

Examples of the thermosetting resin include phenol, melamine, and epoxy resin.

Examples of the thermoplastic resin include a polyolefin resin, an elastomer resin, a polystyrene resin, other general-purpose resins, engineering plastics, and super engineering plastics.

The polyolefin-based thermoplastic resin may be a copolymer of an olefin and another monomer, in addition to a homopolymer and a copolymer of an olefin. Specific examples thereof include high-density polyethylene, medium-density polyethylene, low-density polyethylene, and linear low-density polyethylene produced by a low pressure method, a medium pressure method, or a high pressure method; Polypropylene resin; poly-1,2-butadiene resin; ethylene-butene copolymer, and the like. Further, examples thereof include a copolymer of ethylene, propylene or butylene with an acrylate or a methacrylate, and chlorination of the copolymers. Further, a mixture of two or more kinds of the above polymers may be mentioned. Among the polyolefin-based thermoplastic resins, a polyethylene resin and a polypropylene resin are preferable.

Further, examples of the thermoplastic resin of the elastic system include an olefin-based elastomer such as an ethylene propylene-based elastomer and an ethylene-propylene-diene rubber (EPDM)-based elastomer; styrene-butadiene-styrene and styrene-different a styrene-based elastomer such as pentadiene-styrene; a polyamine-based elastomer; an urethane-based elastomer; and a polyester-based elastic Sexuality, etc.

Further, examples of the polystyrene-based thermoplastic resin include polystyrene, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, and acrylonitrile-acrylic rubber-styrene. (AAS) resin, etc.

As other general-purpose resins, polyvinyl chloride (PVC) resin, ethylene-ethyl acrylate (EEA) resin, ethylene-vinyl acetate (EVA) resin, acrylonitrile-ethylene/propylene rubber-styrene (AES) resin may be mentioned. , ethylene-vinyl alcohol resin and polylactic acid.

As engineering plastics, polyamine resins such as 6-nylon, 6,6-nylon, 6,10-nylon, 12-nylon and MXD-nylon resin; polycarbonate resin, polyethylene terephthalate A polyester resin such as an ester resin or a polybutylene terephthalate resin; a polyacetal resin; and a modified polyphenylene ether resin.

As super engineering plastics, polypyrene resin, modified polyfluorene resin, polyphenylene resin, polyketone resin, polyether phthalimide resin, polyarylate resin, polyphenylene sulfide resin, liquid crystal polymer, poly Ether oxime resin, polyether ether ketone resin, polyimine resin, polyamidimide resin, fluororesin, and the like.

The polycarbonate resin may, for example, be an aromatic polycarbonate resin obtained by reacting an aromatic dihydroxy compound with phosgene or a diester of carbonic acid, and by using an alicyclic dihydroxy compound instead of the above. An alicyclic polycarbonate resin obtained by an aromatic dihydroxy compound.

Examples of the aromatic dihydroxy compound include 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, and 2 , 2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, and 4,4'-dihydroxybiphenyl.

Examples of the alicyclic dihydroxy compound include isosorbide and spiroglycerol. (spiroglycol) and cyclohexanediol.

Further, in order to secure physical properties corresponding to the use, the above resin may be blended. Specifically, it can be exemplified by blending of ABS/polycarbonate resin, blending of polybutylene terephthalate resin/polycarbonate resin, and polyphenylene ether resin/polyamide resin/styrene-butene - Blending of a styrene-based elastomer or the like.

The proportion of the resin in the conductive resin composition (100% by mass) of the present invention is preferably from 60.0% by mass to 99.5% by mass, more preferably from 70.0% by mass to 97.0% by mass. When the ratio of the above resin is at least the lower limit value, the decrease in strength of the conductive resin composition is suppressed. When the ratio of the above resin is at most the upper limit value, it is easy to obtain a conductive resin composition having excellent conductivity.

[Other ingredients]

As other components, for example, in order to improve heat resistance, dimensional stability, rigidity, toughness, impact resistance or mechanical strength, mica, glass fiber, cerium oxide, talc, calcium carbonate, zinc oxide, barium sulfate, stainless steel, oxidation can be adjusted. An inorganic filler such as copper, nickel, nickel oxide or zirconium silicate. Further, in order to prevent deterioration of the thermoplastic resin and carbon black during kneading or deterioration over time, and to improve moldability, a molding aid or a processing aid may be blended. Specific examples thereof include known phenol-based antioxidants, lubricants such as phosphorus-based antioxidants, metal soaps, and fatty guanamine derivatives. Further, a known flame retardant, plasticizer or the like may be used depending on the application.

When the conductive resin composition of the present invention contains other components, the ratio of the other components in the conductive resin composition (100% by mass) of the present invention is preferably 0.1% by mass to 40.0% by mass, more preferably 1.0. Mass%~30.0% by mass.

The method for producing the conductive resin composition of the present invention is not particularly limited, and examples thereof include a resin, carbon black, and a known method by a known method. And mix and mix other ingredients as needed.

In the conductive resin composition of the present invention, for example, each component may be melt-kneaded to form a particulate composite. The method of forming the conductive resin composition of the present invention into a particulate composite is not particularly limited, and a method using a known apparatus or equipment can be employed. For example, a method in which each component is supplied to a kneader, melt-kneaded, extruded from a die, and pelletized using a pelletizer or the like is exemplified.

Each component of the conductive resin composition of the present invention may be uniformly kneaded by, for example, a premixer such as a tumbler or a Henschel mixer, and then kneaded. Further, the specific components may be separately supplied to the kneading machine by a feeder or a volume feeder to perform kneading.

Examples of the kneading machine include a single-shaft extruder equipped with a vent, a counter-rotating twin-screw extruder, a co-rotating twin-screw extruder, a high-speed mixer (Supermixer), and a Banbury mixer ( Banbury mixer), kneader, roller and two-way kneader (ko-kneader).

In the present invention, since the dispersibility of carbon black is good, a conductive resin composition in which carbon black is well dispersed in a resin can be easily produced by a known kneading method.

The method for producing a conductive article using the conductive resin composition of the present invention is not particularly limited, and for example, injection molding, extrusion molding, or the like can be appropriately selected depending on the application.

The use of the conductive resin composition of the present invention is not particularly limited, and examples thereof include a conductive material for automobiles, a semiconductor package, and a power cable.

[Composite electrode material]

The composite electrode material of the present invention is, for example, a composite electrode material for forming an electrode material of a nonaqueous battery, and contains the carbon black, the composite metal oxide, and the binder resin of the present invention.

The proportion of carbon black in the composite electrode material (100% by mass) of the present invention is preferably 0.05% by mass to 15% by mass, more preferably 0.5% by mass to 12% by mass, still more preferably 1% by mass to 10% by mass. It is preferably 1.5% by mass to 8% by mass. When the ratio of the above carbon black is at least the lower limit value, stable battery performance is easily obtained. When the ratio of the above carbon black is at most the upper limit value, stable battery performance is easily obtained. Further, by reducing the proportion of carbon black, it becomes possible to increase the proportion of the composite metal oxide in the electrode material, and it becomes easy to simultaneously achieve an improvement in energy density and stable battery performance.

The composite metal oxide is not particularly limited, and a composite metal oxide which is generally used as an electrode active material can be used.

Examples of the composite metal oxide include a lithium transition metal composite oxide represented by Li _x MO ₂ (wherein M represents one or more transition metals and is 0.05 ≦ x ≦ 1.10). As M, at least one selected from the group consisting of Mn, Co or Ni is preferred.

Specific examples of the lithium transition metal composite oxide include LiCoO ₂ , LiNiO ₂ , LiMnO ₂ , LiMn ₂ O ₄ , Li ₂ MnO ₃ , LiMn _1/2 Ni _1/2 O _{2 ,} and LiNi _1/3 Co. _1/3 Mn _1/3 O ₂ and the like.

Further, as the composite metal oxide, for example, olives such as LiFePO ₄ , LiFeP ₂ O ₇ , LiMnPO ₄ , LiCoPO ₄ , LiNiPO ₄ , Li ₂ FeSiO ₄ , Li ₂ MnSiO ₄ , Li ₂ NiSiO _{4 ,} and Li ₂ CoSiO _{4 may be used} . Stone-type metal lithium salt.

The composite electrode material of the present invention may have one type of composite metal oxide. There are two or more types.

The proportion of the composite metal oxide in the composite electrode material (100% by mass) of the present invention is preferably 70% by mass to 99.9% by mass, more preferably 76% by mass to 99% by mass. When the ratio of the above composite metal oxide is at least the lower limit value, stable battery performance is easily obtained. When the ratio of the above composite metal oxide is at most the upper limit value, stable battery performance is easily obtained.

[Binder Resin]

The binder resin is not particularly limited, and a binder resin generally used for an electrode material can be used.

Specific examples of the binder resin include fluorine-based resins such as polyvinylidene fluoride and polytetrafluoroethylene, and unsaturated bonds such as styrene/butadiene rubber, isoprene rubber, and butadiene rubber. Polymers, etc.

The binder resin contained in the composite electrode material of the present invention may be one type or two or more types.

The proportion of the binder resin in the composite electrode material (100% by mass) of the present invention is preferably from 0.05% by mass to 15% by mass, more preferably from 0.5% by mass to 12% by mass. When the ratio of the above binder resin is at least the lower limit value, stable battery performance is easily obtained. When the ratio of the above binder resin is at most the upper limit value, stable battery performance is easily obtained.

[Other ingredients]

The composite electrode material of the present invention may further contain other components than carbon black, a composite metal oxide, and a binder resin, as needed. As another component, a surfactant etc. are mentioned, for example.

In the case where the composite electrode material of the present invention contains other components, the present invention The proportion of the other components in the composite electrode material (100% by mass) is preferably 0.05% by mass to 15% by mass, more preferably 0.5% by mass to 12% by mass.

The method of producing the electrode material using the composite electrode material of the present invention is not particularly limited. For example, a slurry obtained by dissolving or dispersing a composite electrode material in a solvent is applied to a current collector to form a solvent. a method of volatilization; and a method of applying a kneaded material of each component of a composite electrode material to a current collector.

As the current collector, a current collector which is generally used as a current collector of an electrode material can be used, and examples thereof include a metal foil containing aluminum and an alloy containing aluminum as a main component.

As the solvent, a solvent which is usually used for the production of an electrode material can be used, and examples thereof include alkyl alcohols (such as methanol, ethanol, and propanol), alkyl ketones (such as acetone and methyl ethyl ketone), and ethers. (tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, etc.), and guanamines (diethylformamide, dimethylformamide, N-methyl-2-pyrrolidone, and dimethyl Imidazolidinone, etc.).

[Examples]

Hereinafter, the present invention will be described in detail by way of examples, but the invention should not be construed as limited.

[test methods]

(DPB oil absorption of carbon black)

The DPB oil absorption of carbon black was measured at a sample amount of 9 g under the conditions of ASTM D 2414.

(BET specific surface area of carbon black)

The BET specific surface area of the carbon black was measured under the conditions in accordance with ASTM D 3037.

(carbon black ratio D ₉₀ /D _mod )

The ratio of carbon black D ₉₀ /D _mod is calculated based on the result of the measurement method of the aggregate diameter described in JIS K6217-6.

Specifically, an accurately weighed carbon black was added to a 20% by volume aqueous solution of ethanol dropwise added with three drops of a surfactant ("NONIDET P-40" manufactured by Sigma Chemical Co.). A sample liquid having a carbon black concentration of 0.01% by mass. The sample liquid was subjected to dispersion treatment for 20 minutes using an ultrasonic cleaner (ULTRASONIC STIRRING BATH: manufactured by LAKOMANUFACTURING CO.) to obtain a carbon black slurry. Into a centrifugal sedimentation type particle size distribution measuring apparatus ("BI-DCP PARTICLSIZER" manufactured by BROOK HAVEN INSTRUMENTS), 10 mL of a spin liquid (pure water) was injected, and a buffer solution (20 volumes) was injected. % ethanol aqueous solution) 1 mL. Thereafter, 1 mL of the above carbon black slurry was injected, and centrifugal precipitation was performed at a number of revolutions of 10,000 rpm, and a stokes equivalent diameter was calculated with a true specific gravity of 1.78. A histogram of the relative frequency of occurrence relative to the Stoker equivalent diameter as shown in Figure 1 was made.

The line B is drawn from the peak A of the histogram so as to be parallel to the Y axis, and the intersection of the straight line B and the X axis of the histogram is C. At this time, the Shrek diameter at C becomes the mode diameter (D _mod ). Further, in the histogram, the straight line E is drawn so as to be parallel to the Y-axis from the point D at which the cumulative amount is 90%, and the intersection of the straight line E and the X-axis of the histogram is F. The Shrek diameter at F at this time becomes the D90 diameter (D ₉₀ ).

(average primary particle size of carbon black)

The average primary particle diameter of carbon black was determined using a transmission electron microscope. Specifically, a carbon black sample was dispersed in chloroform for 10 minutes by a 150 kHz, 0.4 kW ultrasonic disperser to prepare a dispersion sample, which was sprinkled on a carbon-reinforced support film. And fixed. The image was magnified by a transmission electron microscope, and the particle size of 1000 or more carbon blacks was randomly measured using an apparatus of Endter according to an image magnified to 50,000 to 200,000 times, and the average value of the above particle diameters was averaged once. Particle size.

(carbon black volatiles)

First, the magnetic crucible (15 mm in diameter, 30 mm in height, 10 mL in capacity) and the lid were air-fired at 950±20 ° C for 30 minutes, and then cooled to room temperature (25 ° C) in a desiccator, and the magnetic crucible and the lid were placed. The mass (M _A ) is accurately weighed to the nearest 0.1 mg unit. Then, 2 g of carbon black was filled into the magnetic crucible to the extent not exceeding 2 mm below the lid, and the lid was placed, and the mass (M _B ) was accurately weighed to the nearest 0.1 mg unit. Thereafter, it was heated in an electric furnace at 950 ± 20 ° C for 7 minutes, cooled to room temperature (25 ° C) in a desiccator, and the mass (M _C ) was accurately weighed again to the nearest 0.1 mg unit, and according to the following The formula calculates the volatile matter of the carbon black.

Volatile matter (% by mass) = (M _{B -} M _C ) / (M _{B -} M _A )

(carbon black ash)

The ash of carbon black was measured under the conditions of ASTM D 1506.

(carbon black 24M4DBP oil absorption)

The measurement was carried out under the conditions described in JIS K 6217-4 using a sample amount of 20 g.

(CTAB adsorption specific surface area of carbon black)

The measurement was carried out under the conditions described in JIS K 6217-3.

(Iodine adsorption amount of carbon black)

The measurement was carried out by the method described in JIS K 6217-1.

(pH determination of carbon black)

Accurately weigh carbon black 1g ± 0.01g, accurate to 0.01g, and take to 20mL In the beaker. Thereafter, 1 mL of ethanol and 10 mL of distilled water which had been boiled in advance were added to prepare a dispersion of carbon black, which was covered with a watch glass, and left to stand in a constant temperature room at 25 ° C for 60 minutes. After confirming that the dispersion liquid was 25° C., the pH value meter corrected by the pH standard liquids 4, 7, and 9 was used, and the instruction value one minute after the start of the measurement was read.

[Performance evaluation of carbon black]

(carbon black slurry viscosity)

Carbon black and N-methyl-2-pyrrolidone were sequentially placed in a mixing machine at a mixing temperature of 25 ° C and a number of revolutions of 300 rpm for 10 minutes using a planetary rotary ball mill (manufactured by ITO CORPORATION). The mixture was kneaded, whereby a slurry having a carbon black concentration of 5% by mass was obtained. Then, the slurry was measured for viscosity using a rotary viscometer (Physica MCR301, manufactured by Anton Parr) at 25 ° C, a shear rate of 1/13 / sec, and 5 minutes.

(Dispersion properties of carbon black)

Carbon black and N-methyl-2-pyrrolidone were placed in this order at a kneading temperature of 25 ° C and a number of revolutions of 300 rpm using a planetary rotary ball mill (manufactured by Ito Seisakusho Co., Ltd. (ITO CORPORATION)). The mixture was kneaded in minutes, whereby a slurry having a carbon black concentration of 5% by mass was obtained. A polyethylene (PE) coating frame (thickness: 0.2 mm) was placed on a wood free paper (30 mm × 100 mm), and the dispersibility when the slurry was applied using a glass rod was evaluated on the basis of the following criteria.

A: There are no protrusions that can be confirmed by visual observation.

B: The number of protrusions which can be visually confirmed is less than 10.

C: The number of the protrusions which can be visually confirmed is 10 or more and less than 100.

D: The number of protrusions which can be visually confirmed is 100 or more.

(surface resistance value of carbon black)

A planetary rotary ball mill (Ito Seisakusho Co., Ltd. (ITO CORPORATION) Ltd.), kneading at a temperature of 25 ℃, under the conditions of rotation number of 300rpm, sequentially as the active material into the LiFePO ₄ 1.2g, carbon black 0.12g, as 0.12 g of polyvinylidene fluoride and 1.7 g of N-methyl-2-pyrrolidone as a binder were kneaded for 10 minutes to obtain a slurry. A PET coating frame (thickness 0.2 mm) was placed on a forest paper (30 mm × 100 mm), and the above slurry was coated with a glass rod. Thereafter, the slurry coated darin paper was heated at 80 ° C for 30 minutes using a hot stirrer HS-5BH (manufactured by AS ONE CORPORATION). The N-methyl-2-pyrrolidone is volatilized. After the surface was flattened using a SUS (Steel Use Stainless) roll, the coated tape was cut into 20 mm × 20 mm, and the cut piece was flattened using a SUS roll, and a hand press was used. (Hand Press) SSP-10A (Shimadzu Corporation) was pressed (pressing temperature 25 ° C, pressing pressure 370 MPa, pressing time 1 minute). Further, a vacuum oven (Isotemp Vacuum Oven Model 280A, manufactured by Fischer Scientific) was used, and dried under reduced pressure at 60 ° C for 6 hours to prepare a model positive electrode composition film. The surface resistance value of the positive electrode composition film of this model was measured by a resistivity meter (Loresta GP MCP-T610 type, manufactured by Mitsubishi Chemical Corporation ANALYTECH Co., Ltd.).

[raw material oil]

The properties of the stock oil used in the present production examples are shown below.

Type: EHE oil

Initial distillation temperature: 198 ° C

10% distillation temperature: 220 ° C

50% distillation temperature: 279 ° C

C/H ratio: 13.5

Impurities: sodium 3 mass ppm, iron 4 mass ppm, nickel 2 mass ppm, copper 2 mass ppm, manganese 2 mass ppm, sulfur 10 mass ppm

BMCI value: 145

[Manufacturing Example 1]

In the furnace, the supply amount (oil supply amount) of the raw material oil into the furnace is 1400 kg/hr, and the ratio (vapor ratio) of the water vapor supplied to the furnace per ton of the raw material oil is set to 250 kg/t, the oxygen ratio was set to 570 Nm ³ /t, the methane concentration was set to 0.70% by volume, the furnace temperature was set to 1335 ° C, and the furnace pressure was set to 30 kg/cm ² to obtain carbon black. Further, the obtained carbon black was dried at 450 ° C in a nitrogen atmosphere. The yield of carbon black per ton of feedstock oil was 223 kg/t.

[Production Example 2 to Production Example 4]

Carbon black was obtained in the same manner as in Production Example 1 except that the oil supply amount, the vapor ratio, the oxygen ratio, the methane concentration, the furnace temperature, and the furnace pressure were changed as shown in Table 1.

[Manufacturing Example 5]

In the furnace, the supply amount of the emulsified raw material oil into the furnace was 2,222 kg/hr (the supply amount of the raw material oil was 2000 kg/hr), and the water vapor supplied to the furnace per ton of the raw material oil was used. The ratio (vapor ratio) was set to 515 kg/t, the oxygen ratio was set to 635 Nm ³ /t, the methane concentration was set to 0.83 vol%, the furnace temperature was set to 1305 ° C, and the furnace pressure was set to 30 kg/cm ^{2 .} And get carbon black. Further, the obtained carbon black was dried at 450 ° C in a nitrogen atmosphere. The yield of carbon black per 1 ton of feedstock oil was 130 kg/t.

The DBP oil absorption, BET specific surface area, D _mod , D ₉₀ , ratio D ₉₀ /D _mod , average primary particle diameter, yield, ash, CTAB adsorption specific surface area of the carbon black obtained in Production Example 1 to Production Example 5, The ratios of (CTAB/BET), 24M4DBP oil absorption, iodine adsorption amount, and 1% by mass aqueous solution are shown in Table 1.

[Example 1 to Example 4]

The carbon black obtained in Production Example 1 to Production Example 4 was evaluated for the properties of the slurry viscosity, dispersibility, and surface resistivity.

[Comparative Example 1]

The DBP oil absorption amount obtained in Production Example 5 of the carbon black to be compared was 324 cm ³ /100 g, the BET specific surface area was 800 m ² /g, and the ratio D ₉₀ /D _mod was 1.80 (D ₉₀ =0.200 μm, D _mod The carbon black of =0.111 μm was evaluated for performance.

[Comparative Example 2]

The DBP oil absorption amount of the carbon black to be compared was 193 cm ³ /100 g, the BET specific surface area was 55 m ² /g, and the ratio D ₉₀ /D _mod was 3.47 (D ₉₀ =0.406 μm, D _mod =0.117 μm). Carbon black was evaluated for performance.

[Comparative Example 3]

The DBP oil absorption amount of the carbon black to be compared was 166 cm ³ /100 g, the BET specific surface area was 256 m ² /g, and the ratio D ₉₀ /D _mod was 1.70 (D ₉₀ =0.292 μm, D _mod =0.172 μm). Carbon black was evaluated for performance.

[Comparative Example 4]

The DBP oil absorption obtained by blending the carbon black of Comparative Example 1 with the carbon black of Comparative Example 3 at a mass ratio of 59/41 was 280 cm ³ /100 g, the BET specific surface area was 576 m ² /g, and the ratio D ₉₀ /D was obtained. The carbon black having a _mod of 1.75 (D ₉₀ = 0.238 μm, D _mod =0.136 μm) was evaluated for performance.

[Comparative Example 5]

The DBP oil absorption obtained by blending the carbon black of Comparative Example 1 with the carbon black of Comparative Example 2 at a mass ratio of 52/48 was 280 cm ³ /100 g, the BET specific surface area was 443 m ² /g, and the ratio D ₉₀ /D was obtained. The carbon black having a _mod of 2.62 (D ₉₀ = 0.299 μm, D _mod = 0.114 μm) was evaluated for performance.

The DBP oil absorption, the BET specific surface area, the ratio D ₉₀ /D _mod , and the evaluation results of the carbon black in the examples and the comparative examples are shown in Table 2.

As shown in Table 2, the carbon blacks of Examples 1 to 4 which satisfy the conditions (1) to (3) have good dispersibility, a small surface resistivity, and good electrical conductivity.

On the other hand, the carbon black of Comparative Example 1 which satisfies the condition (2) but does not satisfy the conditions (1) and (3) has good conductivity, but the slurry viscosity is remarkably high, and the dispersibility is poor. Further, the carbon blacks of Comparative Examples 2 and 3 which were not satisfied by the conditions (1), (2), and (3) were large in surface resistivity and inferior in electrical conductivity.

Further, Comparative Examples 4 and 5 in which two types of carbon black were blended which did not satisfy the conditions (1) and (2) but did not satisfy the condition (3) were inferior in conductivity and were not sufficiently dispersed. Sex.

[Example 1a]

10 parts by mass of carbon black obtained in Production Example 1 and a polycarbonate resin (trade name "Iupilon S-3000", Mitsubishi Engineering Plastics) at a cylinder temperature of 260 ° C to 290 ° C by a twin-screw extruder 90 parts by mass of the company was kneaded, extruded, and cooled. Thereafter, a conductive resin composition in which a columnar granular composite was formed by a granulator was obtained.

[Example 2a to Example 4a]

A conductive resin composition was obtained in the same manner as in Example 1a except that the carbon black to be used was changed as shown in Table 2.

[Comparative Example 1a]

The DBP oil absorption amount obtained in Production Example 5 using carbon black as a comparison object was 324 cm ³ /100 g, the BET specific surface area was 800 m ² /g, and the ratio D ₉₀ /D _mod was 1.80 (D ₉₀ =0.200 μm, D _mod A conductive resin composition was obtained in the same manner as in Example 1a except that 8 parts by mass of the carbon black and 92 parts by mass of the polycarbonate resin were used.

[Comparative Example 2a]

The DBP oil absorption amount of the carbon black to be compared was 193 cm ³ /100 g, the BET specific surface area was 55 m ² /g, and the ratio D ₉₀ /D _mod was 3.47 (D ₉₀ =0.406 μm, D _mod =0.117 μm). A conductive resin composition was obtained in the same manner as in Example 1a except that 10 parts by mass of carbon black was used.

[Comparative Example 3a]

The DBP oil absorption amount of the carbon black to be compared was 193 cm ³ /100 g, the BET specific surface area was 55 m ² /g, and the ratio D ₉₀ /D _mod was 3.47 (D ₉₀ =0.406 μm, D _mod =0.117 μm). A conductive resin composition was obtained in the same manner as in Example 1a except that 17 parts by mass of carbon black and 83 parts by mass of a polycarbonate resin were used.

[Comparative Example 4a]

The DBP oil absorption amount of the carbon black to be compared was 166 cm ³ /100 g, the BET specific surface area was 256 m ² /g, and the ratio D ₉₀ /D _mod was 1.70 (D ₉₀ =0.292 μm, D _mod =0.172 μm). A conductive resin composition was obtained in the same manner as in Example 1a except that 17 parts by mass of carbon black and 83 parts by mass of a polycarbonate resin were used.

[Comparative Example 5a]

Carbon black DBP oil absorption of carbon black used in Comparative Example 1a Comparative Example 3a a mass ratio of 59/41, was blended obtained becomes 280cm ³ / 100g, BET specific surface area becomes 576m ² / g, ratio of D ₉₀ / D _A conductive resin composition was obtained in the same manner as in Example 1a except that 12 parts by mass of carbon black of 1.75 (D ₉₀ = 0.238 μm, D _mod = 0.136 μm) and 88 parts by mass of a polycarbonate resin were used.

[Comparative Example 6a]

The DBP oil absorption obtained by blending the carbon black of Comparative Example 1a with the carbon black of Comparative Example 2a at a mass ratio of 52/48 was 280 cm ³ /100 g, and the BET specific surface area was 443 m ² /g, and the ratio D ₉₀ /D was used. _A conductive resin composition was obtained in the same manner as in Example 1a except that 14 parts by mass of carbon black of 2.62 (D ₉₀ = 0.299 μm, D _mod = 0.114 μm) and 86 parts by mass of a polycarbonate resin.

[Volume resistivity]

By using the injection molding of the particles of the conductive resin composition obtained in each of the examples, a plate-shaped evaluation test piece having a thickness of 3.2 mm, a length of 76 mm, and a width of 76 mm was produced, and a digital multimeter manufactured by Yokogawa Kitamoto Electric Co., Ltd. was used. Multimeter) Model 2506A, measured for volume resistivity according to ISO 1853. The smaller the value of the volume resistivity, the more excellent the conductivity.

[surface smoothness]

A film having a thickness of 80 μm to 100 μm × a width of 10 cm × a length of 10 cm was produced by inflation molding using particles of the conductive resin composition obtained in each of the examples. The surface of the film was observed by visual observation, and the number of carbon agglomerates of 0.2 mm or more was counted, and the surface smoothness was evaluated based on the following evaluation criteria. Further, the smaller the number of carbon aggregates, the more excellent the dispersibility of carbon black.

"B": The number of carbon agglomerates is less than 10.

"D": The number of carbon agglomerates is 10 or more.

[Mechanical strength]

By using the injection molding of the particles of the conductive resin composition obtained in each of the examples, the type 1 test body described in ISO 179 (length 80 mm × width 10 mm × thickness 4 mm, notched) was obtained, according to ISO 179/ 1 eA for the Charpy impact test. The higher the Charpy impact strength, the more excellent the mechanical strength.

The DBP oil absorption, the BET specific surface area, the ratio D ₉₀ /D _mod , and the evaluation results of the carbon black used in the examples and the comparative examples are shown in Table 2a.

As shown in Table 2a, the conductive resin compositions of Examples 1a to 4a satisfying the carbon blacks of the conditions (1) to (3) were used to obtain high mechanical strength, good surface smoothness, and electrical conductivity.

On the other hand, in Comparative Example 1a in which carbon black which satisfies the condition (2) but did not satisfy the conditions (1) and (3), the dispersibility of the carbon black was insufficient and the surface was smooth. Poor sex. In addition, in Comparative Example 2a to Comparative Example 4a in which carbon black which was not satisfied by the use conditions (1) to (3), any one of conductivity, surface smoothness, and mechanical strength was inferior.

Further, in Comparative Example 5a and Comparative Example 6a in which two kinds of carbon blacks were blended which satisfy the conditions (1) and (2) but did not satisfy the condition (3), the dispersibility of the carbon black was insufficient, and the surface was insufficient. Poor smoothness.

[Example 1b]

(Manufacture of electrode materials)

Using a planetary rotary ball mill LP-1 (manufactured by Ito Seisakusho Co., Ltd.), 100 parts by mass of LiFePO ₄ as a composite metal oxide was placed in a mixing temperature of 25 ° C and a number of revolutions of 300 rpm, and in Production Example 1. 10 parts by mass of the obtained carbon black, 10 parts by mass of polyvinylidene fluoride as a binder resin, and 170 parts by mass of N-methyl-2-pyrrolidone were kneaded for 10 minutes to obtain a composite electrode material. Slurry. A polyethylene (PE) coating frame (thickness 0.2 mm) was placed on an aluminum foil (30 mm × 140 mm), and the above slurry was coated with a glass rod. Thereafter, the aluminum foil coated with the slurry was heated at 110 ° C for 1 hour using a heating stirrer HS-5BH (manufactured by AS ONE CORPORATION) to obtain N-methyl- 2-pyrrolidone is volatilized. After the surface was flattened using a SUS roll, the coated aluminum foil was cut into 20 mm × 20 mm. Thereafter, the cut piece was flattened using a SUS roll, and pressed using a hand press SSP-10A (Shimadzu Corporation) (pressing temperature 25 ° C, pressing pressure 370 MPa, and pressing time 1 minute) . Further, a vacuum oven (Isotemp Vacuum Oven Model 280A, manufactured by Fischer Scientific) was used, and dried under reduced pressure at 110 ° C for 5 hours to prepare an electrode material. The electrode material was fabricated in a plurality of electrode materials having a thickness of 25 ± 3 mm measured in a dry box in an argon atmosphere for evaluation of battery characteristics.

(manufacturing of evaluation unit)

The assembly of the evaluation unit was carried out in a dry box in an argon atmosphere. A lithium foil (25 mm × 25 mm) was fixed to a nickel plate (25 mm × 25 mm) by a resin roll. Then, a separator (26 mm × 26 mm) was laminated on the lithium foil, and the electrode material (20 mm × 20 mm) was laminated so that the slurry coated surface became the separator side, and a laminated aluminum plate (22 mm ×) 22mm). Then, a 26 mm × 55 mm packaging material having the same material as the above-mentioned separator is folded in a square shape so as to sandwich a nickel plate, a lithium foil, a separator, an electrode material, and a laminate of aluminum sheets. The inside of the casing provided with the electrolyte injection portion is inserted. At this time, the internal resistance of the circuit was measured using a digital tester (CDM-03D (manufactured by CUSTOM Co., Ltd.)), and it was confirmed that the resistance value was less than 0.001 Ω, and no short circuit occurred.

The heat sealer FT-130 (manufactured by FUJI IMPULSE Co., Ltd.) was used to seal the portion other than the electrolyte injection portion in the casing, and then an electrolyte solution (including 1 M LiPF ₆ ) was injected from the electrolyte injection portion. The ethyl carbonate (EC) / dimethyl carbonate (DMC) = 1/2) 0.6 mL was allowed to stand at 90 Torr for 5 minutes, whereby the electrolyte solution was immersed in the electrode material, and the electrolyte was sufficiently diffused inside the battery. Thereafter, the electrolyte injection portion of the casing was sealed by a heat sealer FT-130 to prepare an evaluation unit.

[Example 2b to Example 11b]

An evaluation unit was produced in the same manner as in Example 1b except that the carbon black, the composite metal oxide, and the binder resin were changed as shown in Table 2b.

[Comparative Example 1b]

The carbon black having a DBP oil absorption amount of 324 cm ³ /100 g, a BET specific surface area of 800 m ² /g, and a D ₉₀ /D _mod of 1.80 (D ₉₀ =0.200 μm, D _mod =0.111 μm) obtained in Production Example 5 was used. An evaluation unit was obtained in the same manner as in Example 1b except for the carbon black to be compared.

[Comparative Example 2b]

Commercially available carbon black having a DBP oil absorption of 193 cm ³ /100 g, a BET specific surface area of 55 m ² /g, and a D ₉₀ /D _mod of 3.47 (D ₉₀ =0.406 μm, D _mod =0.117 μm) was used as a carbon for comparison. Black, except for this, an evaluation unit was obtained in the same manner as in Example 1b.

[Comparative Example 3b]

Commercially available carbon black having a DBP oil absorption of 166 cm ³ /100 g, a BET specific surface area of 256 m ² /g, and a D ₉₀ /D _mod of 1.70 (D ₉₀ =0.292 μm, D _mod =0.172 μm) was used as a carbon for comparison. Black, except for this, an evaluation unit was obtained in the same manner as in Example 1b.

[Comparative Example 4b]

The DBP oil absorption obtained by blending the carbon black of Comparative Example 1b with the carbon black of Comparative Example 3b at a mass ratio of 59/41 was 280 cm ³ /100 g, the BET specific surface area was 576 m ² /g, and the ratio D ₉₀ /D was used. _Mod became a carbon black of 1.75 (D ₉₀ = 0.238 μm, D _mod =0.136 μm).

[Comparative Example 5b]

The DBP oil absorption obtained by blending the carbon black of Comparative Example 1b with the carbon black of Comparative Example 2b at a mass ratio of 52/48 was 280 cm ³ /100 g, the BET specific surface area was 443 m ² /g, and the ratio D ₉₀ /D was used. _Mod became a carbon black of 2.62 (D ₉₀ = 0.299 μm, D _mod = 0.114 μm).

[Comparative Example 6b to Comparative Example 8b]

The evaluation unit was obtained in the same manner as in Example 1b except that the carbon black of Comparative Example 2b was used, and the carbon black, the composite metal oxide, and the binder resin were changed as shown in Table 3b.

[Battery characteristics]

The evaluation unit was taken out from the drying oven, and the battery electrode portion was fixed by a torque of 15 Nm using a SUS plate. The open-circuit voltage was measured using a pocket tester (manufactured by CUSTOM Co., Ltd.), and the charging and discharging device HJ1001SD8 (manufactured by Hokuto Electric Co., Ltd.) was used for charging and discharging. Determination. In the charge and discharge measurement, the battery was charged at a constant current of 0.2 C for 5 hours, and further charged at a constant voltage of 4.1 V for 2.5 hours, and allowed to stand for 30 minutes. Thereafter, the battery was discharged at a rate of 30 C to 2.0 V. The ratio of the discharge capacity in the discharge at the rate of 30 C to the theoretical capacity of the evaluation unit was defined as the capacity retention ratio.

Further, the rate 1C represents a current value at which the theoretical capacity of the evaluation unit can be discharged in one hour.

[battery resistance]

The evaluation unit was fabricated in the same manner as the evaluation of the battery characteristics.

The evaluation unit was taken out from the drying oven, and the battery electrode portion was fixed by a torque of 15 Nm using a SUS plate. The open circuit voltage was measured using a pocket tester (manufactured by CUSTOM Co., Ltd.), and a charge/discharge device HJ1001SD8 (manufactured by Hokuto Denko Co., Ltd.) was used for the evaluation unit for displaying a voltage of 3.4 V to have a SOC of 50%. Thereafter, using a frequency response analyzer (frequency response) The analyzer model 1260 (manufactured by Solartron Co., Ltd.) and the potential/current type 1287 (manufactured by Solartron Co., Ltd.) were used for AC resistance measurement. The measurement conditions were set to an amplitude AC potential of 2 mV, a DC potential of 0 CV, and a measurement frequency of 25 mHz to 100 kHz.

[Dispersion performance]

The electrode material obtained in each example was visually observed and counted, and the number of the protrusions was counted, and the dispersibility was evaluated based on the following criteria.

A: There are no protrusions that can be confirmed by visual observation.

B: The number of protrusions which can be visually confirmed is less than 10.

C: The number of the protrusions which can be visually confirmed is 10 or more and less than 100.

D: The number of the protrusions which can be visually confirmed is 100 or more.

[Proportion of composite metal oxides]

The ratio of the composite metal oxide in the composite electrode material obtained in each example was calculated according to the following formula.

Ratio of composite metal oxide [% by mass] = composite metal oxide [parts by mass] / (composite metal oxide [parts by mass] + carbon black [parts by mass] + binder resin [parts by mass] × 100

The DBP oil absorption, the BET specific surface area, the ratio D ₉₀ /D _mod , and the evaluation results of the carbon black used in the examples and the comparative examples are shown in Table 2b and Table 3b.

As shown in Table 2b and Table 3b, in Examples 1b to 11b using carbon black which satisfies the conditions (1) to (3), the dispersibility of carbon black was good, and the capacity retention rate at a rate of 30 C was sufficient. High, low battery resistance for excellent battery performance. Further, in Examples 9b to 11b, stable battery performance was obtained even when the content of carbon black was small. Thereby, it can be clarified that by increasing the ratio of the composite metal oxide, stable battery performance can be obtained, and the energy density of the battery can be improved.

On the other hand, as shown in Table 4b and Table 5b, in Comparative Example 1b in which carbon black which satisfies the condition (2) but does not satisfy the conditions (1) and (3), the dispersibility of carbon black is insufficient. The battery resistance is extremely low, and there is an internal short circuit. Further, in Comparative Example 2b and Comparative Example 3b in which carbon black which was not satisfied by the use conditions (1) to (3), the capacity retention rate at the rate of 30 C was low, and the battery performance was inferior to those of Examples 1b to 8b.

Further, in Comparative Examples 4b and 5b in which two kinds of carbon blacks were blended which satisfy the conditions (1) and (2) but did not satisfy the condition (3), the dispersibility of the carbon black was insufficient.

Further, in Comparative Examples 6 to 8 which are carbon black which are not satisfied by the use conditions (1) to (3), Examples 9 to 11 in which composite electrode materials having the same composition are used, except for carbon black, are used. In comparison, the capacity retention rate at a rate of 30 C is low, and battery performance is poor.

Claims (3)

One kind of carbon black which satisfies the following conditions (1) through the condition (3), (1) BET specific surface area of ^{350m 2 / g ~ 650m 2 /} g; (2) DBP oil absorption 270cm ³ / 100g ~ 340cm ³ / 100g; (3) measuring method described in JIS K6217-6 by aggregate diameters measured D90 diameter (D ₉₀₎ with respect to the mode diameter (D _mod) ratio D ₉₀ / D _mod 1.90 to 2.20 . A conductive resin composition containing the carbon black and the resin according to claim 1, wherein the content of the carbon black is 0.5% by mass to 40% based on the total mass of the conductive resin composition. The mass%, the content of the resin is from 60.0% by mass to 99.5% by mass. A composite electrode material comprising the carbon black, the composite metal oxide, and the binder resin according to claim 1, wherein the carbon black content is 0.05 mass relative to the total mass of the composite electrode material. % to 15% by mass, the content of the composite metal oxide is 70% by mass to 99.9% by mass, and the content of the binder resin is 0.05% by mass to 15% by mass.