RESIN COMPOSITION

Abstract

The present invention provides a resin composition that has excellent application properties and excellent adhesion, can achieve high electron conductivity simultaneously with the dispersibility and dispersion stability of fibrous carbon materials, and enables production of lithium secondary batteries having high capacity retention. Provided is a resin composition containing: a fibrous carbon material; a non-aqueous solvent; and a polyvinyl acetal resin, the polyvinyl acetal resin including a structural unit containing an acidic functional group, and having an average degree of polymerization of 150 or greater and 1,500 or less and a hydroxy group content of 40.0 mol % or greater and 80.0 mol % or less.

Claims

1. A resin composition comprising: a fibrous carbon material; a non-aqueous solvent; and a polyvinyl acetal resin, the polyvinyl acetal resin including a structural unit containing an acidic functional group, and having an average degree of polymerization of 150 or greater and 1,500 or less and a hydroxy group content of 40.0 mol % or greater and 80.0 mol % or less.

2. The resin composition according to claim 1, wherein the acidic functional group is at least one selected from the group consisting of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

3. The resin composition according to claim 1, wherein the structural unit containing an acidic functional group is contained in an amount of 0.01 mol % or greater and 20.0 mol % or less relative to all structural units of the polyvinyl acetal resin.

4. The resin composition according to claim 1, wherein the acidic functional group is a Br?nsted acidic group, and the polyvinyl acetal resin has a Br?nsted acid content of 0.1 mg/g or greater and 200 mg/g or less.

5. The resin composition according to claim 1, wherein the fibrous carbon material is a carbon nanotube.

Description

DESCRIPTION OF EMBODIMENTS

[0159] The present invention is more specifically described in the following with reference to, but not limited to, examples.

Production Example 1

[0160] An amount of 500 g of a carboxylic acid-modified polyvinyl alcohol resin (average degree of polymerization 150, degree of saponification 98 mol %, the amount of a structural unit represented by the formula (2-1) (R.sup.17 is a methylene group and X.sup.17 is a hydrogen atom) 0.01 mol %) was added to 2,500 g of pure water and stirred at 90? C. for two hours for dissolution. This solution was cooled to 40? C., and to the solution was added 10 g of hydrochloric acid having a concentration of 35% by weight. The solution temperature was cooled to 5? C. and 62.99 g of acetaldehyde was added. This temperature was maintained and acetalization reaction was performed to precipitate out a reaction product. The solution was maintained at a solution temperature of 65? C. for five hours to complete the reaction, and 40 g of an aqueous sodium hydroxide solution was added for neutralization reaction. Then, 5,000 g of pure water was added, stirred, and then 5,000 g of water was removed by decantation. Further, the step of adding 5,000 g of pure water, stirring, and removing water by decantation was repeated three times in total. The solid content of the resin was then adjusted to 20% by weight using ion-exchanged water, whereby a polyvinyl acetal resin A1 was obtained.

[0161] The obtained polyvinyl acetal resin was analyzed by .sup.1H-NMR (nuclear magnetic resonance spectroscopy) to measure the acetal group content, the hydroxy group content, and the acetyl group content. Table 1 shows the results. .sup.1H-NMR measurement was performed using deuterated DMSO as a solvent.

[0162] The Br?nsted acid content was measured by acid-base titration in conformity with JIS K0070-1992. Specifically, it was measured by following method. First, a main test was performed as follows. About 1 g of the obtained polyvinyl acetal resin as a sample was precisely weighed into a conical flask, and 40 ml of an ethanol/water (volume ratio 9:1) solvent mixture was added thereto, followed by shaking for dissolution. After dissolution, with a 1% by weight phenolphthalein solution as an indicator, the sample was titrated using a 0.02 mol/L potassium hydroxide ethanolic solution with a microburet until a point at which a faint pink color lasted for at least 30 seconds. Separately, a blank test was performed, and the Br?nsted acid content was determined by the following formula. The result was 0.2 mg/g.

Br?nsted acid content=[(A?B)?f?( 1/50)?(C/1,000)]?100/D [0163] A: The amount (mL) of the potassium hydroxide ethanolic solution dropped in the main test [0164] B: The amount (mL) of the potassium hydroxide ethanolic solution dropped in the blank test [0165] C: The molecular weight of a structural unit containing an acidic functional group [0166] D: The amount (g) of the sample [0167] f: The titer of the 0.02 mol/L potassium hydroxide ethanolic solution.

[0168] The glass transition temperature (Tg) of the obtained polyvinyl acetal resin was measured using a differential scanning calorimeter (DSC) at a temperature increase rate of 10? C./min. The result was 93? C.

Production Example 2

[0169] A polyvinyl acetal resin A2 was obtained as in Production Example 1 except that a sulfonic acid-modified polyvinyl alcohol resin (average degree of polymerization 500, degree of saponification 98 mol %, the amount of a structural unit represented by the formula (3) (R.sup.24 is a methylene group and X.sup.24 is a hydrogen atom) 1.0 mol %) was used and the amount of acetaldehyde added was 32.99 g.

Production Example 3

[0170] A polyvinyl acetal resin A3 was obtained as in Production Example 1 except that a phosphoric acid-modified polyvinyl alcohol resin (average degree of polymerization 1,000, degree of saponification 92 mol %, the amount of a structural unit represented by the formula (4) (R.sup.25 is a methylene group, and X.sup.25 and X.sup.26 are each a hydrogen atom) 10.0 mol %) was used and the amount of acetaldehyde added was 46.99 g.

Production Example 4

[0171] A polyvinyl acetal resin A4 was obtained as in Production Example 1 except that a phosphoric acid-modified polyvinyl alcohol resin (average degree of polymerization 1,250, degree of saponification 98 mol %, the amount of a structural unit represented by the formula (4) (R.sup.25 is a vinylene group, and X.sup.25 and X.sup.26 are each a hydrogen atom) 0.1 mol %) was used and the amount of acetaldehyde added was 22.9 g.

Production Example 5

[0172] A polyvinyl acetal resin A5 was obtained as in Production Example 1 except that a sulfonic acid-modified polyvinyl alcohol resin (average degree of polymerization 1,500, degree of saponification 98 mol %, the amount of a structural unit represented by the formula (3) (R.sup.24 is a methylene group and X.sup.24 is a sodium element) 10.0 mol %) was used and the amount of acetaldehyde added was 53 g.

Production Example 6

[0173] An amount of 250 g of a carboxylic acid-modified polyvinyl alcohol resin (average degree of polymerization 500, degree of saponification 98 mol %, the amount of a structural unit represented by the formula (2-1) (R.sup.17 is a methylene group and X.sup.17 is a hydrogen atom) 1.0 mol %) and 250 g of an unmodified polyvinyl alcohol resin (average degree of polymerization 500, degree of saponification 98 mol %) were used. The amount of acetaldehyde added was 52 g. Except for these changes, a polyvinyl acetal resin A6 was obtained as in Production Example 1.

Production Example 7

[0174] An amount of 250 g of a carboxylic acid-modified polyvinyl alcohol resin (average degree of polymerization 1,000, degree of saponification 92 mol %, the amount of a structural unit represented by the formula (2-1) (R.sup.17 is a methylene group and X.sup.17 is a hydrogen atom) 0.1 mol %) and a 250 g of a sulfonic acid-modified polyvinyl alcohol resin (average degree of polymerization 1,000, degree of saponification 92 mol %, the amount of a structural unit represented by the formula (3) (R.sup.24 is a vinylene group and X.sup.24 is a hydrogen atom) 0.1 mol %) were used. The amount of acetaldehyde added was 26.9 g. Except for these changes, a polyvinyl acetal resin A7 was obtained as in Production Example 1.

Production Example 8

[0175] An amount of 250 g of a carboxylic acid-modified polyvinyl alcohol resin (average degree of polymerization 1,250, degree of saponification 98 mol %, the amount of a structural unit represented by the formula (2-1) (R.sup.17 is a methylene group and X.sup.17 is a hydrogen atom) 0.01 mol %) and 250 g of a phosphoric acid-modified polyvinyl alcohol resin (average degree of polymerization 1,250, degree of saponification 98 mol %, the amount of a structural unit represented by the formula (4) (R.sup.25 is a methylene group, and X.sup.25 and X.sup.26 are each a sodium atom) 0.1 mol %) were used. The amount of acetaldehyde added was 42.89 g. Except for these changes, a polyvinyl acetal resin A8 was obtained as in Production Example 1.

Production Example 9

[0176] A polyvinyl acetal resin A9 was obtained as in Production Example 1 except that a carboxylic acid-modified polyvinyl alcohol resin (average degree of polymerization 1,250, degree of saponification 98 mol %, the amount of a structural unit represented by the formula (2-1) (R.sup.17 is a methylene group and X.sup.17 is a hydrogen atom) 15.0 mol %) was used and the amount of acetaldehyde added was 38 g.

Production Example 10

[0177] A polyvinyl acetal resin B1 was obtained as in Production Example 1 except that a carboxylic acid-modified polyvinyl alcohol resin (average degree of polymerization 100, degree of saponification 98 mol %, the amount of a structural unit represented by the formula (2-1) (R.sup.17 is a methylene group and X.sup.17 is a hydrogen atom) 0.1 mol %) was used and the amount of acetaldehyde added was 57.9 g.

Production Example 11

[0178] A polyvinyl acetal resin B2 was obtained as in Production Example 1 except that a sulfonic acid-modified polyvinyl alcohol resin (average degree of polymerization 1,700, degree of saponification 98 mol %, the amount of a structural unit represented by the formula (3) (R.sup.24 is a methylene group and X.sup.24 is a hydrogen atom) 10.0 mol %) was used and the amount of acetaldehyde added was 53 g.

Production Example 12

[0179] A polyvinyl acetal resin B3 was obtained as in Production Example 1 except that a phosphoric acid-modified polyvinyl alcohol resin (average degree of polymerization 500, degree of saponification 98 mol %, the amount of a structural unit represented by the formula (4) (R.sup.25 is a vinylene group, and X.sup.25 and X.sup.26 are each a hydrogen atom) 1.0 mol %) was used and the amount of acetaldehyde added was 67 g.

Production Example 13

[0180] A polyvinyl acetal resin B4 was obtained as in Production Example 1 except that a carboxylic acid-modified polyvinyl alcohol resin (average degree of polymerization 1,250, degree of saponification 98 mol %, the amount of a structural unit represented by the formula (2-1) (R.sup.17 is a methylene group and X.sup.17 is a hydrogen atom) 0.01 mol %) was used and the amount of acetaldehyde added was 17.99 g.

Production Example 14

[0181] A polyvinyl acetal resin B5 was obtained as in Production Example 1 except that an unmodified polyvinyl alcohol resin (average degree of polymerization 500, degree of saponification 92 mol %) was used and the amount of acetaldehyde added was 37 g.

Production Example 15

[0182] A polyvinyl acetal resin B6 was obtained as in Production Example 1 except that a carboxylic acid-modified polyvinyl alcohol resin (average degree of polymerization 1,700, degree of saponification 98 mol %, the amount of a structural unit represented by the formula (2-1) (R.sup.17 is a methylene group and X.sup.17 is a hydrogen atom) 0.01 mol %) was used.

Production Example 16

[0183] A polyvinyl acetal resin B7 was obtained as in Production Example 1 except that a carboxylic acid-modified polyvinyl alcohol resin (average degree of polymerization 150, degree of saponification 98 mol %, the amount of a structural unit represented by the formula (2-1) (R.sup.17 is a methylene group and X.sup.17 is a hydrogen atom) 0.01 mol %) was used and the amount of acetaldehyde added was 73.0 g.

Production Example 17

[0184] A polyvinyl acetal resin A10 was obtained as in Production Example 1 except that a sulfonic acid-modified polyvinyl alcohol resin (average degree of polymerization 500, degree of saponification 98 mol %, the amount of a structural unit represented by the formula (3) (R.sup.24 is a methylene group and X.sup.24 is a hydrogen atom) 1.0 mol %) was used and 62 g of butyraldehyde was added instead of acetaldehyde.

Production Example 18

[0185] A polyvinyl acetal resin A11 was obtained as in Production Example 1 except that a carboxylic acid-modified polyvinyl alcohol resin (average degree of polymerization 150, degree of saponification 98 mol %, the amount of a structural unit represented by the formula (2-1) (R.sup.17 is a methylene group and X.sup.17 is a hydrogen atom) 0.1 mol %) was used and 62 g of butyraldehyde was added instead of acetaldehyde.

Production Example 19

[0186] A polyvinyl acetal resin A12 was obtained as in Production Example 1 except that a carboxylic acid-modified polyvinyl alcohol resin (average degree of polymerization 500, degree of saponification 98 mol %, the amount of a structural unit represented by the formula (2-1) (R.sup.17 is a methylene group and X.sup.17 is a hydrogen atom) 0.1 mol %) and 52.9 g of hexylaldehyde was added instead of acetaldehyde.

Production Example 20

[0187] A polyvinyl acetal resin A13 was obtained as in Production Example 1 except that a carboxylic acid-modified polyvinyl alcohol resin (average degree of polymerization 500, degree of saponification 98 mol %, the amount of a structural unit represented by the formula (2-1) (R.sup.17 is a methylene group and X.sup.17 is a hydrogen atom) 0.005 mol %) was used and 63.0 g of butyraldehyde was added instead of acetaldehyde.

Production Example 21

[0188] A polyvinyl acetal resin A14 was obtained as in Production Example 1 except that a carboxylic acid-modified polyvinyl alcohol resin (average degree of polymerization 500, degree of saponification 98 mol %, the amount of a structural unit represented by the formula (2-1) (R.sup.17 is a methylene group and X.sup.17 is a hydrogen atom) 0.001 mol %) was used and 63.0 g of butyraldehyde was added instead of acetaldehyde.

Production Example 22

[0189] A polyvinyl acetal resin A15 was obtained as in Production Example 1 except that a carboxylic acid-modified polyvinyl alcohol resin (average degree of polymerization 500, degree of saponification 98 mol %, the amount of a structural unit represented by the formula (2-1) (R.sup.17 is a methylene group and X.sup.17 is a hydrogen atom) 14.5 mol %) was used and 48.5 g of butyraldehyde was added instead of acetaldehyde.

Production Example 23

[0190] A polyvinyl acetal resin A16 was obtained as in Production Example 1 except that a phosphoric acid-modified polyvinyl alcohol resin (average degree of polymerization 500, degree of saponification 98 mol %, the amount of a structural unit represented by the formula (4) (R.sup.25 is a methylene group, and X.sup.25 and X.sup.26 are each a hydrogen atom) 1.0 mol %) was used and 62.0 g of butyraldehyde was added instead of acetaldehyde.

Production Example 24

[0191] A polyvinyl acetal resin B8 was obtained as in Production Example 1 except that an unmodified polyvinyl alcohol resin (average degree of polymerization 150, degree of saponification 98 mol %) was used and 63.0 g of butyraldehyde was added instead of acetaldehyde.

Production Example 25

[0192] A polyvinyl acetal resin B9 was obtained as in Production Example 1 except that a carboxylic acid-modified polyvinyl alcohol resin (average degree of polymerization 150, degree of saponification 98 mol %, the amount of a structural unit represented by the formula (2-1) (R.sup.17 is a methylene group and X.sup.17 is a hydrogen atom) 0.01 mol %) was used and 17.99 g of butyraldehyde was added instead of acetaldehyde.

Production Example 26

[0193] A polyvinyl acetal resin B10 was obtained as in Production Example 1 except that a carboxylic acid-modified polyvinyl alcohol resin (average degree of polymerization 100, degree of saponification 98 mol %, the amount of a structural unit represented by the formula (2-1) (R.sup.17 is a methylene group and X.sup.17 is a hydrogen atom) 0.01 mol %) was used and 62.99 g of butyraldehyde was added instead of acetaldehyde.

Production Example 27

[0194] A polyvinyl acetal resin B11 was obtained as in Production Example 1 except that a carboxylic acid-modified polyvinyl alcohol resin (average degree of polymerization 500, degree of saponification 98 mol %, the amount of a structural unit represented by the formula (2-1) (R.sup.17 is a methylene group and X.sup.17 is a hydrogen atom) 0.01 mol %) was used and 82.99 g of butyraldehyde was added instead of acetaldehyde.

TABLE-US-00001 TABLE 1 Raw material PVA Amount of structural unit Mixing Degree of containing acidic ratio saponification functional group (weight Aldehyde Type (mol %) (mol %) ratio) type Production Example 1 Polyvinyl acetal resin A1 Carboxylic acid-modified PVA 98 0.01 Acetaldehyde Production Example 2 Polyvinyl acetal resin A2 Sulfonic acid-modified PVA 98 1.0 Acetaldehyde Production Example 3 Polyvinyl acetal resin A3 Phosphoric acid-modified PVA 92 10.0 Acetaldehyde Production Example 4 Polyvinyl acetal resin A4 Phosphoric acid-modified PVA 98 0.1 Acetaldehyde Production Example 5 Polyvinyl acetal resin A5 Sulfonic acid-modified PVA 98 10.0 Acetaldehyde Production Example 6 Polyvinyl acetal resin A6 Carboxylic acid-modified PVA 98 1.0 50:50 Acetaldehyde Unmodified PVA 98 0 Production Example 7 Polyvinyl acetal resin A7 Carboxylic acid-modified PVA 92 0.1 50:50 Acetaldehyde Sulfonic acid-modified PVA 92 0.1 Production Example 8 Polyvinyl acetal resin A8 Carboxylic acid-modified PVA 98 0.01 50:50 Acetaldehyde Phosphoric acid-modified PVA 98 0.1 Production Example 9 Polyvinyl acetal resin A9 Carboxylic acid-modified PVA 98 15.0 Acetaldehyde Production Example 10 Polyvinyl acetal resin B1 Carboxylic acid-modified PVA 98 0.1 Acetaldehyde Production Example 11 Polyvinyl acetal resin B2 Sulfonic acid-modified PVA 98 10.0 Acetaldehyde Production Example 12 Polyvinyl acetal resin B3 Phosphoric acid-modified PVA 98 1.0 Acetaldehyde Production Example 13 Polyvinyl acetal resin B4 Carboxylic acid-modified PVA 98 0.01 Acetaldehyde Production Example 14 Polyvinyl acetal resin B5 Unmodified PVA 92 0 Acetaldehyde Production Example 15 Polyvinyl acetal resin B6 Carboxylic acid-modified PVA 98 0.01 Acetaldehyde Production Example 16 Polyvinyl acetal resin B7 Carboxylic acid-modified PVA 98 0.01 Acetaldehyde Production Example 17 Polyvinyl acetal resin A10 Sulfonic acid-modified PVA 98 1.0 Butyraldehyde Production Example 18 Polyvinyl acetal resin A11 Carboxylic acid-modified PVA 98 0.1 Butyraldehyde Production Example 19 Polyvinyl acetal resin A12 Carboxylic acid-modified PVA 98 0.1 Hexylaldehyde Production Example 20 Polyvinyl acetal resin A13 Carboxylic acid-modified PVA 98 0.005 Butyraldehyde Production Example 21 Polyvinyl acetal resin A14 Carboxylic acid-modified PVA 98 0.001 Butyraldehyde Production Example 22 Polyvinyl acetal resin A15 Carboxylic acid-modified PVA 98 14.5 Butyraldehyde Production Example 23 Polyvinyl acetal resin A16 Phosphoric acid-modified PVA 98 1.0 Butyraldehyde Production Example 24 Polyvinyl acetal resin B8 Unmodified PVA 98 0.0 Butyraldehyde Production Example 25 Polyvinyl acetal resin B9 Carboxylic acid-modified PVA 98 0.01 Butyraldehyde Production Example 26 Polyvinyl acetal resin B10 Carboxylic acid-modified PVA 98 0.01 Butyraldehyde Production Example 27 Polyvinyl acetal resin B11 Carboxylic acid-modified PVA 98 0.01 Butyraldehyde Polyvinyl acetal resin Amount of structural Average Hydroxy Acetal Acetyl unit containing Br?nsted degree of group group group acidic functional group acic polymer- content content content Amount content Tg ization (mol %) (mol %) (mol %) Type (mol %) (mg/g) (? C.) Production Example 1 Polyvinyl acetal resin A1 150 40.0 57.99 2.0 Carboxylic acid group 0.01 0.2 93 Production Example 2 Polyvinyl acetal resin A2 500 70.0 27.00 2.0 Sulfonic acid group 1.0 19.2 83 Production Example 3 Polyvinyl acetal resin A3 1000 50.0 32.00 8.0 Phosphoric acid group 10.0 169 85 Production Example 4 Polyvinyl acetal resin A4 1250 80.0 17.9 2.0 Phosphoric acid group 0.1 2.3 82 Production Example 5 Polyvinyl acetal resin A5 1500 40.0 48.0 2.0 Sulfonic acid group 10.0 169 94 Production Example 6 Polyvinyl acetal resin A6 500 50.0 47.5 2.0 Carboxylic acid group 0.50 11.5 85 Production Example 7 Polyvinyl acetal resin A7 1000 70.0 21.9 8.0 Carboxylic acid group 0.05 2.3 83 Sulfonic acid group 0.05 Production Example 8 Polyvinyl acetal resin A8 1250 60.0 37.945 2.0 Carboxylic acid group 0.005 1.25 80 Phosphoric acid group 0.05 Production Example 9 Polyvinyl acetal resin A9 1250 50.0 33.0 2.0 Carboxylic acid group 15.0 252 84 Production Example 10 Polyvinyl acetal resin B1 100 45.0 52.9 2.0 Carboxylic acid group 0.1 2.3 86 Production Example 11 Polyvinyl acetal resin B2 1700 40.0 48.0 2.0 Sulfonic acid group 10.0 169 85 Production Example 12 Polyvinyl acetal resin B3 500 35.0 62.0 2.0 Phosphoric acid group 1.0 19.2 95 Production Example 13 Polyvinyl acetal resin B4 1250 85.0 12.99 2.0 Carboxylic acid group 0.01 0.2 78 Production Example 14 Polyvinyl acetal resin B5 500 60.0 32.0 8.0 0 0 80 Production Example 15 Polyvinyl acetal resin B6 1700 40.0 57.99 2.0 Carboxylic acid group 0.01 0.2 94 Production Example 16 Polyvinyl acetal resin B7 150 35.0 62.99 2.0 Carboxylic acid group 0.01 0.2 94 Production Example 17 Polyvinyl acetal resin A10 500 40.0 57.0 2.0 Sulfonic acid group 1.0 19.2 75 Production Example 18 Polyvinyl acetal resin A11 150 50.0 47.9 2.0 Sulfonic acid group 0.1 2.3 78 Production Example 19 Polyvinyl acetal resin A12 500 50.0 47.9 2.0 Carboxylic acid group 0.1 2.3 64 Production Example 20 Polyvinyl acetal resin A13 500 40.0 57.995 2.0 Carboxylic acid group 0.005 0.15 74 Production Example 21 Polyvinyl acetal resin A14 500 40.0 57.999 2.0 Carboxylic acid group 0.001 0.05 73 Production Example 22 Polyvinyl acetal resin A15 500 40.0 43.5 2.0 Carboxylic acid group 14.5 250 77 Production Example 23 Polyvinyl acetal resin A16 500 40.0 57.0 2.0 Phosphoric acid group 1.0 19.2 76 Production Example 24 Polyvinyl acetal resin B8 150 40.0 58.0 2.0 0.0 0 72 Production Example 25 Polyvinyl acetal resin B9 150 85.0 12.99 2.0 Carboxylic acid group 0.01 0.2 81 Production Example 26 Polyvinyl acetal resin B10 100 40.0 57.99 2.0 Carboxylic acid group 0.01 0.2 72 Production Example 27 Polyvinyl acetal resin B11 500 35.0 62.99 2.0 Carboxylic acid group 0.01 0.2 67

Examples 1 to 23 and Comparative Examples 1 to 15

[0195] A polyvinyl acetal resin, a fibrous carbon material, and a non-aqueous solvent were mixed in accordance with the formulation shown in Table 2 to prepare a resin composition.

[0196] The following non-aqueous solvent, carbon materials, and resins were used.

<Non-Aqueous Solvent>

N-methylpyrrolidone

<Carbon Material>

[0197] MW-1: Multi-walled carbon nanotube (produced by Sigma-Aldrich, average fiber diameter 9 nm, average fiber length 13 ?m, specific gravity 1.8, specific surface area 200 m.sup.2/g, G/D ratio 8.0) [0198] MW-2: Multi-walled carbon nanotube (produced by Cnano Technology, average fiber diameter 10 nm, average fiber length 150 ?m, specific gravity 1.9, specific surface area 3,000 m.sup.2/g, G/D ratio 20) [0199] MW-3: Multi-walled carbon nanotube (produced by Cnano Technology, average fiber diameter 10 nm, average fiber length 15 ?m, specific gravity 1.8, specific surface area 250 m.sup.2/g, G/D ratio 20) [0200] VGCF: Vapor-grown carbon fiber (produced by Showa Denko K.K., average fiber diameter 150 nm, average fiber length 15 ?m, specific gravity 2.1, specific surface area 13 m.sup.2/g, G/D ratio 5.5) [0201] SW-1: Single-walled carbon nanotube (produced by OCSIAL, average fiber diameter 1.2?0.5 nm, average fiber length 4 ?m or greater, specific gravity 1.3, G/D ratio 80) [0202] AB: Particulate acetylene black (produced by Denka Company Limited, average particle size 35 nm, specific surface area 68 m.sup.2/g, G/D ratio 1.27)

<Resin>

[0203] PVDF: Polyvinylidene fluoride (produced by Kureha Corporation, weight average molecular weight 630,000) [0204] PVP: Polyvinylpyrrolidone (produced by Tokyo Chemical Industry Co., Ltd., weight average molecular weight 40,000)

<Evaluation>

[0205] The resin compositions obtained in the examples and the comparative examples were evaluated as follows. Table 2 shows the results.

(1) Average Surface Roughness (Dispersibility)

[0206] The obtained resin composition was applied to a release-treated polyethylene terephthalate (PET) film to a dried thickness of 20 ?m, dried, and separated from the PET film. A sheet was thus prepared.

[0207] The average surface roughness Ra of the obtained sheet was measured in conformity with JIS B 0601 (1994) and evaluated based on the following criteria. [0208] ? (Good): An Ra of less than 5 ?m [0209] ? (Fair): An Ra of 5 ?m or greater and less than 8 ?m [0210] x (Poor): An Ra of 8 or greater

[0211] A low average surface roughness Ra indicates excellent smoothness and excellent dispersibility.

(2) Adhesion

[0212] The obtained resin composition was applied to aluminum foil (thickness 20 ?m) to a dried thickness of 20 ?m and dried to form a specimen including a sheet of the resin composition on the aluminum foil.

[0213] This specimen was cut to a size of 1 cm in length and 2 cm in width. With AUTOGRAPH (produced by Shimadzu Corporation, AGS-J), the sheet was pulled up while the specimen was fixed, and the peeling force (N) necessary to completely separate the sheet from the aluminum foil was measured. The peeling force (N) was then evaluated based on the following criteria. [0214] ? (Good): A peeling force of 8.0 N or greater [0215] ? (Fair): A peeling force of 5.0 N or greater and less than 8.0 N [0216] x (Poor): A peeling force of less than 5.0 N

(3) Application Properties

[0217] The obtained resin composition was applied to a glass plate with a doctor blade and dried in an air circulating oven at 150? C. for five minutes to prepare a coating film. The obtained coating film was visually observed and evaluated based on the following criteria. [0218] ? (Good): No fracture or crack was observed on the coating film surface, and the film thickness was uniform. [0219] ? (Fair): Slight fractures or cracks were observed on the coating film surface. [0220] x (Poor): Fractures or cracks were observed on the coating film surface, and the film thickness varied.

(4) Increase in Viscosity (Dispersion Stability)

[0221] The viscosity of the obtained resin composition (10 parts by weight) was measured using a rheometer (produced by REOLOGICA Instruments, parallel plates with a diameter of 10 mm were used) at a shear rate of 0.1 to 1,000 s.sup.?1. The viscosity at a shear rate 1 s.sup.?1 was taken as the paste viscosity of the sample. The measurement temperature was 20? C.

[0222] The viscosity after the sample was left to stand at 20? C. for one week was also measured. The viscosity increase rate was calculated using the following formula from the viscosity immediately after preparation and the viscosity after one week, and evaluated based on the following criteria.

Viscosity increase rate (%)=(Viscosity after one week/Viscosity immediately after production)?100 [0223] ? (Good): A viscosity increase rate of 150% or less [0224] ? (Fair): A viscosity increase rate of greater than 150% and 300% or less [0225] x (Poor): A viscosity increase rate of greater than 300%

[0226] A low viscosity increase rate indicates excellent dispersion stability.

(5) Electrical Conductivity

[0227] The obtained resin composition was applied to a release-treated polyethylene terephthalate (PET) film to a dried thickness of 20 ?m, dried, and separated from the PET film. A sheet was thus prepared.

[0228] The electrode resistance of the obtained sheet was measured using an electrode resistance meter (produced by Hioki E.E. Corporation) and evaluated based on the following criteria. [0229] ? (Good): An electrode resistance value of less than 100 ?/sq [0230] ? (Fair): An electrode resistance value of 100 ?/sq or greater and less than 200 ?/sq [0231] x (Poor): An electrode resistance value of greater than 200 ?/sq

[0232] A low surface resistance value indicates excellent electron conductivity.

(6) Direct Current Resistance

[0233] To the obtained resin composition were added 10 g of NCM622 (LiNi.sub.0.6Co.sub.0.2Mn.sub.0.2O.sub.2) as a positive electrode active material and 0.2 g of PVDF #7200 (polyvinylidene fluoride, produced by Kureha Corporation), whereby a positive electrode composition was obtained. The obtained positive electrode composition was applied to aluminum foil (thickness 20 ?m) and dried to give a positive electrode sheet having a dried thickness of 80 ?m. A piece (? 11 mm) was punched out from this positive electrode sheet to give a positive electrode layer. Separately, a piece (? 11 mm) was punched out from metal lithium foil having a thickness of 100 ?m to give a negative electrode layer. A solvent mixture (EC:DEC:EMC=3:4:3) containing 1 mol/L of LiPF.sub.6 was used as an electrolyte solution. A positive electrode collector, the positive electrode layer, a porous PP membrane separator (thickness 25 ?m), and the metal lithium foil (negative electrode layer) were stacked in this order. They were compressed using a crimper to prepare a sealed coin cell. The direct current resistance of the obtained coin cell was measured using a charge/discharge tester (produced by Hokuto Denko Corp.).

[0234] The voltage was measured at applied currents of 0.2 C, 1.0 C, 8.0 C, and 16.0 C. The direct current resistance value was calculated using Ohm's law and evaluated based on the following criteria. [0235] ? (Good): A direct current resistance value of 8? or less [0236] ? (Fair): A direct current resistance value of greater than 8? and 15? or less [0237] x (Poor): A direct current resistance value of greater than 15 ?

(7) Capacity Retention

[0238] The capacity retention of the obtained coin cell was measured using a charge/discharge measuring device (produced by Hohsen Corp.). The capacity retention was measured in the voltage range from 0.1 to 1.5 V at an evaluation temperature of 25? C. The percentage of the capacity at the 100th cycle relative to the discharge capacity at the 5th cycle was calculated as the capacity retention (%) and evaluated based on the following criteria. [0239] ? (Good): A capacity retention of 90% or greater [0240] ? (Fair): A capacity retention of 70 or greater and less than 90% [0241] x (Poor): A capacity retention of less than 70%

TABLE-US-00002 TABLE 2 Non-aqueous carbon material composition Evaluation Polyvinyl Non- Carbon material acetal resin aqueous Surface Amount Amount Amount solvent roughness Adhesion Type (g) Type (g) Type (g) (g) (?m) (N) Example 1 MW-1 10 A1 2 188 3.1 ? 6.3 ? Example 2 MW-1 10 A2 5 185 2.8 ? 7.2 ? Example 3 MW-1 10 A3 10 130 2.7 ? 12.9 ? Example 4 MW-1 10 A4 20 70 4.5 ? 13.5 ? Example 5 MW-2 10 A5 2 130 3.1 ? 14.6 ? Example 6 MW-1 10 A6 5 135 4.2 ? 11.1 ? Example 7 MW-1 10 A7 10 130 3.1 ? 11.3 ? Example 8 MW-1 10 A8 20 170 4.4 ? 12.5 ? Example 9 MW-1 10 A9 2 200 4.5 ? 8.6 ? Example 10 MW-2 10 A2 2 288 4.1 ? 12.9 ? Example 11 MW-3 10 A3 2 388 3.1 ? 13.4 ? Example 12 VGCF 10 A1 2 138 3.9 ? 9.9 ? Example 13 SW-1 10 A6 5 585 3.9 ? 15.0 ? Example 14 MW-1 3 AB 7 A1 2 88 4.9 ? 10.0 ? Example 15 SW-1 1 AB 9 A4 10 130 4.3 ? 12.3 ? Example 16 MW-3 7 SW-1 3 A3 5 1290 6.4 ? 13.9 ? Example 17 MW-1 10 A10 2 188 4.4 ? 12.8 ? Example 18 MW-2 10 A11 2 188 3.6 ? 15.1 ? Example 19 MW-3 10 A12 2 188 5.8 ? 13.9 ? Example 20 MW-4 10 A13 2 188 4.1 ? 11.9 ? Example 21 MW-5 10 A14 2 188 4.8 ? 12.1 ? Example 22 MW-6 10 A15 2 188 4.3 ? 13.1 ? Example 23 MW-7 10 A16 2 188 2.9 ? 9.4 ? Comparative Example 1 MW-1 10 B1 2 188 4.6 ? 2.1 x Comparative Example 2 MW-1 10 B2 2 188 11.2 x 15.5 ? Comparative Example 3 MW-1 10 B3 2 188 3.4 ? 9.5 ? Comparative Example 4 MW-1 10 B4 5 185 9.7 x 9.9 ? Comparative Example 5 MW-1 10 B5 2 188 3 ? 10.4 ? Comparative Example 6 MW-1 10 B6 2 188 8.7 x 16.4 ? Comparative Example 7 MW-1 10 B7 2 188 3.1 ? 5.6 ? Comparative Example 8 MW-1 10 0 190 8.2 x 1.8 x Comparative Example 9 AB 10 A2 2 38 4.3 ? 14.3 ? Comparative Example 10 MW-1 10 PVDF 2 88 9.7 x 7.8 ? Comparative Example 11 MW-1 10 PVP 5 185 2.9 ? 3.4 x Comparative Example 12 MW-1 10 B8 2 188 4.5 ? 6.8 ? Comparative Example 13 MW-1 10 B9 2 188 3.7 ? 9.2 ? Comparative Example 14 MW-1 10 B10 2 188 4.1 ? 5.9 ? Comparative Example 15 MW-1 10 B11 2 188 4.5 ? 11.2 ? Evaluation Increase in Electrical Direct current Capacity Application viscosity conductivity resistance retention properties (%) (?/sq) (?) (%) Example 1 ? 187 ? 95 ? 7.94 ? 99 ? Example 2 ? 134 ? 77 ? 9.59 ? 99 ? Example 3 ? 110 ? 87 ? 5.53 ? 88 ? Example 4 ? 128 ? 145 ? 9.17 ? 96 ? Example 5 ? 127 ? 82 ? 6.21 ? 93 ? Example 6 ? 126 ? 82 ? 4.99 ? 98 ? Example 7 ? 148 ? 90 ? 9.52 ? 94 ? Example 8 ? 142 ? 151 ? 9.83 ? 91 ? Example 9 ? 204 ? 76 ? 4.14 ? 98 ? Example 10 ? 125 ? 100 ? 5.96 ? 88 ? Example 11 ? 149 ? 71 ? 6.09 ? 99 ? Example 12 ? 141 ? 86 ? 8.02 ? 89 ? Example 13 ? 112 ? 83 ? 6.29 ? 89 ? Example 14 ? 126 ? 91 ? 9.26 ? 95 ? Example 15 ? 149 ? 86 ? 5.21 ? 99 ? Example 16 ? 125 ? 79 ? 5.12 ? 97 ? Example 17 ? 124 ? 56 ? 8.83 ? 93 ? Example 18 ? 142 ? 75 ? 7.98 ? 93 ? Example 19 ? 115 ? 78 ? 5.82 ? 92 ? Example 20 ? 109 ? 79 ? 6.99 ? 90 ? Example 21 ? 100 ? 89 ? 5.93 ? 98 ? Example 22 ? 110 ? 81 ? 9.34 ? 92 ? Example 23 ? 129 ? 69 ? 9.16 ? 99 ? Comparative Example 1 ? 153 ? 278 x 28.33 x 59 x Comparative Example 2 ? 124 ? 291 x 13.63 ? 67 x Comparative Example 3 ? 349 x 82 ? 9.59 ? 75 ? Comparative Example 4 ? 132 ? 84 ? 12.95 ? 57 x Comparative Example 5 x 133 ? 278 x 13.16 ? 84 ? Comparative Example 6 ? 121 ? 242 x 4.57 ? 63 x Comparative Example 7 ? 411 x 93 ? 25.06 x 50 x Comparative Example 8 x 326 x 88 ? 13.46 ? 54 x Comparative Example 9 ? 139 ? 220 x 25.66 x 43 x Comparative Example 10 ? 138 ? 84 ? 7.29 ? 95 ? Comparative Example 11 ? 363 x 97 ? 4.58 ? 83 ? Comparative Example 12 ? 132 ? 154 ? 14.26 ? 41 x Comparative Example 13 ? 322 x 97 ? 29.74 x 48 x Comparative Example 14 ? 164 ? 89 ? 11.63 ? 42 x Comparative Example 15 ? 113 ? 88 ? 17.89 x 52 x

INDUSTRIAL APPLICABILITY

[0242] The present invention can provide a resin composition that has excellent application properties and excellent adhesion, can achieve high electron conductivity simultaneously with the dispersibility and dispersion stability of fibrous carbon materials, and enables production of lithium secondary batteries having high capacity retention.