JP5002792B2 - Polysaccharide-modified phenolic resin, production method of polysaccharide-modified phenolic resin, resin-coated sand, polysaccharide-modified phenolic resin carbonized material, conductive resin composition, carbon material for electrode, electrode for secondary battery, electric double layer capacitor polarizability electrode - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing polysaccharide-modified phenol resins usable for various applications. <P>SOLUTION: The method of obtaining a resol type polysaccharide-modified phenol resin comprises addition condensation reaction of a phenol, an aldehyde and a polysaccharide in the presence of a reaction catalyst, which phenol resin can be made insoluble and infusible state by heating and is usable for various applications. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a polysaccharide-modified phenolic resin modified with a polysaccharide such as starch and a method for producing the same, and a resin-coated sand, a polysaccharide-modified phenolic resin carbonized material using the polysaccharide-modified phenolic resin, a conductive property, and the like. The present invention relates to a resin composition and an electrode carbon material, and further to an electrode for a secondary battery and an electrode for an electric double layer capacitor formed of an electrode carbon material obtained from a polysaccharide-modified phenol resin.

  The present applicant has previously found that a resin equivalent to a phenol resin can be obtained by reacting cellulose and phenols (see Patent Document 1).

  The invention of Patent Document 1 is obtained by reacting cellulose powder and phenols in the presence of an acid, and the phenolic resin obtained by reacting in this way corresponds to a novolak type, It can be cured by mixing with a curing agent such as hexamethylenetetramine and heating.

Thus, the thing of patent document 1 does not have a self-hardening property, but the phenolic resin obtained by complete | finishing reaction needs to mix | blend and use hardeners, such as hexamethylenetetramine, and a use is restrict | limited. Will be.
JP-A-4-39001

  On the other hand, the present inventor is considering using the same polysaccharide as cellulose instead of cellulose, but when the polysaccharide and phenol are reacted in the same manner as in Patent Document 1, the molecular weight is small, Similarly, a resin having self-curing properties cannot be obtained. Even if the reaction molar ratio of polysaccharides to phenols is increased, the molecular weight increases only slightly, and a resin that becomes insoluble and infusible by curing reaction cannot be obtained just by applying heat. For this reason, the use is limited like the thing of patent document 1, and it had the problem that it cannot apply to various uses.

  The present invention has been made in view of the above points, and aims to provide a polysaccharide-modified phenolic resin that can be used in various applications and a method for producing the same, and the polysaccharide-modified phenol. The purpose is to provide a resin-coated sand, a polysaccharide-modified phenol resin carbonized material, a conductive resin composition, a carbon material for an electrode, an electrode for a secondary battery, and an electric double layer capacitor polarizable electrode using a resin. It is what.

The method for producing a polysaccharide-modified phenolic resin according to claim 1 of the present invention comprises a phenol, an aldehyde, a polysaccharide selected from starch sugar, dextrin, xanthan gum, curdlan, pullulan, cycloamylose, chitin, and starch. Is subjected to an addition condensation reaction in the presence of a basic reaction catalyst .

  According to the present invention, a resole-type polysaccharide-modified phenol resin can be obtained by reacting phenols with aldehydes and polysaccharides, and can be brought into an insoluble and infusible state by heating. It can be used for various purposes. The cured product of the polysaccharide-modified phenolic resin has a characteristic that it exhibits flexibility and is resistant to impact, and when heated, it can be easily pyrolyzed to become brittle and rapidly reduce its strength. In addition, when heated in an oxygen-free atmosphere, the carbide yield decreases and the specific surface area of the carbide can be increased, and it can be used for various applications utilizing these characteristics. It is something that can be done.

  The invention of claim 2 is characterized in that, in claim 1, the addition condensation reaction is carried out in the presence of a dispersing agent with stirring.

  According to this invention, the polysaccharide-modified phenol resin can be prepared in the form of spherical particles.

  The invention of claim 3 is characterized in that, in claim 1 or 2, the addition condensation reaction is stopped in a state where the produced polysaccharide-modified phenol resin has thermosetting properties.

  According to this invention, the polysaccharide-modified phenol resin can be prepared in a state of being uncured and cured by applying heat, and can be used as a molding material or a binder.

  The invention of claim 4 is characterized in that, in claim 1 or 2, the addition condensation reaction is continued after the produced polysaccharide-modified phenol resin is in an insoluble and infusible state.

  According to this invention, since the obtained polysaccharide-modified phenol resin is in a cured state, the polysaccharide-modified phenol resin can be used as a filler or the like.

The polysaccharide-modified phenol resin according to claim 5 of the present invention is obtained by the production method according to claim 3 .

  According to this invention, the obtained polysaccharide-modified phenol resin can be used for various uses such as molding materials and binders as described above.

The polysaccharide-modified phenolic resin according to claim 6 of the present invention is obtained by the production method according to claim 4 .

  According to this invention, the obtained polysaccharide-modified phenol resin can be used for various uses such as a filler as described above.

The invention of claim 7 is characterized in that the polysaccharide-modified phenolic resin of claim 5 is heat-treated into an insoluble and infusible state.
The invention of claim 8 is characterized in that, in any of claims 5 to 7, the content of polysaccharide is 1.0 to 60% by mass.

  According to the present invention, the polysaccharide-modified phenol resin can be given necessary and sufficient characteristics due to polysaccharide modification.

The resin-coated sand according to claim 9 of the present invention is characterized in that the polysaccharide-modified phenolic resin according to claim 5 is coated on the surface of a refractory aggregate.

  According to the present invention, the resin-coated sand polysaccharide-modified phenol resin can be used as a binder for molding a mold.

The polysaccharide-modified phenolic resin carbonized material according to claim 10 of the present invention is characterized in that the polysaccharide-modified phenolic resin according to claim 6 or 7 is carbonized by heat treatment in a non-oxidizing atmosphere. It is what.

  According to the present invention, the polysaccharide-modified phenol resin is carbonized to form a carbonized material, which can be used for applications such as conductive fillers and electrode materials.

A conductive resin composition according to an eleventh aspect of the present invention is characterized in that the polysaccharide-modified phenolic resin carbonized material according to the tenth aspect is blended with a resin as a conductive filler.

  According to the present invention, it is possible to mold a molded article having excellent conductivity using a polysaccharide-modified phenol resin carbonized material as a conductive filler.

An electrode for a secondary battery according to a twelfth aspect of the present invention is formed using the polysaccharide-modified phenol resin carbonized material according to the tenth aspect as an electrode material.

  According to this invention, an electrode excellent in electrode characteristics can be formed using a polysaccharide-modified phenol resin carbonized material.

A carbon material for an electrode according to claim 13 of the present invention is characterized in that the polysaccharide-modified phenol resin carbonized material according to claim 10 is activated.

  According to this invention, the specific surface area and the pore volume can be increased by activating the polysaccharide-modified phenolic resin carbonized material, and an electrode having excellent electrode characteristics can be formed.

An electric double layer capacitor polarizable electrode according to claim 14 of the present invention is characterized in that the polysaccharide-modified phenol resin carbonized material according to claim 10 is used as an electrode material.

  According to the present invention, an electric double layer capacitor polarizable electrode having excellent electrode characteristics can be formed using a polysaccharide-modified phenol resin carbonized material.

An electric double layer capacitor polarizable electrode according to a fifteenth aspect of the present invention is characterized by being formed using the carbon material for an electrode according to the thirteenth aspect as an electrode material.

  According to the present invention, an electric double layer capacitor polarizable electrode having a high discharge / charge capacity can be formed by using a polysaccharide-modified phenol resin carbonized material whose specific surface area and pore volume are increased by activation treatment. Is.

According to the present invention, phenols, aldehydes, and polysaccharides selected from starch sugar, dextrin, xanthan gum, curdlan, pullulan, cycloamylose, chitin, and starch are subjected to addition condensation in the presence of a basic reaction catalyst. By reacting, a resol-type polysaccharide-modified phenol resin can be obtained, and by heating, it can be made insoluble and infusible, resin-coated sand, carbonized material, conductive resin composition, electrode It can be used for various applications such as carbon materials for use, electrodes for secondary batteries, and electric double layer capacitor polarizable electrodes.

  Hereinafter, the best mode for carrying out the present invention will be described.

  The polysaccharide-modified phenolic resin of the present invention can be obtained by subjecting phenols, aldehydes, and polysaccharides to an addition condensation reaction in the presence of a basic reaction catalyst.

  As phenols used in the reaction, phenol derivatives can be used in addition to phenol. Examples of phenol derivatives include trifunctional compounds such as m-cresol, resorcinol and 3,5-xylenol, tetrafunctional compounds such as bisphenol A, bisphenol S, and dihydroxydiphenylmethane, o-cresol, p-cresol, List bifunctional o- or p-substituted phenols such as p-ter-butylphenol, p-phenylphenol, p-cumylphenol, p-nonylphenol, 2,4- or 2,6-xylenol In addition, halogenated phenols substituted with chlorine or bromine can also be used. As phenols, one type can be selected and used, or a plurality of types can be mixed and used.

  As the aldehydes used in the reaction, formalin, which is a formaldehyde aqueous solution, is optimal, but paraformaldehyde, acetaldehyde, benzaldehyde, trioxane, tetraoxane, and other aldehydes can be used. It is also possible to use those in which part or most of them are replaced with furfural or furfuryl alcohol.

As also polysaccharides, starch sugar, dextrin, xanthan gum, curdlan, pullulan, cycloamylose, chitin, in include Npun, select one of these, or in combination of plural kinds, it is used it can. Starches include potato starch, corn starch, tapioca starch, wheat starch, rice starch, etc., and hydroxypropyl starch, carboxymethyl starch, cationic starch, acetate starch, octenyl succinate, Acid starch, glycerol starch, grafted starch, or roasted white dextrin, yellow dextrin, British gum, maltodextrin, soluble starch, unmodified pregelatinized starch, modified pregelatinized starch, and the like can also be used.

Further, as a reaction catalyst used for the addition condensation reaction, a basic substance that reacts phenols and aldehydes to form a = NCH ₂ -bond between the benzene nucleus and the benzene nucleus, such as hexamethylenetetramine, ammonia, Primary and secondary amines such as methylamine, dimethylamine, ethylenediamine, and monoethanolamine can be used. Also, alkali metal oxides such as sodium, potassium, lithium, hydroxides, carbonates, or alkaline earth metal oxides such as calcium, magnesium, barium, hydroxides, carbonates, tertiary amine compounds, etc. Can also be mentioned. Specific examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, calcium hydroxide, magnesium hydroxide, barium hydroxide, calcium carbonate, magnesium oxide, calcium oxide, trimethylamine, triethylamine, triethanol. Amines, 1,8-diazabicyclo [5,4,0] undecene-7, and the like.

  The blending amount of each of the above components is such that the blending amount of the aldehydes with respect to the phenols is set in a range of 1.0 to 3.0 moles with respect to 1 mole of the phenols, and 100 parts by weight of the phenols. On the other hand, the range of 1-70 mass parts of polysaccharides is preferable. Moreover, although the compounding quantity of a reaction catalyst changes greatly with the kind of reaction catalyst, the range of 0.05-10 mass% with respect to phenols is preferable.

  As described above, a resol-type polysaccharide-modified phenol resin can be prepared. In addition, when preparing a polysaccharide-modified phenol resin having spherical particles, the above addition condensation reaction is performed with a dispersant added. The dispersant acts as a kind of emulsifier, and examples thereof include gum arabic, polyvinyl alcohol, glue, guar gum, tara gum, gatter gum, carboxymethyl cellulose, hydroxyethyl cellulose, solubilized starch, agar, and sodium alginate. These can be used alone or in combination of two or more. Among these, gum arabic, tara gum, and polyvinyl alcohol can be preferably used. The amount of the dispersant added varies greatly depending on the emulsifying effect of the dispersant and is not particularly limited, but is preferably in the range of 0.1 to 10.0% by mass, particularly 0.5 to The range of 7.0% by mass is more preferable.

  The addition condensation reaction performed by adding a dispersant is performed while stirring in an amount of water sufficient to stir the reaction system, and the reaction solution is transparent at the beginning of the reaction, but the addition condensation reaction proceeds. The condensation reaction product begins to separate from the water in the system, which aggregates into a spherical shape by the action of the dispersant and precipitates in the reaction system. Then, after the reaction has proceeded to the desired extent, cooling and stirring are stopped, it settles in the water of the reaction system and separates from the water. The material thus settled is a microspherical water-containing granular material, but it can be easily separated from water by filtration. By drying this, a spherical polysaccharide-modified phenolic resin is obtained. Can be obtained.

  In the polysaccharide-modified phenol resin obtained as described above, the content of the polysaccharide is preferably in the range of 1.0 to 60% by mass in order to obtain necessary and sufficient characteristics due to polysaccharide modification. For example, when a polysaccharide-modified phenol resin is used as the binder of the resin-coated sand as will be described later, when the content of the polysaccharide is less than 1.0% by mass, it becomes impossible to mold a mold having good disintegration. When the saccharide content exceeds 60% by mass, the bending strength of the mold becomes insufficient, and there is a possibility that bending or the like may occur when the molten metal is cast, making it impossible to manufacture a good casting. Alternatively, when used as a carbon material as described later, when the polysaccharide content is less than 1.0% by mass, the specific surface area increases little, and when the polysaccharide content exceeds 60% by mass, the specific surface area is Although increasing, the carbide becomes brittle and it becomes difficult to obtain a good electrode.

  The polysaccharide-modified phenolic resin has thermosetting properties because the molecular weight of the resin is increased because the phenols, aldehydes, and polysaccharides are condensed, and the resin is prepared into a resol type. . For this reason, the polysaccharide-modified phenol resin which is uncured and has thermosetting property can be obtained by stopping the addition condensation reaction in a state where the resin has thermosetting property.

  This uncured and thermosetting polysaccharide-modified phenolic resin can be used as a molding material because it is melted and cured by heating. The molding can be performed by any molding method such as injection molding in which a polysaccharide-modified phenol resin is injected into a mold, or compression molding in which the mold is filled and heated and pressurized. The heating at this time is preferably performed with the mold temperature set in the range of 130 to 250 ° C., and the pressing is preferably performed at a surface pressure in the range of 10 to 200 MPa.

  Further, a resin-coated sand can be obtained using this uncured and thermosetting polysaccharide-modified phenol resin. The resin-coated sand is produced, for example, by heating a refractory aggregate for a mold such as silica sand to about 150 ° C., and the heated refractory aggregate is uncured and thermosetting polysaccharide-modified phenolic resin 0.8-3. About 0.0% by mass can be added, kneaded and then cooled, and a smooth resin-coated sand can be obtained.

  This resin-coated sand can form a mold such as a shell mold using a polysaccharide-modified phenol resin coated on a refractory aggregate as a binder. Here, for example, in the automobile industry, in order to reduce weight and reduce fuel consumption, casting is often performed using lighter aluminum or magnesium alloy than cast iron, but the melting temperature of these metals is 600 to 700. As low as ℃. Since phenolic resins that have been widely used for resin-coated sands have high heat resistance, molds made with resin-coated sands that use such phenolic resins as binders are sufficient to use phenolic resin binders at the temperature of the molten metal. It cannot be pyrolyzed, and there is a problem in the mold disintegration after casting. On the other hand, the polysaccharide-modified phenolic resin of the present invention can lower the thermal decomposition temperature by polysaccharide modification. By using this polysaccharide-modified phenolic resin as a binder for resin-coated sand, the disintegration is good. A mold can be formed.

  Further, in preparing the polysaccharide-modified phenol resin as described above, the addition condensation reaction is continued until the produced polysaccharide-modified phenol resin becomes insoluble and infusible, and then is completely cured. The polysaccharide-modified phenolic resin can be obtained. In obtaining a fully cured polysaccharide-modified phenol resin, the addition condensation reaction is continued until the polysaccharide-modified phenol resin thus produced becomes insoluble and infusible. After preparing an uncured polysaccharide-modified phenolic resin, it may be heat-treated to completely cure the polysaccharide-modified phenolic resin.

  The polysaccharide-modified phenolic resin that has been completely cured to be insoluble and infusible can be used, for example, as a filler. In particular, a polysaccharide-modified phenol resin prepared in a spherical shape by performing an addition condensation reaction in the presence of a dispersant can be used as a filler excellent in fluidity.

  Further, the polysaccharide-modified phenol resin carbonized material can be obtained by heat-treating the polysaccharide-modified phenol resin in a completely cured state in a non-oxidizing atmosphere to carbonize the polysaccharide-modified phenol resin. The non-oxidizing atmosphere is not particularly limited as long as the polysaccharide-modified phenolic resin is not oxidized. For example, an inert gas atmosphere such as argon, helium, or nitrogen gas can be set. The heat treatment conditions are preferably set to 400 to 3000 ° C. and about 1 to 100 hours in order to calcine and carbonize the polysaccharide-modified phenol resin.

  This polysaccharide-modified phenolic resin carbonized material can be used as a conductive filler, and a conductive resin composition can be obtained by blending a polysaccharide-modified phenolic resin carbonized material with a resin. In particular, a polysaccharide-modified phenol resin carbonized material obtained by carbonizing a polysaccharide-modified phenol resin prepared in a spherical shape by performing an addition condensation reaction in the presence of a dispersant can be used as a conductive filler having excellent fluidity. It can be done.

  Examples of the resin of the conductive resin composition include polyphenylene sulfide resin, polyphenylene ether resin, liquid crystal polymer, polystyrene resin, ABS resin, polyacetal resin, polycarbonate resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, polyamide resin, polystyrene resin, etc. Thermosetting resins such as phenolic resins, unsaturated polyester resins, and epoxy resins can be used. Although the compounding quantity of the polysaccharide modification phenol resin carbonization material mix | blended as an electroconductive filler can be set arbitrarily, 0.01-1.5 is a polysaccharide modification phenol resin carbonization material with respect to the resin 1 by mass ratio. It is preferable to set a range of about.

  By molding the conductive resin composition thus prepared by an arbitrary method such as injection molding or compression molding, it is possible to manufacture parts of electric / electronic devices having high conductivity.

  In addition, when the polysaccharide-modified phenolic resin is heat-treated in a non-oxidizing atmosphere as described above, the polysaccharide-modified phenolic resin undergoes thermal decomposition when exposed to heat, and the decomposition product that has become a low molecular weight substance is present. Volatilization occurs and the traces become voids, so that a large number of pores are formed in the particles of the polysaccharide-modified phenol resin carbonized material. In particular, the yield of the carbide of the polysaccharide-modified phenol resin is smaller than that of a general phenol resin, and the pyrolysis gas easily escapes accordingly, and the pore volume is large and the specific surface area is large. For this reason, the polysaccharide modified phenolic resin carbonized material particles can also exhibit the same effect as activated carbon.

  Therefore, this polysaccharide-modified phenol resin carbonized material can be used as a carbon material for forming an electrode of a secondary battery such as a negative electrode of a lithium ion secondary battery. In producing an electrode such as a negative electrode of a lithium ion secondary battery using a polysaccharide-modified phenol resin carbonized material as an electrode carbon material, for example, a polysaccharide-modified phenol resin carbonized material is dispersed in a solvent together with a binder. The slurry can be formed into a slurry, applied to a metal foil such as a copper foil, dried, press-molded, and the like.

  Furthermore, this electrode can be used as a polarizable electrode to form an electric double layer capacitor that forms an electric double layer formed at the interface of the electrolytic solution.

  Thus, by producing the electrode for a secondary battery or the electric double layer capacitor polarizable electrode using the polysaccharide-modified phenol resin carbonized material of the present invention, the secondary battery or the electric double layer having a high charge / discharge capacity. A capacitor can be obtained.

  Here, as the polarizable electrode of the electric double layer capacitor, activated carbon having a large specific surface area is used as an electrode material so that many ions can be adsorbed, and the polysaccharide-modified phenolic resin carbonized material according to the present invention is also described above. Thus, it has the pore which has the same effect as activated carbon by carbonizing the polysaccharide modified phenolic resin by heat treatment, and has a large specific surface area and pore volume.

  However, the pores generated by the carbonization of the polysaccharide-modified phenol resin are not sufficiently large in specific surface area and pore volume, and are not always satisfactory. Therefore, in the present invention, the polysaccharide-modified phenolic resin carbonized material is activated by a gas phase activation method using water vapor or carbon dioxide, a chemical solution activation method using molten potassium hydroxide, etc., and the unit mass of the polysaccharide-modified phenolic resin carbonized material. A carbon material for an electrode having an increased physical surface area and pore volume and improved physical and chemical adsorption performance is manufactured. An electric double layer capacitor having a high charge / discharge capacity can be obtained by producing an electric double layer capacitor polarizable electrode using the carbon material for an electrode.

  Next, the present invention will be specifically described with reference to examples.

(Example 1: Production of uncured starch-modified phenol resin)
In a reaction vessel, phenol is 400 parts by weight, starch is 100 parts by weight of cross-linked starch “PB-7000” manufactured by Nissho Kagaku Co., Ltd., 405 parts by weight of 37% by weight formalin, 500 parts by weight of water, basic As a reaction catalyst, 50 parts by mass of hexamethylenetetramine was charged, and the mixture was stirred and heated for about 60 minutes until the internal temperature reached 70 ° C., and an addition condensation reaction was carried out at the internal temperature of 70 ° C. for 6 hours.

  Next, vacuum degassing was started at 0.01 MPa (100 Torr), and after 90 ° C., the reaction product was discharged into a stainless steel vat and cooled.

  When the softening point and gelation time of the obtained resol-type starch-modified phenol resin were measured according to JIS K 6910, the softening point was 76.8 ° C. and the gelation time at 150 ° C. was 98 seconds. The amount of fixed carbon was 47.6% by mass.

(Example 2: Production of uncured spherical starch-modified phenol resin)
In Example 1 above, an addition condensation reaction was performed in the same manner as in Example 1 except that 10 parts by mass of Kuraray Co., Ltd. polyvinyl alcohol “PVA-224” was added as a dispersant.

  And it cooled without carrying out pressure reduction liquid removal, it filtered by Nutsche, the spherical product was taken out, and the spherical starch modified phenol resin was obtained by air-drying on the paper mounted on the vat for one week.

  The resulting spherical starch-modified phenol resin had a softening point of 75.2 ° C., a gel time at 150 ° C. of 113 seconds, and a fixed carbon content of 43.8% by mass. The average particle size was 33 μm.

(Example 3: Production of cured starch-modified phenolic resin)
The starch-modified phenolic resin obtained in Example 1 above is spread on a stainless steel vat, placed in a drier previously set at 100 ° C., and cured for 10 hours, and further cured at 120 ° C. for 5 hours. By doing so, the starch-modified phenolic resin was cured.

  Next, after cooling, it was pulverized with a hammer crusher equipped with a 0.5 mm net to obtain a starch-modified phenol resin cured in an insoluble and infusible state.

(Example 4: Production of cured spherical starch-modified phenol resin)
In Example 2 described above, the addition condensation reaction was carried out at the temperature for 4 hours while stirring and was brought to the boiling reflux state for 60 minutes. In other respects, a spherical starch-modified phenol resin cured in an insoluble and infusible state was obtained in the same manner as in Example 2 above.

(Comparative Example 1: Production of uncured phenol resin)
A reaction vessel was charged with 660 parts by weight of phenol, 712 parts by weight of formalin having a concentration of 37% by weight, 75 parts by weight of hexamethylenetetramine, and 120 parts by weight of water, and the temperature was raised to 70 ° C. in about 60 minutes. The reaction was performed for 4 hours.

  Next, vacuum degassing was started at 0.01 MPa (100 Torr), and after 90 ° C., the reaction product was discharged into a stainless steel vat and cooled.

  The resulting resol-type phenol resin had a softening point of 77.3 ° C. and a gel time at 150 ° C. of 93 seconds. The amount of fixed carbon was 51.2% by mass.

(Comparative Example 2: Production of uncured spherical phenol resin)
In a reaction vessel equipped with a stirrer, 450 parts by mass of phenol, 460 parts by mass of 37% by weight formalin, 50 parts by mass of hexamethylenetetramine, 4.5 parts by mass of gum arabic as a dispersant, and 120 parts by mass of water The mixture was charged and stirred for about 60 minutes, and the temperature was raised to 80 ° C., and the addition condensation reaction was carried out for 3 hours as it was.

  Next, after cooling until the internal temperature of the reaction vessel reaches 30 ° C., the product is filtered with Nutsche, and the spherical product is taken out and air-dried on paper placed on a bat for one week to obtain a spherical phenol resin. It was.

  The obtained spherical phenol resin had a softening point of 76.5 ° C., a gelation time at 150 ° C. of 98 seconds, and a fixed carbon content of 52.3 mass%. The average particle size was 43 μm.

(Comparative Example 3: Production of cured phenolic resin)
The phenol resin obtained in the above Comparative Example 1 was heated and cured in the same manner as in Example 3 and pulverized to obtain a phenol resin cured in an insoluble and infusible state.

(Comparative Example 4: Production of cured spherical phenol resin)
In the above Comparative Example 2, the addition condensation reaction was brought to a boiling reflux state with stirring for 60 minutes and carried out at this temperature for 4 hours to obtain a spherical phenol resin cured in an insoluble and infusible state. The average particle diameter of the obtained spherical phenol resin was 48 μm.

(Examples 5-6)
Add 30 kg of flattered silica sand heated to 145 ° C. to a whirl mixer, add 450 g of uncured starch-modified phenolic resin obtained in Example 1 or Example 2, knead for 30 seconds, and then add 450 g of water. The mixture was kneaded until the sand grains collapsed. Next, after adding 30 g of calcium stearate and kneading for 30 seconds, this was discharged from a whirl mixer, aerated and cooled to obtain a resin-coated sand in which the surface of silica sand was coated with a starch-modified phenol resin.

  This resin-coated sand had a starch-modified phenolic resin coating amount of 1.5% by mass with respect to silica sand, and was excellent in fluidity.

(Comparative Examples 5-6)
Resin-coated sand in which the surface of silica sand was coated with phenol resin was obtained in the same manner as in Examples 5-6 except that the uncured phenol resin obtained in Comparative Example 1 or Comparative Example 2 was used. This resin-coated sand had a phenol resin coating amount of 1.5% by mass with respect to silica sand.

  About the resin coated sand obtained in Examples 5-6 and Comparative Examples 5-6 as described above, the fusion point, bulk specific gravity, flow-down time, and angle of repose were measured. The fusion point was measured according to JACT test method C-1, and the bulk specific gravity was measured according to JIS K 6721 using a bulk specific gravity measuring instrument A type manufactured by Kyowa Rika Kogyo Co., Ltd. The flow-down time was measured according to JACT test method S-5 using a Ford cup defined in JIS K5402. The angle of repose was measured using an “AOD powder property measuring instrument” manufactured by Tsutsui Riken Kikai Co., Ltd.

  Moreover, using the resin-coated sand obtained in Examples 5 to 6 and Comparative Examples 5 to 6, test pieces were prepared according to the bending strength test method of JIS K 6910, and the bending strength was measured. Then, this unfired bending strength is compared with the bending strength after firing by exposure to heat, and (the bending strength after firing / the bending strength before firing) as the strength retention, Disintegration was evaluated. Firing is performed by wrapping the test piece prepared for measuring the bending strength as described above in aluminum foil and heat-treating it in an electric furnace set at 350 ° C. or 400 ° C. for 30 seconds or 60 seconds. Later, the bending strength was measured.

  As seen in Table 1, it is confirmed that the examples 5 and 6 have low retention after firing and good mold disintegration.

(Example 7: Production of starch-modified phenolic resin carbonized material)
The cured starch-modified phenolic resin obtained in Example 3 was baked by heat treatment under a nitrogen atmosphere at a heating rate of 100 ° C./h up to 800 ° C. and maintained at 800 ° C. for 3 hours, Starch-modified phenolic resin carbonized particles were obtained. The yield of the starch-modified phenolic resin carbonized material was 45.8% by mass.

(Example 8: Production of starch-modified phenolic resin carbonized material)
Baking was performed in the same manner as in Example 7 except that the cured starch-modified phenol resin obtained in Example 4 was used, and particles of the starch-modified phenol resin carbonized material were obtained. The yield of the starch-modified phenolic resin carbonized material was 43.3% by mass.

(Comparative Example 7: Production of phenolic resin carbonized material)
Baking was performed in the same manner as in Example 7 except that the cured phenol resin obtained in Comparative Example 3 was used, thereby obtaining particles of a phenol resin carbonized material. The yield of this phenol resin carbonized material was 51.3% by mass.

(Comparative Example 8: Production of phenol resin carbonized material)
Baking was performed in the same manner as in Example 7 except that the cured phenol resin obtained in Comparative Example 4 was used, thereby obtaining particles of a phenol resin carbonized material. The yield of this phenol resin carbonized material was 52.1% by mass.

(Examples 9 to 10, Comparative Examples 9 to 10)
40 parts by mass of the carbonized material obtained in Examples 7 to 8 and Comparative Examples 7 to 8 above and 60 parts by mass of polyphenylene ether resin (“Iupiace AH8” manufactured by Mitsubishi Engineering Plastics) were dry blended. Then, it melt-kneaded uniformly at 320 degreeC using the laboratory test mill. And after cooling and solidifying this, the conductive resin composition was obtained by grind | pulverizing.

  Next, this conductive resin composition was injection-molded to produce a resin molded body having a length and width of 100 mm and a thickness of 2 mm. About this resin molding, a resistivity was measured based on JISK7194, and the result is shown in Table 2.

  As seen in Table 2, it is confirmed that each example has a low resistivity and excellent conductivity.

(Examples 11-12 and Comparative Examples 11-12)
3 g of a binder prepared by dissolving 10% by mass of polyvinylidene fluoride in N-methylpyrrolidone was added to 3 g of the carbonized material obtained in Examples 7 to 8 and Comparative Examples 7 to 8, and this was mixed to form a slurry. did. Then, this slurry was applied to a circular copper foil having a thickness of 20 μm and a diameter of 12 mm, vacuum-dried at 130 ° C. for 10 hours, and then press-molded under reduced pressure to produce an electrode.

  The charge / discharge capacity of the electrodes obtained in Examples 11 to 12 and Comparative Examples 11 to 12 was measured. A two-electrode cell was used for charge / discharge capacity measurement. Metal lithium was used for the counter electrode, a carbon material was used for the working electrode, and a polypropylene porous membrane was used for the separator. As the electrolytic solution, an ethylene carbonate / diethylene carbonate solution (50/50% by mass) of 1 molar lithium perchlorate was used. Charging / discharging was carried out by flowing a constant current of 25 mA / g between the positive electrode and the negative electrode, and the change over time in the potential difference between the two electrodes was measured to determine the discharge time and the charge time. The discharge capacity was determined by integrating the discharge time or the charge time with the current density because the current density was constant. In addition, the discharge capacity was determined in the same manner even after 20 cycles of charging and discharging were repeated with this discharge as one cycle. The results are shown in Table 3.

  As can be seen from Table 3, it is confirmed that each of the examples has a large discharge capacity, and even when charging and discharging are repeated, the decrease in the discharge capacity is small and the battery life can be extended.

(Examples 13-14 and Comparative Examples 13-14)
The carbonized materials obtained in Examples 7 to 8 and Comparative Examples 7 to 8 were activated by treating them at 850 ° C. for 2 hours in a mixed gas atmosphere of a rotary kiln furnace circulated at a water flow rate of 5 ml and a nitrogen flow rate of 2 l / min. Activated carbon was obtained. About the obtained activated carbon, the specific surface area was measured with the specific surface area measuring apparatus "NOVE2000" by QUANTACHROME by the BET multipoint method, and the packing density was measured based on JISK1474. The results are shown in Table 4.

  Moreover, after taking 1 mass part of activated carbon obtained as mentioned above and adding a carbon nanotube (Showa Denko Co., Ltd. product "VGCF-H") in the ratio of 1.0 mass% with respect to activated carbon, it is 30 mass. The mixture was impregnated with 1.5 parts by mass of sulfuric acid having a concentration of% and kneaded to obtain a paste. An electric double layer capacitor was manufactured by applying 0.9 g of this paste to each of two circular platinum electrodes having a diameter of 30 mm and pressing the electrodes together through a polypropylene separator.

  Then, after charging the electric double layer capacitors of Examples 13 to 14 and Comparative Examples 13 to 14 at 0.9 V for 1 hour, a discharge current of 10 mA was discharged, and the voltage of the electric double layer capacitor was 0.54 to 0.0. The time required to drop to 45 V was measured, and the weight capacitance, which is the capacitance per unit time, and the capacitance capacitance, which is the capacitance per unit volume, were determined. The results are shown in Table 4.

  As can be seen in Table 4, it is confirmed that each example has a large specific surface area and a large capacitance.

Claims (15)

It is characterized by an addition condensation reaction of phenols, aldehydes, and polysaccharides selected from starch sugar, dextrin, xanthan gum, curdlan, pullulan, cycloamylose, chitin, and starch in the presence of a basic reaction catalyst. A method for producing a polysaccharide-modified phenolic resin.   The method for producing a polysaccharide-modified phenol resin according to claim 1, wherein the addition condensation reaction is carried out in the presence of a dispersant while stirring.   The method for producing a polysaccharide-modified phenol resin according to claim 1 or 2, wherein the addition condensation reaction is stopped in a state where the produced polysaccharide-modified phenol resin has thermosetting properties.   The method for producing a polysaccharide-modified phenol resin according to claim 1 or 2, wherein the addition condensation reaction is stopped after the produced polysaccharide-modified phenol resin is continued until it is in an insoluble and infusible state. A polysaccharide-modified phenolic resin obtained by the production method according to claim 3 . A polysaccharide-modified phenolic resin obtained by the production method according to claim 4 . A polysaccharide-modified phenolic resin obtained by heat-treating the polysaccharide-modified phenolic resin according to claim 5 into an insoluble and infusible state. The polysaccharide-modified phenol resin according to any one of claims 5 to 7, wherein the polysaccharide content is 1.0 to 60 mass%. 6. A resin-coated sand, wherein the polysaccharide-modified phenolic resin according to claim 5 is coated on the surface of a refractory aggregate.   A polysaccharide-modified phenolic resin carbonized material, wherein the polysaccharide-modified phenolic resin according to claim 6 or 7 is carbonized by heat treatment in a non-oxidizing atmosphere. A conductive resin composition comprising the polysaccharide-modified phenolic resin carbonized material according to claim 10 blended with a resin as a conductive filler. An electrode for a secondary battery, wherein the polysaccharide-modified phenolic resin carbonized material according to claim 10 is used as an electrode material. 11. A carbon material for an electrode, wherein the polysaccharide-modified phenolic resin carbonized material according to claim 10 is activated. An electric double layer capacitor polarizable electrode, wherein the polysaccharide-modified phenolic resin carbonized material according to claim 10 is used as an electrode material. An electric double layer capacitor polarizable electrode, wherein the carbon material for an electrode according to claim 13 is used as an electrode material.