JP2000160143A - Organic electroconductive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an organic electroconductive material capable of manifesting heat resistance, adhesion to a base material, transparency and electroconductivity by including a new compound where sulfonic acid groups are introduced into a terpene material. SOLUTION: This organic electroconductive material includes at least one of new compounds of formulas I-VII [wherein, X1-X4 are each H, a 1-5C alkyl or hydroxyl; Ya and Yb are each proton (H+), a positive ion from a basic compound; (n) is 0-15; (r)+(s)=0.1-2; (m) is 0-30; and R1 and R2 are each a alkyl or H]. The compounds of formula I and II are obtained by reacting a monoterpene compound (e.g. α-pinene) with a phenolic compound (e.g. phenol), followed by sulfonation. Their sulfonates are obtained by the acid-base reaction of the sulfonated product with a basic compound. Materials suitable for improving performance such as electroconductivity, heat resistance and waterproof can be provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic conductive material having a terpene skeleton, which is useful in electrode materials, capacitors, electromagnetic wave shielding materials, antistatic materials, display elements, electronic devices, conductive pastes, and the like. The present invention relates to an organic conductive material used for removing charges from fibers, paper, and composite articles thereof and preventing the occurrence of static electricity.

[0002]

2. Description of the Related Art Conventionally, for example, surfactants and polymers having a π-electron conjugated system have been proposed as organic conductive materials for the purpose of preventing static electricity. In general, plastic products such as molded products and films of various plastics have high electrical insulation properties. During processing or use, dust and dust adhere to the product due to static electricity, or discharge occurs, resulting in product contamination, functional deterioration or damage. And so on. In order to prevent such an electrostatic damage, an antistatic treatment is performed by forming a conductive film on a plastic surface. In many cases, such a coating is required to have no coloring and to be transparent so as not to impair the texture and color of the plastic product.

[0003]

When an antistatic agent of various surfactant types such as anionic, cationic and nonionic is used as a conductive material, the coating film is colorless and transparent. Activator is an ion conduction mechanism that leaks electric charge by trapping moisture in the air, so the antistatic performance is highly dependent on humidity, and the performance deteriorates significantly in a low humidity environment where static electricity is most likely to occur There's a problem.

One of the materials for solving such a problem is a conductive polymer. Conductive polymer is π
Since it is a polymer with an electron conjugated system and an electron conductive mechanism, it is a material that can exhibit antistatic performance even in a low humidity environment, but light absorption due to the molecular structure of the conjugated system is For this reason, coloring is inevitable and there is a problem that the appearance of the product is significantly impaired depending on the use.

There is also a method of dispersing conductive fine particles in a binder resin having good adhesion to a substrate.
Even when conductive fine particles are dispersed, the antistatic mechanism is electronically conductive, so it can exhibit antistatic performance even in a low humidity environment.However, in order to obtain sufficient antistatic performance, In addition, it is necessary to increase the concentration of the conductive fine particles in the coating, and therefore, there is a drawback that haze based on coloring and light scattering of the coating by the conductive fine particles occurs, thereby impairing the transparency of the product. Accordingly, an object of the present invention is to provide a novel organic conductive material having excellent conductivity and transparency.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to overcome the drawbacks of the prior art, and as a result, by introducing a sulfone group into some compounds having a terpene skeleton, the sulfonated terpene is introduced. The present inventors have found that a system compound has excellent conductivity, and have reached the present invention. That is, the present invention provides an organic conductive material comprising at least one compound represented by the following general formulas 1 to 7.

[0007]

[0008] (X ₁ , X ₂ , X ₃ and X ₄ in the above formula are the same or different,
It represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a hydroxyl group. Ya, Yb and Yc are the same or different and represent a proton (H ⁺ ) or a positive ion of a basic compound;
Represents an integer of １５15. The sum of r and s represents a numerical value of 0.1 to 2, m represents an integer of 0 to 30, and R ₁ and R ₂ represent an alkyl group or a hydrogen atom independently or bonded to each other.
p represents a numerical value of 0.1 to 10, and q represents a numerical value of 1 to 20)

[0009]

Next, the present invention will be described in more detail with reference to preferred embodiments. As a terpene compound as a raw material for producing the organic conductive material of the present invention, a monoterpene compound having 10 carbon atoms is generally used. The monoterpene compound may be a monocyclic terpene compound or a bicyclic terpene compound. Specifically, for example, α-pinene, β-pinene, dipentene, limonene, α-pherandrene, β-pherandrene, α-terpinene, γ-
Terpinene, terpinolene, 1,8-cineole, 1,
Examples thereof include, but are not limited to, 4-cineole, α-terpineol, β-terpineol, γ-terpineol, and paramentadienes. These monoterpene compounds are generally raw materials that can be industrially obtained as components of plant essential oils and rosins.

The phenols used as a raw material for producing the organic conductive compounds represented by the above-mentioned general formulas 1 to 4, 6 and 7 include phenol or an alkyl group having 1 to 5 carbon atoms and / or a hydroxyl group. A phenol compound substituted by Specifically, examples of the phenol compound to which an alkyl group having 1 to 5 carbon atoms is added include o-cresol, p-cresol, m-cresol, 2,6-
Xylenol, 2,4-xylenol, propylphenol, o-ethylphenol, m-ethylphenol,
p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol,
Examples include compounds such as 3,6-xylenol and p-phenylphenol, but are not limited to these compounds.
Examples of the hydroxyl-substituted phenol compound include compounds such as catechol, resorcin, hydroquinone, and pyrogallol, but are not limited to these compounds.

Examples of the alkyl sultone used as a raw material for producing the compounds having organic conductivity represented by the general formulas 3 and 4 include 1,3-propane sultone and 1,4-butane sultone. But
It is not limited to these compounds. The above alkyl sultones have 0 to 15 carbon atoms, preferably 1 to 8 carbon atoms.

The compounds represented by the above general formulas 1 and 2 in which one molecule of a terpene is reacted with two molecules of a phenol and a sulfonic acid group is further introduced are novel compounds. For example, a monoterpene compound is reacted with a phenol. And further sulfonated. The sulfonate is produced by further subjecting the sulfonated product to an acid-base reaction with a basic compound.

The reaction between one molecule of terpene and two molecules of phenols is, for example, using 0.5 to 20 moles, preferably 2 to 12 moles of phenols per mole of monoterpene, in the presence of an acidic catalyst. At a temperature of 40-160 ° C.
The reaction is carried out for 10 to 10 hours. Examples of the acidic catalyst used in this case include hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, boron trifluoride or a complex thereof, a cation exchange resin, a heteropolyacid, and activated clay. In this reaction, a reaction solvent need not be used, but a solvent such as an aromatic hydrocarbon, an alcohol, or an ether can also be used.

The sulfonation of the reaction product of one molecule of terpene and two molecules of phenols is usually carried out by reacting with a sulfonating agent such as sulfuric acid, sulfuric anhydride, fuming sulfuric acid, chlorosulfonic acid and the like. Can be. The reaction temperature for the sulfonation is usually from -50 to 150C, preferably from 0 to 100C. When the reaction temperature is lower than −50 ° C., the reaction rate is low, and when it exceeds 150 ° C., side reactions such as resinification become remarkable, which is not preferable. or,
A solvent may not be used in the sulfonation reaction, but usually a chlorine-based solvent such as chloroform or ethylene dichloride is used. The target substance can be obtained by directly collecting the solvent and concentrating and purifying the obtained sulfonated product.However, since the sulfonating agent usually remains in the reaction product, a recrystallization method using a solvent or a dialysis membrane is used. By performing purification, a highly pure sulfonated product can be obtained.

The basic compound used for producing the sulfonate of the compound represented by the above general formulas 1 and 2 includes, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonia. , Pyridine,
Examples include, but are not limited to, organic bases such as triethylamine and tetramethylammonium hydroxide.

Preferred examples of the compounds having organic conductivity represented by the general formulas 1 and 2 include, for example, the following chemical formula 1 in which a terpene diphenol compound shown in JP-A-8-198791 is sulfonated, and An analog is a compound represented by the following chemical formula 2.

[0017]

Next, one molecule of terpene contains two phenols.
The compounds represented by the above-mentioned general formulas 3 and 4 obtained by a molecular reaction and further reaction with an alkyl sultone are novel compounds, and their production is the same as that of the compound represented by the chemical formula 1 in the same manner as in the case of the compound represented by the chemical formula 1. And phenols, and then by reacting an alkylsultone. Further, the sulfonate is produced by subjecting the above-mentioned reaction product with the alkyl sultone to an acid-base reaction with the above-mentioned basic compound.

The reaction between one molecule of a terpene and two molecules of a phenol is carried out in the same manner as in the case of the compounds represented by the above general formulas 1 and 2. One molecule of terpene and phenols 2
The reaction between the reactant with the molecule and the alkyl sultone can be usually carried out by reacting the alkyl sultone in the presence of a catalyst. As the catalyst, for example, lithium hydride, sodium hydride, potassium hydride and the like can be used. In that case, the reaction is usually carried out using a solvent such as dimethylacetamide. The reaction temperature with the alkyl sultone is usually from 0 to
Performed at 150 ° C. When the reaction temperature is lower than 0 ° C., the reaction rate is low, and when the reaction temperature is higher than 150 ° C., side reactions become remarkable, which is not preferable.

The obtained reaction product is dissolved in purified water, purified by a dialysis membrane, and the catalyst is removed to obtain a compound having a sulfonic acid group at the end. As the dialysis membrane used at that time, for example, cellulose ester or the like is used, but is not limited thereto. Examples of the basic compound used for producing the sulfonate of the reaction product with the obtained alkyl sultones include inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonia, pyridine and triethylamine. And organic bases such as tetramethylammonium hydroxide, but are not limited thereto.

As another method for producing the sulfonate, when a reaction product of one molecule of a terpene and two molecules of a phenol is reacted with an alkyl sultone, the reaction is carried out without a catalyst in the presence of a basic compound. In this way, a target substance having a terminal sulfonate can be obtained. Further, the sulfonic acid salt is subjected to ion exchange with sulfuric acid or hydrochloric acid, dissolved in purified water, and purified by a dialysis membrane, whereby the terminal can be converted into a compound having a sulfonic acid group.

Preferred specific examples of the compound having organic conductivity represented by the general formula 3 include, for example, Japanese Patent Application Laid-Open No.
-198791, a compound of the following chemical formula 3 obtained by reacting 1,3-propanesultone with a terpene diphenol compound. Also, general formula 4
Preferred specific examples of the compound having organic conductivity represented by are a compound of the following chemical formula 4, which is an analog of the compound of the chemical formula 3.

[0023]

[0024]

Next, a method for producing a compound in which a sulfonic acid group is introduced into a terpene-based aromatic compound represented by the above general formula 5 is usually carried out by converting a terpene-based aromatic compound into sulfuric acid, sulfuric anhydride,
The reaction can be carried out using a sulfonating agent such as fuming sulfuric acid or chlorosulfonic acid. The sulfonate is produced by further subjecting the sulfonated product to an acid-base reaction with a basic compound. The method of sulfonation and the method of producing the sulfonate can be carried out in the same manner as in the compound of the above-mentioned general formula 1. Preferred examples of the compound represented by Formula 5 are shown in Chemical Formula 5 below.

[0026]

Next, two molecules of phenol are added to one terpene molecule.
The compound represented by the above general formula 6 in which a molecular reaction is carried out, which is subjected to a condensation reaction with aldehydes or ketones, and further a sulfonic acid group is introduced is a novel compound, and its production method is the same as that of the compound represented by the chemical formula 1. Similarly, it can be produced, for example, by reacting a monoterpene compound with a phenol, followed by a condensation reaction with an aldehyde or a ketone, and further sulfonation. The sulfonate is produced by further subjecting the sulfonated product to an acid-base reaction with a basic compound.

The reaction between one molecule of terpene and two molecules of phenols is performed in the same manner as in the case of the compounds represented by the above general formulas 1 and 2. The condensation reaction between a reaction product of one molecule of terpene and two molecules of phenols and aldehydes or ketones can be usually carried out by reacting in the presence of an acidic catalyst. As the acidic catalyst, inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as formic acid, acetic acid, oxalic acid, and toluenesulfonic acid can be used.
At that time, inert solvents such as aromatic hydrocarbons, alcohols and ethers can be used. The reaction temperature with the aldehydes and ketones is usually 0 to 200 ° C.
Done in When the reaction temperature is lower than 0 ° C., the reaction rate is low, and when the reaction temperature is higher than 200 ° C., side reactions become remarkable, which is not preferable. The condensation degree (m) of the condensate is usually 0 to 30,
Preferably it is 0-20.

The aldehydes and ketones used in the condensation reaction include, for example, formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde,
Examples include, but are not limited to, benzaldehyde, hydroxybenzaldehyde, phenylacetaldehyde, furfural, acetone, cyclohexanone, and the like.

The method for sulfonating a condensate obtained by reacting an aldehyde or ketone with a reaction product of one molecule of a terpene and two molecules of a phenol and a method for producing a sulfonate are the same as those of the compound of the above-mentioned general formula 1. It can be carried out. The sulfonic acid group introduction ratio (the sum of r and s) is usually
For one reactant of a molecule and two molecules of phenols,
0.1 to 2, preferably 0.5 to 2.

Preferable specific examples of the compound having an organic conductivity represented by the general formula 6 include, for example,
JP-A-198791 discloses a compound represented by the following chemical formula 6 in which a condensate obtained by reacting formaldehyde with a terpene diphenol compound is sulfonated.

[0032] (In the above formula, m represents an integer of 0 to 30.)

Next, the compound represented by the above general formula 7 in which a sulfonic acid group is introduced into a copolymer of a terpene and a phenol is a novel compound. The reaction can be performed by using a sulfonating agent such as sulfuric acid, sulfuric anhydride, fuming sulfuric acid, and chlorosulfonic acid. The sulfonate is produced by further subjecting the sulfonated product to an acid-base reaction with a basic compound. The sulfonation method and the method for producing the sulfonate can be carried out in the same manner as in the compound of the general formula 1.

The method for producing a copolymer of a terpene and a phenol can be carried out by subjecting a monoterpene compound and a phenol to a polymerization reaction in the presence of a Friedel-Crafts type catalyst. The Friedel-Crafts type catalyst includes, but is not limited to, aluminum chloride, boron trifluoride or a complex thereof.
The reaction temperature of the polymerization reaction is usually -30 to 150.
Performed at ° C. If the reaction temperature is lower than −30 ° C., the reaction rate is slow, and if it exceeds 150 ° C., side reactions become remarkable, which is not preferable. The copolymerization ratio (p) of terpene to phenol is usually 0.1 to 1 for terpene per 1 molecule of phenol.
0, preferably 0.3 to 6. The polymerization degree (q) of the polymer is usually 1 to 20, preferably 2 to 12.

A preferred specific example of the compound having organic conductivity represented by the general formula 7 is, for example, a compound of the following chemical formula 7 in which a terpene phenol copolymer is sulfonated by reacting a monoterpene compound with phenol. No.

[0036] (In the above formula, p represents a numerical value of 0.1 to 10, and q is 1 to
Represents the numerical value of 20. According to the present invention, the main skeleton has heat resistance,
By introducing a sulfonic acid group into a terpene-based material having excellent substrate adhesion and transparency, an organic conductive material having heat resistance, substrate adhesion, transparency and conductivity can be provided.

[0037]

Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. Example 1 [Synthesis Example of Compound Represented by Chemical Formula 1] 564 g of phenol was placed in a 1-liter four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a condenser.
And after charging 34 g of a strongly acidic cation exchange resin,
While maintaining the temperature at ° C., 136 g of α-pinene was added dropwise over 4 hours, and then reacted by stirring for 2 hours. Next, the cation exchange resin was removed from the mixture by filtration, and the obtained reaction solution was washed twice with distilled water.
The mixture was kept at 250 ° C. for 30 minutes under a reduced pressure of Hg to distill off residual phenol and by-products to obtain a pale yellow resin. This pale yellow resinous material was purified by repeating recrystallization using a solvent (toluene) to obtain 32 g of a white crystal of a terpene diphenol compound.

Next, 200 g of ethylene dichloride and 32 g of the above white crystals were charged into a 500 ml four-necked flask equipped with a thermometer, a stirrer, a dropping funnel and a condenser, and then kept at a temperature of 5 ° C. Sulfuric anhydride 15.8g
Was added dropwise over 1 hour, and then reacted by stirring for 4 hours.
The reaction product was concentrated to dryness at 40 ° C. under a reduced pressure of 10 mmHg to obtain 45 g of yellow-brown crystals. The obtained crystal was subjected to structural analysis by nuclear magnetic resonance spectroscopy (NMR) and mass spectroscopy (MS) under the following measurement conditions (the same applies to Example 2 and thereafter). As a result, the compound represented by Chemical Formula 1 was obtained. Was identified. Nuclear magnetic resonance spectrum of ¹ H and ¹³ C, indicating NMR-DEPT spectrum of ^{13 C, NMR-CH-COSY} , a chart of the mass spectrum in Figure 1-5. The obtained crystals had a purity of 93% by weight as determined by high performance liquid chromatography analysis (HPLC).

Example 2 [Synthesis Example of Compound Represented by Chemical Formula 2] A pale yellow resinous material was obtained in the same manner as in Example 1 and then recrystallized with a solvent (toluene), and the mother liquor was concentrated. To obtain a resinous material. This resinous material was further purified by recrystallization with a solvent (chloroform) to obtain 28 g of a white crystal of a terpene diphenol compound.

Next, 200 g of ethylene dichloride and 28 g of the above white crystals were charged into a 500 ml four-necked flask equipped with a thermometer, a stirrer, a dropping funnel and a cooling tube, and then kept at 35 ° C. Chlorosulfonic acid (20.2 g) was added dropwise over 30 minutes, and then stirred for 4 hours to react. The reaction was performed under reduced pressure of 10 mmHg at 50 ° C.
And dried to give 39.6 g of yellow-brown crystals. The obtained crystal was subjected to structural analysis by NMR analysis and MS analysis, and as a result, was identified to be a compound represented by Chemical Formula 2. ¹ H and ¹³ C nuclear magnetic resonance spectra, ¹³ C NM
The charts of the R-DEPT spectrum, NMR-CH-COSY, and mass spectrum are shown in FIGS. The obtained crystals had a purity of 92% by weight according to HPLC analysis.

Example 3 [Synthesis example of the compound represented by the chemical formula 3] A thermometer, a stirrer, a dropping funnel and a cooling tube equipped with a cooling pipe were prepared.
A 0 ml four-necked flask was charged with 32 g of white crystals of a terpene diphenol compound obtained in the same manner as in Example 1, 130 g of acetonitrile, and 69.8 g of a 25% by weight aqueous solution of tetramethylammonium hydroxide. While maintaining the temperature, 23.7 g of 1,3-propanesultone was added dropwise over 1 hour, and the mixture was stirred and reacted for 2 hours. The reaction product was concentrated to dryness at 70 ° C. under a reduced pressure of 50 mmHg to obtain 67.2 g of white crystals. The obtained crystal was subjected to structural analysis by NMR analysis and MS analysis, and as a result, was identified to be a compound represented by Chemical Formula 3. ¹ H and ¹³ C nuclear magnetic resonance spectra, ¹³
NMR-DEPT spectrum of C, NMR-CH-CO
SY and mass spectrum charts are shown in FIGS. The obtained crystals had a purity of 96 by HPLC analysis.
% By weight.

Example 4 [Synthesis Example of Compound Represented by Chemical Formula 4] In the same manner as in Example 3, except that 32 g of a white crystal of a terpene diphenol compound obtained in the same manner as in Example 2 was used. By operation, 66.8 g of white crystals were obtained. The obtained crystal was subjected to structural analysis by NMR analysis and MS analysis, and as a result, was identified to be a compound represented by Chemical Formula 4. ¹ H and ¹³ C nuclear magnetic resonance spectra, ¹³
NMR-DEPT spectrum of C, NMR-CH-CO
SY and mass spectrum charts are shown in FIGS. The obtained crystals had a purity of 94% by weight according to HPLC analysis.

Example 5 [Synthesis example of the compound represented by the chemical formula 5] A 50 equipped with a thermometer, a stirrer, a dropping funnel and a cooling pipe.
Ethylene dichloride 200 in a 0 ml four-necked flask
g and 40 g of paracymene, 23.2 g of sulfuric anhydride was added dropwise over 1 hour while maintaining the temperature at 5 ° C.
Thereafter, the mixture was reacted by stirring for 4 hours. Reactant is 10mmH
g under reduced pressure at 50 ° C. to give 60.5 g of a black-brown viscous body. The obtained viscous body was subjected to structural analysis by NMR analysis and MS analysis, and as a result, it was identified as paracymensulfonic acid. FIG. 21 is a chart of the nuclear magnetic resonance spectrum and mass spectrum of ¹ H and ¹³ C.
To 23. The obtained viscous body had a purity of 95% by weight according to HPLC.

Example 6 Synthesis Example of Mixture of Compounds Represented by Chemical Formulas 1 and 2 564 g of phenol was placed in a 1-liter four-necked flask equipped with a thermometer, a stirrer, a dropping funnel and a condenser.
And after charging 34 g of a strongly acidic cation exchange resin,
While maintaining the temperature at ° C., 136 g of d-limonene was added dropwise over 4 hours, and then the mixture was stirred and reacted for 2 hours.
Next, the cation exchange resin was removed from the mixture by filtration, and the obtained reaction solution was washed twice with distilled water.
The mixture was kept at 250 ° C. for 30 minutes under a reduced pressure of Hg to distill off residual phenol and by-products to obtain a pale yellow resin. The pale yellow resinous material was further distilled by thin-film distillation to obtain 85 g of slightly yellow crystals of a terpene diphenol compound.

Next, 200 g of ethylene dichloride and 32 g of the above white crystals were charged into a 500 ml four-necked flask equipped with a thermometer, a stirrer, a dropping funnel and a condenser, and then kept at a temperature of 5 ° C. Sulfuric anhydride 15.8g
Was added dropwise over 1 hour, followed by stirring for 4 hours to cause a reaction.
The reaction product was concentrated to dryness at 40 ° C. under a reduced pressure of 10 mmHg to obtain 45 g of yellow-brown crystals. NMR of the obtained crystal
As a result of structural analysis by analysis and MS analysis, it was identified as a mixture of the compounds represented by Chemical Formula 1 and Chemical Formula 2. Charts of nuclear magnetic resonance spectra and mass spectra of ¹ H and ¹³ C are shown in FIGS. The obtained crystals had a purity of 87% by weight according to HPLC analysis, and the composition ratio of the compound of Formula 1 to the compound of Formula 2 was 66:34.

Example 7 [Synthesis Example of Mixture of Compounds Represented by Chemical Formulas 3 and 4] In Example 3, except that 32 g of white crystals of a terpene diphenol compound obtained in the same manner as in Example 6 was used. The same operation as in Example 3 was performed to obtain 66.5 g of white crystals. The obtained crystal was subjected to structural analysis by NMR analysis and MS analysis, and as a result, was identified to be a mixture of the compounds represented by Chemical Formulas 3 and 4. Charts of ¹ H and ¹³ C nuclear magnetic resonance spectra and mass spectra are shown in FIGS.
29. The obtained crystals were analyzed by HPLC to have a purity of 90% by weight, and the composition ratio of the compound of Formula 1 to the compound of Formula 2 was 66:34.

Example 8 [Synthesis Example of Compound Represented by Chemical Formula 6] A slightly yellow crystal of a terpene diphenol compound obtained in the same manner as in Example 6 was placed in a glass-lined autoclave equipped with a stirrer and a thermometer. 50 g, 5 g of 37% aqueous formalin solution, 0.25 g of hydrochloric acid and 15 g of water
The mixture was charged and reacted at 120 ° C. for 4 hours with stirring in a closed state. Next, the mixture was cooled to 70 ° C., 60 g of toluene was charged and washed with water three times, and then toluene was removed by distillation to obtain 51 g of a condensate of terpene diphenol compound as a slightly yellow crystal with formaldehyde.

Next, 400 g of ethylene dichloride and 50 g of the above-mentioned pale yellow crystals were charged into a 500 ml four-necked flask equipped with a thermometer, a stirrer, a dropping funnel and a cooling tube. Sulfonic acid (40 g) was added dropwise over 1 hour, followed by stirring for 4 hours to react. The reaction product was concentrated to dryness at 50 ° C. under a reduced pressure of 10 mmHg to obtain 77 g of a tan crystal as a target compound. As a result of analysis by gel permeation chromatography (GPC), the obtained compound was a mixture represented by the chemical formula 6 and having a condensation degree (m) of 0 to 6. Nuclear magnetic resonance spectra and GPC charts of ¹ H and ¹³ C are shown in FIGS.

Example 9 [Synthesis Example of Compound Represented by Chemical Formula 6] The terpene diphenol compound obtained in Example 8 was condensed with formaldehyde using a high-vacuum molecular distillation apparatus and the terpene having a condensation degree (m) of 0 was obtained. 50 g of a condensate having a degree of condensation (m) of 1 to 6 obtained by removing the diphenol compound
Except for using, sulfonation was carried out in the same manner as in Example 8, to obtain 76 g of yellow-brown crystals. As a result of analysis by GPC, the obtained compound was a mixture represented by the chemical formula 6 and having a degree of condensation (m) of 1 to 6. The nuclear magnetic resonance spectra and GPC charts of ¹ H and ¹³ C are shown in FIGS.
Shown in

Example 10 [Synthesis Example of Compound Represented by Chemical Formula 7] A thermometer, a stirrer, a dropping funnel and a cooling tube equipped with a cooling tube were prepared.
Ethylene dichloride 400 in a 0 ml 4-day flask
g and 50 g of a terpene phenol copolymer having a degree of polymerization (q) of 1 to 8 obtained by copolymerizing 1 mol of phenol and 0.7 mol of limonene, and then keeping the temperature at 30 ° C. with chlorosulfonic acid. 23.5 g was added dropwise over 1 hour, and then reacted for 4 hours with stirring. The reactant is 10 mmHg
The solution was concentrated to dryness at 50 ° C. under reduced pressure to obtain 68 g of a tan crystal as a target compound. The obtained compound was obtained by GPC
As a result of the analysis, the mixture was a compound represented by the chemical formula 7 and having a degree of polymerization (q) of 1 to 8. The nuclear magnetic resonance spectra and GPC charts of ¹ H and ¹³ C are shown in FIGS.
Shown in

The analysis in each of the above embodiments was performed under the following conditions.
Done. "Examples 1, 2 and 6" NMR: JNM-LA400 manufactured by JEOL Ltd., frequency 400 MHz Solvent is acetone-d6 (FIGS. 1-4, 6-9, 24, 25) MS: liquid chromatography mass spectrometry Apparatus Column; Inertsil ODS-3 φ4.6 × 150 mm MS, manufactured by GL Sciences; LSMS-QP8000, manufactured by Shimadzu Corporation Ionization mode: electrospray (ESI) Polarity: negative (FIGS. 5, 10, 26) “Example 3” NMR : The model is the same as in Example 1, and the solvent is
CD _ThreeOD, FIGS. 12 and 13 show D_TwoO MS: all the same as in Example 1 (FIG. 15)

Example 4 NMR: The model is the same as in Example 1, and the solvent is shown in FIGS.
19 is CD _ThreeOD, FIG. 17 is D_TwoO MS: Infusion analysis (MS direct introduction)
The other conditions were the same as those in Example 1 (FIG. 20). “Example 5” NMR: The model was the same as in Example 1, and the solvent was CD. _ThreeOD use
(FIGS. 21 and 22) MS: All the same as in Example 1 (FIG. 23) “Example 7” NMR: Model is the same as in Example 1, solvent is CD in FIG. _Three
OD, FIG. 28 is D_TwoOMS: Same as Example 4 (FIG. 2)
9) "Examples 8 and 9" NMR: Model is the same as in Example 1, solvent is CD _ThreeOD (FIGS. 30, 31, 33, 34) GPC: Model: ALLIANCE2690 manufactured by Waters Column: Shodex Asahipak GF-310 HQ (7.6 × 300 mm) Mobile phase manufactured by Showa Denko: DMF 10 mM LiBr added Flow rate: 0. 6 ml / min. Detection: UV 270 nm Injection amount: 5 μl Molecular weight calibration: monodisperse polystyrene (Polymer Laboratories) (FIGS. 32, 35) “Example 10” NMR: Model is the same as in Example 1, solvent is acetone-d6
Use (FIGS. 36, 37) GPC: Measurement conditions are the same as in Example 8 (FIG. 38)

Example of Use A 10% by weight solution of each of the organic conductive materials of Examples 1, 2, 5 and 6 in methyl ethyl ketone was prepared.
One surface of an ET (polyethylene terephthalate) film was applied using a Miya Bar # 4, and dried in an oven at 100 ° C. for 5 minutes to form a conductive layer having an application amount of 0.1 g / m ² . Also, a 10% by weight methanol solution of each of the organic conductive materials of Examples 3, 4 and 7 was prepared, and applied to one surface of the PET film using a Miya bar # 4.
Dry in an oven at 00 ° C for 5 minutes and apply 0.1 g / m
^Two conductive layers were formed. A 5% by weight solution of each of the organic conductive materials of Examples 8 and 9 in methyl ethyl ketone was prepared, and 2.5% by weight of the organic conductive material of Example 10 was prepared.
Mix methyl ethyl ketone solutions and use each to prepare P
One side of the ET film was applied using a Miya Bar # 4, dried in an oven at 100 ° C. for 5 minutes, and applied in an amount of 0.1
g / m ² of the conductive layer was formed.

Comparative Example 1 Using a mixed solution of water / IPA (weight ratio: 1: 1), a 5% by weight solution of Elecon 50B (manufactured by Soken Chemical Co., Ltd., quaternary ammonium salt / cationic conductive agent) was prepared. One side of the film was coated using a Myrbar # 4 and dried with hot air to form a conductive layer having a coating amount of 0.1 g / m ² . Comparative Example 2 Using a mixed solution of water / IPA (weight ratio 1: 1), AS
-170 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., phosphate ester anionic conductive agent) is prepared in a 5% by weight solution, applied to one surface of the PET film using a Miya bar # 4, and dried by warm air. A conductive layer having an amount of 0.1 g / m ² was formed.

Comparative Example 3 Aq was prepared using a mixed solution of water / IPA (weight ratio: 1: 1).
A 5% by weight solution of ua-PASS (Sulfonated polyaniline, π-conjugated conductive polymer, manufactured by Nitto Kagaku Kogyo Co., Ltd.) was prepared, applied to one surface of a PET film using a Miya bar # 4, and dried with hot air. Thus, a conductive layer having a coating amount of 0.1 g / m ² was formed.

Evaluation of antistatic performance of antistatic treated film
Method Various physical properties (surface specific resistance and coloring) were evaluated using the coating films of the organic conductive materials of the above Examples and Comparative Examples according to the following methods. The results are shown in the table. Measurement conditions of surface resistivity: Measured with an applied voltage of 100 V using Hiresta IP manufactured by Mitsubishi Yuka Corporation.・ Colorability: Visual evaluation

Table 1 Conductivity and coloring properties of Examples and Comparative Examples

[0058]

According to the present invention, the main skeleton has heat resistance,
By introducing a sulfonic acid group into a terpene-based material having excellent substrate adhesion and transparency, an organic conductive material having heat resistance, substrate adhesion, transparency and conductivity can be provided. Therefore, the organic conductive material of the present invention is a material suitable for improving the performance of various articles such as conductivity, heat resistance and water resistance.

[Brief description of the drawings]

FIG. 1 is a ¹ HNMR spectrum of a compound obtained in Example 1.

FIG. 2 is a ¹³ C NMR spectrum of the compound obtained in Example 1.

FIG. 3 is a DEPT spectrum of the compound obtained in Example 1.

FIG. 4 shows C-HCOSY of the compound obtained in Example 1.
Spectrum

FIG. 5 is an MS spectrum of the compound obtained in Example 1.

FIG. 6 shows a ¹ H NMR spectrum of the compound obtained in Example 2.

FIG. 7 is a ¹³ C NMR spectrum of the compound obtained in Example 2.

FIG. 8 is a DEPT spectrum of the compound obtained in Example 2.

FIG. 9 shows C-HCOSY of the compound obtained in Example 2.
Spectrum

FIG. 10 is an MS spectrum of the compound obtained in Example 2.

FIG. 11 shows a ¹ HNMR spectrum of the compound obtained in Example 3.

FIG. 12 is a ¹³ C NMR spectrum of the compound obtained in Example 3.

FIG. 13 is a DEPT spectrum of the compound obtained in Example 3.

FIG. 14 shows C-HCOS of the compound obtained in Example 3.
Y spectrum

FIG. 15 is an MS spectrum of the compound obtained in Example 3.

FIG. 16 shows a ¹ H NMR spectrum of the compound obtained in Example 4.

FIG. 17 shows a ¹³ C NMR spectrum of the compound obtained in Example 4.

FIG. 18 is a DEPT spectrum of the compound obtained in Example 4.

FIG. 19 shows C-HCOS of the compound obtained in Example 4.
Y spectrum

FIG. 20 is an MS spectrum of the compound obtained in Example 4.

FIG. 21 shows a ¹ HNMR spectrum of the mixture obtained in Example 5.

FIG. 22 shows a ¹³ C NMR spectrum of the mixture obtained in Example 5.

FIG. 23 shows the MS spectrum of the mixture obtained in Example 5.

FIG. 24 shows a ¹ HNMR spectrum of the mixture obtained in Example 6.

FIG. 25 ¹³ C NMR spectrum of the mixture obtained in Example 6

FIG. 26 is an MS spectrum of the mixture obtained in Example 6.

FIG. 27 ¹ HNMR spectrum of the mixture obtained in Example 7

FIG. 28 ¹³ C NMR spectrum of the mixture obtained in Example 7

FIG. 29 shows the MS spectrum of the mixture obtained in Example 7.

FIG. 30 shows a ¹ HNMR spectrum of the compound obtained in Example 8.

FIG. 31 shows a ¹³ C NMR spectrum of the compound obtained in Example 8.

FIG. 32 shows a GPC spectrum of the compound obtained in Example 8.

FIG. 33 shows a ¹ HNMR spectrum of the compound obtained in Example 9.

FIG. 34 ¹³ C NMR spectrum of the compound obtained in Example 9

FIG. 35 is a GPC spectrum of the compound obtained in Example 9.

FIG. 36 ¹ HNMR of the compound obtained in Example 10
Spectrum

FIG. 37 ¹³ C NMR of the compound obtained in Example 10
Spectrum

FIG. 38 is a GPC spectrum of the compound obtained in Example 10.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shinobu Mineyama 1080, Takagicho, Fuchu City, Hiroshima Prefecture Inside Yashara Chemical Co., Ltd. (72) Asumi Nishizawa 1-1-1, Ichigaga-cho, Shinjuku-ku, Tokyo Dainippon In Printing Co., Ltd. (72) Inventor Norikatsu Ono 1-1-1, Ichigaya-Kaga-cho, Shinjuku-ku, Tokyo Dai-Nippon Printing Co., Ltd. (72) Inventor Naoya Ogata 6-29-6F, Asayakita, Suginami-ku, Tokyo Terms (reference) 5G067 AA70 CA01 DA02

Claims (1)

[Claims] 1. An organic conductive material comprising at least one compound represented by the following general formulas 1 to 7. (X ₁ , X ₂ , X ₃ and X ₄ in the above formula are the same or different,
It represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a hydroxyl group. Ya, Yb and Yc are the same or different and represent a proton (H ⁺ ) or a positive ion of a basic compound;
Represents an integer of １５15. The sum of r and s represents a numerical value of 0.1 to 2, m represents an integer of 0 to 30, and R ₁ and R ₂ represent an alkyl group or a hydrogen atom independently or bonded to each other.
p represents a numerical value of 0.1 to 10, and q represents a numerical value of 1 to 20. )