JP2009126949A - Conductive polyaniline composition, method for producing the same and molded article formed therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive polyaniline composition having high safety. <P>SOLUTION: The conductive polyaniline composition contains (a) a protonated substituted or unsubstituted polyaniline complex and (b) a compound having an aromatic alcoholic hydroxyl group, wherein these components are dissolved in an essentially water-immiscible organic solvent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel conductive polyaniline composition, a method for producing the same, and a molded article obtained therefrom, and particularly relates to a conductive polyaniline composition excellent in safety.

  Polyaniline is a well-known material as one of conductive polymers. In addition to its electrical properties, polyaniline has the advantage and property of being able to be synthesized relatively easily from inexpensive aniline and exhibiting excellent stability against air or the like in a state of conductivity.

  As a method for producing polyaniline, a method of electrolytic oxidation polymerization or chemical oxidation polymerization of aniline or aniline derivatives is known.

  In electrolytic oxidation polymerization, a film having excellent electrical properties can be obtained. However, in general, the production cost is higher than chemical oxidation polymerization, and it is not suitable for mass production. Have difficulty.

  On the other hand, in order to obtain a conductive aniline or aniline derivative polymer by chemical oxidative polymerization, in general, a dopant (doping agent) is added to polyaniline obtained in a non-conductive base state (so-called emeraldine base state). The process of nation is required. However, polyaniline in the non-conductive base state is not suitable for industrial production because it hardly dissolves in most organic solvents. Furthermore, the conductive polyaniline (so-called emeraldine salt state) generated after the protonation is substantially insoluble and infusible, and it is difficult to easily manufacture a conductive composite material and a molded body thereof.

In response to the above problems, the present inventors have developed a soluble conductive polyaniline complex and a composition thereof that are easy to manufacture and handle (Patent Document 1). Moreover, this polyaniline composition has a high electrical conductivity.
International Publication No. 2005/052058 Pamphlet

The polyaniline composition described in Patent Document 1 has excellent properties, but the phenolic compound used as a raw material has a high toxicity and has a safety problem.
Accordingly, an object of the present invention is to provide a highly safe conductive polyaniline composition.

According to the present invention, the following conductive polyaniline composition and the like are provided.
1. A conductive polyaniline composition comprising (a) a protonated substituted or unsubstituted polyaniline complex, and (b) a compound having an aromatic alcoholic hydroxyl group, dissolved in an organic solvent that is substantially immiscible with water.
2. 2. The conductive polyaniline composition according to 1, wherein the molar number concentration of the compound (b) having an aromatic alcoholic hydroxyl group in the entire composition is in the range of 0.01 mol / L to 5 mol / L.
3. (A) The conductive polyaniline composition according to 1 or 2, wherein the concentration of the substituted or unsubstituted polyaniline complex subjected to protonation is in the range of 0.01 to 300 g / L with respect to the organic solvent.
4). (A) The conductive polyaniline composition according to any one of 1 to 3, wherein the content of the substituted or unsubstituted polyaniline in the protonated substituted or unsubstituted polyaniline complex is 20% by weight to 70% by weight. .
5). (A) The protonated substituted or unsubstituted polyaniline complex has a substituted or unsubstituted polyaniline represented by the following formula (I):
HXARn (I)
{In the formula, X is an acidic group, A is a hydrocarbon group which may contain a substituent, and R is independently -R ¹ , -OR ¹ , -COR ¹ , -COOR ^1. , —CO (COR ¹ ), or —CO (COOR ¹ ) [wherein R ¹ is a hydrocarbon group, silyl group, — (R ² O) x -R which may contain a substituent having 4 or more carbon atoms. ³ groups or-(OSiR ³ ₂ ) x -OR ³ groups (R ² is an alkylene group, R ³ is a hydrocarbon group which may be the same or different, and x is an integer of 1 or more). And n is an integer greater than or equal to 2}
5. The conductive polyaniline composition according to any one of 1 to 4, which is protonated with an organic protonic acid represented by the formula:
6). The organic protonic acid represented by the formula (I) is represented by the following formula (II)
HXCR ⁴ (CR ⁵ ₂ COOR ⁶ ) COOR ⁷ (II)
{In the formula, X is an acidic group, R ⁴ and R ⁵ are each independently a hydrogen atom, a hydrocarbon group or an R ⁸ ₃ Si- group (wherein R ⁸ is a hydrocarbon group, Three R ⁸ may be the same or different, and R ⁶ and R ⁷ are each independently a hydrocarbon group or a — (R ⁹ O) _q —R ¹⁰ group [where R ⁹ is carbon A hydrogen group or a silylene group, R ¹⁰ is a hydrogen atom, a hydrocarbon group or R ¹¹ ₃ Si— (R ¹¹ is a hydrocarbon group, and three R ¹¹ may be the same or different); q is an integer greater than or equal to 1]}
6. The conductive polyaniline composition according to 5, which is an organic protonic acid represented by the formula:
7). The organic protonic acid represented by the formula (II) is represented by the following formula (III)
HO ₃ SCH (CH ₂ COOR ¹² ) COOR ¹³ (III)
{Wherein R ¹² and R ¹³ are each independently a hydrocarbon group or — (R ¹⁴ O) _r —R ¹⁵ group [wherein R ¹⁴ is a hydrocarbon group or a silylene group, and R ¹⁵ is hydrogen An atom, a hydrocarbon group, or an R ¹⁶ ₃ Si— group (where R ¹⁶ is a hydrocarbon group, and three R ¹⁶ may be the same or different), and r is an integer of 1 or more.] Is}
7. The conductive polyaniline composition according to 6, which is a sulfosuccinic acid derivative represented by the formula:
8). (B) The conductive polyaniline composition according to 1 to 7, wherein the compound having an aromatic alcoholic hydroxyl group is selected from the group consisting of benzyl alcohol and o-, m-, p-, and α-substituted benzyl alcohol.
9. The conductive polyaniline composition according to any one of 1 to 8, wherein the organic solvent substantially immiscible with water is selected from the group consisting of hydrocarbon solvents, halogen-containing solvents, and ester solvents.
10. (I) In an organic solvent substantially immiscible with water, the following formula (I ′)
M (XARn) m (I ′)
{Wherein M is a hydrogen atom or an organic or inorganic free radical, X is an acidic group, A is a hydrocarbon group which may contain a substituent, and R is independently- R ¹ , —OR ¹ , —COR ¹ , —COOR ¹ , —CO (COR ¹ ), or —CO (COOR ¹ ) [wherein R ¹ may include a substituent having 4 or more carbon atoms. Group, silyl group, (R ² O) x -R ³ group or-(OSiR ³ ₂ ) x -OR ³ group (R ² is an alkylene group, and R ³ is a hydrocarbon group which may be the same or different. And x is an integer greater than or equal to 1)], n is an integer greater than or equal to 2, and m is the valence of M}
And (a) a protonated substituted or unsubstituted polyaniline complex soluble in the organic solvent by chemical oxidative polymerization of the substituted or unsubstituted aniline in the presence of the organic protonic acid or salt thereof And (ii) adding (b) an aromatic alcoholic compound to the (a) protonated substituted or unsubstituted polyaniline complex dissolved in an organic solvent that is substantially immiscible with water. A method for producing a conductive polyaniline composition.
11. A conductive molded article obtained by molding the conductive polyaniline composition according to any one of 11.1 to 9.
12. A surface conductive article obtained by applying the conductive polyaniline composition according to any one of 12.1 to 9 to a substrate.

  According to the present invention, a highly safe conductive polyaniline composition can be provided.

  The conductive polyaniline composition of the present invention (hereinafter referred to as the composition of the present invention) is dissolved in an organic solvent that is substantially immiscible with water, (a) a protonated substituted or unsubstituted polyaniline complex, And (b) a compound having an aromatic alcoholic hydroxyl group.

The compound (b) having an aromatic alcoholic hydroxyl group (hereinafter referred to as (b) an aromatic alcoholic compound) used in the composition of the present invention is not particularly limited, and is represented by the general formula Ar (CR ²¹ ₂ ) nCR ²² ₂ OH. Here, Ar is an aryl group or a substituted aryl group, R ²¹ and R ²² are hydrogen or a hydrocarbon group, and n is an integer of 0 or more. Examples include benzyl alcohol and o-, m-, p-, α-substituted benzyl alcohol. Specifically, o-, m- or p-methylbenzyl alcohol, o-, m- or p-ethylbenzyl alcohol, o-, m- or p-propylbenzyl alcohol, o-, m- or p-butyl. Examples include hydrocarbon-substituted benzyl alcohol such as benzyl alcohol, halogen-substituted benzyl alcohol such as o-, m- or p-chlorobenzyl alcohol, alkoxy or aryloxy-substituted benzyl alcohol such as o-, m- or p-methoxybenzyl alcohol. it can. These aromatic rings may be substituted with a plurality of the same or different substituents. Further, α-substituted benzyl alcohol such as α-phenethyl alcohol, β-phenethyl alcohol and the like can also be exemplified.

［式中、Ｒ’は炭素数１〜４のアルキル基、アルコキシ基，ハロゲン又は水素であり、ｔは０又は１である。］ Suitable aromatic alcoholic compounds can be represented by the following formula:

[Wherein, R ′ is an alkyl group having 1 to 4 carbon atoms, an alkoxy group, halogen or hydrogen, and t is 0 or 1. ]

  In the composition of the present invention, the (b) aromatic alcohol compound is present as a dopant, not as a solvent. (B) that the aromatic alcoholic compound is a dopant, the molded body produced from the composition of the present invention to which (1) (b) the aromatic alcoholic compound is added is compared to the molded body to which this is not added. Obtained from the conductive polyaniline composition of the present invention containing very high electrical conductivity (see Examples and Comparative Examples), and (2) after removal of the organic solvent, containing (b) an aromatic alcoholic compound. The molded body after the organic solvent has been removed by supporting the molded body and the molded body obtained from the polyaniline composition containing no aromatic alcoholic compound (b) by showing different UV-vis (ultraviolet-visible) spectra. It is clear that (b) the aromatic alcoholic compound remains therein. That is, if the (b) aromatic alcoholic compound is a simple solvent, it is easily volatilized and removed by applying heat when forming a molded body. However, it is charged when it is present as a dopant, so that it requires a large amount of energy to be removed from the polyaniline and cannot be removed by heating to a degree of volatilization.

The amount of (b) aromatic alcoholic compound added in the composition of the present invention is usually 0.01 to 1000% by mass, preferably 0, with respect to the (a) protonated substituted or unsubstituted polyaniline complex. It is the range of 5-500 mass%.
Moreover, it is preferable that the mole number density | concentration of the compound which has (b) aromatic alcoholic hydroxyl group is the range of 0.01 mol / L-5 mol / L in the whole composition. If the amount of this compound added is too small, the effect of improving the electrical conductivity may not be obtained. In addition, when the amount is too large, the uniformity of the composition is impaired, and when removing the solvent by volatilization, a great amount of heat and time are required, resulting in a material with impaired transparency and electrical characteristics. There is a fear.

The (a) protonated substituted or unsubstituted polyaniline complex (hereinafter referred to as (a) polyaniline complex) used in the composition of the present invention is a substituted or unsubstituted polyaniline (hereinafter simply referred to as polyaniline), Formula (I)
HXARn (I)
Those obtained by protonation with an organic protonic acid represented by (hereinafter referred to as organic protonic acid (I)) are preferred.

Examples of the substituent of the substituted polyaniline include a linear or branched hydrocarbon group such as a methyl group, an ethyl group, a hexyl group, and an octyl group, an alkoxyl group such as a methoxy group and a phenoxy group, an aryloxy group, and a CF ₃ group. And halogen-containing hydrocarbon groups.

In the present invention, the substituted or unsubstituted polyaniline preferably has a weight average molecular weight of 20,000 g / mol or more. Thereby, the intensity | strength and ductility of the electroconductive article obtained from a composition can be improved.
The molecular weight of polyaniline is measured by gel permeation chromatography (GPC). Details of the measurement method will be described in Examples described later.

In the above formula (I), X is an acidic group. For example, —SO ₃ ^— group, —PO ₃ ^2- group, —PO ₄ (OH) ^— group, —OPO ₃ ^2- group, —OPO ₂ ( OH) ^- group, -COO ^- group and the like, -SO ₃ ^- group.
A is a hydrocarbon group which may contain a substituent, for example, a linear or branched alkyl or alkenyl group having 1 to 24 carbon atoms, a substituent such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, menthyl and the like. Including optionally substituted cycloalkyl groups, dicyclohexyl groups such as bicyclohexyl, norbornyl, adamantyl or the like or polycycloalkyl groups, phenyl, tosyl, thiophenyl, pyrrolinyl, pyridinyl, furanyl and the like An aryl group containing an aromatic ring, naphthyl, anthracenyl, fluorenyl, 1,2,3,4-tetrahydronaphthyl, indanyl, quinolinyl, indonyl, etc., may be condensed diaryl group or polyaryl group, alkylaryl group, etc. Is mentioned.
Each R is independently —R ¹ , —OR ¹ , —COR ¹ , —COOR ¹ , —CO (COR ¹ ), or —CO (COOR ¹ ). Here, R ¹ is a hydrocarbon group, silyl group, — (R ² O) x —R ³ group, or — (OSiR ³ ₂ ) x—OR ³ group (which may contain a substituent having 4 or more carbon atoms) ( R ² is an alkylene group, R ³ is a hydrocarbon group which may be the same or different, and x is an integer of 1 or more. Examples of when R ¹ is a hydrocarbon group include linear or branched butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, pentadecyl, eicosanyl, etc. Can be mentioned.
n is an integer of 2 or more.

As the compound represented by the formula (I), dialkylbenzenesulfonic acid, dialkylnaphthalenesulfonic acid, and a compound represented by the following formula (II) can be preferably used.
HXCR ⁴ (CR ⁵ ₂ COOR ⁶ ) COOR ⁷ (II)
In the above formula (II), X is an acidic group, for example, —SO ₃ ^— group, —PO ₃ ^2- group, —PO ₄ (OH) ^{2 —} group, —OPO ₃ ^2- group, —OPO ₂ ( OH) ^- group, -COO ^- group and the like, -SO ₃ ^- group.

R ⁴ and R ⁵ are each independently a hydrogen atom, a hydrocarbon group or an R ⁸ ₃ Si— group (wherein R ⁸ is a hydrocarbon group, and three R ⁸ may be the same or different). ). Examples of the hydrocarbon group when R ⁴ and R ⁵ are hydrocarbon groups include a linear or branched alkyl group having 1 to 24 carbon atoms, an aryl group containing an aromatic ring, and an alkylaryl group. The hydrocarbon group when R ⁸ is a hydrocarbon group is the same as in the case of R ⁴ and R ⁵ .

R ⁶ and R ⁷ are each independently a hydrocarbon group or — (R ⁹ O) _q —R ¹⁰ group [wherein R ⁹ is a hydrocarbon group or a silylene group, and R ¹⁰ is a hydrogen atom or a hydrocarbon, A group or R ¹¹ ₃ Si— (R ¹¹ is a hydrocarbon group, three R ¹¹ may be the same or different), and q is an integer of 1 or more. The hydrocarbon group in the case where R ⁶ and R ⁷ are hydrocarbon groups is a linear or branched alkyl group having 1 to 24 carbon atoms, preferably 4 or more carbon atoms, an aryl group containing an aromatic ring, or an alkylaryl Specific examples of the hydrocarbon group when R ⁶ and R ⁷ are hydrocarbon groups include, for example, a linear or branched butyl group, pentyl group, hexyl group, octyl group, decyl group Etc.

In R ⁶ and R ⁷ , when R ⁹ is a hydrocarbon group, the hydrocarbon group includes a linear or branched alkylene group having 1 to 24 carbon atoms, an arylene group containing an aromatic ring, an alkylarylene group, an aryl An alkylene group and the like; The hydrocarbon group in R ⁶ and R ⁷ when R ¹⁰ and R ¹¹ are hydrocarbon groups is the same as in the case of R ⁴ and R ⁵ , and q is 1 to 10. preferable.

（式中、Ｘは−ＳＯ_３基等である）で示される基が挙げられる。 Specific examples of the case where R ⁶ and R ⁷ are — (R ⁹ O) _n —R ¹⁰ group include, for example,

(Wherein, X is a —SO ₃ group or the like).

The organic protonic acid (II) is more preferably a sulfosuccinic acid derivative represented by the following formula (III) (hereinafter referred to as a sulfosuccinic acid derivative (III)).
HO ₃ SCH (CH ₂ COOR ¹² ) COOR ¹³ (III)
In the above formula (III), R ¹² and R ¹³ are each independently a hydrocarbon group or — (R ¹⁴ O) _r —R ¹⁵ group [where R ¹⁴ is a hydrocarbon group or a silylene group; ¹⁵ is a hydrogen atom, a hydrocarbon group or an R ¹⁶ ₃ Si— group (wherein R ¹⁶ is a hydrocarbon group, and three R ¹⁶ may be the same or different), and r is an integer of 1 or more It is].

The hydrocarbon group when R ¹² and R ¹³ are hydrocarbon groups is the same as R ⁶ and R ⁷ .

In R ¹² and R ¹³ , the hydrocarbon group in the case where R ¹⁴ is a hydrocarbon group is the same as R ⁹ described above. In R ¹² and R ¹³ , the hydrocarbon group in the case where R ¹⁵ and R ¹⁶ are hydrocarbon groups is the same as R ⁴ and R ⁵ described above.

  r is preferably from 1 to 10.

Specific examples when R ¹² and R ¹³ are a — (R ¹⁴ O) _q —R ¹⁵ group are the same as those for — (R ⁹ O) _n —R ¹⁰ in R ⁶ and R ⁷ .

The hydrocarbon group in the case where R ¹² and R ¹³ are hydrocarbon groups is the same as R ⁶ and R ⁷ and is preferably a butyl group, a hexyl group, a 2-ethylhexyl group, a decyl group, or the like.

  The organic protonic acid (I) has a function of protonating polyaniline, and (a) is present as a dopant (counter anion) in the polyaniline complex. That is, in the composition of the present invention, two types of compounds, the organic protonic acid (I) and the (b) aromatic alcoholic compound, function as dopants. The organic protonic acid (I) is considered to exist as a cation in the composition of the present invention.

  (A) In the polyaniline complex, the composition ratio of polyaniline and organic protonic acid (I) is not particularly limited, but the molar ratio of monomer unit of polyaniline / organic protonic acid (I) is usually 0.1 to 2, Preferably it is 0.1-0.5. When the proportion of the organic protonic acid (I) is too small, the electrical conductivity does not increase. Moreover, when too much, the ratio of the polyaniline which dominates the electrical property of a molded article decreases, and electrical conductivity falls. Although the weight composition ratio varies depending on the molecular weight of the protonic acid, (a) a complex containing 20% to 70% by weight of the substituted or unsubstituted polyaniline in the protonated substituted or unsubstituted polyaniline complex. In some cases, high electrical characteristics are exhibited, which is preferable.

  Examples of organic solvents that are substantially immiscible with water (hereinafter referred to as water-immiscible organic solvents) used in the composition of the present invention include hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and tetralin; methylene chloride Halogen-containing solvents such as chloroform, carbon tetrachloride, dichloroethane, trichloroethane, and tetrachloroethane; ester solvents such as ethyl acetate; and toluene, xylene, chloroform, trichloroethane, and ethyl acetate are preferable.

  In the composition of the present invention, the proportion of the (a) polyaniline complex in the water-immiscible organic solvent depends on the type of the water-immiscible organic solvent, but is usually 900 g / L or less, preferably 0.01. It is the range of -300 g / L or less. (A) If the content of the polyaniline complex is too large, the solution state cannot be maintained, the handling at the time of molding the molded body becomes difficult, the uniformity of the molded body is impaired, and consequently the electrical properties of the molded body and There is a risk of lowering mechanical strength and transparency.

The conductive polyaniline composition of the present invention comprises
(I) In an organic solvent substantially immiscible with water, the following formula (I ′)
M (XARn) m (I ′)
{Where,
M is a hydrogen atom or an organic or inorganic free radical;
X is an acidic group,
A is a hydrocarbon group which may contain a substituent,
Each R is independently -R ¹ , -OR ¹ , -COR ¹ , -COOR ¹ , -CO (COR ¹ ), -CO (COOR ¹ ) [where R ¹ has 4 or more carbon atoms; A hydrocarbon group, a silyl group, a — (R ² O) x—R ³ group, or a — (OSiR ³ ₂ ) x—OR ³ group (R ² may be an alkylene group, and R ³ may be the same as each other) Is a hydrocarbon group which may be different, and x is an integer of 1 or more.]
n is an integer greater than or equal to 2,
m is the valence of M}
(A) a protonated substituted or unsubstituted polyaniline complex soluble in the organic solvent by chemical oxidative polymerization of the substituted or unsubstituted aniline in the presence of the organic protonic acid or salt thereof represented by And (ii) adding (b) a compound having an aromatic alcoholic hydroxyl group to the (a) protonated substituted or unsubstituted polyaniline complex dissolved in an organic solvent immiscible with water It is preferable to manufacture by the manufacturing method of the electroconductive polyaniline composition characterized by including the process to carry out.

The polyaniline complex can be produced by a chemical oxidative polymerization method or an electrolytic polymerization method.
Preferably, the substituted or unsubstituted aniline is chemically oxidatively polymerized in an organic solvent substantially immiscible with water in the presence of the organic protonic acid represented by the above formula (I) or a salt thereof.
Reference can be made to the above-mentioned International Publication No. 2005/052058 for specific production conditions of the chemical oxidative polymerization method and electrolytic polymerization method.

In the above formula (I ′), M is a hydrogen atom or an organic or inorganic free radical. Examples of the organic free radical include a pyridinium group, an imidazolium group, and an anilinium group. Examples of the inorganic free radical include sodium, lithium, potassium, cerium, and ammonium. m is the valence of M.
X, A, R, and n are the same as in the above formula (I).

As the compound represented by the formula (I ′), dialkylbenzene sulfonic acid, dialkyl naphthalene sulfonic acid, sulfophthalic acid ester, and a compound represented by the following formula (II ′) can be preferably used.
M (XCR ⁴ (CR ⁵ ₂ COOR ⁶ ) COOR ⁷ ) _p (II ′)
In the above formula (II ′), M is the same as in the formula (I ′). X, R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same as in the above formula (II). p is the valence of M.

The organic protonic acid or a salt thereof (II ′) is more preferably a sulfosuccinic acid derivative represented by the following formula (III ′) (hereinafter referred to as sulfosuccinic acid derivative (III ′)).
M (O ₃ SCH (CH ₂ COOR ¹² ) COOR ¹³ ) _m (III ′)
In the above formula (III ′), M and m are the same as in the above formula (I ′). R ¹² and R ¹³ are the same as in the above formula (III).

  The organic protonic acid (I) or a salt thereof (I ′) used in the present invention can be produced using a known method. For example, the corresponding sulfophthalic acid ester derivative or succinic acid ester derivative can be obtained by reacting a sulfophthalic acid derivative or sulfosuccinic acid derivative with a desired alcohol. It is also known to obtain a corresponding sulfosuccinate derivative by hydrosulfonylating a maleate with sodium bisulfite or the like.

  A commercially available organic protonic acid (I) or a salt thereof (I ′) can also be used. Examples of commercially available products include Aerosol OT (Diisooctyl Sodium Sulfosuccinate; manufactured by Wako Pure Chemical Industries, Ltd.), Ripar 87OP (manufactured by Lion Corporation), and the like. Some commercial products have different purities, but can be selected and used as necessary.

  In order to obtain the composition of the present invention (conductive polyaniline composition) containing (a) a polyaniline complex and (b) an aromatic alcohol compound dissolved in a water-immiscible organic solvent, water-immiscibility is obtained. (B) Aromatic alcoholic compound is added to (a) polyaniline complex in a state dissolved in an organic solvent. Specifically, (b) the aromatic alcoholic compound may be added in a solid state or in a liquid state, or may be added in a state dissolved or suspended in a water-immiscible solvent. Preferably, an appropriate solvent addition method is selected so as to be in a dissolved state even after the addition.

Next, the electroconductive molded object of this invention (henceforth the molded object of this invention) shape | molds the said composition (electroconductive polyaniline composition) of the said invention, It is characterized by the above-mentioned.
The molded product obtained from the composition of the present invention has improved electrical characteristics such as electrical conductivity compared to the composition.

  Depending on the purpose, other resin materials; other compounding agents such as inorganic materials, curing agents, and plasticizers may be added to the composition of the present invention.

  Other resin materials are added for the purpose of, for example, a binder substrate, a plasticizer, a matrix substrate, and specific examples thereof include, for example, polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polycarbonate, polyethylene glycol, polyethylene oxide, Examples thereof include polyacrylic acid, polyacrylic acid ester, polymethacrylic acid ester, and polyvinyl alcohol. When the composition of the present invention contains other resin materials, the composition of the present invention becomes a conductive composite material.

  Inorganic materials are added for the purpose of, for example, improving strength, surface hardness, dimensional stability and other mechanical properties. Specific examples thereof include silica (silicon dioxide), titania (titanium oxide), alumina ( Aluminum oxide) and the like.

  The curing agent is added, for example, for the purpose of improving strength, surface hardness, dimensional stability and other mechanical properties, and specific examples thereof include, for example, thermosetting agents such as phenol resins, acrylate monomers and photopolymerization. Examples thereof include a photo-curing agent using a property initiator.

  The plasticizer is added for the purpose of improving mechanical properties such as tensile strength and bending strength, and specific examples thereof include phthalic acid esters and phosphoric acid esters.

  The molded body of the present invention is formed by molding the conductive polyaniline composition.

The electrical conductivity of the molded body of the present invention shows a high value of, for example, 20 S / cm or more.
Here, the electrical conductivity can be measured by a method such as a two-terminal method, a four-terminal method, a four-probe method, and a van der Pau method by spreading the composition of the present invention on a glass substrate. In addition, the electrical conductivity in this specification is a value measured using a Lorester GP (manufactured by Mitsubishi Chemical Corporation; based on the four-probe method) which is a commercially available resistivity meter.

  The molded article of the present invention may be composed of only a single conductive composition, that is, only a polyaniline base composition, or may be composed of several polymers constituting the conductive composite.

  The surface transparent conductive article of the present invention comprises a composition of the present invention containing (a) a polyaniline complex and (b) an aromatic alcohol compound dissolved in a water-immiscible organic solvent in a desired shape. It can be manufactured by applying to a substrate such as glass, a resin film, or a sheet having a water-immiscible organic solvent.

  As a method for applying the composition of the present invention to a substrate, known general methods such as a casting method, a spray method, a dip coating method, a doctor blade method, a barcode method, a spin coating method, a screen printing, a gravure printing method, etc. The method can be used.

  In order to remove the water-immiscible organic solvent, the organic solvent may be volatilized by heating. As a method for volatilizing the water-immiscible organic solvent, for example, heating is performed at a temperature of 250 ° C. or less, preferably 50 to 200 ° C. under an air stream, and further, heating is performed under reduced pressure as necessary. Note that the heating temperature and the heating time are not particularly limited, and may be appropriately selected depending on the material to be used.

  The thin film obtained by applying the composition of the present invention to a substrate and removing the water-immiscible organic solvent can also be a self-supporting molded article having no substrate. In the case of forming a self-supporting molded article, a molded article having a desired mechanical strength can be obtained by adding the above-mentioned other resin material other than polyaniline to the composition of the present invention.

  When the molded product of the present invention is a film or a film, the thickness is usually 1 mm or less, preferably 10 nm to 50 μm.

Further, the surface resistance value of the surface transparent conductive article of the present invention is preferably 10 ⁵ Ω / □ or less.
The light transmittance at 450 nm is preferably 70% or more. In the present invention, it is a composition to which an aromatic alcohol compound is added, and because of its uniformity, a highly transparent conductive article can be obtained.

<Production Example 1>
Manufacture of conductive polyaniline complex 144 g of aerosol OT (sodium diisooctylsulfosuccinate, purity 75% or more) manufactured by Wako Pure Chemical Industries, Ltd. was stirred and dissolved in 4 L of toluene, and a 30 L glass reactor (mechanical type) This solution was placed in a stirrer, jacket, thermometer, and dropping funnel, and 150 g of raw material aniline was added and dissolved by stirring.
Stirring and cooling of the flask with a refrigerant was started, and 12 L of 1N hydrochloric acid was added to the solution.

Next, in a state where the solution was cooled to −3 ° C., a solution obtained by dissolving 214 g of chemical ammonium persulfate in 4 L of 1N hydrochloric acid was dropped with a dropping funnel, and the reaction was completed in 3 hours and 10 minutes. Stirring was performed for 18 hours and 30 minutes from the start of dropping while keeping the internal temperature of the solution at 0 ° C. ± 1 ° C. Thereafter, 8 L of toluene was added, the solution temperature was raised to 19 ° C., and the mixture was allowed to stand.
The aqueous phase (lower phase) separated into two phases by standing was withdrawn from the lower part of the reactor to obtain a crude polyaniline complex toluene solution.

Further, 4 L of ion exchange water was added to the complex solution and stirred, and then allowed to stand to separate the aqueous phase. After this operation was performed again, the complex solution was washed in the same manner with 4 L of 1N hydrochloric acid aqueous solution, allowed to stand, and then the acidic aqueous solution was separated to recover the toluene solution of the polyaniline complex.
Some insoluble matter contained in this complex solution was removed with # 5C filter paper, and a toluene solution of a polyaniline complex soluble in toluene was recovered. This solution was transferred to an evaporator, heated in a hot water bath at 60 ° C., and reduced in pressure to evaporate and remove volatile components to obtain 208 g of a polyaniline complex.

The elemental analysis when the volatile matter is substantially removed from the polyaniline composite is shown below.
Carbon: 61.70 wt%, Hydrogen: 8.20 wt%, Nitrogen: 3.90 wt%, Sulfur: 5.50 wt%, Chlorine: 0.12 wt%
From the ratio of nitrogen wt% based on the aniline raw material and sulfur wt% based on the sulfosuccinate ester, the molar fraction of aniline monomer unit / sulfo succinate ester in this composite was 0.62. The weight average molecular weight of the polyaniline skeleton in this polyaniline complex was 90,000 g / mol.

  The molecular weight measurement was determined by gel permeation chromatography (GPC). Specifically, TOSOH TSK-GEL GMHHR-H was used as a column, a 0.01 M LiBr / N-methylpyrrolidone solution was used, and measurement was performed at 60 ° C. and a flow rate of 0.35 ml / min. As a sample, 100 μL of a 0.2 g / L solution was injected and detected by UV at 260 nm. As a standard, the average molecular weight was calculated by the PS (polystyrene) conversion method.

<Example 1>
(1) Preparation of conductive polyaniline composition 1 g of the conductive polyaniline complex obtained in the above <Production Example 1> was dissolved again in 20 ml of toluene to prepare a uniform conductive polyaniline complex solution. 20 mmol of alcohol was added to obtain a conductive polyaniline composition having a benzyl alcohol concentration of about 0.88 mol / L.

(2) Production of conductive polyaniline molded body About 1 ml of the conductive polyaniline composition obtained in the above (1) is developed on a glass substrate in a range of 17 mm × 51 mm, and dried at 80 ° C. for 60 minutes in an air stream. A conductive coating film having a thickness of 44 μm was prepared, and the electrical conductivity was measured using a Lorester GP (manufactured by Mitsubishi Chemical Corporation; resistivity meter based on a four-probe method). The conductivity of the obtained coating film was 43 S / cm.

<Example 2>
(1) Preparation of conductive polyaniline composition 1 g of the conductive polyaniline complex obtained in the above <Production Example 1> is dissolved again in 20 ml of toluene to prepare a uniform conductive polyaniline complex solution. -17 mmol of phenethyl alcohol was added, and the electroconductive polyaniline composition whose (alpha) -phenethyl alcohol density | concentration is about 0.75 mol / L was obtained.

(2) Production of conductive polyaniline molded body About 1 ml of the conductive polyaniline composition obtained in the above (1) is developed on a glass substrate in a range of 17 mm × 51 mm, and dried at 80 ° C. for 60 minutes in an air stream. A conductive coating film having a thickness of 35 μm was prepared, and the electrical conductivity was measured using a Lorester GP (manufactured by Mitsubishi Chemical Corporation; resistivity meter based on a four-probe method). The conductivity of the obtained coating film was 29 S / cm.

<Example 3>
(1) Preparation of conductive polyaniline composition 1 g of the conductive polyaniline complex obtained in the above <Production Example 1> was dissolved again in 20 ml of toluene to prepare a uniform conductive polyaniline complex solution. -15.7 mmol of chlorobenzyl alcohol was added to obtain a conductive polyaniline composition having an m-chlorobenzyl alcohol concentration of about 0.72 mol / L.

(2) Production of Conductive Polyaniline Molded Body About 1 ml of the conductive polyaniline composition obtained in (1) above is developed in a range of 18 mm × 51 mm on a glass substrate and dried at 80 ° C. for 60 minutes in an air stream. A conductive coating film having a thickness of 35 μm was prepared, and the electrical conductivity was measured using a Lorester GP (manufactured by Mitsubishi Chemical Corporation; resistivity meter based on a four-probe method). The electric conductivity of the obtained coating film was 39 S / cm.

<Comparative Example 1>
(1) Preparation of conductive polyaniline composition 1 g of the conductive polyaniline complex obtained in the above <Production Example 1> was dissolved again in 20 ml of toluene to prepare a uniform conductive polyaniline complex solution. A conductive polyaniline complex solution was prepared in the same manner as in Example 1 except that it was not added.

(2) Production of Conductive Polyaniline Molded Body About 1 ml of the conductive polyaniline composition obtained in (1) above is developed in a range of 18 mm × 51 mm on a glass substrate and dried at 80 ° C. for 60 minutes in an air stream. A conductive coating film having a thickness of 47.5 μm was prepared, and the electrical conductivity was measured using a Lorester GP (manufactured by Mitsubishi Chemical Corporation; resistivity meter based on a four-probe method). The conductivity of the obtained coating film was 6 S / cm.

  The conductive polyaniline composition and molded body of the present invention are used in the field of power electronics and optoelectronics. Electrostatic / antistatic materials, transparent electrodes and conductive film materials, electroluminescent element materials, circuit materials, capacitor dielectrics and electrolytes It can be used as an electrode material for solar cells and secondary batteries, a fuel cell separator material, and the like.

Claims (12)

A conductive polyaniline composition comprising (a) a protonated substituted or unsubstituted polyaniline complex, and (b) a compound having an aromatic alcoholic hydroxyl group, dissolved in an organic solvent that is substantially immiscible with water.   2. The conductive polyaniline composition according to claim 1, wherein the molar concentration of the compound having (b) an aromatic alcoholic hydroxyl group in the whole composition is in the range of 0.01 mol / L to 5 mol / L.   The conductive polyaniline composition according to claim 1 or 2, wherein the concentration of (a) the protonated substituted or unsubstituted polyaniline complex with respect to the organic solvent is in the range of 0.01 to 300 g / L.   The conductive polyaniline according to any one of claims 1 to 3, wherein the content of the substituted or unsubstituted polyaniline in the (a) protonated substituted or unsubstituted polyaniline complex is 20 wt% to 70 wt%. Composition. (A) The protonated substituted or unsubstituted polyaniline complex has a substituted or unsubstituted polyaniline represented by the following formula (I):
HXARn (I)
{In the formula, X is an acidic group, A is a hydrocarbon group which may contain a substituent, and R is independently -R ¹ , -OR ¹ , -COR ¹ , -COOR ^1. , —CO (COR ¹ ), or —CO (COOR ¹ ) [wherein R ¹ is a hydrocarbon group, silyl group, — (R ² O) x -R which may contain a substituent having 4 or more carbon atoms. ³ groups or-(OSiR ³ ₂ ) x -OR ³ groups (R ² is an alkylene group, R ³ is a hydrocarbon group which may be the same or different, and x is an integer of 1 or more). And n is an integer greater than or equal to 2}
The conductive polyaniline composition according to claim 1, which is protonated with an organic protonic acid represented by the formula: The organic protonic acid represented by the formula (I) is represented by the following formula (II)
HXCR ⁴ (CR ⁵ ₂ COOR ⁶ ) COOR ⁷ (II)
{In the formula, X is an acidic group, R ⁴ and R ⁵ are each independently a hydrogen atom, a hydrocarbon group or an R ⁸ ₃ Si- group (wherein R ⁸ is a hydrocarbon group, Three R ⁸ may be the same or different, and R ⁶ and R ⁷ are each independently a hydrocarbon group or a — (R ⁹ O) _q —R ¹⁰ group [where R ⁹ is carbon A hydrogen group or a silylene group, R ¹⁰ is a hydrogen atom, a hydrocarbon group or R ¹¹ ₃ Si— (R ¹¹ is a hydrocarbon group, and three R ¹¹ may be the same or different); q is an integer greater than or equal to 1]}
The conductive polyaniline composition according to claim 5, which is an organic protonic acid represented by the formula: The organic protonic acid represented by the formula (II) is represented by the following formula (III)
HO ₃ SCH (CH ₂ COOR ¹² ) COOR ¹³ (III)
{Wherein R ¹² and R ¹³ are each independently a hydrocarbon group or — (R ¹⁴ O) _r —R ¹⁵ group [wherein R ¹⁴ is a hydrocarbon group or a silylene group, and R ¹⁵ is hydrogen An atom, a hydrocarbon group, or an R ¹⁶ ₃ Si— group (where R ¹⁶ is a hydrocarbon group, and three R ¹⁶ may be the same or different), and r is an integer of 1 or more.] Is}
The conductive polyaniline composition according to claim 6, which is a sulfosuccinic acid derivative represented by the formula:   (B) The conductive polyaniline composition according to claim 1, wherein the compound having an aromatic alcoholic hydroxyl group is selected from the group consisting of benzyl alcohol and o-, m-, p-, and α-substituted benzyl alcohol. object.   The conductive polyaniline composition according to claim 1, wherein the organic solvent substantially immiscible with water is selected from the group consisting of hydrocarbon solvents, halogen-containing solvents, and ester solvents. (I) In an organic solvent substantially immiscible with water, the following formula (I ′)
M (XARn) m (I ′)
{Wherein M is a hydrogen atom or an organic or inorganic free radical, X is an acidic group, A is a hydrocarbon group which may contain a substituent, and R is independently- R ¹ , —OR ¹ , —COR ¹ , —COOR ¹ , —CO (COR ¹ ), or —CO (COOR ¹ ) [wherein R ¹ may include a substituent having 4 or more carbon atoms. Group, silyl group, (R ² O) x -R ³ group or-(OSiR ³ ₂ ) x -OR ³ group (R ² is an alkylene group, and R ³ is a hydrocarbon group which may be the same or different. And x is an integer greater than or equal to 1)], n is an integer greater than or equal to 2, and m is the valence of M}
And (a) a protonated substituted or unsubstituted polyaniline complex soluble in the organic solvent by chemical oxidative polymerization of the substituted or unsubstituted aniline in the presence of the organic protonic acid or salt thereof And (ii) adding (b) an aromatic alcoholic compound to the (a) protonated substituted or unsubstituted polyaniline complex dissolved in an organic solvent that is substantially immiscible with water. A method for producing a conductive polyaniline composition.   The electroconductive molded object formed by shape | molding the electroconductive polyaniline composition in any one of Claims 1-9.   The surface conductive article formed by apply | coating the electroconductive polyaniline composition in any one of Claims 1-9 to a base material.