JP2003336069A - Sulfonic acid type liquid crystal material, its manufacturing method, proton transporting material, and proton transporting material utilizing molecular configuration by liquid crystalline state - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel material having excellent proton transportability, its manufacturing method, a proton transporting material using the same, and a proton transporting method to bring about the excellent proton transportability. <P>SOLUTION: There are provided a sulfonic acid type liquid crystal material represented by formula (1) (wherein A indicates a 5-18C alkylene group, -C<SB>6</SB>H<SB>4</SB>-CH<SB>2</SB>-, -CO-O-(CH<SB>2</SB>)<SB>n-</SB>- or -CO-; and B indicates an alkylene group), its manufacturing method, the proton transporting material using it, and the proton transporting method. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a sulfonic acid type liquid crystal material having an excellent proton transporting ability, a method for producing the same, a proton transporting material using the same, and a proton transporting method utilizing a molecular arrangement in a liquid crystal state. is there.

[0002]

2. Description of the Related Art It has been conventionally known that a sulfonic acid group and a phosphonic acid group have a proton transporting ability. Organic compounds having such a proton transport ability have been studied in many fields. The conventionally known mechanism of proton transport is, for example, in the case of a perfluorosulfonic acid-based proton membrane, a fairly large ion channel (cluster diameter of several nanometers) composed of SO ₃ H groups is formed in the membrane. Ion conductivity is obtained by H + hopping between the water molecules trapped in the water and the SO ₃ H groups on the channel wall. In this case, since SO ₃ H groups are present at random positions, it is considered that fairly irregular H ⁺ hopping occurs. Not only these membranes but also the properties required for proton transport include the demand that the ion channels be finer and more densely distributed.

[0003]

Liquid crystal compounds are applied to various devices as display materials, and are used in, for example, watches, calculators, televisions, personal computers, mobile phones and the like.
Liquid crystal substances are classified into thermotropic liquid crystals (temperature transition type liquid crystals) and lyotropic liquid crystals (concentration transition type liquid crystals) based on the means of giving a phase transition. These liquid crystals are classified into three types, that is, smectic liquid crystals, nematic liquid crystals and cholesteric liquid crystals, in terms of molecular alignment. In particular,
It is interesting that a compound having a smectic phase as a liquid crystal phase, in the liquid crystal state of the smectic phase, the overlapping of molecules called the smectic phase overlap in a dense liquid crystal state, and the present inventors have previously found that the molecular alignment of the smectic phase In view of the above, a method for transporting electric charges utilizing the characteristics (Japanese Patent Laid-Open No. 2001-351786) was proposed.

Further, while the inventors of the present invention have been earnestly researching a novel functional material utilizing the property of the smectic phase, the novel sulfonic acid type liquid crystalline material represented by the general formula (1) is obtained. The inventors have found that when protons are transported by utilizing the molecular arrangement of the succinic phase, they exhibit an excellent proton transporting ability than ever before, and have completed the present invention.

That is, the present invention provides a novel liquid crystal material having an excellent proton-transporting ability, a method for producing the same, a proton-transporting material using the same, and a proton-transporting method for expressing the excellent proton-transporting ability. To aim.

[0006]

SUMMARY OF THE INVENTION In the actual situation, the present inventors firstly describe the following general formula (1):

[Chemical 8] (In the formula, A is an alkylene group having 5 to 18 carbon atoms, -C ₆ H _{4
-CH 2 -, - CO-O-} (CH 2) n - or -CO-,
B represents an alkylene group. ) A sulfonic acid type liquid crystal material represented by the following general formula (2)

[Chemical 9] (In the formula, A is an alkylene group having 5 to 18 carbon atoms, -C ₆ H _{4
-CH 2 -, - CO-O-} (CH 2) n - or -CO-,
X represents a halogen atom. ) And the following general formula (3)

[Chemical 10] By reacting with 4,4′-biphenol represented by the following general formula (4)

[Chemical 11] (In the formula, A has the same meaning as above.) After obtaining the phenol derivative represented by the following formula, the obtained phenol derivative represented by the formula (4) and the following formula (5)

[Chemical 12] (In the formula, X represents a halogen atom, B represents an alkylene group, and M represents an alkali metal atom.), And the halogenated sulfonate represented by the following formula (6)

[Chemical 13] (Wherein A, B, and M have the same meanings as described above), and the obtained sulfonate represented by the general formula (6) is reacted with an acid. The following general formula (1)

[Chemical 14] (In the formula, A and B have the same meanings as described above.) Thirdly, the method for producing a sulfonic acid type liquid crystal material represented by the general formula (1) contains a sulfonic acid type liquid crystal material. Fourthly, a proton transporting method using a molecular arrangement in a liquid crystal state, characterized in that the proton transporting material is used in a liquid crystal state of a smectic phase. Provided is a method for transporting a proton using a molecular arrangement in a liquid crystal state, which is used in a solid state generated by a phase transition from a smectic phase.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. (Sulfonic acid type liquid crystal material) sulfonic acid-type liquid crystal material represented by the above general formula (1) of the present invention (hereinafter, Compound (1) hereinafter) wherein, A is an alkylene group, -C ₆ H ₄ -CH
_{In the} group represented by _2-, -CO-O- (CH2) n- or -CO-, the alkylene group may be linear or branched. Specifically, the alkylene group has 5 carbon atoms.
To 18 are preferable, and examples thereof include a hexylene group, an octadecylene group, a nonylene group, a decylene group, a dodecylene group, and a tetradecylene group. Among these, 6 carbon atoms are included.
Particularly preferred are alkylene groups of -12. Also, -CO-
O- (CH _{2) n} - is of n things 1-18 are particularly preferred. In the compound (1) of the present invention, B represents an alkylene group, which may be linear or branched. Specifically, those having 1 to 18 carbon atoms are preferable, for example, methylene group, ethylene group, trimethylene group, tetramethylene group,
Pentamethylene group, ethylethylene group, propylene group,
Examples thereof include a butylene group, a hexylene group, an octadecylene group, a nonylene group, a decylene group, and a dodecylene group. Among them, an alkylene group having 3 to 10 carbon atoms is particularly preferable. A
And B may be the same alkylene group or different alkylene groups.

Preferred compounds of the compound (1) include
3- [6- (heptyloxy) biphenyloxy] propylsulfonic acid, 4- [6- (heptyloxy) biphenyloxy] butylsulfonic acid, 5- [6- (heptyloxy) biphenyloxy] pentylsulfonic acid, 6- [6-
(Heptyloxy) biphenyloxy] hexylsulfonic acid, 7- [6- (heptyloxy) biphenyloxy]
Heptylsulfonic acid 8- [6- (heptyloxy) biphenyloxy] octylsulfonic acid 9- [6- (heptyloxy) biphenyloxy] nonylsulfonic acid, 10-
[6- (heptyloxy) biphenyloxy] decylsulfonic acid, 3- [6- (octyloxy) biphenyloxy] propylsulfonic acid, 4- [6- (octyloxy)
Biphenyloxy] butylsulfonic acid, 5- [6- (octyloxy) biphenyloxy] heptylsulfonic acid,
6- [6- (octyloxy) biphenyloxy] hexylsulfonic acid, 7- [6- (octyloxy) biphenyloxy] heptylsulfonic acid 8- [6- (octyloxy) biphenyloxy] octylsulfonic acid 9- [6 −
(Octyloxy) biphenyloxy] nonylsulfonic acid, 10- [6- (octyloxy) biphenyloxy]
Decyl sulfonic acid, 3- [6- (nonyloxy) biphenyloxy] propyl sulfonic acid, 4- [6- (nonyloxy) biphenyloxy] butyl sulfonic acid, 5- [6-
(Nonyloxy) biphenyloxy] heptylsulfonic acid, 6- [6- (nonyloxy) biphenyloxy] hexylsulfonic acid, 7- [6- (nonyloxy) biphenyloxy] heptylsulfonic acid 8- [6- (nonyloxy) biphenyloxy] Octyl sulfonic acid 9- [6-
(Nonyloxy) biphenyloxy] nonylsulfonic acid, 10- [6- (nonyloxy) biphenyloxy] decylsulfonic acid, 3- [6- (decyloxy) biphenyloxy] propylsulfonic acid, 4- [6- (decyloxy) biphenyloxy ] Butylsulfonic acid, 5- [6-
(Decyloxy) biphenyloxy] pentylsulfonic acid 6- [6- (decyloxy) biphenyloxy] hexylsulfonic acid, 7- [6- (decyloxy) biphenyloxy] heptylsulfonic acid 8- [6- (decyloxy)
Biphenyloxy] octylsulfonic acid, 9- [6- (decyloxy) biphenyloxy] nonylsulfonic acid, 1
0- [6- (decyloxy) biphenyloxy] decylsulfonic acid, 3- [6- (undecyloxy) biphenyloxy] propylsulfonic acid, 4- [6- (undecyloxy) biphenyloxy] butylsulfonic acid, 5 -[6-
(Undecyloxy) biphenyloxy] heptylsulfonic acid, 6- [6- (undecyloxy) biphenyloxy] hexylsulfonic acid, 7- [6- (undecyloxy) biphenyloxy] heptylsulfonic acid 8- [6-
Examples include (undecyloxy) biphenyloxy] octylsulfonic acid, 9- [6- (undecyloxy) biphenyloxy] nonylsulfonic acid, 10- [6- (undecyloxy) biphenyloxy] decylsulfonic acid, and the like. be able to.

(Production Method) Next, a method for producing the compound (1) will be described. The production method of the present invention basically comprises the following three reaction steps. <First Step> The first step is the following reaction formula (A).

[Chemical 15] (In the formula, A and X have the same meanings as described above.) In the step of producing the phenol derivative represented by the general formula (4).

The reaction in the first step is performed by reacting the halide represented by the general formula (2) with the halide represented by the general formula (3).
React with 4'-biphenol in the presence of base.

Examples of the base include inorganic bases such as sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, potassium carbonate, potassium hydrogen carbonate, calcium hydroxide, calcium carbonate, barium hydroxide and calcium hydroxide, trimethylamine. , N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N, N-dimethylbenzylamine, N, N'-dimethylpiperazine, N, N-dimethylaniline, N, N-
Diethylaniline, N, N, N ', N'-tetramethyl-1,3-propanediamine, pyridine, α-picoline, β-picoline, γ-picoline, 4-ethylmorpholine, triethylenediamine, 1,3-diazabicyclo [5,4,0] undecene, 1,8-diazabicyclo [5,4,0] -7-undecene, N-ethylpiperidine, quinoline, isoquinoline, N, N-dimethylpiperazine, N, N-diethylpiperazine, quinaldine , 2-
Ethylpyridine, 4-ethylpyridine, 3,5-lutidine, 2,6-lutidine, 4-methylmorpholine, 2,
The organic bases such as 4,6-collidine and the like, and the ion-exchange resins having a pyridyl group or a dimethylaminobenzyl group may be used alone or in combination of two or more, but are not particularly limited thereto. The addition amount of these bases is usually 1 to 2 times mol, preferably 1 to 4, mol of 4,4′-bisphenol.
It is 1.2 times the molar amount.

As the reaction solvent, for example, dioxane,
One or more of ethers such as tetrahydrofuran and dibutyl ether, nitriles such as acetonitrile and propionitrile, alcohols such as methanol and ethanol, dimethylformamide, acetone, water and the like are used.

The addition amount of 4,4'-bisphenol represented by the general formula (3) is 1 to 1.5 times mol, preferably the molar amount of the halide represented by the general formula (2). It is 1 to 1.2 times the molar amount.

The reaction conditions include a reaction temperature of 0 to 100.
C, preferably 20-50 C, with a reaction time of 0.5
The reaction is carried out for ~ 50 hours, preferably 10-30 hours.

After completion of the reaction, if desired, the product is washed with an acid by a conventional method, and subjected to various purification operations such as extraction, washing, dehydration, recrystallization and column chromatography to give the phenol derivative represented by the general formula (4). obtain.

<Second Step> The second step is the following reaction formula (B).

[Chemical 16] (In the formula, A and B are as defined above. X is a halogen atom and M is an alkali metal atom.) To produce the sulfonate represented by the general formula (6). Is.

The above-mentioned general formula (5) of the raw material used in the second step
The halogenated sulfonate represented by the following formula can be produced by a known method, and if one example thereof is shown, the following reaction formula (C)

[Chemical 17] (In the formula, B and M have the same meanings as described above, and X represents a halogen atom.) To easily produce the desired halogenated sulfonate represented by the general formula (5). (J. Med. Chem., Vol.
35, 224143-3149, 1992). Further, for example, BrCH ₂ SO ₃ Na, Br (CH ₂ ) ₃ SO ₃ N
a, Br (CH ₂ ) ₄ SO ₃ Na and the like are commercially available from Tokyo Chemical Industry Co., Ltd.

In the reaction of the second step, the phenol derivative represented by the general formula (4) and the halogenated sulfonate represented by the general formula (5) are reacted in the presence of a base.

As the base, inorganic bases such as sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, potassium carbonate, potassium hydrogen carbonate, calcium hydroxide, calcium carbonate, barium hydroxide, calcium hydroxide, and trimethylamine. , N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N, N-dimethylbenzylamine, N, N'-dimethylpiperazine, N, N-dimethylaniline, N, N-
Diethylaniline, N, N, N ', N'-tetramethyl-1,3-propanediamine, pyridine, α-picoline, β-picoline, γ-picoline, 4-ethylmorpholine, triethylenediamine, 1,3-diazabicyclo [5,4,0] undecene, 1,8-diazabicyclo [5,4,0] -7-undecene, N-ethylpiperidine, quinoline, isoquinoline, N, N-dimethylpiperazine, N, N-diethylpiperazine, quinaldine , 2-
Ethylpyridine, 4-ethylpyridine, 3,5-lutidine, 2,6-lutidine, 4-methylmorpholine, 2,
The organic bases such as 4,6-collidine and the like, and the ion-exchange resins having a pyridyl group or a dimethylaminobenzyl group may be used alone or in combination of two or more, but are not particularly limited thereto. The addition amount of these bases is the same as in the general formula (4).
It is usually 2 to 8 times mol, preferably 3 to 5 times mol, of the phenol derivative represented by.

Examples of the reaction solvent include dioxane,
One or more of ethers such as tetrahydrofuran and dibutyl ether, nitriles such as acetonitrile and propionitrile, alcohols such as methanol and ethanol, dimethylformamide, acetone, water and the like are used.

The addition amount of the halogenated phosphonate represented by the general formula (5) is 2 to 8 times, preferably 3 times the molar amount of the phenol derivative represented by the general formula (4).
~ 5 times the molar amount.

The reaction conditions include a reaction temperature of 0 to 100.
℃, preferably 20-80 ℃, reaction time 0.5
The reaction is carried out for -100 hours, preferably 10-50 hours.

After completion of the reaction, if desired, the product is purified by a conventional purification means such as recrystallization and washing, and then dried to obtain the desired sulfonate represented by the general formula (6).

<Third Step> The third step is the following reaction formula (C).

[Chemical 18] (In the formula, A, B, and M have the same meanings as described above.) In the process, the sulfonic acid type liquid crystal material represented by the general formula (1) is obtained.

In the reaction of the third step, the sulfonate represented by the general formula (6) is reacted with an acid.

The acid is not particularly limited and, for example, commonly used acids such as hydrochloric acid, nitric acid, phosphoric acid and sulfuric acid can be used. The amount of the acid added is 1 time mol or more with respect to the sulfonate represented by the general formula (6).

As the reaction solvent, water, acetone, methanol, ethanol or a mixed solvent thereof is used.

The reaction conditions include a reaction temperature of 0 to 100.
C, preferably 20-50 C, with a reaction time of 0.5
The reaction is carried out for ~ 50 hours, preferably 10-30 hours.

After completion of the reaction, filtration, washing and drying are carried out to obtain the desired sulfonic acid type liquid crystal material having a polymerizable group represented by the general formula (1).

(Proton Transport Material) Next, the proton transport material of the present invention will be described. The proton transport material according to the present invention contains the compound (1), and may be used as the compound (1) alone, as a mixture of two or more kinds thereof, or as a composition containing the compound (1). it can. Such a composition comprises at least 30 compounds (1).
It is contained in an amount of not less than 50% by weight, preferably not less than 50% by weight, more preferably not less than 90% by weight. Other components in the composition include a liquid crystal compound exhibiting a smectic phase or a nematic phase, an alkylsulfonic acid, a compound having a Nafion film system structure, an alkylcarboxylic acid, an alkylsulfonic acid and the like. The composition can be prepared as follows. That is, after dissolving the compound (1) and the desired above components in a solvent, the solvent is removed by heating, reduced pressure, or the like, or the compound (1) and the desired above components are mixed and melted by heating, or sputtering, It can be prepared by performing vacuum deposition or the like.

(Proton Transport Method) Next, the proton transport method of the present invention will be described. The proton transport method according to the present invention uses the proton transport material containing the compound (1) in a liquid crystal state in a smectic phase (hereinafter,
This is referred to as "1 proton transport method". ) Or a solid state resulting from a phase transition from a smectic phase, specifically,
Used in crystalline phase, glassy state, amorphous solid (hereinafter referred to as “2
Proton transport method ". ) Thereby exhibiting excellent proton transport ability.

The above-mentioned proton transport method is one in which the proton transport material of the present invention is brought into a smectic phase at a predetermined temperature, and the proton transport is carried out in the liquid crystal state of this smectic phase. In this case, the smectic phases are A, B, C,
It may be in any of the D, E, F, G, and H phases.

In the second proton transport method, the proton transport material of the present invention is once heated to a smectic phase, and the temperature is lowered from this state to carry out proton transport in a solid state in which the molecular orientation of the smectic phase is maintained. It is a thing.

As shown in FIG. 1, the conventional mechanism of proton transport in a compound having a sulfonic acid group forms a considerably large ion channel (cluster diameter of several nanometers) composed of SO ₃ H group, and is incorporated therein. Ion conductivity is obtained by H ⁺ hopping between the water molecules and SO ₃ H groups on the channel wall surface. On the other hand, in the proton transport material of the present invention, when the compound having a smectic phase as the above-mentioned liquid crystal phase is used, in the smectic phase state, an orientation having a layered arrangement as shown in FIG. Efficient proton transport can be performed because the sulfonic acid group portion serving as a conductive group is closely stacked in a liquid crystal state for proton transport.

The proton-transporting material and the proton-transporting method according to the present invention have excellent proton-transporting ability. For example, electrolytes for batteries, display elements, electrochromic elements, electrolytes for various sensors, and electrolyte membranes for fuel cells. It can be preferably used as a raw material of.

[0036]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. Example 1 <First step> -Synthesis of 4-decyloxyphenylphenol 0.02 mol (94%; 0.85) of sodium hydroxide
g) was dissolved in 50 ml of ethanol. Add this solution to 4,
To 100 ml ethanol in which 0.02 mol (3.72 g) of 4'-biphenol was dissolved was added little by little, and ethanol was removed under reduced pressure. To the residue was added 150 ml of DMF and dissolved while heating (solution A). 0.02 mol of 1-bromodecane was dissolved in 50 ml of DMF (B
liquid). While stirring at 40 ° C., solution B was added dropwise to solution A over 30 minutes and reacted for 24 hours. After the reaction was completed, the reaction solution was cooled and 300 ml of cold dilute hydrochloric acid (distilled water 270 ml + HC
125 ml + ice), extracted with 200 ml of diethyl ether, and washed with cold distilled water. The ether layer was dehydrated with anhydrous sodium sulfate overnight. The sodium sulfate was then filtered off and the ether was removed under reduced pressure. 200 ml of hexane was added to the residue, and the mixture was stirred for 30 minutes while heating, and the precipitate obtained by filtration was further mixed with 20 ml of hexane.
0 ml was added, stirred and filtered to obtain a precipitate. To this, 150 ml of benzene was added and heated, and the benzene-soluble portion was purified by column chromatography using benzene to obtain 4-decyloxyphenylphenol.

<Second Step / Third Step> -Synthesis of 3- [6- (decyloxy) biphenyloxy] propylsulfonic acid 1,8-diazabicyclo [5,4,4] in 25 ml of DMF.
0] -7-undensen (DBU) 0.008 mol
(1.22 g) and 4-decyloxyphenylphenol obtained above (0.002 mol), sodium 3-bromopropanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.008
Mol (1.80 g) was dissolved, and under a nitrogen atmosphere, 60
Stir at 48 ° C. for 48 hours. After completion of the reaction, the solvent was concentrated, diethyl ether was added, and the precipitate was obtained by filtration.
Next, the precipitate was washed thoroughly with distilled water. Next, the washed precipitate was stirred in 6 mol / L HCl for 24 hours, the reaction solution was filtered, and then vacuum dried to obtain 3- [6- (decyloxy) biphenyloxy] propylsulfonic acid 0.18
g was obtained. (Identification data) ¹ H-NMR (δ, d-DMSO) 0.93 (t, 3H), 1.2 to 1.5 (m, 14H),
1.7 to 1.8 (m, 2H), 2.0 to 2.1 (m, 2)
H) 2.6-2.7 (m, 2H), 4 (t, 2H),
4.1 (t, 2H), 7.0-7.1 (m, 4H), 7.
5 to 7.6 (m, 4H)

Further, the phase transition temperature of the obtained compound was measured and the following results were obtained.

[Equation 1] Cyst. ; Crystal, SmA; Smectic A phase, Is
o. Isotropic liquids

<Evaluation of Proton Transportability> A cell equipped with an ITO electrode (electrode area: 0.16 cm ² , distance between electrodes: 5)
0 [mu] m, manufactured by EHC) and obtained with 3- [6-
20 mg of (decyloxy) biphenyloxy] propylsulfonic acid was injected into the cell at a temperature of 132 ° C. or higher.
Then, the cell was gradually cooled to 40 ° C., and the cell was measured with a micro-ammeter (R8340 manufactured by Advantest Co., Ltd.) to reach 0.
A voltage of 5 V was applied and the current value per unit volume at 50 ° C. (solid state) and 115 ° C. (liquid crystal state) was measured. The results are shown in Table 1.

[Table 1]

The current value per unit area at 50 ° C. was 1.8 × 10 ⁻⁶ μA / cm ² when the molecular alignment of the liquid crystal was destroyed by rapid cooling after the cell injection.

From the above results, 10 ⁴ to 10 ^{5 in the} liquid crystal state
It is considered that a double proton transfer occurred, and a 10-fold proton transfer occurred in the solid state in which molecular orientation during liquid crystal was maintained by cooling.

[0042]

INDUSTRIAL APPLICABILITY As described above, the sulfonic acid type liquid crystal material of the present invention is a novel compound having an excellent proton transporting ability, and this liquid crystal compound is produced by the liquid crystal state of the smectic phase or the phase transition from the smectic phase. It exhibits excellent ionic conductivity when used in the solid state. Therefore, the phosphonic acid type liquid crystal material of the present invention can be suitably used as, for example, an electrolyte of a battery, a display element, an electrochromic element, an electrolyte of various sensors, and an electrolyte of a fuel cell.

[Brief description of drawings]

FIG. 1 is a schematic view showing a mechanism of proton transport of a conventional compound having a sulfonic acid group.

FIG. 2 is a schematic view showing a mechanism of proton transport when the sulfonic acid type liquid crystal material of the present invention is used in a liquid crystal state of a smectic phase.

Claims (5)

[Claims] 1. The following general formula (1): (In the formula, A is an alkylene group having 5 to 18 carbon atoms, -C ₆ H _{4
-CH 2 -, - CO-O-} (CH 2) n - or -CO-,
B represents an alkylene group. ) A sulfonic acid type liquid crystal material characterized by being represented by: 2. The following general formula (2): (In the formula, A is an alkylene group having 5 to 18 carbon atoms, -C ₆ H _{4
-CH 2 -, - CO-O-} (CH 2) n - or -CO-,
X represents a halogen atom. ) And the following general formula (3): By reacting with 4,4'-biphenol represented by the following general formula (4): (In the formula, A has the same meaning as described above.) After obtaining the phenol derivative represented by the following general formula (4), the phenol derivative represented by the following general formula (5) (In the formula, X is a halogen atom, B is an alkylene group, and M is an alkali metal atom.) And is reacted with a halogenated sulfonate to give a compound represented by the following general formula (6): (Wherein A, B, and M have the same meanings as described above), and the obtained sulfonate represented by the general formula (6) is reacted with an acid. The following general formula (1) (In the formula, A and B are as defined above.) A method for producing a sulfonic acid type liquid crystal material. 3. A proton transport material comprising the sulfonic acid type liquid crystal material represented by the general formula (1). 4. A proton transport method using molecular alignment in a liquid crystal state, wherein the proton transport material according to claim 3 is used in a liquid crystal state in a smectic phase. 5. A proton transport method using molecular alignment in a liquid crystal state, wherein the proton transport material according to claim 3 is used in a solid state generated by a phase transition from a smectic phase.