JPWO2015016156A1 - Dispersant-containing carbon material film containing photoresponsive dispersant, and carbon material film manufacturing method using the dispersant-containing carbon material film - Google Patents

Abstract

Use of a dispersant-containing carbon material film that can easily form a carbon material film such as CNT that does not contain a dispersant at all or contains only a small amount of the dispersant, and the dispersant-containing carbon material film It is an object of the present invention to provide a method for producing a carbon material film such as a patterned carbon material film, and the dispersant-containing carbon material film has photoresponsiveness and is represented by the following general formula (I). It contains a stilbene-based or azobenzene-based dispersant. [Wherein, R 1 to R 6 are each independently hydrogen or a linear or branched alkyl group having 1 to 5 carbon atoms or a straight chain or having 3 to 6 carbon atoms.] A is a carbon atom or a nitrogen atom. X is an anion. n is a number at which nX becomes -2 valent. [Selection] Figure 1

Description

  The present invention uses a dispersant-containing carbon material film containing a photoresponsive carbon material dispersant, which is useful for the production of a carbon material film typified by carbon nanotubes (CNT), and the dispersant-containing carbon material film. The present invention relates to a carbon material film manufacturing method capable of obtaining a patterned carbon material film, and an electronic / electric device manufacturing method including the carbon material film manufacturing method.

  Carbon nanotubes (CNTs) have attracted attention in recent years as a new material for nanotechnology. Among them, single-walled carbon nanotubes (SWCNT) are expected to be applied in various fields due to their simple structure and unique physicochemical properties.

  However, CNTs are associated with high van der Waals interactions (bundling). Therefore, in order to obtain CNT films and to obtain CNT films with a predetermined pattern, solubilization / dispersion techniques in solvents and CNT Film patterning technology is indispensable.

Conventional techniques for solubilizing and dispersing CNTs in solvents include mixing CNTs with a method of generating functional groups that promote solubility in solvents by sonicating CNTs in acidic solutions. Are known to promote dispersion (solubilization) in solvents, and as dispersants, ionic amphiphilic compounds, compounds having aromatic functional groups, naturally derived polymers, synthetic polymers, etc. have been reported. (See Patent Document 1).
However, in many cases, the dispersant adsorbed on the CNTs can only be removed by long-term washing, low-temperature incineration, and decomposition and removal by chemicals. It remains a challenge.
Furthermore, the development of recyclable dispersants that can be used repeatedly by repeatedly performing dispersibility control as needed and appropriately collecting the dispersed CNTs after reaggregation is a resource-saving approach. It is also important from a viewpoint.

For these reasons, several examples have been developed that control the dispersibility by changing the structure and solubility of the dispersant under arbitrary conditions, but there are still problems to be solved in each example. Yes.
For example, CNTs are dispersed in micellar form with an amphiphilic compound in which polyethylene glycol is substituted for malachite green, which is a pigment, and the dispersed CNTs are recycled using the solubility change caused by photolytic ionization of malachite green by light irradiation. For the agglomerated material (see Non-Patent Document 1), it is necessary to add a dispersing agent as much as 10 times by weight with respect to CNT, and it cannot be said that CNT is efficiently dispersed.
For those using an amphiphilic oligopeptide as a dispersant, biodegrading only the dispersant using a proteolytic enzyme after CNT dispersion, and isolating the precipitated CNT (see Patent Document 2), In principle, the use is limited only under conditions where the enzyme is active, and the irreversible degradation makes it difficult to recover and reuse the dispersant.
Dispersing agents composed of metal complexes are used to control the affinity for CNTs by utilizing the conformational changes (= changes in molecular structure) caused by chemical oxidation / reduction of the central metal, thereby dispersibility In order to solubilize CNTs, the high-speed vibration pulverization method that requires a special device and the high-power ultrasonic irradiation method are used in combination. However, the method of preparing the dispersion is not simple, and chloroform and amide organic solvents are used as the dispersion solvent. Is concerned.

  The inventors of the present invention have previously described that CNT is stably dispersed in a solvent (water) that does not burden the environment, and that the dispersion state can be easily and efficiently and effectively adjusted, and the repeated dispersion state In order to provide a technique that can change the ionic organic compound, a dispersant for an ionic organic compound having a photochromic chemical structure has been developed (see Patent Document 4). This dispersant is excellent in that CNT can be easily and effectively dispersed in an aqueous solution, and further, the dispersibility of CNT in water can be controlled by photoisomerization reaction of the dispersant by light irradiation. However, it only describes the dispersion reduction, aggregation, and precipitation behavior due to the photoisomerization reaction of CNTs in dispersed aqueous solution, and does not mention the formation of “solid film” or the reactivity in “solid film” at all. .

On the other hand, the following (1) to (5) are known as techniques for manufacturing a CNT film having a predetermined pattern.
(1) A resist material coating process in which a resist material is included in a CNT film or a resist film is laminated (see Patent Documents 5 to 8).
(2) Those requiring an etching process using oxygen plasma, acid, base or the like (see Patent Documents 9 to 11).
(3) Those requiring a step of applying or laminating a film removing agent on the CNT film (see Patent Document 12).
(4) Insulating only by ultraviolet irradiation (see Patent Document 13).
(5) A material in which CNT is dispersed in a resist (see Patent Documents 13 to 16).

However, the above (1) has a problem that a resist process is required and the process operation is complicated, and the above (2) requires a severe etching process, which damages the substrate supporting the CNT film. In the above (3), it is necessary to use a CNT film remover and various solvents, so there is a problem that the process operation is complicated, and the above (4) is an unnecessary part. It is clear that the above (5) has a problem that it requires a large amount of resist and lacks conductivity because the CNT content in the film cannot be made high. It has become.
As described above, in the prior art, there is no method capable of easily forming a patterned CNT film, and there is no concept of a dispersant having a photoresist function.
In addition, carbon black, carbon fiber, graphite particles, etc., which are carbon materials other than CNT, have been completely reported on solubilization / dispersion technology and carbon material film patterning technology to obtain the carbon material film. It has never been done.

JP 2004-2850 A JP 2007-153716 A JP 2009-23886 A WO2011 / 52604A1 Japanese Patent No. 4998619 JP-A-6-252056 Special table 2007-529884 gazette JP-T-2006-513557 JP-A-2005-347378 JP 2002-234000 A JP 2000-90809 A JP 2013-8897 A WO2012 / 176905A1 JP 2008-177165 A JP 2009-93186 A Japanese Patent No. 4270452 Japanese Patent No. 4632341

S. Chen, et al., Langmuir, 24, 9233 (2008). K. Nobusawa et al., Angew. Chem. Int. Ed., 47, 4577 (2008).

The present invention has been made against the background of the prior art as described above, and can easily form a carbon material film such as a CNT film that does not contain a dispersant at all or contains only a small amount of the dispersant. It is a first object to provide a dispersant-containing carbon material film that can be used.
In addition, the present invention provides a carbon material film or a patterned carbon material film that can easily form a carbon material film such as a CNT film that does not contain a dispersant at all or contains a very small amount of the dispersant. Providing a method is a second problem.
In addition, the present invention easily manufactures a patterned carbon material film such as a patterned CNT film having a fine pattern without using a developing means having a severe removal technique such as oxygen plasma or acidic / basic developer. It is a third problem or an auxiliary problem to provide a method for producing a patterned carbon material film that can be performed.

In the course of further researching the related behaviors of various dispersants, including the previously developed dispersants of ionic organic compounds (see Patent Document 4 above) and carbon materials such as CNTs, etc. The following findings (a) to (d) were obtained.
(A) When the dispersant-containing CNT film formed from the CNT dispersion containing the dispersant of the ionic organic compound is exposed to light and then rinsed with a rinse solution, the dispersant is not contained at all. Even if it contains, a CNT film with an extremely small content can be formed.
(A) Therefore, almost the entire amount of the dispersant contained in the dispersant-containing CNT film can be efficiently recovered.
(C) After partially exposing the dispersant-containing CNT film in a predetermined pattern and rinsing with a rinsing liquid, the unexposed part dissolves in the rinsing liquid and flows out. As in photolithography, a negative type Patterned CNT film can be formed.
(D) When the above ionic organic compound dispersant is used, a carbon material dispersion can be prepared for carbon materials such as carbon black, carbon fiber, and graphite particles in the same manner as in the CNT. Since the dispersibility of the carbon material can be controlled by light, it can be used as an alternative to a CNT film.

［式中、Ｒ₁〜Ｒ₆は、それぞれ独立して水素又は炭素数１〜５の直鎖状若しくは炭素数３〜６の分岐状アルキル基である。Ａは炭素原子又は窒素原子である。Ｘはアニオンである。ｎはｎＸが−２価となる数である。］
（２）Ｘは、ハロゲン原子(F，Cl，Br，I)、テトラフルオロホウ酸基(BF₄)、ヘキサフルオロリン酸(PF₆)、ビス(トリフルオロメタンスルホニル)イミド、チオイソシアネート(SCN)、硝酸基(NO₃)、硫酸基(SO₄)、チオ硫酸基(S₂O₃)、炭酸基(CO₃)、炭酸水素基(HCO₃)、リン酸基、亜リン酸基、次亜リン酸基、各ハロゲン酸化合物酸基(AO₄，AO₃，AO₂，AO：A＝Cl，Br，I)、トリス(トリフルオロメチルスルホニル)炭素酸基、トリフルオロメチルスルホン酸基、ジシアンアミド基、酢酸基(CH₃COO)、ハロゲン化酢酸基((CA_nH_3-n)COO，A＝F，Cl，Br，I；n＝1，2，3)、テトラフェニルホウ酸基(BPh₄)及び、その誘導体(B(Aryl)₄：Aryl＝置換フェニル基)から選ばれた少なくとも１種である(１)に記載の分散剤含有炭素材料膜。
（３）基板上に形成されたものである(１)又は(２)に記載の分散剤含有炭素材料膜。
（４）前記炭素材料が、SWCNT、MWCNT、カーボンブラック、炭素繊維、黒鉛粒子からなる群から選択される１種又は２種以上である(１)〜(３)のいずれか１項に記載の分散剤含有炭素材料膜。
（５）(１)〜(４)のいずれか１項に記載の分散剤含有炭素材料膜を含む電子又は電気デバイス製造用材料。
（６）(１)〜(４)のいずれか１項に記載の分散剤含有炭素材料膜を全面露光処理、又は、所定パターンで部分露光処理する露光工程、露光処理された分散剤含有炭素材料膜をリンス液で処理することにより、未露光部分を溶解除去するとともに、露光部分の分散剤を除去するリンス工程を備えることを特徴とする、炭素材料膜又はパターン化炭素材料膜の製造方法。
（７）リンス液は、水又は有機溶媒である(６)に記載の炭素材料膜又はパターン化炭素材料膜の製造方法。
（８）(６)又は(７)に記載の炭素材料膜又はパターン化炭素材料膜の製造方法を含む電気又は電子デバイスの製造方法。The present invention has been completed based on these findings (a) to (d).
That is, this application provides the following inventions.
(1) A dispersant-containing carbon material film having photoresponsiveness and containing a stilbene-based or azobenzene-based dispersant represented by the following general formula (I).

[In formula, R < ₁ > -R < ₆ > is respectively independently hydrogen or a C1-C5 linear or C3-C6 branched alkyl group. A is a carbon atom or a nitrogen atom. X is an anion. n is a number at which nX becomes -2 valent. ]
(2) X is a halogen atom (F, Cl, Br, I), tetrafluoroboric acid group (BF ₄ ), hexafluorophosphoric acid (PF ₆ ), bis (trifluoromethanesulfonyl) imide, thioisocyanate (SCN) , Nitrate group (NO ₃ ), sulfate group (SO ₄ ), thiosulfate group (S ₂ O ₃ ), carbonate group (CO ₃ ), hydrogen carbonate group (HCO ₃ ), phosphate group, phosphite group, Phosphorous acid group, each halogen acid compound acid group (AO ₄ , AO ₃ , AO ₂ , AO: A = Cl, Br, I), tris (trifluoromethylsulfonyl) carbon acid group, trifluoromethylsulfonic acid group, Dicyanamide group, acetic acid group (CH ₃ COO), halogenated acetic acid group ((CA _n H _3-n ) COO, A = F, Cl, Br, I; n = 1, 2, 3), tetraphenylboric acid group The dispersant-containing carbon material film according to (1), which is at least one selected from (BPh ₄ ) and derivatives thereof (B (Aryl) ₄ : Aryl = substituted phenyl group).
(3) The dispersant-containing carbon material film according to (1) or (2), which is formed on a substrate.
(4) The carbon material according to any one of (1) to (3), wherein the carbon material is one or more selected from the group consisting of SWCNT, MWCNT, carbon black, carbon fiber, and graphite particles. Dispersant-containing carbon material film.
(5) A material for manufacturing an electronic or electrical device, comprising the dispersant-containing carbon material film according to any one of (1) to (4).
(6) An exposure process in which the dispersant-containing carbon material film according to any one of (1) to (4) is subjected to an overall exposure process or a partial exposure process in a predetermined pattern, and the dispersant-containing carbon material subjected to the exposure process. A method for producing a carbon material film or a patterned carbon material film, comprising a rinsing step of dissolving and removing an unexposed portion by treating the film with a rinsing liquid and removing a dispersant in the exposed portion.
(7) The method for producing a carbon material film or a patterned carbon material film according to (6), wherein the rinse liquid is water or an organic solvent.
(8) A method for producing an electrical or electronic device, comprising the method for producing a carbon material film or a patterned carbon material film according to (6) or (7).

Furthermore, this invention can also include the following aspects.
(9) The dispersant-containing carbon material film according to any one of (1) to (4), wherein the alkyl group of R _{1 to} R ₆ has 4 or less carbon atoms.
(10) The dispersant-containing carbon material film according to any one of (1) to (4) and (9), wherein a weight ratio of the carbon material and the dispersant is 1: 0.5 to 1:10.
(11) The dispersant-containing carbon material according to any one of (1) to (4), (9), and (10), wherein the content of the liquid solvent capable of dissolving or dispersing the carbon material is less than 5 wt%. film.
(12) The dispersion according to any one of (1) to (4) and (9) to (11), comprising a carbon material, a dispersant, and impurities of less than 1 wt% (including the case of 0 wt%). Agent-containing carbon material film.
(13) The dispersant-containing carbon material film according to any one of (1) to (4) and (9) to (12) having a thickness of 1 nm to 100 μm.
(14) The dispersant-containing carbon material film according to (3), wherein the substrate is made of glass, synthetic resin, ceramics, metal, semiconductor, a composite thereof, a single crystal, or a laminate thereof.
(15) An exposure process in which the dispersant-containing carbon material film according to any one of (9) to (14) is subjected to a whole surface exposure process or a partial exposure process in a predetermined pattern, and the dispersant-containing carbon material subjected to the exposure process. A method for producing a carbon material film or a patterned carbon material film, comprising a rinsing step of dissolving and removing an unexposed portion by treating the film with a rinsing liquid and removing a dispersant in the exposed portion.
(16) X is at least one selected from a halogen atom (F, Cl, Br, I), a nitrate group (NO ₃ ), and a sulfate group (SO ₄ ), and the rinse liquid is water (6) Or the manufacturing method of the carbon material film or patterned carbon material film as described in (15).
(17) X is at least one selected from a tetrafluoroboric acid group (BF ₄ ), a hexafluorophosphoric acid (PF ₆ ), and a tetraphenylboric acid group (BPh ₄ ), and the rinse liquid is dimethyl sulfoxide. The method for producing a carbon material film or a patterned carbon material film according to (6) or (15), which is at least one organic solvent selected from (DMSO), dimethylformamide (DMF), and tetrahydrofuran (THF).

If the dispersant-containing carbon material film of the present invention is used, it is only necessary to rinse with a rinsing liquid such as water after the exposure process. A carbon material film having an extremely low content can be easily obtained. Therefore, the produced carbon material film can effectively exhibit the original performance and characteristics of the carbon material.
In addition, when the dispersant-containing carbon material film of the present invention is used, it has an arbitrary pattern (fine pattern) as in conventional photolithography by a simple process including an exposure process of a predetermined pattern and a subsequent rinsing process. Patterned carbon material films can be manufactured. The patterned carbon material film to be produced does not contain a dispersant at all, or even if it contains a dispersant, as in the case of the above-mentioned carbon material film, the content is extremely small, so that the original performance and characteristics of the carbon material are exhibited. be able to.
Furthermore, the method for producing the patterned carbon material film uses a developing means in which removal methods such as oxygen plasma and acidic / basic developer are severe conditions after exposure, as in the conventional patterning method. Therefore, there is no possibility of damaging the substrate supporting the carbon material film. Therefore, even a substrate having poor solvent resistance such as PET can be used effectively without fear of damage.
In the rinsing process of forming a carbon material film or a patterned carbon material film from the dispersant-containing carbon material film, almost all of the dispersant contained in the dispersant-containing carbon material film can be efficiently recovered. Therefore, the dispersant can be effectively used at low cost.
The above-described effects can be obtained not only when the carbon material is SWCNT or MWCNT CNT but also with carbon black, carbon fiber, graphite particles, or the like.

The flowchart which shows the manufacturing process of the patterned CNT film | membrane which has a fine pattern as an embodiment of this invention. (1) A photograph of a CNT film of Comparative Example 1 formed using the dispersant of the Comparative Example [Formula (2), R ₃ , R ₄ = Linear C ₈ H ₁₇ ]. (2) A photograph of the CNT film of Example 1 formed using the dispersant [formula (2), R ₃ , R ₄ = linear C ₄ H ₉ ] of the example of the present invention. The drawing which shows the ultraviolet visible near-infrared absorption spectrum before and behind the water washing | cleaning at the time of carrying out the water washing of the dispersing agent containing CNT film | membrane manufactured based on Example 1 unexposed. The dotted line shows the spectrum before water washing, and the solid line shows the spectrum after water washing. (A) shows the entire range of wavelengths 200 to 1800 nm, and (B) and (C) are partially enlarged views thereof. (B) is an enlarged view of the wavelength range of 200 to 600 nm including the absorption region of the dispersant, and (C) is an enlarged view of the wavelength range of 600 to 1800 nm including the absorption region of CNT. 1 is a drawing showing an ultraviolet-visible near-infrared absorption spectrum for a dispersant-containing CNT film produced based on Example 1. FIG. The two-dot double-short chain line shows the spectrum after film formation, the dotted line shows the spectrum after light irradiation (385 nm, 100 mW / cm ² , 1 hr), and the solid line shows the spectrum after light irradiation and water washing. (A) shows the entire range of wavelengths 200 to 1800 nm, and (B) and (C) are partially enlarged views thereof. (B) is an enlarged view of the wavelength range of 200 to 600 nm including the absorption region of the dispersant, and (C) is an enlarged view of the wavelength range of 600 to 1800 nm including the absorption region of CNT. About the dispersant-containing CNT dispersion film of the embodiment of the present invention, the upper figure shows a state where it is partially irradiated with light using a mask or the like, and the lower figure shows a state where it is partially irradiated with light and then rinsed with water. Drawing which shows typically. BRIEF DESCRIPTION OF THE DRAWINGS Drawing which shows typically the manufacturing process of the patterned CNT film | membrane as an embodiment of this invention. 3 is an optical micrograph of a patterned CNT film formed on a quartz substrate based on Example 1. FIG. 3 is an optical micrograph of a patterned CNT film formed on a PET substrate based on Example 2. FIG. 2 is a drawing showing a photoisomerization reaction (absorption spectra before and after light irradiation) in an aqueous solution of an azobenzene dispersant used alone in Example 3. FIG. The solid line shows the spectrum before light irradiation, and the dotted line shows the spectrum after light irradiation (385 nm, 100 mW / cm ² , 15 min). 4 is a drawing showing an ultraviolet-visible near-infrared absorption spectrum of a dispersant-containing CNT film produced based on Example 3. FIG. The two-dot double-short chain line shows the spectrum after film formation, the dotted line shows the spectrum after light irradiation (385 nm, 100 mW / cm ² , 1 hr), and the solid line shows the spectrum after light irradiation and water washing. (A) shows the entire range of wavelengths 200 to 1800 nm, and (B) and (C) are partially enlarged views thereof. (B) is an enlarged view of the wavelength range of 200 to 600 nm including the absorption region of the dispersant, and (C) is an enlarged view of the wavelength range of 600 to 1800 nm including the absorption region of CNT. 4 is a micrograph of a patterned CNT film formed on a quartz substrate based on Example 3. FIG. When the carbon material is carbon black # 2600, (A) is a photograph of an example dispersion liquid containing a stilbene compound as a dispersant. (B) is a photograph showing the dispersibility of the Example dispersion before and after light irradiation. (C) is a photograph showing a comparative example containing no dispersant. When the carbon material is carbon black # 4000, (A) is a photograph of an example dispersion liquid containing a stilbene compound as a dispersant. (B) is a photograph showing the dispersibility of the Example dispersion before and after light irradiation. (C) is a photograph showing a comparative example containing no dispersant. (D) is a photograph in which the container is tilted and its bottom is enlarged in the comparative example. When the carbon material is vapor grown carbon fiber VGCF, (A) is a photograph of an example dispersion liquid containing a stilbene compound as a dispersant. (B) Drawing which shows the UV-vis-NIR absorption spectrum of the Example dispersion liquid using heavy water. (C) is a photograph showing a comparative example containing no dispersant. In the case where the carbon material is natural high-purity graphite particles, (A) is a photograph of an example dispersion liquid containing a stilbene compound as a dispersant. (B) Drawing which shows the UV-vis-NIR absorption spectrum of the Example dispersion liquid using heavy water. (C) is a photograph showing a comparative example containing no dispersant. In the case where the carbon material is Meijo nanocarbon SWCNT APJ, (A) is a photograph of an example dispersion liquid containing a stilbene compound as a dispersant and dispersed in heavy water by bath-type ultrasonic waves. (B) is a drawing showing the UV-vis-NIR absorption spectrum of the dispersion liquid of the example dispersed in heavy water by bath ultrasonic waves. (C) is a photograph of an example dispersion containing a stilbene compound as a dispersant and dispersed in heavy water by horn type ultrasonic waves. (D) is a drawing showing the UV-vis-NIR absorption spectrum of the dispersion liquid of the example dispersed in heavy water by horn type ultrasonic waves. In the case where the carbon material is Meijo nanocarbon SWCNT SO, (A) is a photograph of an example dispersion liquid containing a stilbene compound as a dispersant and dispersed in heavy water by bath-type ultrasonic waves. (B) is a drawing showing the UV-vis-NIR absorption spectrum of the dispersion liquid of the example dispersed in heavy water by bath ultrasonic waves. (C) is a photograph of an example dispersion containing a stilbene compound as a dispersant and dispersed in heavy water by horn type ultrasonic waves. (D) is a drawing showing the UV-vis-NIR absorption spectrum of the dispersion liquid of the example dispersed in heavy water by horn type ultrasonic waves. When the carbon material is super growth, (A) is a photograph of an example dispersion liquid containing a stilbene compound as a dispersing agent and dispersed in heavy water by bath-type ultrasonic waves. (B) is a drawing showing the UV-vis-NIR absorption spectrum of the dispersion liquid of the example dispersed in heavy water by bath ultrasonic waves. (C) is a photograph of an example dispersion containing a stilbene compound as a dispersant and dispersed in heavy water by horn type ultrasonic waves. (D) is a drawing showing the UV-vis-NIR absorption spectrum of the dispersion liquid of the example dispersed in heavy water by horn type ultrasonic waves. When the carbon material is SWeNT, SG65, (A) is a photograph of an example dispersion liquid containing a stilbene compound as a dispersing agent and dispersed in heavy water by bath-type ultrasonic waves. (B) is a drawing showing the UV-vis-NIR absorption spectrum of the dispersion liquid of the example dispersed in heavy water by bath ultrasonic waves. (C) is a photograph of an example dispersion containing a stilbene compound as a dispersant and dispersed in heavy water by horn type ultrasonic waves. (D) is a drawing showing the UV-vis-NIR absorption spectrum of the dispersion liquid of the example dispersed in heavy water by horn type ultrasonic waves. The photograph of the Example dispersion liquid which disperse | distributed with the bath type | mold ultrasonic wave in the ultrapure water containing a stilbene compound as a dispersing agent about various multi-walled carbon nanotubes. (A) is MWCNT (Wako Chemical, 40-60 nm), (B) is MWCNT (Ube Industries, AMG), (C) is MWCNT (C-Nano, FloTube 9000 (GI)), (D) is MWCNT ( Kawaken Fine Chemicals, KC-CNT).

  The present invention has a photoresponsiveness, a dispersant-containing carbon material film such as a dispersant-containing CNT film containing a stilbene-based or azobenzene-based dispersant represented by the above general formula (I), and the dispersion This is a method for producing a carbon material film or a patterned carbon material film using an agent-containing carbon material film.

<< dispersant >>
The dispersant represented by the general formula (I) is a stilbene or azobenzene type, exhibits photoresponsiveness or photochromic properties, and is usually non-crystalline.
In the general formula (I), when R _{1 to} R ₆ are long alkyl chains such as linear C ₈ H ₁₇ , the crystallinity is high, and the heterogeneity is poor and the photoresponsiveness is poor. Therefore, in the present invention, R _{1 to} R ₆ are each independently hydrogen, straight chain having 1 to 5 carbon atoms or 3 to 6 carbon atoms so that the dispersant compound exhibits photoresponsiveness and photochromic properties. Selected from the following branched alkyl groups. Such alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neo-pentyl, tert-pentyl. Group, isohexyl group and the like.

In the general formula (I), X is an anion, and usually a monovalent one can be preferably used, but an anion other than a monovalent can also be used by anion exchange. The anion X is, for example, a halogen atom (F, Cl, Br, I), a tetrafluoroboric acid group (BF ₄ ), hexafluorophosphoric acid (PF ₆ ), bis (trifluoromethanesulfonyl) imide, thioisocyanate (SCN) ), Nitrate group (NO ₃ ), sulfate group (SO ₄ ), thiosulfate group (S ₂ O ₃ ), carbonate group (CO ₃ ), bicarbonate group (HCO ₃ ), phosphate group, phosphite group, Hypophosphorous acid group, each halogen acid compound acid group (AO ₄ , AO ₃ , AO ₂ , AO: A = Cl, Br, I), tris (trifluoromethylsulfonyl) carbon acid group, trifluoromethylsulfonic acid group , Dicyanamide group, acetic acid group (CH ₃ COO), halogenated acetic acid group ((CA _n H _3-n ) COO, A = F, Cl, Br, I; n = 1, 2, 3), tetraphenylboric acid It is selected from the group (BPh ₄ ) and its derivatives (B (Aryl) ₄ : Aryl = substituted phenyl group).
A preferred anion is a halogen atom such as Cl.

<< carbon material >>
Examples of the carbon material used in the present invention include various CNTs, carbon black, carbon fibers, and graphite particles. The raw material carbon material used in the present invention may be any material as long as at least a part of the carbon material can be dispersed in a solvent using the ionic organic compound dispersant, and the carbon material dispersed in the solvent is a dispersant-containing carbon material. It can be a carbon material of a film or a carbon material film formed therefrom. Therefore, when the raw material carbon material is in the form of particles, it contains particles having a particle diameter of 50 μm or less that can be dispersed in a solvent (for example, a volume-based average particle diameter D ₅₀ measured using a laser diffraction scattering method). Is 100 μm or less, preferably 50 μm or less, etc. Note that the lower limit of the average particle diameter is not necessarily limited from the viewpoint of dispersibility, but is usually 0.5 nm or more. In addition, fibers containing fibers having a fiber length of 50 μm or less that can be dispersed in a solvent (for example, fibers having an average fiber length of 50 μm or less, preferably 30 μm or less, etc. In addition, from the viewpoint of dispersibility, the lower limit of the average fiber length Is not necessarily limited, but is usually 5 nm or more.
The CNT used in the present invention may be produced by any production method such as HiPco method, arc method, laser ablation method, CVD method, super growth CVD method, DIPS method, etc. ), Multiple layers (MWCAT) such as two-layer (DWCNT), or a mixture thereof. Further, after the production of CNTs, the product may be separated by properties such as semiconductivity and metallic properties, structure, size, and / or purified for impurity removal.

<< Dispersant-containing carbon material film, production thereof >>
Although the manufacturing method of the dispersant-containing carbon material film of the present invention is not limited, for example, it can be manufactured by the following steps (see FIG. 1 using CNT as a representative example of the carbon material).
(1) Carbon material dispersion preparation step (1-1) Preparation of dispersant solution (1-2) Mixing of dispersant solution and carbon material (2) Dispersant-containing carbon material film formation step

As a solvent for the dispersant solution, water or various organic solvents can be used depending on the hydrophilicity of the anion X of the dispersant.
For example, water can be suitably used for an anionic X dispersant having a particularly high hydrophilicity, such as a halogen atom (F, Cl, Br, I), a nitrate group (NO ₃ ), and a sulfate group (SO ₄ ).
On the other hand, a dispersing agent for anion X, such as tetrafluoroboric acid group (BF ₄ ), hexafluorophosphoric acid (PF ₆ ), and tetraphenylboric acid group (BPh ₄ ), which is relatively less hydrophilic than halogen atoms and the like. For example, polar organic solvents such as dimethyl sulfoxide (DMSO), dimethylformamide (DMF), and tetrahydrofuran (THF) can be preferably used.

The mixing ratio (weight basis) of the carbon material and the dispersant is not limited, but is 1: 0.5 to 1:10, preferably 1: 0.7 to 1: 8, more preferably 1: 0. .8 to 1: 5, more preferably 1: 0.9 to 1: 3.
The dispersing agent solution and the carbon material are preferably subjected to ultrasonic dispersion treatment using a known appropriate ultrasonic device so that the mixing is uniform. Depending on the type, shape, diameter, length, and the like of the carbon material, there may be a case where the output, the output frequency, and the like can be dispersed by selecting an appropriate ultrasonic device.
In addition, when the CNT to be used is not sufficiently separated and purified in advance, a separation step such as centrifugation can be added to remove impurities such as metal catalyst and amorphous carbon after mixing and dispersion treatment. . For example, in the case of centrifugation, impurities can be precipitated, and the CNT dispersion from which impurities have been removed can be obtained by collecting the entire supernatant and about 70 to 95% (preferably about 75 to 85%) of the supernatant.

  The carbon material dispersion can be formed into a dispersant-containing carbon material film using a known film forming means such as a casting method or a coating method (coating method). The substrate on which the dispersant-containing carbon material film is formed is not limited, but glass (for example, quartz glass such as fused silica), synthetic resin (for example, polyester resin such as PET, polyimide, fluorine-based resin, etc. ), Ceramics, metals, semiconductors, composites, single crystals, or laminates thereof can be used. Examples of the single crystal include single crystals that are transparent in the ultraviolet, visible, and near infrared regions, such as calcium fluoride and sapphire. The substrate may be bonded so that the dispersant-containing carbon material film cannot be peeled, or the surface may be pretreated so as to increase the bonding strength, or a material that can be easily peeled after film formation. The thing of which the surface was peeled off may be sufficient.

For example, in the case of forming a film by the casting method, a sheet having cast through holes is brought into close contact with the substrate surface, and the above carbon material dispersion is injected with the through hole having the substrate surface as a bottom surface as a molding space. Can be cast. The sheet is not limited, but is about 0.1 to 1 mm thick (preferably about 0.2 to 0.8 mm) thicker than the film to be formed, and has adhesion to the substrate and releasability to the dispersant-containing carbon material film. It is preferably made of a good material. Suitable materials for the sheet include, but are not limited to, various rubbers such as silicon rubber and thermoplastic elastomer, and fluorine resins.
Instead of using a sheet serving as a frame for such a molding space, a substrate having a concave portion serving as a molding space on the surface can be used.

The carbon material dispersion injected into the forming space is formed into a dispersant-containing carbon material film by removing all or most of the solvent by an appropriate drying means or solvent removal means such as drying under reduced pressure. At this time, the content of the solvent is set to 5 wt% or less (preferably 1 wt% or less, more preferably 0.1 wt% or less, most preferably 0 wt%) so that the film shape is maintained.
The dispersant-containing carbon material film preferably does not contain components other than the carbon material, the dispersant, and the solvent, but in a range that does not hinder the responsiveness of the dispersant and the rinse treatment with the rinse liquid (for example, 5 wt% or less, (Preferably 2 wt% or less, more preferably 1 wt% or less) The inclusion of other components is acceptable.

The formed dispersant-containing carbon material film may have any planar shape and width depending on the purpose and application. The thickness of the dispersant-containing carbon material film is not limited, but when forming a carbon material film bonded to the substrate, the light irradiated on the front surface is the dispersant on the back surface side (side closer to the substrate surface). 1 nm to 300 μm (e.g., within a range of 10 nm to 200 μm, 20 nm to 100 μm, etc.) so that the light reaches and is irradiated.
In order to form a relatively thick dispersant-containing carbon material film, the first dispersant-containing carbon material primary thin film is formed by the step (2), and then the step (2) is repeated a plurality of times. The carbon material primary thin film may be laminated on the thin film a plurality of times.

<< Production of carbon material film or patterned carbon material film >>
When the dispersant-containing carbon material film formed as described above is used, the carbon material film or the patterned carbon material film can be easily manufactured by the following steps.
(3) Exposure processing step (entire film exposure or partial exposure with a predetermined pattern)
(4) Rinsing process

Through the exposure processing step, the exposed part of the dispersant develops photoresponsiveness and isomerizes from E form (trans form) to Z form (cis form).
As light used in the exposure processing step, light in the visible ultraviolet region (about 200 nm to 600 nm) can be used as long as it can perform EZ isomerization, but preferably ultraviolet light of 200 to 400 nm (for example, , 365nm bandpass filter or 385nm bandpass filter, monochromatic LED light source, etc.).

  The exposure process with the predetermined pattern can be performed by covering the dispersant-containing carbon material film with a mask on which the predetermined pattern is formed and irradiating light from above the mask (see FIG. 5 and FIG. 6 (3)). Further, the direct exposure method may be used in which the irradiation means for irradiating only a predetermined region is moved relative to the dispersant-containing carbon material film along a predetermined pattern without using a mask.

When the dispersion-containing carbon material film after exposure treatment is treated with a rinse liquid, the dispersant loses affinity with the carbon material due to EZ isomerization in the exposed part and is peeled off from the carbon material. The material loses solubility and remains in a state of being associated (bundled) with each other as a carbon material film on the substrate. The dispersant that has lost its affinity with the carbon material is dissolved in the rinse liquid and flows out together with the rinse liquid. Therefore, the exposed portion does not contain any dispersant (dispersant content is 0 wt%), or even if it contains a dispersant, the carbon material film has a very low content (such as a rinse liquid flow rate for rinsing) Depending on the degree of processing time, the dispersant content is less than 1 wt%, preferably less than 0.1 wt%, more preferably less than 0.01 wt%). It becomes.
On the other hand, if there is an unexposed part, the dispersant remains in the E form and maintains affinity with the carbon material in the unexposed part. Therefore, the carbon material adsorbed by the dispersant is dissolved or dispersed in the rinse liquid. The carbon material film is not formed at all because it flows out together with the rinse liquid. Therefore, a negative patterned carbon material film is formed as in the negative photolithography.

As the rinsing liquid used in the rinsing step, water or various organic solvents can be used depending on the hydrophilicity of the anion X of the dispersant.
For example, water can be suitably used for an anionic X dispersant having a particularly high hydrophilicity, such as a halogen atom (F, Cl, Br, I), a nitrate group (NO ₃ ), and a sulfate group (SO ₄ ).
On the other hand, dispersion of anions X such as tetrafluoroboric acid group (BF ₄ ), hexafluorophosphoric acid (PF ₆ ), tetraphenylboric acid group (BPh ₄ ), etc., which is relatively less hydrophilic than halogen atoms etc. As the agent, for example, a polar organic solvent such as dimethyl sulfoxide (DMSO), dimethylformamide (DMF), tetrahydrofuran (THF) and the like can be suitably used.

As described above, in the present invention, by using the above-described dispersant-containing carbon material film, a carbon material film or a patterned carbon material that does not contain a dispersant or has a very small content even if it contains a dispersant. The membrane can be easily manufactured.
The produced carbon material film and the patterned carbon material film are not limited, but may be widely used in technical fields such as electrical circuits and electronic devices such as wiring circuits, electrodes such as pad electrodes and capacitor electrodes. it can.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these Examples.

Example 1
<Production of dispersant-containing CNT film using stilbene-based dispersant and patterned CNT film using the dispersant-containing CNT film>
Preparation of CNT dispersion 3 mg of a stilbene compound represented by the following general formula (II), in which R ₃ and R ₄ are butyl groups, was weighed and purified with 3 ml of ultrapure water (Purelab / ELGA) Dispersed in water) to prepare a dispersant aqueous solution. 1 mg of SWCNT (prepared by HiPco method / NanoIntegris) was weighed and mixed with the aqueous dispersant solution. The mixed aqueous solution was treated with bath-type ultrasonic waves (37kHz, 80W, 1hr) to promote CNT dispersion. The resulting black liquid is centrifuged (25000xg, 4hrs, 5417R / eppendorf) to precipitate impurities such as catalytic metals and amorphous carbon, and 80% of the supernatant is recovered to remove the impurities. It was.

Preparation of dispersant-containing CNT film A fused quartz substrate (hereinafter referred to as quartz substrate) measuring 3 cm wide × 3 cm long × 1 mm thick was ultrasonically cleaned with ethanol (37 kHz, 80 W, 1 hr). Thereafter, the substrate was dried under reduced pressure to obtain a clean substrate surface. A silicon rubber sheet having a width of 3 cm, a length of 3 cm, and a thickness of 0.5 mm, with a hole of φ16 mm, was prepared and adhered to the quartz substrate described above. 300 μl of the above CNT dispersion was poured into a recess (molding space) surrounded by a quartz substrate and a silicon rubber sheet. The obtained liquid film was decompressed in a desiccator, and the solvent was removed to obtain a cast dispersant-containing CNT film (weight ratio of CNT to dispersant in the dispersant-containing CNT film was about 1: 3, liquid solvent Content is less than 0.1 wt%).

-Examination of change in solubility due to light irradiation Regarding the obtained dispersant-containing CNT film, the difference in solubility of the film with and without light irradiation was investigated. When the unexposed film was rinsed with ultrapure water, the dispersant-containing CNT film dissolved. FIG. 3 shows the measurement results of the ultraviolet visible near infrared absorption spectrum. It was found that the water washing reduced absorption due to the dispersant and CNT, and the dispersant-containing CNT film was removed from the substrate. Next, the effect of light irradiation was investigated. FIG. 4 shows ultraviolet-visible near-infrared absorption spectra (385 nm, 100 mW / cm ² , 1 hr) of the film before irradiation, after irradiation, and after washing with water. The photoreaction of the dispersing agent in the film proceeded sufficiently by irradiation with light. Furthermore, it was found that the dispersant was removed by washing with water after light irradiation (dispersant content in the CNT film was less than 0.1 wt%). On the other hand, since the CNT from which the dispersant was peeled lost its solubility, it remained on the substrate even after washing with water. From the above results, it was found that the exposed portion and the unexposed portion have different solubility in water (exposed portion: insolubilized, unexposed portion: dissolved). FIG. 5 shows a schematic representation of the mechanism using CNT as a representative example of the carbon material.

-Pattern formation by mask exposure The knowledge obtained above was applied to fine structure formation by mask exposure. FIG. 6 shows a mask exposure process using CNT as a representative example of the carbon material. The cast film (dispersant-containing CNT film) produced according to the above-mentioned process was subjected to mask exposure through a test pattern made by letterpress printing (385 nm, 100 mW / cm ² , 1 hr). After the exposure, rinsing with water and washing away the unexposed part formed a negative type patterned CNT film [see FIG. 7, “L / S: numerical value μm” is the wiring width (L ) And the interval (S) are the numerical values (μm). The same applies to FIGS. 8 and 11 below). It was found that line widths of 10 μm or less, which is difficult with screen printing, can be processed.
The CNT used here may be a single layer or a multilayer. In addition, any CNT can be used regardless of the production method.

(Comparative Example 1)
A CNT dispersion liquid and a dispersant-containing CNT film were prepared in the same manner as in Example 1 except that R ₃ and R ₄ in the general formula (II) were linear C ₈ H _17. It was. When R ₃ and R ₄ are long alkyl chains such as linear C ₈ H ₁₇ , the crystallinity becomes high, resulting in a heterogeneous film with poor photoresponsiveness (see FIG. 2 (1)).

(Example 2)
<Production of dispersant-containing CNT film using stilbene-based dispersant and patterned CNT film using the dispersant-containing CNT film>
In the method shown in Example 1, the above compound was used as a photoresponsive CNT dispersant, and HiPco was used as a SWCNT to produce a dispersant-containing CNT film on a PET (East Lermir U35, readily accessible untreated surface) substrate ( The weight ratio of CNT and dispersant in the dispersant-containing CNT film was about 1: 3, and the liquid solvent content was less than 0.1 wt%) and fine processing was performed through mask exposure (containing the dispersant in the patterned CNT film) The amount is less than 0.1wt%). Even with a poorly hydrophilic substrate such as PET (a substrate with poor CNT dispersion), a cast film could be easily produced by forming a frame with a Si rubber sheet. The result of the optical microscope observation of the obtained finely processed film is shown in FIG. It was found that line widths of 10 μm or less, which is difficult with screen printing, can be processed.
The CNT used here may be a single layer or a multilayer. In addition, any CNT can be used regardless of the production method.

(Example 3)
<Manufacture of a dispersant-containing CNT film using an azobenzene-based dispersant and a patterned CNT film using the dispersant-containing CNT film>
In the method shown in Example 1, instead of the stilbene compound of the general formula (II), an azobenzene compound represented by the following general formula (III) (wherein R ₃ and R ₄ are ethyl groups) is a photoresponsive CNT. Used as a dispersant, HiPco as SWCNT, and produced a dispersant-containing CNT film on a fused quartz substrate (weight ratio of CNT and dispersant in the dispersant-containing CNT film was about 1: 3, and the content of liquid solvent was 0.1 less than wt%) and fine processing via mask exposure (dispersant content in the patterned CNT film is less than 0.1 wt%). As shown in the spectrum of FIG. 9, the compound represented by the general formula (III) undergoes EZ isomerization by irradiation with 385 nm light, and quickly returns to the E form in the dark. The effect of light irradiation was investigated on the obtained CNT film. FIG. 10 shows ultraviolet-visible near-infrared absorption spectra (385 nm, 100 mW / cm ² , 1 hr) of the film before irradiation, after irradiation, and after washing with water. The photoreaction of the dispersing agent in the film proceeded sufficiently by irradiation with light. Furthermore, it was found that the dispersant was removed by washing with water after light irradiation. On the other hand, since the CNT from which the dispersant was peeled lost its solubility, it remained on the substrate even after washing with water. It has been found that even when the EZ photoisomerization reaction of the azobenzene compound is used, an effect similar to that of the stilbene compound can be obtained. The result of optical microscope observation of the microfabricated film obtained by mask exposure of the dispersant-containing CNT film is shown in FIG.
The CNT used here may be a single layer or a multilayer. In addition, any CNT can be used regardless of the production method.

Example 4
Preparation of carbon black dispersion 2.96 mg of a stilbene compound represented by the general formula (II) used in Example 1, wherein R ₃ and R ₄ are butyl groups, was weighed and 3 ml of ultrapure water (Purelab Dissolving agent in water / ELGA purified water) to prepare a dispersant aqueous solution. 0.95 mg of carbon black (Mitsubishi Chemical # 2600, arithmetic average particle size 13 nm) was weighed and mixed with the aqueous dispersant solution. The mixed aqueous solution was treated with bath-type ultrasonic waves (37kHz, 80W, 1hr) to promote the dispersion of carbon black. The resulting black liquid was used as a carbon black dispersion. The state of the dispersion is shown in FIG.

・ Dispersion control by light of carbon black dispersion liquid The carbon black dispersion liquid obtained above is injected into a dialysis tube (SPECTRUM, Spectra por7, membrane 1000), and then ultra-pure water (water purified by Purelab / ELGA) overnight. Dialysis operation was performed. By this operation, excess dispersant can be removed, and the next photoreaction operation can proceed smoothly.
When the carbon black dispersion liquid after dialysis was transferred to a PMMA cell and irradiated with light (365 nm, 50 mW / cm 2, 7 hours), carbon black that lost dispersibility due to the photoreaction of the stilbene compound was precipitated (FIG. 12 ( See B)).

(Comparative Example 2)
The dispersion of carbon black (Mitsubishi Chemical # 2600, 1.03 mg) was promoted in the same manner as in Example 4 except that ultrapure water containing no stilbene compound was used in Example 4. In this case, a carbon black dispersion liquid could not be obtained due to strong aggregation of the carbon blacks (see FIG. 12C).

(Example 5)
-Preparation of carbon black dispersion In the method shown in Example 4, # 4000B (1.04 mg, arithmetic average particle size 24 nm) was used instead of # 2600 (dispersant: 2.96 mg used). Similarly, a carbon black dispersion was obtained. The state of the dispersion is shown in FIG.

-Dispersion control by light of carbon black dispersion liquid The dispersibility of carbon black can be controlled by light in the same manner as in Example 4 except that # 4000B is used instead of # 2600. did it. See FIG.

(Comparative Example 3)
The dispersion of carbon black (# 4000B, 1.17 mg) was promoted in the same manner as in Example 5 except that ultrapure water containing no stilbene compound was used in Example 5. In this case, oil film-like precipitates, precipitates, and the like were confirmed, and a homogeneous carbon black dispersion could not be obtained (see FIG. 13C).

(Example 6)
-Preparation of gas-phase-process carbon fiber VGCF dispersion 31.35 mg of a stilbene compound represented by the general formula (II) used in Example 1, wherein R ₃ and R ₄ are butyl groups, was weighed in excess of 20 ml. Dispersant aqueous solution was prepared by dissolving in pure water (water purified by Purelab / ELGA). 10.43 mg of vapor grown carbon fiber VGCF (Showa Denko, VGCF-H, fiber diameter 150 nm, hereinafter referred to as “VGCF”) was weighed and mixed with the aqueous dispersant solution. The mixed aqueous solution was pretreated with bath-type ultrasonic waves (37 kHz, 80 W, 1 hr), and then promoted dispersion of VGCF by horn-type ultrasonic waves (19 kHz, 60 W, 10 h). The obtained black liquid was used as a VGCF dispersion. The state of the dispersion is shown in FIG. Further, the same operation was performed using heavy water, and a UV-vis-NIR absorption spectrum was measured (see FIG. 14B).

(Reference Example 1)
3.41 mg of stilbene compound 3 represented by the general formula (II) used in Example 1, wherein R ₃ and R ₄ are butyl groups, was weighed and purified by 3 ml of ultrapure water (Purelab / ELGA). Dispersed in water) to prepare a dispersant aqueous solution. 1.18 mg of VGCF (Showa Denko, VGCF-H) was weighed and mixed with the aqueous dispersant solution. The mixed aqueous solution was treated with bath-type ultrasonic waves (37 kHz, 80 W, 1 hr), but precipitation occurred due to the low output frequency, and a good dispersion could not be obtained (see FIG. 14C).

(Example 7)
-Preparation of natural high-purity graphite particle dispersion 30.00 mg of a stilbene compound represented by the general formula (II) used in Example 1, wherein R ₃ and R ₄ are butyl groups, was weighed and 20 ml of ultrapure Dispersant aqueous solution was prepared by dissolving in water (water purified by Purelab / ELGA). 11.45 mg of natural high-purity graphite particles (SEC carbon, SNO-30, containing particles having a particle size of about 30 μm) were weighed and mixed with the aqueous dispersant solution. The mixed aqueous solution was pretreated with bath-type ultrasonic waves (37 kHz, 80 W, 1 hr), and then promoted dispersion of natural high-purity graphite particles by horn-type ultrasonic waves (19 kHz, 60 W, 10 hr). The resulting black liquid was used as a natural high purity graphite dispersion. The state of the dispersion is shown in FIG. Further, the same operation was performed using heavy water, and a UV-vis-NIR absorption spectrum was measured (see FIG. 15B).

(Reference Example 2)
30.58 mg of a stilbene compound represented by the general formula (II) used in Example 1, wherein R ₃ and R ₄ are butyl groups, was weighed, and 20 ml of ultrapure water (water purified by Purelab / ELGA) ) To prepare a dispersant aqueous solution. 9.89 mg of natural high purity graphite particles (SEC carbon, SNO-30) were weighed and mixed with the aqueous dispersant solution. The mixed aqueous solution was treated with bath-type ultrasonic waves (37 kHz, 80 W, 1 hr), but precipitation occurred due to the low output frequency, and a good dispersion could not be obtained (see FIG. 15C).

(Example 8)
・ Preparation of Meijo Nanocarbon SWCNT APJ Dispersion Weighed 3.36 mg of a stilbene compound represented by the general formula (II) used in Example 1, wherein R ₃ and R ₄ are butyl groups, and added to 3 ml of heavy water. Dissolved to prepare a dispersant aqueous solution. Single-walled carbon nanotubes (Meijo Nanocarbon, APJ, φ1.4 nm, length 1-5 μm) were weighed 1.01 mg and mixed with the aqueous dispersant solution. The mixed aqueous solution was made into a black liquid by bath-type ultrasonic waves (37 kHz, 80 W, 1 hr). This black liquid was processed by centrifugation (25000 × g, 4 hrs, 5417R / eppendorf) to obtain a CNT dispersion. The state of the dispersion is shown in FIG. In addition, a UV-vis-NIR absorption spectrum was measured (see FIG. 16B).
Further, 9.99 mg of a stilbene compound represented by the general formula (II) used in Example 1, wherein R ₃ and R ₄ are butyl groups, is weighed and dissolved in 20 ml of heavy water to prepare a dispersant aqueous solution. did. 6.69 mg of single-walled carbon nanotubes (Meijo Nanocarbon, APJ) were weighed and mixed with the aqueous dispersant solution. The mixed aqueous solution was made into a black liquid by horn type ultrasonic waves (19 kHz, 20 W, 4 hr). This black liquid was processed by centrifugation (25000 × g, 4 hrs, 5417R / eppendorf) to obtain a CNT dispersion. The state of the dispersion is shown in FIG. In addition, a UV-vis-NIR absorption spectrum was measured (see FIG. 16D).

Example 9
・ Preparation of Meijo Nanocarbon SWCNT SO Dispersion 3.62 mg of stilbene compound represented by the general formula (II) used in Example 1, wherein R ₃ and R ₄ are butyl groups, was weighed into 3 ml of heavy water. Dissolved to prepare a dispersant aqueous solution. 0.98 mg of single-walled carbon nanotubes (Meijo Nanocarbon, SO, φ1-2.5 nm, length—10 μm) was weighed and mixed with the aqueous dispersant solution. The mixed aqueous solution was made into a black liquid by bath-type ultrasonic waves (37 kHz, 80 W, 1 hr). This black liquid was processed by centrifugation (25000 × g, 4 hrs, 5417R / eppendorf) to obtain a CNT dispersion. The state of the dispersion is shown in FIG. In addition, a UV-vis-NIR absorption spectrum was measured (see FIG. 17B).
Further, 10.03 mg of a stilbene compound represented by the general formula (II) used in Example 1, wherein R ₃ and R ₄ are butyl groups, is weighed and dissolved in 20 ml of heavy water to prepare an aqueous dispersion solution. did. 6.72 mg of single-walled carbon nanotube (Meijo Nanocarbon, APJ) was weighed and mixed with the aqueous dispersant solution. The mixed aqueous solution was made into a black liquid by horn type ultrasonic waves (19 kHz, 20 W, 4 hr). This black liquid was processed by centrifugation (25000 × g, 4 hrs, 5417R / eppendorf) to obtain a CNT dispersion. The state of the dispersion is shown in FIG. In addition, a UV-vis-NIR absorption spectrum was measured (see FIG. 17D).

(Example 10)
-Preparation of Super Growth Dispersion Weighed 3.57 mg of a stilbene compound represented by the general formula (II) used in Example 1, wherein R ₃ and R ₄ are butyl groups, and dissolved in 3 ml of heavy water. A dispersant aqueous solution was prepared. Single-walled carbon nanotubes (supergrowth, diameter and length are unknown) were weighed 1.01 mg and mixed with the aqueous dispersant solution. The mixed aqueous solution was made into a black liquid by bath-type ultrasonic waves (37 kHz, 80 W, 1 hr). This black liquid was processed by centrifugation (25000 × g, 4 hrs, 5417R / eppendorf) to obtain a CNT dispersion. The state of the dispersion is shown in FIG. In addition, a UV-vis-NIR absorption spectrum was measured (see FIG. 18B).
Further, 10.02 mg of a stilbene compound represented by the general formula (II) used in Example 1, wherein R ₃ and R ₄ are butyl groups, is weighed and dissolved in 20 ml of heavy water to prepare an aqueous dispersion solution. did. 6.72 mg of single-walled carbon nanotubes (Super Growth) was weighed and mixed with the aqueous dispersant solution. The mixed aqueous solution was made into a black liquid by horn type ultrasonic waves (19 kHz, 20 W, 4 hr). This black liquid was processed by centrifugation (25000 × g, 4 hrs, 5417R / eppendorf) to obtain a CNT dispersion. The state of the dispersion is shown in FIG. In addition, a UV-vis-NIR absorption spectrum was measured (see FIG. 18D).

(Example 11)
-Preparation of SWeNT SG65 dispersion 3.58 mg of a stilbene compound represented by the general formula (II) used in Example 1, wherein R ₃ and R ₄ are butyl groups, was dissolved in 3 ml of heavy water. A dispersant aqueous solution was prepared. Single-walled carbon nanotubes (SWeNT, SG65, φ0.78 nm, length 1.5 μm) were weighed in 1.02 mg and mixed with the aqueous dispersant solution. The mixed aqueous solution was made into a black liquid by bath-type ultrasonic waves (37 kHz, 80 W, 1 hr). This black liquid was processed by centrifugation (25000 × g, 4 hrs, 5417R / eppendorf) to obtain a CNT dispersion. The state of the dispersion is shown in FIG. In addition, a UV-vis-NIR absorption spectrum was measured (see FIG. 19B).
Further, 9.97 mg of a stilbene compound represented by the general formula (II) used in Example 1, wherein R ₃ and R ₄ are butyl groups, is weighed and dissolved in 20 ml of heavy water to prepare an aqueous dispersion solution. did. 6.68 mg of single-walled carbon nanotube (SWeNT, SG65) was weighed and mixed with the aqueous dispersant solution. The mixed aqueous solution was made into a black liquid by horn type ultrasonic waves (19 kHz, 20 W, 4 hr). This black liquid was processed by centrifugation (25000 × g, 4 hrs, 5417R / eppendorf) to obtain a CNT dispersion. The state of the dispersion is shown in FIG. In addition, a UV-vis-NIR absorption spectrum was measured (see FIG. 19D).

(Example 12)
-Preparation of multi-walled carbon nanotube (MWCNT) dispersion 3.61 mg of stilbene compound represented by the general formula (II) used in Example 1, wherein R ₃ and R ₄ are butyl groups, was weighed and more than 3 ml Dispersant aqueous solution was prepared by dissolving in pure water (water purified by Purelab / ELGA). 0.98 mg of MWCNT (Wako Chemical, φ40-60 nm, length 5-15 μm) was weighed and mixed with the aqueous dispersant solution. The mixed aqueous solution was treated with bath-type ultrasonic waves (37kHz, 80W, 1hr) to promote dispersion of MWCNT. The obtained black liquid was used as a MWCNT dispersion. The state of the dispersion is shown in FIG.

(Example 13)
-Preparation of multi-wall carbon nanotube (MWCNT) dispersion 3.57 mg of a stilbene compound represented by the general formula (II) used in Example 1, wherein R ₃ and R ₄ are butyl groups, was weighed in excess of 3 ml. Dispersant aqueous solution was prepared by dissolving in pure water (water purified by Purelab / ELGA). 1.03 mg of MWCNT (Ube Industries, AMG, φ11 nm, length 20 μm) was weighed and mixed with the aqueous dispersant solution. The mixed aqueous solution was treated with bath-type ultrasonic waves (37kHz, 80W, 1hr) to promote dispersion of MWCNT. The obtained black liquid was used as a MWCNT dispersion. The state of the dispersion is shown in FIG.

(Example 14)
Preparation of multi-wall carbon nanotube (MWCNT) dispersion 3.59 mg of a stilbene compound represented by the general formula (II) used in Example 1, wherein R ₃ and R ₄ are butyl groups, was weighed over 3 ml. Dispersant aqueous solution was prepared by dissolving in pure water (water purified by Purelab / ELGA). 1.03 mg of MWCNT (C-Nano, FloTube 9000 (GI), φ11 nm, length 10 μm) was weighed and mixed with the aqueous dispersant solution. The mixed aqueous solution was treated with bath-type ultrasonic waves (37kHz, 80W, 1hr) to promote dispersion of MWCNT. The obtained black liquid was used as a MWCNT dispersion. The state of the dispersion is shown in FIG.

(Example 15)
-Preparation of multi-wall carbon nanotube (MWCNT) dispersion 3.57 mg of a stilbene compound represented by the general formula (II) used in Example 1, wherein R ₃ and R ₄ are butyl groups, was weighed in excess of 3 ml. Dispersant aqueous solution was prepared by dissolving in pure water (water purified by Purelab / ELGA). 1.02 mg of MWCNT (Kawaken Fine Chemicals, KC-CNT, φ70 nm, length 50 μm) was weighed and mixed with the aqueous dispersant solution. The mixed aqueous solution was treated with bath-type ultrasonic waves (37kHz, 80W, 1hr) to promote dispersion of MWCNT. The obtained black liquid was used as a MWCNT dispersion. The state of the dispersion is shown in FIG.

  Regarding carbon materials such as carbon black and carbon fibers used in Examples 4 to 15 above, specific examples of the production of a dispersant-containing carbon material film and the production of a carbon material film using the dispersant-containing carbon material film Although not described, the carbon material dispersions could be prepared using the stilbene dispersant in the same manner as the CNTs used in Examples 1 to 3, and the carbon blacks of Examples 4 and 5 were In consideration of the dispersibility being controlled by light irradiation in the same manner as the CNT used in 3, carbon black, carbon fiber, graphite particles, single-walled carbon nanotubes, multi-walled carbon nanotubes used in Examples 4 to 15 above Production of a dispersant-containing carbon material film or a carbon material film using the dispersant-containing carbon material film is easily performed by those skilled in the art in the same manner as in the CNTs of Examples 1 to 3. Can It is clear.

  If the dispersant-containing carbon material film of the present invention is used, a carbon material film such as SWCNT, MWCNT, carbon fiber, graphite particles, etc., which contains no dispersant or contains a dispersant at a very low content. And a patterned carbon material film can be easily manufactured, and thus can be widely applied to fields where a carbon material film is required, such as manufacturing of electric / electronic devices.

Claims (8)

A dispersant-containing carbon material film having photoresponsiveness and containing a stilbene-based or azobenzene-based dispersant represented by the following general formula (I).

[In formula, R < ₁ > -R < ₆ > is respectively independently hydrogen or a C1-C5 linear or C3-C6 branched alkyl group. A is a carbon atom or a nitrogen atom. X is an anion. n is a number at which nX becomes -2 valent. ] X is a halogen atom (F, Cl, Br, I), tetrafluoroboric acid group (BF ₄ ), hexafluorophosphoric acid (PF ₆ ), bis (trifluoromethanesulfonyl) imide, thioisocyanate (SCN), nitric acid group (NO ₃ ), sulfate group (SO ₄ ), thiosulfate group (S ₂ O ₃ ), carbonate group (CO ₃ ), bicarbonate group (HCO ₃ ), phosphate group, phosphite group, hypophosphorous acid Group, each halogen acid compound acid group (AO ₄ , AO ₃ , AO ₂ , AO: A = Cl, Br, I), tris (trifluoromethylsulfonyl) carbon acid group, trifluoromethylsulfonic acid group, dicyanamide group, Acetic acid group (CH ₃ COO), halogenated acetic acid group ((CA _n H _3-n ) COO, A = F, Cl, Br, I; n = 1, 2, 3), tetraphenylboric acid group (BPh ₄ And a derivative thereof (B (Aryl) ₄ : Aryl = substituted phenyl group). The dispersant-containing carbon material film according to claim 1.   The dispersant-containing carbon material film according to claim 1 or 2, which is formed on a substrate.   The dispersant-containing carbon material according to any one of claims 1 to 3, wherein the carbon material is one or more selected from the group consisting of SWCNT, MWCNT, carbon black, carbon fiber, and graphite particles. film.   The material for electronic or electrical device manufacture containing the dispersing agent containing carbon material film | membrane of any one of Claims 1-4.   5. An exposure process in which the dispersant-containing carbon material film according to claim 1 is exposed entirely or partially exposed in a predetermined pattern, and the dispersant-containing carbon material film subjected to the exposure process is rinsed. A method for producing a carbon material film or a patterned carbon material film, comprising a rinsing step of dissolving and removing an unexposed portion by treatment and removing a dispersant in the exposed portion.   The method for producing a carbon material film or a patterned carbon material film according to claim 6, wherein the rinse liquid is water or an organic solvent.   The manufacturing method of the electric or electronic device containing the manufacturing method of the carbon material film or patterned carbon material film of Claim 6 or 7.

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