JP6487740B2 - Polysiloxane compound, method for producing the same, and conductive carbon material-containing composition comprising polysiloxane compound and conductive carbon material - Google Patents

Description

The present invention relates to a polysiloxane compound, a method for producing the same, and a conductive carbon material-containing composition containing a polysiloxane compound and a conductive carbon material. More specifically, a polysiloxane compound, a method for producing a polysiloxane compound, and a polysiloxane compound and conductive carbon that can be suitably used for various applications such as mounting applications, optical applications, display device applications, and electrical / electronic component materials. The present invention relates to a composition containing a conductive carbon material.

A polysiloxane compound is a compound having a Si—O bond (siloxane bond) and has been widely used as a raw material for various industrial products. And nowadays, it has been applied to various uses due to characteristics such as heat resistance caused by siloxane bonds. As an example of a composition using such a siloxane compound, a composition in which an organic skeleton having an imide bond is bonded to a silicon atom forming a siloxane bond as a curable resin composition capable of giving a cured product having excellent heat resistance A resin composition containing a silane compound having a unit and an organic resin is disclosed (for example, see Patent Document 1).

Incidentally, carbon nanotubes (hereinafter also referred to as CNT) are cylindrical compounds composed only of carbon having excellent electrical conductivity and mechanical strength, and are expected to be used in various applications. However, CNTs are difficult to disperse due to strong cohesion due to high van der Waals interactions, and their application to functional materials is limited.
As one of the utilization forms of such CNTs, a conductive thin film using CNTs has been studied. A conductive thin film using CNTs is produced by applying an ink composition in which CNTs are dispersed in a solvent by various printing methods and coating methods. At this time, hydrophilic polymers and various surfactants are used as CNT dispersants, but problems such as changing the electrical properties of the thin film due to deterioration due to air contact when these surfactants are exposed to heat. was there.
On the other hand, CNT dispersion using a polysiloxane compound has been studied as an attempt to increase the heat resistance of the CNT dispersion (see, for example, Non-Patent Document 1).

Japanese Patent No. 5193217

T ARAKE and five others "Polymer", (Netherlands) 2013, Vol. 54, p5643-5647 Y Kaneko and five others "Chemistry of Materials" (USA) 2004, Vol. 16, p3417-3423

As described above, various types of polysiloxane compounds are widely used as raw materials for various industrial products, but the properties required for polysiloxane compounds vary depending on the application, so the number of variations in the structure of polysiloxane compounds should be further increased. Is preferable from the viewpoint of expanding the range of selection of the polysiloxane compound having the optimum characteristics according to the application.
In addition, the composition using the polysiloxane compound as described above as a CNT dispersant is a new use of the polysiloxane compound. However, in the composition described in Non-Patent Document 1, the heat resistance and the composition From the viewpoint of the properties and film-forming properties of the coating film produced from the above, there is room for developing a polysiloxane compound suitable as a dispersant for conductive carbon materials such as carbon nanotubes.

The present invention has been made in view of the above-described present situation, and develops a polysiloxane compound having a new structure that has not been provided so far, and provides a polysiloxane compound suitable as a dispersant for conductive carbon materials such as carbon nanotubes. For the purpose.

As a result of various studies on the polysiloxane compound, the present inventor has found a new polysiloxane compound having a ladder-like polysiloxane skeleton, an imide structure in the side chain, and a specific number average molecular weight. Was successfully synthesized and a suitable synthesis method for such a new polysiloxane compound was found. Furthermore, the inventor of the present invention uses a polysiloxane compound having a ladder-like polysiloxane skeleton and having a nonionic substituent such as an imide structure in the side chain as a dispersant for conductive carbon materials such as carbon nanotubes. It has also been found that it is suitable, and the present invention has been achieved.

That is, the present invention is a polysiloxane compound having a ladder-like polysiloxane skeleton, an imide structure in the side chain, and a number average molecular weight of 3,000 or more.

The present invention is also a method for producing a polysiloxane compound, which comprises a step of reacting an acid anhydride with an acid salt of a hydrolysis-condensation product of an alkoxysilane having a ladder structure having an amino group. It is also a method for producing a polysiloxane compound.

The present invention further includes a conductive carbon material-containing composition comprising a polysiloxane compound having a polysiloxane skeleton having a ladder-like structure and having a nonionic substituent in a side chain and a conductive carbon material. It is also a thing.
The present invention is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

The polysiloxane compound of the present invention has a ladder-like polysiloxane skeleton. Ladder-shaped polysiloxane skeleton has two linear siloxane chains composed of siloxane bonds, and constitutes one linear siloxane chain and another linear siloxane chain. This means a skeleton in which the two linear siloxane chains are located in parallel by bonding to the silicon atom through one oxygen atom.
When the polysiloxane skeleton of the polysiloxane compound has a ladder-like structure, the polysiloxane compound of the present invention has excellent heat resistance.
The polysiloxane compound has the following formula (1):

(Wherein R ¹ is the same or different and represents a monovalent organic group, hydroxyl group, halogen atom or hydrogen atom, and at least one of R ¹ is an organic skeleton having an imide bond. R ² is the same. Or differently, it represents a monovalent organic group, a hydroxyl group, a halogen atom, a hydrogen atom or an OR ³ group, wherein R ³ represents an alkyl group having 1 to 20 carbon atoms, an acyl group, an aryl group and an unsaturated aliphatic residue. It represents any group, and may have a substituent such as an alkyl group, a halogen atom and an aromatic group, and n represents the degree of polymerization.
The n is preferably 10 to 1,000. More preferably, it is 15-800, More preferably, it is 20-500. If the degree of polymerization is in the above preferred range, the polysiloxane compound of the present invention will be more excellent in heat resistance.

In the polysiloxane compound, the proportion of the polysiloxane skeleton is preferably 80 to 10% by mass in 100% by mass of the polysiloxane compound. More preferably, it is 70-15 mass%, More preferably, it is 50-20 mass%.

The polysiloxane compound of the present invention has an imide structure in the side chain, and the imide structure means a structure (an organic skeleton having an imide bond) in which an imide bond is essential, and an imide bond site in the structure. If it contains, the structure of another site | part will not be restrict | limited in particular. The imide bond site is represented by the following formula (2):

(Wherein R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom or a monovalent or divalent organic group. R ⁴ and R ⁵ may combine to form a ring structure. .) Is preferable.
When the organic group is a monovalent organic group, the monovalent organic group is preferably a hydrocarbon group having 1 to 10 carbon atoms.
When the organic group is a divalent organic group, that is, when R ⁴ and R ⁵ are bonded to form a ring structure with the —C—N—C— moiety, Is preferably a maleimide structure or an imide bond site structure in the formula (3) described later.

As an organic skeleton having an imide bond, a group in which an imide bond site is composed of a ring structure of an aromatic compound (aromatic ring), a ring structure of a heterocyclic compound (heterocycle), and a ring structure of an alicyclic compound (alicyclic ring) It is preferable to have at least one structure selected from the above.
The organic skeleton having an imide bond is any one of (1) a structure having an alkylene group having 1 to 6 carbon atoms, (2) a structure having a secondary amino group, and (3) a structure having a tertiary amino group. Those having an imide bond site at the end of the structure are preferred. Among these, (1) a structure having an imide bond site at the terminal of an alkylene group having 1 to 6 carbon atoms is more preferable in that it becomes a polysiloxane compound having high thermal stability.

The organic skeleton having an imide bond is not particularly limited as long as it is an organic group containing an imide bond, but is preferably a group represented by the following formula (3).

(Wherein R ⁶ represents at least one structure selected from the group consisting of aromatic, heterocyclic and alicyclic rings. X and z are the same or different and are integers of 0 or more and 5 or less, y is 0 or 1.)
At least one structure selected from the group consisting of aromatic, heterocyclic and alicyclic rings is a group in which R ⁶ has a ring structure (aromatic ring) of an aromatic compound, or a ring structure (heterocycle) of a heterocyclic compound. And at least one group selected from the group consisting of a group having a ring structure and an alicyclic compound ring structure (alicyclic ring).
Examples of the aromatic compound include benzene, biphenylene, terphenylene, naphthalene, anthracene, and perylene. Examples of the heterocyclic compound include pyrrolidine, pyrrole, piperidine, imidazole, pyrazole, thiazole, imidazoline, indole, purine, quinoline and the like. Examples of the saturated aliphatic cyclic hydrocarbon of the alicyclic compound include cyclobutane, cyclopentane, cyclohexane, cyclooctane, norbornane, decahydronaphthalene and the like, and the unsaturated aliphatic cyclic hydrocarbon of the alicyclic compound. Examples thereof include cyclobutene, cyclopentene, cyclohexene, cyclooctene, and norbornene. R ⁶ is preferably a phenylene group, a naphthylidene group, a norbornene divalent group, an (alkyl) cyclohexylene group, a cyclohexenyl group, or the like. When R ⁶ is a phenylene group, the organic skeleton having the imide bond is a group represented by the following formula (3-1). When R ⁶ is an (alkyl) cyclohexylene group, the imide bond is When the organic skeleton having the polysiloxane compound represented by the following formula (3-2) and R ⁶ is a naphthylidene group, the organic skeleton having the imide bond is represented by the following formula (3-3) or (3-4) When R ⁶ is a norbornene divalent group, the organic skeleton having the imide bond is a polysiloxane compound represented by the following formula (3-5), and R ⁶ is cyclohexenyl. When it is a group, the organic skeleton having the imide bond is a polysiloxane compound represented by the following formula (3-6).

In the above formula (3), x and z are the same or different and are integers of 0 or more and 5 or less.
X + z may be an integer of 0 or more and 10 or less, preferably 3 to 7, more preferably 3 to 5, and particularly preferably 3. The y is 0 or 1, and is preferably 0.

In the above formulas (3-1) to (3-6), x, y and z are the same as x, y and z in the above formula (2), respectively.
In the above formula (3-1), R ^{7 to} R ¹⁰ are the same or different and represent at least one structure selected from the group consisting of a hydrogen atom, an alkyl group, a halogen atom and an aromatic. As said R < ⁷ > -R < ¹⁰ >, the form whose all are hydrogen atoms is preferable.
In the formula (3-2), R ^{11 to} R ¹⁴ and R ^{11 ′} to R ^{14 ′} are the same or different and are at least one selected from the group consisting of a hydrogen atom, an alkyl group, a halogen atom and an aromatic. Represents the structure. As the ^R 11 ^{to R 14} and ^R 11' ^{to R 14',} forms all ^{R 12} or ^{R 13} are the remaining methyl group is a hydrogen atom, ^or, R 11 ^{to R 14} and ^R 11' ^{to R 14 'all} are hydrogen atom form ^or embodiment R 11 ^{to R 14} and ^R 11' ^{to R 14'} all are a fluorine atom is preferable. More preferably, R ¹² or R ¹³ is a methyl group and the rest are all hydrogen atoms.

In the above formula (3-3), R ^{15 to} R ²⁰ are the same or different and represent at least one structure selected from the group consisting of a hydrogen atom, an alkyl group, a halogen atom and an aromatic. As said R < ¹⁵ > -R < ²⁰ >, the form whose all are hydrogen atoms or the form whose all are fluorine atoms is preferable. More preferred is a form in which all are hydrogen atoms.
In the above formula (3-4), R ^{21 to} R ²⁶ are the same or different and represent at least one structure selected from the group consisting of a hydrogen atom, an alkyl group, a halogen atom and an aromatic. As said R < ²¹ > -R < ²⁶ >, the form in which all are hydrogen atoms, or the form in which all are fluorine atoms is preferable. More preferred is a form in which all are hydrogen atoms.
In said formula (3-5), R < ²⁷ > -R < ³² > is the same or different and represents at least 1 type of structure chosen from the group which consists of a hydrogen atom, an alkyl group, a halogen atom, and an aromatic. As said R < ²⁷ > -R < ³² >, the form in which all are hydrogen atoms, the form that all are fluorine atoms, or the form in which all are chlorine atoms is preferable. More preferred is a form in which all are hydrogen atoms.
In the above formula ^{(3-6), R 33 ~R 36} , R 33' and ^{R 36 'are} the same or different, a hydrogen atom, an alkyl group, at least one selected from the group consisting of halogen atoms and the aromatic Represents the structure. As said R ^{< 33 >} -R ^{< 36 >} , R ^{< 33 ' >} and R ^{< 36 ' >} , the form in which all are hydrogen atoms, the form in which all are fluorine atoms, or the form in which all are chlorine atoms is preferable. More preferred is a form in which all are hydrogen atoms.

Among the structural units represented by the above formula (3), the following formula (3-7):

(Wherein R ³⁷ represents a structural unit represented by at least one structure selected from the group consisting of aromatic, heterocyclic and alicyclic rings). That is, the polysiloxane compound having an imide structure of the present invention preferably includes a polysiloxane compound in which the organic skeleton having the imide bond is a structural unit represented by the above formula (3-7). R ³⁷ in the above formula (3-7) is preferably the same as R ⁶ described in the above formula (3).

As the particularly preferred form of the polysiloxane compound having the imide structure, poly (γ-phthalimidopropylsilsesquioxane) in which R ³⁷ is a phenylene group; poly {γ- (he) in which R ³⁷ is a methylcyclohexylene group. Kisahidoro -4-methyl phthalimide) propyl ^{silsesquioxane}; R 37} is naphthylidene group poly {.gamma. (1,8-naphthalimide) propyl ^{silsesquioxane}; R 37} is naphthylidene group poly {gamma -(2,3-naphthalimido) propylsilsesquioxane}; poly {γ- (5-norbornene-2,3-imido) propylsilsesquioxane} in which R ³⁷ is a divalent group of norbornene; R ³⁷ Is a cyclohexenyl group, poly [(cis-4-cyclohexene-1,2-imido) propylsilsesqui Oxane]. More preferably, poly (γ-phthalimidopropylsilsesquioxane), poly {γ- (1,8-naphthalimide) propylsilsesquioxane}, poly {γ- (2,3-naphthalimide) propylsilsesquioxane. Oxan}. The structures of these compounds can be identified by measuring ¹ H-NMR, ¹³ C-NMR, and MALDI-TOF-MS.

In the polysiloxane compound having the imide structure, the proportion of the organic skeleton having the imide bond is preferably 20 to 100 mol with respect to 100 mol of silicon atoms contained in the polysiloxane compound having the imide structure. . More preferably, it is 50-100 mol, More preferably, it is 70-100 mol, Most preferably, it is 80-100 mol, Most preferably, it is 100 mol. According to this, heat resistance, hydrolysis resistance and the like can be improved, and when a resin composition containing a polysiloxane compound having an imide structure and an organic resin is used, the solubility in the organic resin is improved. be able to.

The polysiloxane compound having the imide structure preferably has a silanol group amount of 0.1 or less determined by the following calculation formula (α).
[Si—OH bond moles] / [Si—O bond moles] (α)
According to this, the composition containing the polysiloxane compound having the imide structure is remarkably reduced in viscosity, and the composition and its cured product can be extremely excellent in moisture absorption resistance. More preferably, it is 0.05 or less as a silanol group amount calculated | required by the said Formula ((alpha)), More preferably, it is 0.01 or less. Particularly preferably, the polysiloxane compound does not have a residual silanol group. Here, [Si—OH bond mole number] represents the bond number between Si and OH in moles. For example, when two OH groups are bonded to each 1 mol of Si atoms, the [number of moles of Si—OH bond] is 2 mol. The number of moles of Si—O bonds is counted similarly.

As described later, the polysiloxane compound having an imide structure is preferably produced by a hydrolysis / condensation reaction of an alkoxysilyl group using a compound having an alkoxysilyl group as a raw material.
In the polysiloxane compound having the imide structure, the number of silicon atoms having one alkoxysilyl group among the silicon atoms constituting the polysiloxane compound is T ₂ , and the number of silicon atoms having no alkoxysilyl group is T _{3. When,} it is preferable the value of _{T 2 / (T 2 + T} 3) it is 0.15 or less. When the value of T ₂ / (T ₂ + T ₃ ) is 0.15 or less, it can be said that the ratio of the polysiloxane skeleton with a ladder structure in the polysiloxane compound is high, and the dispersant for conductive carbon materials such as carbon nanotubes It becomes more suitable as. The value of T ₂ / (T ₂ + T ₃ ) is more preferably 0.14 or less, still more preferably 0.13 or less, and particularly preferably 0.12 or less. Moreover, although a minimum in particular is not restrict | limited, Usually, it is 0.01 or more.
Among the silicon atoms constituting the polysiloxane compound, the number of silicon atoms having one alkoxysilyl group (T ₂ ) and the number of silicon atoms not having an alkoxysilyl group (T ₃ ) were confirmed by Si-NMR measurement. can do.

The polysiloxane compound having an imide structure may have other groups other than the imide structure in the side chain, and the other groups are not particularly limited. For example, a hydrogen atom, a hydroxyl group, a halogen atom, and an OR Aromatic residues such as ³⁸ groups, alkyl groups, aryl groups, aralkyl groups, and unsaturated aliphatic residues. These may have a substituent. Preferably, it is an aromatic residue such as an alkyl group having 1 to 8 carbon atoms or an aryl group or an aralkyl group, which may have a substituent. R ³⁸ is the same or different and is an alkyl group, an acyl group, an aryl group, or an unsaturated aliphatic residue.

The polysiloxane compound having the imide structure is excellent in heat resistance, pressure resistance, mechanical / chemical stability, and thermal conductivity, and can impart various properties such as excellent heat resistance to various materials. For example, when the composition includes a polysiloxane compound having the imide structure and a conductive carbon material such as a carbon nanotube, the composition can be provided with heat resistance, and the organic skeleton having an imide bond is an ion. Therefore, it is possible to obtain a composition with low ionicity and to improve the dispersibility of the conductive carbon material in a solvent. Moreover, when it is set as the composition containing the polysiloxane compound which has the said imide structure, and a polymer, heat resistance, pressure resistance, etc. can be easily given to this polymer by showing high compatibility with respect to various polymers. it can.

The number average molecular weight of the polysiloxane compound having the imide structure is 3,000 or more. When the number average molecular weight of the polysiloxane compound having an imide structure is within the above range, when the polysiloxane compound having an imide structure is used as a dispersant in forming a thin film using a conductive carbon material, the coating film is dried. It is possible to prevent the cracks and the surface from becoming rough and to improve the film forming property. This is considered to be due to the improvement of the film strength of the thin film due to the entanglement between molecules. The number average molecular weight is preferably 4,000 or more, more preferably 4,500 or more. The number average molecular weight is preferably 100,000 or less. Moreover, it is preferable that a weight average molecular weight is 5,000 or more, More preferably, it is 6,000 or more. The weight average molecular weight is preferably 200,000 or less.
The molecular weight (number average molecular weight and weight average molecular weight) of the polysiloxane compound having an imide structure can be determined by GPC (gel permeation chromatography) measurement under the measurement conditions described later.

Although the manufacturing method in particular of the polysiloxane compound which has the said imide structure is not restrict | limited, For example, the manufacturing method mentioned later is preferable.

<Method for producing polysiloxane compound>
The present invention is also a method for producing a polysiloxane compound, which comprises a step of reacting an acid anhydride with an acid salt of a hydrolysis-condensation product of an alkoxysilane having a ladder structure having an amino group. It is also a method for producing a polysiloxane compound. In the conventional production method, it is difficult to synthesize a polysiloxane compound having a ladder structure with a large molecular weight, and the types of substituents on the side chain are limited. However, the production method of the present invention is a ladder with a large molecular weight. It is a manufacturing method which enables manufacture of the new compound which has an imide structure in the side chain of the polysiloxane compound of a shape structure.

The production method of the hydrolysis-condensation salt of an alkoxysilane having a ladder-like structure having an amino group in the production method (hereinafter also referred to as the hydrolysis-condensation salt) is not particularly limited, and has an amino group. After forming the ladder-like structure alkoxysilane, it may be a method of reacting an amino group and an acid to form an acid salt, but reacting an amino group of an alkoxysilane compound having an amino group with an acid, A method obtained by forming a polysiloxane skeleton having a ladder structure by hydrolysis / condensation reaction of an alkoxysilyl group after forming an acid salt is preferable.

The alkoxysilane compound having an amino group is not particularly limited as long as it has an amino group and an alkoxysilyl group. (1) A structure having an alkylene group having 1 to 6 carbon atoms on a silicon atom, (2) a secondary amino group (3) A structure in which any structure of a structure having a tertiary amino group is bonded and an amino group is bonded to the terminal of the structure opposite to the silicon atom is preferable. Among the above (1) to (3), (1) a structure having an alkylene group having 1 to 6 carbon atoms is more preferable.
Examples of the alkoxysilane compound having an amino group include the following formula (4):

(In the formula, R ³⁹ is the same or different and represents at least one group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an acyl group, an aryl group and an unsaturated aliphatic residue; X and z are the same or different and are an integer of 0 or more and 5 or less, and y is 0 or 1. In the above formula (4), y is more preferably 0, and the total of x and z is more preferably 3.

R ³⁹ in the above formula (4) is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

As the alkoxysilane compound having an amino group, 3-aminopropyl-trimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyl-tripropoxysilane, 3-aminopropyltri (isopropoxy) silane, 3 -Aminopropyltributoxysilane.

The acid in the above production method is not particularly limited, and examples thereof include hydrogen halide, oxo acid, etc., preferably hydrogen chloride, hydrogen fluoride, hydrogen bromide, hydrogen iodide, nitric acid, sulfuric acid, methylsulfonic acid Benzenesulfonic acid and p-toluenesulfonic acid, more preferably hydrogen chloride, hydrogen iodide and p-toluenesulfonic acid.

The reaction between the alkoxysilane compound having an amino group and the acid can be performed by a commonly used method.

The hydrolysis reaction in the hydrolysis / condensation reaction of the alkoxysilyl group is shown below.
SiOR ³⁹ ₃ + 3H ₂ O (hydrolysis) → Si (OH) ₃ + 3R ³⁹ OH
(Wherein R ³⁹ is as described above.)
By the condensation reaction of the silanol group (Si (OH) ₃ ) obtained by the hydrolysis reaction, the following formula (5):

(In the formula, R ⁴⁰ is the same or different and represents an organic skeleton having an amino group, an organic skeleton having a salt structure formed by reacting an amino group and an acid, or other groups described later. The degree of polymerization can be obtained. The preferable range of n is the same as that of the polysiloxane compound having the imide structure.
By hydrolyzing and condensing the alkoxysilyl group in this way, a hydrolyzed condensate having a high degree of polymerization of the polysiloxane skeleton can be obtained. A polysiloxane compound having a higher degree of polymerization and a higher molecular weight than before can be synthesized by a reaction between an acid salt of a hydrolysis condensate having a high degree of polymerization of the polysiloxane skeleton and an acid anhydride described later.

The acid salt of the hydrolysis-condensation product has at least one organic skeleton in the side chain having a salt structure formed by reacting an amino group and an acid (hereinafter also referred to as an amino acid salt structure). However, the proportion of the organic skeleton having an amino acid salt structure is preferably 20 to 100 moles with respect to 100 moles of silicon atoms contained in the acid salt of the hydrolysis condensate. . More preferably, it is 50-100 mol, More preferably, it is 70-100 mol, Most preferably, it is 80-100 mol, Most preferably, it is 100 mol.

The acid salt of the hydrolysis condensate may have an amino group or other group other than the acid salt structure of the amino group in the side chain, and the other group is not particularly limited. Aromatic residues such as atoms, hydroxyl groups, halogen atoms and OR ⁴¹ groups, alkyl groups, aryl groups and aralkyl groups, unsaturated aliphatic residues, and the like. These may have a substituent. Preferably, it is an aromatic residue such as an alkyl group having 1 to 8 carbon atoms or an aryl group or an aralkyl group, which may have a substituent. R ⁴¹ is the same or different and is an alkyl group, an acyl group, an aryl group, or an unsaturated aliphatic residue.

In the hydrolysis / condensation reaction, water is used, and it is preferable that 10 to 2000% by mass of water is added to react with 100% by mass of the acid salt of the alkoxysilane compound. More preferably, it is 10-500 mass%, More preferably, it is 20-400 mass%.
As the water used for the above reaction, any of ion-exchanged water, pH-adjusted water and the like may be used, but water having a pH of around 7 is preferably used. By using such water, the amount of ionic impurities in the composition can be reduced, and a resin composition having low hygroscopicity or high insulation can be obtained. The purity of water is preferably pH 7, but hydrogen chloride, oxalic acid, pyridine, triethylamine, etc. are volatilized out of the reaction system at high temperature, so a small amount is added and the pH is in the range of 2-12. You may adjust.
The form of water used may be a form in which it is dropped into the acid salt of the alkoxysilane compound or a form in which it is added all at once.

The reaction temperature in the hydrolysis / polycondensation reaction of the alkoxysilyl group is preferably room temperature to 200 ° C. More preferably, the temperature is from room temperature to 100 ° C., and most preferably, it is maintained under azeotropic reflux of alcohol, water and solvent since alcohol is produced as a by-product. The pressure in the above reaction may be normal pressure, under pressure, or under reduced pressure, but the reaction easily proceeds by efficiently distilling the by-product alcohol out of the reaction system. It is preferable that the pressure is not higher than normal pressure.
The reaction time varies depending on the reaction temperature and reaction composition, but is preferably 2 to 48 hours.

The production method includes a step of reacting the acid salt of the hydrolysis condensate with an acid anhydride.
The acid anhydride is not particularly limited as long as it is a compound obtained by dehydration condensation of two molecules of oxo acid, but is preferably a carboxylic acid anhydride.

The carboxylic acid anhydride is represented by the following formula (6)

(Wherein R ⁴² and R ⁴³ are the same or different and each represents a hydrogen atom or a monovalent or divalent organic group. R ⁴² and R ⁴³ may combine to form a ring structure. .) Is preferable.
When the organic group is a monovalent organic group, the monovalent organic group is preferably a hydrocarbon group having 1 to 10 carbon atoms. Examples of the carboxylic acid anhydride when the organic group is a monovalent organic group include acetic anhydride and propionic anhydride.

When the organic group is a divalent organic group, that is, when R ⁴² and R ⁴³ are bonded to form a ring structure, the carboxylic acid anhydride may be aromatic, heterocyclic or alicyclic. Carboxylic anhydrides having at least one structure selected from the group consisting of
The carboxylic acid anhydride having at least one structure selected from the group consisting of the aromatic, heterocyclic ring and alicyclic ring is not particularly limited, but for example, succinic anhydride, maleic anhydride, itaconic anhydride, octenyl anhydride Succinic acid, dodecenyl succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrabromophthalic anhydride, 2,4-diethyl glutaric anhydride, anhydrous Hymic acid (alias: 5-norbornene-2,3-dicarboxylic anhydride), methyl nadic acid anhydride (aka: methyl-5-norbornene-2,3-dicarboxylic anhydride), dodecyl succinic anhydride, chlorene anhydride Dick acid, trialkyltetrahydrophthalic anhydride, diphenic anhydride Monofunctional acid anhydrides such as pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bis (anhydrotrimate), methylcyclohexene tetracarboxylic acid anhydride (also known as 5- (2,5-dioxo) Tetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride), biphenyltetracarboxylic anhydride, diphenylethertetracarboxylic anhydride, butanetetracarboxylic dianhydride, cyclopentanetetra Bifunctional acid anhydrides such as carboxylic acid anhydrides, benzophenone tetracarboxylic acid anhydrides, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid anhydrides; γ-aconitic anhydride, glycolic anhydride, trimellitic anhydride, polyazeline acid anhydride, etc. Anhydrides having Hanaresan, 1,8-naphthalic anhydride, 2,3-naphthalic anhydride and the like. The carboxylic acid anhydride is preferably phthalic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, 1,8-naphthalic acid anhydride, or 2,3-naphthalic acid anhydride, more preferably phthalic anhydride. Acid, 1,8-naphthalic anhydride, and 2,3-naphthalic anhydride.

In the reaction between the acid salt of the hydrolysis condensate and the acid anhydride, the amount of acid anhydride added is 100 to 300 mol% with respect to 100 mol% of the salt structure in the acid salt of the hydrolysis condensate. Preferably there is. More preferably, it is 100-250 mol%, More preferably, it is 100-150 mol%.

The reaction between the acid salt and the acid anhydride of the hydrolysis condensate is not particularly limited as long as the acid salt and the acid anhydride are reacted. However, the hydrolysis is performed using a carboxylic acid anhydride as the acid anhydride. It is preferred that the acid salt of the condensate is subjected to a ring-opening addition reaction to form an amic acid structure, and an imide structure is formed by a dehydration ring-closing reaction of the obtained amic acid structure.

The reaction temperature for the reaction forming the amic acid structure is preferably room temperature to 250 ° C, more preferably room temperature to 200 ° C.
The ring-opening catalyst is preferably hydrogen chloride, triethylamine or the like.
Solvents are dimethyl sulfoxide, N-methylpyrrolidone, N, N′-dimethylformamide, N, N′-dimethylacetamide, γ-butyrolactone, sulfolane, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, cyclohexanone , Cyclopentanone and the like are preferable.
Although reaction time changes with reaction temperature and reaction composition, 5 minutes-24 hours are preferable.

The reaction temperature for the dehydration ring closure reaction of the amic acid structure is preferably 80 to 250 ° C, more preferably 120 to 200 ° C.
The ring-closing catalyst is preferably tetraalkoxytitanium, titanium chloride, titanium carboxylate, zinc chloride, zinc carboxylate, tin chloride, tin carboxylate or the like.
The solvent is preferably N, N′-dimethylformamide, N, N′-dimethylacetamide, γ-butyrolactone, sulfolane, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, cyclohexanone, cyclopentanone, or the like.
The reaction time varies depending on the reaction temperature and reaction composition, but preferably 2 hours to 24 hours.

An example of a preferable reaction form of the reaction between the acid salt of the hydrolysis condensate and the acid anhydride is shown in the following formula (7).

<Conductive carbon material-containing composition>
The present invention also includes a polysiloxane compound having a ladder-like polysiloxane skeleton and having a nonionic substituent in the side chain (hereinafter also referred to as a polysiloxane compound having a nonionic substituent) and conductivity. It is also a conductive carbon material containing composition containing a conductive carbon material.

The conductive carbon material-containing composition of the present invention includes a polysiloxane compound having a ladder-like structure polysiloxane skeleton and having a nonionic substituent in the side chain and a conductive carbon material. As long as these are included, other components may be included. In addition, the thermosetting resin composition may contain one type of polysiloxane compound having a nonionic substituent and one type of conductive carbon material, or two or more types.

The said nonionic substituent is a substituent which does not have the group (ionic group) which generates ion. As described in Non-Patent Document 1, the polysiloxane compound has been studied as a dispersant for conductive carbon materials such as carbon nanotubes. However, the polysiloxane compound of Non-Patent Document 1 has an ionic side. It has a chain and also contains ionic impurities. When a composition containing a compound having an ionic side chain and an ionic impurity is used as a dispersant for the conductive carbon material, the dispersibility is not sufficient. This is considered to be due to the low affinity between the conductive carbon material and the composition containing an ionic side chain compound and ionic impurities. Moreover, when a coating film is formed using the conductive carbon material containing composition containing such a polysiloxane compound, there exists a possibility that the property of a coating film may be bad and a self-supporting film cannot be formed. In addition, when a conductive thin film is manufactured using carbon nanotubes dispersed with such a polysiloxane compound, there is a risk that leakage or short-circuiting due to ionic impurities may occur and reliability may be impaired. On the other hand, a polysiloxane compound having a nonionic substituent in the side chain exhibits excellent dispersibility when used as a dispersant. This is considered to be due to the higher affinity with the conductive carbon material than the composition containing a compound having an ionic side chain and an ionic impurity. Further, when a coating film is formed using a conductive carbon material-containing composition containing a polysiloxane compound having a nonionic substituent in the side chain, a uniform coating film can be formed. Moreover, when such a composition is used as a material for the conductive thin film, leakage and short-circuiting can be suppressed and a highly reliable composition can be obtained as the material for the conductive thin film.

Examples of the nonionic substituent include the aromatic ring group of the above aromatic compound, the heterocyclic group of the above heterocyclic compound, the alicyclic group of the above alicyclic compound, and an alkyl group having 1 to 20 carbon atoms, Examples thereof include a substituent having an acyclic aliphatic hydrocarbon group such as an alkenyl group and an alkynyl group.
The nonionic substituent is preferably a substituent having at least one structure selected from the group consisting of an aromatic ring, a heterocyclic ring and an alicyclic ring, and more preferably a substituent having an aromatic ring. When the polysiloxane compound having a nonionic substituent has a substituent having an aromatic ring, it is a structure in which a π electron cloud of an aromatic ring and an aromatic ring are continuously formed, and has a π-conjugated structure. It is considered that the dispersibility of the conductive carbon material can be further improved by exhibiting a high affinity with the conductive carbon material due to the superconjugated interaction. The nonionic substituent is more preferably a substituent having at least one aromatic ring selected from the group consisting of benzene, biphenylene, terphenylene, naphthalene, anthracene and perylene. The nonionic substituent is particularly preferably a substituent having the same imide bond as the polysiloxane compound having the imide structure.
The above-mentioned polysiloxane compound having a substituent having an imide structure in the side chain has high heat resistance and is excellent in dispersibility of the conductive carbon material in a solvent. Therefore, the polysiloxane having a nonionic substituent in the side chain When the polysiloxane compound having the above-described substituent having an imide structure in the side chain is used as the compound, a composition having high heat resistance and excellent dispersibility of the conductive carbon material can be obtained.
The substituent having the imide bond is preferably a preferable structure of the organic skeleton having the imide bond.
By having an imide ring among the imide structures, the dispersibility of the conductive carbon material can be further improved. This is probably because the imide ring generally has a π-conjugated structure electronically, and thus the imide ring and the conductive carbon material exhibit high affinity due to superconjugated interaction.

The polysiloxane compound having a nonionic substituent only needs to have at least one nonionic substituent in the side chain. In the polysiloxane compound having a nonionic substituent, the nonionic substituent The proportion of the substituent is preferably 20 to 100 mol% with respect to 100 mol% of silicon atoms contained in the polysiloxane compound having a nonionic substituent. More preferably, it is 50-100 mol%, More preferably, it is 70-100 mol%, Especially preferably, it is 80-100 mol%, Most preferably, it is 100 mol%. If the ratio of the nonionic substituent is substantially 100 mol%, the conductive carbon material-containing composition of the present invention does not substantially contain ionic impurities, so that the conductive carbon material is dispersed in the solvent. And the leakage and short circuit due to the ionic impurities of the thin film produced from the composition can be more sufficiently suppressed.

The number average molecular weight and weight average molecular weight of the polysiloxane compound having a nonionic substituent are not particularly limited, but the number average molecular weight is preferably 3,000 or more, more preferably 4,000 or more, More preferably, it is 4,500 or more. If the number average molecular weight of the polysiloxane compound having a nonionic substituent is within the above-mentioned preferable range, when a film-like thin film is formed from the conductive carbon material-containing composition, the cracks and the surface when the coating film is dried are roughened. This can be prevented and the film-forming property can be improved. This is considered to be due to the improvement of the film strength of the thin film due to the entanglement between molecules. The number average molecular weight is preferably 100,000 or less.
Moreover, it is preferable that a weight average molecular weight is 5,000 or more, More preferably, it is 6,000 or more. The weight average molecular weight is preferably 200,000 or less.
The molecular weight (number average molecular weight and weight average molecular weight) of the polysiloxane compound having a nonionic substituent can be determined by GPC (gel permeation chromatography) measurement under the measurement conditions described later.

The conductive carbon material is not particularly limited as long as it is a conductive carbon material. Examples thereof include carbon nanotubes, carbon nanohorns, carbon nanobuds, graphene, and the like, and carbon nanotubes are preferable.

The carbon nanotube has a structure in which a graphene sheet (six-membered ring network made of carbon) is rolled into a cylindrical shape. The carbon nanotube is not particularly limited, and even a single wall carbon nanotube (hereinafter also referred to as SWCNT) made of a single graphene sheet is referred to as a multi-wall carbon nanotube (hereinafter also referred to as MWCNT) made of a multilayer graphene sheet. MWCNT is preferred.

Although the diameter of the said carbon nanotube is not specifically limited, It is preferable that it is 1-20 nm, More preferably, it is 2-15 nm.

Although the length of the said carbon nanotube is not specifically limited, It is preferable that it is 0.1-800 micrometers, More preferably, it is 0.5-500 micrometers.

It is preferable that content of the polysiloxane compound which has a nonionic substituent in the said conductive carbon material containing composition is 10-1000 mass% with respect to 100 mass% of conductive carbon materials, More preferably, 20- 500% by mass. If content of the polysiloxane compound which has a nonionic substituent is the said preferable range, the effect outstanding as a dispersing agent of an electroconductive carbon material can be exhibited.

The conductive carbon material-containing composition may contain other components in addition to the polysiloxane compound having a nonionic substituent and the conductive carbon material, and the other components are not particularly limited, For example, a solvent etc. are mentioned.
The solvent is preferably a nonpolar solvent such as N-methylpyrrolidone, dimethyl sulfoxide, N, N′-dimethylformamide, and more preferably N-methylpyrrolidone.

Content of the said other component is 10-10,000 mass% with respect to a total of 100 mass% of the mass of the polysiloxane compound which has a nonionic substituent in an electroconductive carbon material containing composition, and an electroconductive carbon material. It is preferably 10 to 5,000% by mass, more preferably 10 to 1,000% by mass, and particularly preferably 20 to 500% by mass. If content of another component is the said preferable range, the effect outstanding as a dispersing agent of an electroconductive carbon material can be exhibited.

The polysiloxane compound of the present invention can be used as a resin composition in combination with an organic resin.
As the organic resin, a compound having at least one glycidyl group and / or an epoxy group, a polyhydric phenol compound, and a maleimide compound are suitable. These compounds may be used alone or in combination of two or more. As the organic resin, the above-described compounds and other organic resins other than those described above are preferably the same as those described in Japanese Patent No. 5193217.
Such a resin composition exhibits excellent heat resistance, and can be suitably used particularly as a mounting material having high heat resistance. In addition to mounting fields that require high thermal stability, optical applications, optical device applications, display device applications, mechanical component materials, electrical / electronic component materials, automotive component materials, civil engineering and building materials, molding materials, paints And can be suitably used as a material for adhesives.

The polysiloxane compound and the conductive carbon material-containing composition of the present invention have the above-described configuration, have excellent heat resistance, and are excellent in dispersibility in a solvent and film formability. It can use suitably for etc.

2 is a diagram showing the results of Si-NMR measurement of ladder-like poly (3-phthalimidopropyl) silsesquioxane (Compound B) synthesized in Example 1. FIG. FIG. 4 is a diagram showing the results of Si-NMR measurement of cage-like {γ- (5-norbornene-2,3-imido) propylsilsesquioxane} (Compound G) synthesized in Comparative Example 3.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

<GPC measurement conditions>
Measuring instrument: “HLC-8220GPC” manufactured by Tosoh Corporation
Column: “TSK-GEL SUPER HZM-N 6.0 * 150” x 4 manufactured by Tosoh Corporation Eluent: 1 mol% lithium bromide N, N′-dimethylformamide solution Flow rate: 0.6 mL / min Temperature: 40 ° C.
Calibration curve: Prepared using polystyrene standard sample (manufactured by Tosoh Corporation).

<TG-DTA measurement conditions>
Measuring instrument: TG-DTA2000SA (manufactured by Bruker AXS)
Measurement conditions: room temperature to 500 ° C., temperature rising rate 10 ° C./min, nitrogen gas flow (flow rate: 100 mL / min)

<NMR measurement conditions>
Measuring instrument: 600 MHz NMR (manufactured by Varian)
Nucleus: 29Si
Integration count: 500-2300
Solvent: DMSO-d6
Temperature: normal temperature

<Comparative Example 1>
Synthesis of ladder-like poly (3-aminopropyl) silsesquioxane hydrochloride (Compound A) Into a 300 mL beaker, 8.695 g of 3-aminopropyltrimethoxysilane and 150 mL of 0.5 mol / L hydrochloric acid were added. Stir with a stirrer for 2 hours at room temperature. Thereafter, heating was performed at 60 ° C. on 5 sheets of 50 mL disposable trays, followed by heating in an oven at 100 ° C. for 10 hours to completely evaporate residual hydrogen chloride, water, and by-product methanol. Step of dissolving the obtained plate-like solid content in 50 mL of purified water in a 300 mL beaker, adding 100 mL of acetone while stirring, collecting the precipitate by decantation, and further adding 100 mL of methanol to the recovered product and washing Was carried out 5 times, and finally, the recovered product was washed with 100 mL of acetone and dried under reduced pressure to obtain 3.667 g of Compound A. Compound A was found to be a ladder-like poly (3-aminopropyl) silsesquioxane hydrochloride from the results of analysis by FT-IR, NMR, and XRD, consistent with the identification results of Non-Patent Document 2. When the molecular weight was measured by GPC, the number average molecular weight Mn was 3,200, the weight average molecular weight Mw was 5,760, and the molecular weight distribution Mw / Mn was 1.80.

<Example 1>
Synthesis of Ladder-like Poly (3-phthalimidopropyl) silsesquioxane (Compound B) 0.145 g of the above compound A was completely dissolved in 1.0 mL of purified water in a 10 mL glass vial, and then 4.0 mL of dimethyl sulfoxide and triethylamine 0.456 g was charged. 0.453 g of phthalic anhydride was added thereto, and stirring was continued at room temperature for 10 minutes with a magnetic stirrer. The vial contents were initially cloudy, but became a pale yellow clear solution by continuing stirring. To this, 5.0 mL of 1.0 mol / L hydrochloric acid was added to make it cloudy, the precipitate was collected by suction filtration, washed with 100 mL of acetone, and dried under reduced pressure to obtain 0.219 g of a white powder.
Next, 15 mL of N, N′-dimethylformamide and 0.219 g of the above white powder were weighed into a 20 mL two-necked flask equipped with a nitrogen introduction tube, and placed in an oil bath maintained at 160 ° C. with a magnetic stirrer. Stir for hours. After stirring, the reaction solution was cooled to room temperature, dropped into 50 mL methanol weighed in a 100 mL beaker, and the precipitate was collected by filtration, washed with methanol three times, and dried under reduced pressure to obtain 0.201 g of compound B. It was. Compound B was confirmed to be ladder-like poly (3-phthalimidopropyl) silsesquioxane from the results of analysis by FT-IR and NMR. When the molecular weight was measured by GPC, the number average molecular weight Mn was 9,070, the weight average molecular weight Mw was 28,980, and the molecular weight distribution Mw / Mn was 3.19. The value of T ₂ / (T ₂ + T ₃ ) described above was 0.10.

<Example 2>
Synthesis of Ladder-like Poly (1,8-Naphthalimidopropyl) silsesquioxane (Compound C) A compound using 0.607 g of 1,8-naphthalic anhydride instead of 0.453 g of phthalic anhydride of Example 1 0.243 g of C was obtained. Compound C was confirmed to be ladder-like poly (1,8-naphthalimidopropyl) silsesquioxane from analysis results by FT-IR and NMR. When the molecular weight was measured by GPC, the number average molecular weight Mn was 4,740, the weight average molecular weight Mw was 6,840, and the molecular weight distribution Mw / Mn was 1.44.

<Example 3>
Synthesis of Ladder-like Poly (2,3-Naphthalimidopropyl) silsesquioxane (Compound D) In place of 0.453 g of phthalic anhydride of Example 1, compound using 0.607 g of 2,3-naphthalic anhydride D0.240 g was obtained. Compound D was confirmed to be ladder-like poly (2,3-naphthalimidopropyl) silsesquioxane from the results of analysis by FT-IR and NMR. When the molecular weight was measured by GPC, the number average molecular weight Mn was 15,700, the weight average molecular weight Mw was 38,900, and the molecular weight distribution Mw / Mn was 2.47.

<Example 4>
Synthesis of Ladder-like Poly (γ- (5-norbornene-2,3-imido) propyl) silsesquioxane (Compound E) Instead of 0.453 g of phthalic anhydride in Example 1, 5-norbornene-2,3- Using 0.202 g of dicarboxylic acid anhydride, 0.215 g of compound E was obtained. Compound E was confirmed to be ladder-like poly (γ- (5-norbornene-2,3-imido) propyl) silsesquioxane from analysis results by FT-IR and NMR. When the molecular weight was measured by GPC, the number average molecular weight Mn was 6,960, the weight average molecular weight Mw was 12,900, and the molecular weight distribution Mw / Mn was 1.86.

<Comparative example 2>
Ladder-like poly (3-aminopropyl) silsesquioxane triiodide salt (Compound F) synthetic anion exchange resin (product name “Amberlite IRA-900”, manufactured by Organo Corporation) having a diameter of 2 cm and a length of 40 cm The column was filled and 50 mL of a 1.0 mol / L potassium iodide aqueous solution was passed through, followed by washing with 150 mL of purified water to replace the anion species of the anion exchange resin with iodide ions. Next, 0.733 g of compound A was dissolved in 30 mL of purified water, charged into this column, and collected in an Erlenmeyer flask. The recovered liquid was subjected to column treatment again 5 times and freeze-dried to obtain 0.9010 g of Compound F. From the results of elemental analysis of compound F by ion chromatography, no chloride ion was confirmed, and instead the same molar amount of iodide ion was detected. Compound F was a ladder-like poly (3-aminopropyl) silsesquioxane iodide. It was confirmed to be a chloride salt. When the molecular weight was measured by GPC, the number average molecular weight Mn was 3,040, the weight average molecular weight Mw was 5,290, and the molecular weight distribution Mw / Mn was 1.74.

<Comparative Example 3>
Synthesis of cage-like {γ- (5-norbornene-2,3-imido) propylsilsesquioxane} (Compound G) A 500 mL four-necked flask equipped with a stirrer, a temperature sensor, and a condenser tube was previously dried with a molecular sieve. 87.9 g of the diglyme and 142.5 g of 3-aminopropyltrimethoxysilane were added, and the temperature was raised to 100 ° C. under a flow of dry nitrogen while stirring to remove moisture in the system. Next, 131.8 g of 5-norbornene-2,3-dicarboxylic anhydride was added in four portions over 30 minutes while maintaining the reaction solution temperature at 100 ° C. It was confirmed by high performance liquid chromatography that 5-norbornene-2,3-dicarboxylic anhydride was completely consumed in 9 hours after the completion of the addition.
Subsequently, 42.9 g of deionized water was added all at once, and the temperature was raised so that by-product methanol was refluxed in the cooling pipe. After holding at 95 ° C. for 10 hours, the temperature was raised again by replacing the cooling pipe with a partial condenser. The reaction liquid temperature was allowed to reach 120 ° C. over 3 hours while collecting by-product methanol and condensed water. When reaching 120 ° C., 0.65 g of cesium carbonate was added and the temperature was raised as it was, reaching 160 ° C. over 3 hours while collecting condensed water, holding at that temperature for 2 hours, and cooling to room temperature. The precipitate was collected by charging and dried to obtain Compound G. Compound G was confirmed to be cage-like {γ- (5-norbornene-2,3-imido) propylsilsesquioxane} from the results of analysis by FT-IR and NMR. When the molecular weight was measured by GPC, the number average molecular weight Mn was 2,340, the weight average molecular weight Mw was 2,570, and the molecular weight distribution Mw / Mn was 1.10. Moreover, the value of T ₂ / (T ₂ + T ₃ ) described above was 0.28.

<Heat resistance evaluation>
The heat resistance evaluation of the compounds A to G was performed using TG-DTA. About 10 mg of each sample was weighed and heated to 500 ° C. at a rate of temperature increase of 10 ° C./min under a nitrogen flow of 100 mL / min, and the temperature at which the weight loss rate was 5% (Td 5%) was determined. A temperature of Td 5% is shown in Table 1.

<CNT dispersibility evaluation>
The CNT dispersibility evaluation of the compounds A to G was performed as follows.
Compound A to G 0.1 g and MWCNT (manufactured by Tokyo Chemical Industry Co., Ltd., diameter 10 nm, total length 1 to 2 μm) 0.1 g are weighed into a 50 mL glass vial, and 10 mL of N-methylpyrrolidone is further added, and an ultrasonic homogenizer is used. Distributed processing. The homogenizer dispersion conditions were an output of 150 W, a treatment liquid temperature of 40 ° C. or less, and a treatment time of 1 hour.
The dispersion stability of the obtained dispersion was allowed to stand at room temperature for 24 hours and evaluated by visually confirming the change in the dispersion state of MWCNT. The determination of the dispersion state was as follows.
◎: Dispersion is uniform without separation and there is no precipitate ○: Dispersion is uniform with little separation, but dispersion is uniform ×: Dispersion is divided into two layers, black and transparent, with sediment at the bottom

<Application performance evaluation>
Furthermore, as for the coating performance of the dispersion liquid, the dispersion liquid is applied on a Tetron film using an applicator so that the dry film thickness is 1 μm, dried in an oven maintained at 150 ° C. for 4 minutes, and the appearance of the coating film is compared. It went by. Appearance judgment was as follows.
A: Uniform coating film B: Coating film was formed, but there were shades depending on the location. X: The dispersion performance and coating performance evaluation results that could be applied but did not become a film were shown in Table 2.

The compounds A and F used in Comparative Examples 1 and 2 are compounds that are precursors of the compounds B, C, D, and E, and the number average molecular weight is sufficiently large as 3,000 or more. However, when Td5% is 300 ° C. or lower, the heat resistance is low, and the MWCNT dispersibility is not so high. As described in Non-Patent Document 1, it is presumed that I ₂ or the like needs to be added as a dispersion aid. Furthermore, the properties of the dried coating films of Compounds A and F were poor and a self-supporting film could not be produced. In addition, Compound G used in Comparative Example 3 has a cage structure, and is a very high heat-resistant compound with a Td of 5% exceeding 350 ° C. However, although the molecular weight was low and MWCNT dispersibility could be confirmed, the properties of the dried coating film were poor and a self-supporting film could not be produced. Although it has the effect of improving the CNT dispersibility due to the imide skeleton of the side chain, it is presumed that the film formability is inferior due to the low molecular weight.
In contrast, the compounds B, C, D and E used in the examples have a high molecular weight, and the Td5% exceeds 350 ° C. due to the silsesquioxane type inorganic structure of the main skeleton and the imide skeleton of the side chain. The heat resistance was very high. Moreover, the molecular weight was high, the dispersibility of the MWCNT dispersion was excellent, and the MWCNT was evenly distributed in the dry coating film prepared using them, and the coating film properties were also good.

Claims (3)

A polysiloxane compound having a ladder-like polysiloxane skeleton, an imide structure in a side chain, and a number average molecular weight of 4,500 or more. A method for producing a polysiloxane compound, comprising:
The method for producing a polysiloxane compound includes a step of reacting an acid anhydride of a hydrolytic condensate of an alkoxysilane having a ladder-like structure having an amino group with an acid anhydride. It has a polysiloxane skeleton of the ladder-like structure, and have a non-ionic substituent in the side chain, and wherein the number average molecular weight and a polysiloxane compound and a conductive carbon material is 3,000 or more A conductive carbon material-containing composition.

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