JP2010121025A - Solution composition and molded article by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solution composition capable of easily molding a seamless semiconductive resin belt and also producing the semiconductive resin belt of which electric resistance is stably regulated at a high resistance region. <P>SOLUTION: This solution composition includes a component (A) of a solvent soluble liquid crystalline polyester, component (B) of an electroconductive substance (such as carbon black or the like) and component (C) of a solvent, and having 1 to 100 pts.wt. component (B) based on 100 pts.wt. component (A). The solution composition is useful for the production of the semiconductive resin belt. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a solution composition containing a liquid crystal polyester, and a molded article obtained using the solution composition. The present invention also relates to a semiconductive resin belt obtained using the solution composition.

In printers using digital color electrophotographic processes and multi-function copiers equipped with FAX functions, they are made of resin that has conductivity in a semiconductive region (resistance value 10 ⁹ to 10 ¹³ Ω /) called an intermediate transfer belt. Belts (hereinafter referred to as “semiconductive resin belts”). In particular, semi-conductive resin belts using polyimide resin are used in high-function and multi-function copiers whose market is expanding in recent years (see, for example, Patent Document 1).

  Polyimide resin is easy to process by cast film formation, has excellent flame retardancy, and by dispersing conductive material such as carbon black, electrical resistance can be stably controlled in the high resistance region. It was useful as a material for manufacturing the semiconductive resin belt. However, it is essentially difficult to recycle waste materials with polyimide resins, and considering the reduction of environmental burden due to recent reductions in waste, it has been desired to apply thermoplastic resins that can replace the polyimide resins.

JP 2008-40231 A

The thermoplastic resin used as a substitute for the polyimide resin that has been studied so far has been intended to produce a semiconductive resin belt by an extrusion method. However, in order to place importance on the fact that the semiconductive resin belt is seamless, the semiconductive resin belt formed by the extrusion molding method has a problem of occurrence of a molten resin merging portion (weld). Further, the required physical properties of other semiconductive resin belts are not always satisfactory.
SUMMARY OF THE INVENTION An object of the present invention is to provide a solution composition that can be molded into a seamless semiconductive resin belt by casting as a belt using a thermoplastic resin applicable to recycling. Another object of the present invention is to provide a molded article useful as a semiconductive resin belt using the solution composition.

As a result of intensive studies and studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention provides the following <1>.
<1> A solution composition comprising the following component (A), component (B) and component (C), wherein component (B) is 1 to 100 parts by weight per 100 parts by weight of component (A) (A) Solvent-soluble liquid crystal polyester (B) Conductive substance (C) Solvent

Furthermore, the present invention provides the following <2> to <4> as preferred embodiments according to the above <1>.
<2> The component (A) has a structural unit represented by the following formula (1), a structural unit represented by the formula (2), and a structural unit represented by the formula (3). The structural unit represented by the formula (1) is 30 to 80 mol%, the structural unit represented by the formula (2) is 35 to 10 mol%, and is represented by the formula (3) with respect to the total of all the structural units. <1> solution composition, wherein the structural unit is a liquid crystal polyester comprising 35 to 10 mol% of a structural unit;
⁽¹⁾ -O-Ar 1 -CO-
(2) —CO—Ar ² —CO—
⁽³⁾ -X-Ar 3 -Y-
(In the formula, Ar ¹ is phenylene, naphthylene; Ar ² is phenylene, naphthylene, or a group represented by the following formula (4); Ar ³ is phenylene or a group represented by the following formula (4); X and Y each independently represent O or NH, wherein the hydrogen atom bonded to the aromatic ring of Ar ¹ , Ar ² and Ar ³ may be substituted with a halogen atom, an alkyl group or an aryl group. .)
^{(4) -Ar 11 -Z-Ar} 12 -
(In the formula, Ar ¹¹ and Ar ¹² each independently represent phenylene or naphthylene. Z represents O, CO, or SO _2. )
<3> The resin composition according to <1> or <2>, wherein the component (B) is carbon black;
<4> The solution composition according to any one of <1> to <3>, wherein the component (C) is an aprotic solvent;

In addition, the present invention provides the following <5> to <8> using any one of the above solution compositions.
<5> A molded product obtained from the solution composition according to any one of <1> to <4>;
<6> A molded article according to <5>, wherein the volume resistivity is in the range of 1 × 10 ⁷ to 1 × 10 ¹⁰ Ω · cm;
<7><5> or <6> molded article used as a semiconductive resin belt;
<8> Molded article of <5> or <6> used as a semiconductive resin belt selected from the group consisting of a transfer belt, an intermediate transfer belt and a transfer fixing belt

  The solution composition of the present invention can easily produce a seamless semiconductive resin belt, and the obtained semiconductive resin belt has an electric resistance sufficiently stably controlled in a high resistance region, It is useful as a transfer belt, an intermediate transfer belt or a transfer fixing belt used in a photographic apparatus. Further, the liquid crystal polyester contained in the solution composition is sufficiently recyclable and can cope with a reduction in environmental load that has been demanded in recent years, and therefore has an extremely high industrial value.

  Hereinafter, preferred embodiments of the present invention will be described.

<Component (A)>
The liquid crystal polyester of component (A) used in the present invention is a polyester that exhibits optical anisotropy at the time of melting and has the property of forming an anisotropic melt at a temperature of 450 ° C. or lower. As this liquid crystalline polyester, a structural unit represented by the following formula (1) (hereinafter referred to as “formula (1) structural unit”) and a structural unit represented by the following formula (2) (hereinafter referred to as “formula (2)”. ) Structural unit) and a structural unit represented by the following formula (3) (hereinafter referred to as “formula (3) structural unit”), the formula (1) It is preferable that the structural unit is 30 to 80 mol%, the formula (2) structural unit is 35 to 10 mol%, and the formula (3) structural unit is 35 to 10%.
⁽¹⁾ -O-Ar 1 -CO-
(2) —CO—Ar ² —CO—
⁽³⁾ -X-Ar 3 -Y-
(In the formula, Ar ¹ is phenylene, naphthylene; Ar ² is phenylene, naphthylene, or a group represented by the following formula (4); Ar ³ is phenylene or a group represented by the following formula (4); X and Y represent O or NH, and X and Y may have the same configuration, wherein the hydrogen atom bonded to the aromatic ring of Ar ¹ , Ar ² and Ar ³ is a halogen atom, an alkyl group or (It may be substituted with an aryl group.)
^{(4) -Ar 11 -Z-Ar} 12 -
(In the formula, Ar ¹¹ and Ar ¹² each independently represent phenylene or naphthylene. Z represents O, CO, or SO _2. )

  The structural unit of the formula (1) is a structural unit derived from an aromatic hydroxycarboxylic acid, and examples of the aromatic hydroxycarboxylic acid include parahydroxybenzoic acid, metahydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, Examples include 2-hydroxy-3-naphthoic acid and 1-hydroxy-4-naphthoic acid.

  The structural unit (2) is a structural unit derived from an aromatic dicarboxylic acid, and examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and 1,5-naphthalenedicarboxylic acid. , Diphenyl ether-4,4′-dicarboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid, diphenyl ketone-4,4′-dicarboxylic acid and the like.

The structural unit (3) is a structural unit derived from an aromatic diol, an aromatic amine having a phenolic hydroxyl group, or an aromatic diamine. Examples of the aromatic diol include hydroquinone, resorcin, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxyphenyl) ether, and bis- (4-hydroxyphenyl) ketone. And bis- (4-hydroxyphenyl) sulfone.
Examples of the aromatic amine having a phenolic hydroxyl group include p-aminophenol and 3-aminophenol. Examples of the aromatic diamine include 1,4-phenylenediamine and 1,3-phenylenediamine. Can be mentioned.

The liquid crystalline polyester used for the component (A) is solvent-soluble, and such solvent-soluble means that it dissolves in a solvent at a temperature of 50 ° C. at a concentration of 1% by weight or more. The solvent in this case is any one of suitable solvents used for preparing the solution composition of the present invention, and details will be described later.
As such a solvent-soluble liquid crystal polyester, those containing a structural unit derived from an aromatic amine having a phenolic hydroxyl group and / or an aromatic diamine as the structural unit of the formula (3) are preferable. That is, the structural unit represented by the formula (3) preferably includes a structural unit in which at least one of X and Y is NH. Substantially all the structural units of the formula (3) are represented by the following formula (3 ′ ) Is more preferred (hereinafter referred to as “formula (3 ′) structural unit”).
(3 ′) — X—Ar ³ —NH—
(In the formula, Ar ³ and X have the same meanings as the formula (3)).
It is more preferable that the structural unit of the formula (3) is contained in the range of 25 to 33 mol% with respect to the total of all the structural units, and by doing so, the solvent solubility is further improved. Thus, the liquid crystal polyester having the structural unit of the formula (3 ′) as the structural unit of the formula (3) is more excellent in solubility in a solvent, and it is easier to produce an insulating layer using a solution composition described later. There is also an advantage of becoming.

  The structural unit of the formula (1) is in the range of 30 to 80 mol% and more preferably in the range of 35 to 50 mol% with respect to the total of all the structural units. The liquid crystal polyester containing the structural unit of the formula (1) at such a molar fraction tends to be more excellent in solubility in a solvent while sufficiently maintaining liquid crystallinity. Furthermore, p-hydroxybenzoic acid and / or 2-hydroxy-6-naphthoic acid are preferred as the aromatic hydroxycarboxylic acid from which the structural unit of formula (1) is derived.

  The structural unit of the formula (2) is in the range of 35 to 10% by mole and more preferably in the range of 25 to 33% by mole with respect to the total of all the structural units. The liquid crystal polyester containing the structural unit of the formula (2) at such a molar fraction tends to be more excellent in solubility in a solvent while sufficiently maintaining liquid crystallinity. As the aromatic dicarboxylic acid for deriving the structural unit of the formula (2), at least one selected from the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid is preferable in that it can be easily obtained.

  In addition, in the point that the obtained liquid crystal ester exhibits higher liquid crystallinity, the molar fraction of the formula (2) structural unit and the formula (3) structural unit is [formula (2) structural unit] / [formula ( 3) Structural unit], a range of 0.9 / 1.0 to 1.0 / 0.9 is preferable.

Next, the manufacturing method of liquid crystalline polyester is demonstrated easily.
The liquid crystalline polyester can be produced by various known methods. In the case of producing a liquid crystal polyester composed of the formula (1) structural unit, the formula (2) structural unit, and the formula (3) structural unit, which is a preferred liquid crystal polyester, a monomer that derives these structural units is used as an ester-forming amide. A method of producing a liquid crystal polyester by polymerization after conversion to a formable derivative is preferred because the operation is simple.

The ester-forming / amide-forming derivatives will be described with examples.
As an ester-forming / amide-forming derivative of a monomer having a carboxyl group, such as an aromatic hydroxycarboxylic acid or an aromatic dicarboxylic acid, an acid is used so that the carboxyl group promotes a reaction to form a polyester or polyamide. Form esters with alcohols, ethylene glycol, etc., such as those with highly reactive groups such as chlorides, acid anhydrides, and the like, such that the carboxyl group generates polyester or polyamide by transesterification / amide exchange reaction And the like.
Examples of ester-forming and amide-forming derivatives of monomers having a phenolic hydroxyl group, such as aromatic hydroxycarboxylic acids and aromatic diols, are those in which the phenolic hydroxyl group is carboxylated so as to produce polyesters and polyamides by transesterification. Examples include those forming esters with acids.
Examples of the amide-forming derivative of a monomer having an amino group, such as an aromatic diamine, include those in which an amino group forms an amide with a carboxylic acid so that a polyamide is formed by an amide exchange reaction. Can be mentioned.

Among these, for easier production of liquid crystalline polyesters, aromatic hydroxycarboxylic acids, aromatic diols, aromatic amines having phenolic hydroxyl groups, monomers having phenolic hydroxyl groups and / or amino groups such as aromatic diamines, Is converted to an ester-forming / amide-forming derivative (acylated product) with a fatty acid anhydride, and then the acyl group of the acylated product and the carboxy group of the monomer having a carboxy group undergo transesterification / amide exchange. Thus, a method of polymerizing and producing a liquid crystal polyester is particularly preferred.
A method for producing such a liquid crystal polyester is described in, for example, Japanese Patent Application Laid-Open No. 2002-220444 or Japanese Patent Application Laid-Open No. 2002-146003.

  In acylation, the amount of fatty acid anhydride used is preferably 1.0 to 1.2 times equivalent to the total of phenolic hydroxyl groups and amino groups, and 1.05 to 1.1 times equivalent. More preferably. When the amount of the fatty acid anhydride used is less than 1.0 times equivalent, the acylated product and the raw material monomer tend to sublime at the time of polymerization and the reaction system tends to be blocked, and when the amount exceeds 1.2 times equivalent Tends to be markedly colored in the liquid crystal polyester obtained.

The acylation is preferably performed at 130 to 180 ° C. for 5 minutes to 10 hours, more preferably at 140 to 160 ° C. for 10 minutes to 3 hours.
The fatty acid anhydride used for the acylation is preferably acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, or a mixture of two or more selected from these, particularly preferably anhydrous, from the viewpoint of price and handleability. Acetic acid.

The polymerization following acylation is preferably carried out at 130 to 400 ° C. while raising the temperature at a rate of 0.1 to 50 ° C./min, and at 150 to 350 ° C. at a rate of 0.3 to 5 ° C./min. More preferably.
Moreover, in superposition | polymerization, it is preferable that the acyl group of an acylation thing is 0.8-1.2 times equivalent of a carboxyl group.

  In the acylation and / or polymerization, in order to shift the equilibrium, it is preferable to distill out by-produced fatty acids and unreacted fatty acid anhydrides by evaporating them.

The acylation or polymerization may be performed in the presence of a catalyst. As the catalyst, those conventionally known as polyester polymerization catalysts can be used, such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, antimony trioxide and the like. And organic compound catalysts such as N, N-dimethylaminopyridine and N-methylimidazole.
However, since a catalyst containing a metal is likely to affect the electrical characteristics when producing a semiconductive resin belt, among the above catalysts, two nitrogen atoms such as N, N-dimethylaminopyridine and N-methylimidazole are included. The heterocyclic compound containing the above is preferably used (see JP 2002-146003 A).
The catalyst is usually charged together with the monomer and it is not always necessary to remove it after acylation. If the catalyst is not removed, the polymerization can be transferred directly from the acylation.

  The liquid crystalline polyester obtained by such polymerization can be used as it is as the component (A), but for further improvement of the properties such as heat resistance and liquid crystallinity, it is preferable to increase the molecular weight. For such high molecular weight, solid phase polymerization is preferably performed. A series of operations relating to this solid phase polymerization will be described. The relatively low molecular weight liquid crystal polyester obtained by the above polymerization is taken out and pulverized into powder or flakes. Subsequently, solid phase polymerization can be performed by an operation in which the pulverized liquid crystal polyester is heat-treated in a solid state at 20 to 350 ° C. for 1 to 30 hours in an atmosphere of an inert gas such as nitrogen, for example. The solid phase polymerization may be performed while stirring or in a state of standing without stirring. In addition, from the viewpoint of obtaining a liquid crystalline polyester having a suitable flow start temperature described later, the preferred conditions for the solid phase polymerization will be described in detail. The reaction temperature is preferably higher than 210 ° C, and more preferably 220 ° C to 350 ° C. Range. The reaction time is preferably selected from 1 to 10 hours.

  The liquid crystal polyester used for the component (A) of the present invention preferably has a flow start temperature of 250 ° C. or higher. The flow start temperature here refers to a temperature at which the melt viscosity of the liquid crystal polyester becomes 4800 Pa · s or less under a pressure of 9.8 MPa in the evaluation of the melt viscosity by a flow tester. The flow initiation temperature is well known to those skilled in the art as a measure of the molecular weight of liquid crystal polyester (Naoyuki Koide, “Liquid Crystal Polymer—Synthesis / Molding / Application—”, pages 95 to 105, CMC. , Issued June 5, 1987).

  The flow initiation temperature of the liquid crystalline polyester is more preferably 250 ° C. or higher and 330 ° C. or lower. If the flow start temperature is 330 ° C. or lower, the solubility of the liquid crystalline polyester in the solvent becomes better, and when the solution composition of the present invention is obtained, the viscosity does not increase significantly. There exists a tendency for the handleability of a thing to become favorable. From this viewpoint, a liquid crystal polyester having a flow start temperature of 260 ° C. or higher and 320 ° C. or lower is more preferable. In order to control the flow start temperature of the liquid crystal polyester within such a suitable range, the polymerization conditions for the solid phase polymerization may be optimized as appropriate.

<Component (B)>
The conductive substance is selected within a range satisfying the semiconductivity described later, and the volume resistance value and the amount used (the conductive substance content in the semiconductive resin belt) of the conductive substance itself are determined. Select with consideration.

  Examples of the conductive material suitable for its volume resistance and dispersibility with respect to the liquid crystalline polyester (A) include carbon fillers such as carbon black, carbon fiber, and graphite, metal conductive fillers, and metal oxide conductives. Examples thereof include ion conductive substances such as fillers and quaternary ammonium salts. Among these, carbon black is advantageous and preferable from the viewpoint of economy.

As the carbon black, acetylene black, furnace black, channel black and the like can be suitably used, and among them, acetylene black which has few functional groups as impurities and hardly causes poor appearance due to carbon aggregation can be particularly suitably used. Further, those having a primary particle diameter of 10 to 100 nm, a specific surface area of 10 to 200 m ² / g, and a pH value of 6 to 11 are more preferable. This carbon black may be used alone or in combination of two or more.

<Ingredient (C)>
Component (C) is a solvent, and the solvent is selected from those capable of dissolving the liquid crystal polyester of component (A) to be used.
As the liquid crystal polyester of the component (A), when the above-mentioned preferred liquid crystal polyester, particularly the liquid crystal polyester containing the structural unit (3 ′) is used, the liquid crystal polyester is free from an aprotic solvent containing no halogen atom. The aprotic solvent is suitable as the component (C) because it exhibits sufficient solubility.
Examples of the aprotic solvent not containing a halogen atom include ether solvents such as diethyl ether, tetrahydrofuran and 1,4-dioxane; ketone solvents such as acetone and cyclohexanone; ester solvents such as ethyl acetate; γ-butyrolactone Lactone solvents such as ethylene carbonate and propylene carbonate; amine solvents such as triethylamine and pyridine; nitrile solvents such as acetonitrile and succinonitrile; N, N-dimethylformamide and N, N-dimethylacetamide Amide solvents such as tetramethylurea and N-methylpyrrolidone; nitro solvents such as nitromethane and nitrobenzene; sulfur solvents such as dimethyl sulfoxide and sulfolane; hexamethylphosphoric acid amide and tri-n-butylphosphoric acid The system solvent, and the like. In addition, the solvent solubility of the above-mentioned liquid crystalline polyester indicates that it is soluble in at least one aprotic solvent selected from these.

  Among the exemplified solvents, it is preferable to use an aprotic polar solvent having a dipole moment of 3 or more and 5 or less from the viewpoint of further improving the solvent solubility of the component (A) and easily obtaining a solution composition. Of these, amide solvents and lactone solvents are preferable, and N, N′-dimethylformamide (DMF), N, N′-dimethylacetamide (DMAc), and N-methyl-2-pyrrolidone (NMP) are more preferable. Furthermore, it is preferable that the solvent is a highly volatile solvent having a boiling point of 180 ° C. or less at 1 atm, since it becomes easier to produce a molded article described later. From this point, DMF and DMAc are used. It is particularly preferred.

<Other ingredients>
In addition to the above-described components, a nonconductive substance may be added to the solution composition of the present invention as long as the obtained molded body has a volume resistivity suitable as a semiconductive resin belt. Examples of the non-conductive substance include various non-conductive inorganic powders and resins, dispersants, silicone-based or fluorine-based release agents, coupling agents, lubricants, antioxidants, and the like.

  Specific examples of the non-conductive inorganic powder include, for example, small-diameter granular materials such as alumina and silica, plate-like and scaly materials such as mica and viscous minerals, short fibers such as aluminum borate and potassium titanate, or Examples include whisker-like substances.

  Examples of resins that are non-conductive materials include polypropylene, polyamide, polyester, polyphenylene sulfide, polyether ketone, polycarbonate, polyether sulfone, polyphenyl ether and modified products thereof, polyether imide, and other thermoplastic resins; glycidyl methacrylate and polyethylene Elastomers typified by these copolymers; thermosetting resins such as phenol resins, epoxy resins, polyimide resins, and cyanate resins, and the like. These are not only one type, but two or more types may be added. However, when using a resin other than the liquid crystal polyester, it is preferable that these resins are also soluble in the component (C) solvent used in the solution composition.

  By adding this non-conductive substance, various physical properties such as the mechanical strength of the semiconductive resin belt can be controlled. Moreover, such a non-conductive substance may moderately assist the dispersion of the conductive substance. The addition of a non-conductive substance having such a dispersion assist property prevents the aggregation of the conductive substance, particularly conductive particles, and facilitates the production of a molded product that exhibits a stable volume resistance value. .

<Solution composition>
The solution composition of the present invention can be produced by mixing the component (A), the component (B) and the component (C). Although the mixing order is not particularly limited, it is preferable that a part or all of the component (A) is dissolved in the component (C) in the solution composition, so that the component (A) and the component ( It is preferable that the component (B) is added to the liquid crystal polyester solution after the component (A) is sufficiently dissolved in the component (C) to prepare a liquid crystal polyester solution. In addition, in the solution composition of the present invention, when other components such as the non-conductive material are contained, a liquid crystal polyester solution is prepared by previously mixing the component (A) and the component (C), It is preferable to add the component (B) and other components to the liquid crystal polyester solution.

Hereinafter, the suitable manufacturing method of the solution composition of this invention is demonstrated. First, the component (A) and the component (C) are charged into a mixer equipped with a suitable heating device and stirring device, and the component (A) is sufficiently dissolved in the component (C). This dissolution can be carried out in the temperature range from room temperature to the boiling point of the component (C) used, and is preferably selected from the temperature range from 50 ° C. to the boiling point of the component (C). The dissolution time is selected from about 0.1 to 10 hours. Moreover, it is preferable to sufficiently replace the inside of the mixer with an inert gas such as nitrogen gas from the viewpoint of satisfactorily preventing oxidative deterioration of the liquid crystal polyester.
Thus, after manufacturing a liquid-crystal polyester solution, a component (B) or a component (B) and another component are added. And after addition, it is preferable to stir so that a component (B) may fully disperse | distribute to a liquid crystalline polyester solution. In the case of dispersing the component (B), a temperature condition of about room temperature is sufficient.

  In the production of the solution composition of the present invention, in order to disperse component (B) and other components satisfactorily in the liquid crystal polyester solution, mixing and dispersion using a planetary mixer, bead mill, ball mill, ultrasonic wave, three rolls, etc. The method is preferably employed. In addition, after performing the mixing / dispersing process in this manner, a defoaming process or the like may be performed.

  In the solution composition of the present invention, the blending ratio of the component (B) is 1 part by weight or more and 100 parts by weight or less, and 3 parts by weight or more and 80 parts by weight with respect to 100 parts by weight of the component (A). Is more preferably 5 parts by weight or more and 60 parts by weight or less. When the blending ratio of the component (B) is too large, the volume resistivity as the semiconductive resin belt becomes too low, and the mechanical properties of the semiconductive resin belt tend to be lowered. On the other hand, when the blending ratio of the component (B) is too small, a desired volume resistivity may not be obtained as a semiconductive resin belt.

Next, the blending ratio of component (C) in the solution composition of the present invention will be described.
When a suitable aprotic solvent is used as the component (C), the component (A) is preferably 3 to 50 parts by weight, preferably 5 to 40 parts by weight with respect to 100 parts by weight of the aprotic solvent. . If component (A) with respect to component (C) is such a blending ratio, component (A) can be sufficiently dissolved in component (C). Further, when the blending ratio of the component (A) is within such a range, the efficiency of producing a semiconductive resin belt by processing the solution composition of the present invention into a sheet (sheeting) is improved, and the sheet Then, when the solvent contained in the sheet is removed by drying, there is a tendency that inconveniences such as unevenness in thickness occur hardly occur.

<Molded body>
The solution composition of the present invention can produce a film-like or plate-like molded product by a known method such as a cast film forming method.
Here, a method for manufacturing a semiconductive resin belt will be described in detail.
The solution composition of the present invention can obtain a seamless semiconductive resin belt by the molding method shown below. Specifically, a semiconductive resin belt can be produced by molding a cylindrical molded body (tubular molded body) from the solution composition.

The cylindrical body is formed by, for example, rotating the cylindrical mold and then applying the solution composition to the inner peripheral surface or the outer peripheral surface of the rotating cylindrical mold, A cylindrical shaped body is formed by injecting the solution composition into the gap using a mold having a cylindrical shape. By further drying the molded body thus obtained, a cylindrical molded body useful for producing a semiconductive resin belt is formed. Further, by further heat-treating the obtained cylindrical molded body, characteristics such as mechanical strength of the cylindrical molded body are further improved, and a semiconductive resin belt is completed. Examples of a method of applying the solution composition to the inner peripheral surface or outer peripheral surface of a mold include a method of coating by a dipping method, a centrifugal method, a coating method, or the like. Such a method for producing a semiconductive resin belt has been conventionally known as a method of using a varnish containing a polyimide resin, and disclosed in JP-A-61-95361, JP-A-64-22514, and JP-A-3. Details are described in Japanese Patent Application No. 180/309. Moreover, after apply | coating to a metal mold | die in this way, in order to volatilize and remove the component (C) used for the solution composition, heat processing are implemented. According to this heat treatment, the mechanical properties and the like of the liquid crystal polyester contained in the molded cylindrical molded body can be further improved. The heat treatment in this case is performed in a temperature range of 200 to 400 ° C.
Next, the obtained semiconductive resin belt and the mold are separated. A mold used for manufacturing such a semiconductive resin belt may be subjected to a release treatment or the like on the surface in contact with the solution composition.

  As described above, by using the solution composition of the present invention and an appropriate mold, a seamless semiconductive resin belt can be formed. After processing the solution composition into a sheet, A semiconductive resin belt can also be manufactured by making the obtained sheet into a cylindrical shape. In this case, for example, after forming a long sheet by using a known cast film from the solution composition, the obtained long sheet is cut into a predetermined length, and both ends thereof are bonded. do it. In such a manufacturing method, for example, if bonding at both ends is performed by a method such as thermocompression bonding, unlike a weld that has occurred in conventional thermoplastic resin extrusion molding, it is a substantially seamless semiconductive resin. A belt can be manufactured.

  The film thickness of the semiconductive resin belt thus produced can be appropriately determined according to the purpose of use, etc. In general, in order to achieve both appropriate strength and appropriate flexibility, the film thickness is 5 to 500 μm. The range of 10 to 300 μm is more preferable, the range of 20 to 200 μm is particularly preferable.

The molded body obtained from the solution composition of the present invention has a volume resistivity in the range of 1 × 10 ³ to 1 × 10 ¹² Ω · cm and is suitable as a semiconductive resin belt. The volume resistivity is more preferably in the range of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm, and particularly preferably in the range of 1 × 10 ⁷ to 1 × 10 ¹⁰ Ω · cm. Here, the volume resistivity is a value measured with a digital superinsulator at a measurement temperature of 23 ° C. and an applied voltage of 100 V after holding the molded body at 23 ° C. for 48 hours or more.

<Application example of semiconductive resin belt>
The semiconductive resin belt obtained by the present invention can be used for various uses according to the conventional semiconductive resin belt. In particular, the semiconductive resin belt is suitably used for a transfer belt, an intermediate transfer belt, or a transfer fixing belt of an electrophotographic recording apparatus. In that case, as the recording agent for forming an image on the printing sheet, various toners that can adhere to the image carrier via static electricity can be used. In addition, since the semiconductive resin belt obtained in the present invention uses liquid crystalline polyester as a thermoplastic resin, the component (A) liquid crystalline polyester is dissolved by a solvent when the semiconductive resin belt is discarded. By removing, it is possible to separate the component (B) conductive material from the liquid crystalline polyester. Therefore, if the characteristics of the liquid crystal polyester and the conductive material are not significantly impaired, they can be recycled (reused).

Examples that specifically show the structure and effects of the present invention will be described below.

(Production Example 1)
[1] Production of Aromatic Liquid Crystalline Polyester A In a reactor equipped with a stirrer, torque meter, nitrogen gas inlet tube, thermometer and reflux condenser, 1976 g (10.5 mol) of 2-hydroxy-6-naphthoic acid, 1474 g (9.75 mol) of 4-hydroxyacetanilide, 1620 g (9.75 mol) of isophthalic acid and 2374 g (23.25 mol) of acetic anhydride were charged. After sufficiently replacing the inside of the reactor with nitrogen gas, the temperature was raised to 150 ° C. over 15 minutes under a nitrogen gas stream, and the mixture was refluxed for 3 hours while maintaining the same temperature.

  Thereafter, while distilling off by-product acetic acid and unreacted acetic anhydride, the temperature was raised to 300 ° C. over 170 minutes. The time point at which an increase in torque was observed was regarded as completion of the reaction, and the contents were taken out. The taken out contents were cooled to room temperature and pulverized with a pulverizer to obtain a liquid crystal polyester powder having a relatively low molecular weight. It was 235 degreeC when the flow start temperature was measured for the obtained powder by Shimadzu Corporation flow tester CFT-500. This liquid crystal polyester powder was subjected to solid phase polymerization such as heat treatment at 223 ° C. for 3 hours in a nitrogen atmosphere. The flow initiation temperature of the liquid crystal polyester A after solid phase polymerization was 270 ° C.

[2] Preparation of Liquid Crystalline Polyester Solution A 2200 g of the liquid crystal polyester A obtained in [1] above was added to 7800 g of N, N-dimethylacetamide (DMAc) and heated and stirred at 100 ° C. for 2 hours to obtain a solution composition (liquid crystal polyester). Solution A) was obtained. The solution viscosity of this liquid crystal polyester solution A was 320 cP. The melt viscosity is a value measured at a measurement temperature of 23 ° C. using a B-type viscometer (manufactured by Toki Sangyo, “TVL-20 type”, rotor No. 21 (rotation speed: 5 rpm)).

[3] Preparation of Liquid Crystalline Polyester Solution Composition A In addition to 85.6 g of the liquid crystal polyester solution A obtained in [2] above, commercially available acetylene black (Electrochemical Industry; trade name Denka Black, granular product, primary particle size 35 nm, 6.65 g of a specific surface area of 69 m ² / g and a specific gravity of 1.95 g / cm ³ were added and stirred at room temperature for 2 hours to obtain a liquid crystal polyester solution composition A. In addition, the mixture ratio of acetylene black with respect to 100 weight part of liquid crystalline polyester A is 26 weight part.

This liquid crystal polyester solution composition A was applied onto a copper foil having a thickness of 18 μm. After the application, heat treatment was performed at 320 ° C. for 3 hours in a nitrogen atmosphere using a hot air dryer. After cooling, a sheet-like molded body A having a thickness of 38 μm was obtained by removing all the copper foil with a ferric chloride solution (40 ° Baume, manufactured by Kida Co., Ltd.).
After the obtained sheet-like molded product A was allowed to stand at 23 ° C. for 72 hours, a digital superinsulator / microammeter (DSM-8104, manufactured by Toa DKK Co., Ltd., flat plate measurement electrode SME-883, applied voltage 100 V) As a result of measuring the resistance value using the film thickness and converting it to the film thickness value, the volume resistivity was 5.37 × 10 ⁷ Ω · cm.

Example 1 [Production of semiconductive resin belt]
The liquid crystalline polyester solution composition A obtained in Production Example 1 was applied to the inner surface of a cylindrical mold, heat-treated at 320 ° C. for 3 hours in a nitrogen atmosphere with a hot air dryer, and then peeled off to be semiconductive. A functional resin belt can be obtained. The obtained semiconductive resin belt is seamless, and in view of the volume resistivity of the sheet-like molded body A, it becomes a good semiconductive one.

(Production Example 2)
[1] Production of aromatic liquid crystal polyester B In a reactor equipped with a stirrer, a torque meter, a nitrogen gas introduction tube, a thermometer and a reflux condenser, 941 g (5.0 mol) of 2-hydroxy-6-naphthoic acid, 273 g (2.5 mol) of 4-aminophenol, 415.3 g (2.5 mol) of isophthalic acid and 1123 g (11 mol) of acetic anhydride were charged. After sufficiently replacing the inside of the reactor with nitrogen gas, the temperature was raised to 150 ° C. over 15 minutes under a nitrogen gas stream, and the mixture was refluxed for 3 hours while maintaining the same temperature.

  Thereafter, the temperature was raised to 320 ° C. over 170 minutes while distilling off the by-product acetic acid and unreacted acetic anhydride, and the time when an increase in torque was observed was regarded as the completion of the reaction, and the contents were taken out. The taken out contents were cooled to room temperature and pulverized with a coarse pulverizer to obtain liquid crystal polyester powder. It was 185 degreeC when the flow start temperature was measured for the obtained powder with the flow tester CFT-500 by Shimadzu Corporation. This liquid crystal polyester powder was subjected to solid phase polymerization such as heat treatment at 225 ° C. for 3 hours in a nitrogen atmosphere. The flow starting temperature of the liquid crystal polyester B after solid phase polymerization was 270 ° C.

[2] Preparation of liquid crystal polyester solution B 80 g of liquid crystal polyester B obtained in [1] above was added to 920 g of N-methylpyrrolidone (NMP) and heated at 140 ° C. for 4 hours to obtain a solution composition (liquid crystal polyester solution B). Got. The solution viscosity of this liquid crystal polyester solution B was 530 cP. The melt viscosity is a value measured at a measurement temperature of 23 ° C. using a B-type viscometer (manufactured by Toki Sangyo, “TVL-20 type”, rotor No. 21 (rotation speed: 5 rpm)).

[3] Preparation of Liquid Crystalline Polyester Solution Composition B In addition to 81 g of the liquid crystal polyester solution B obtained in [2] above, commercially available acetylene black (Electrochemical Industry; trade name Denka Black, granular product, primary particle size 35 nm, specific surface area) 69 m ² / g, specific gravity 1.95 g / cm ³ ) 2.28 g was added and stirred at room temperature for 2 hours to obtain Liquid Crystalline Polyester Solution Composition B. In addition, the mixture ratio of acetylene black with respect to 100 weight part of liquid crystalline polyester B is 26 weight part.

This liquid crystal polyester solution composition B was applied onto a copper foil having a thickness of 18 μm. After the application, heat treatment was performed at 320 ° C. for 3 hours in a nitrogen atmosphere by a hot air dryer. After cooling, a sheet-like formed body B having a film thickness of 17 μm was obtained by removing all the copper foil with a ferric chloride solution (40 ° Baume, manufactured by Kida Co., Ltd.).
The obtained sheet-like molded product B was allowed to stand at 23 ° C. for 72 hours, and then a digital superinsulator / microammeter (DSM-8104, manufactured by Toa DKK, plate sample measuring electrode SME-883, applied voltage 100 V) As a result of measuring the resistance value and converting it with the film thickness value, the volume resistivity was 7.09 × 10 ⁷ Ω · cm.

Example 2 [Production of semiconductive resin belt]
The liquid crystalline polyester solution composition B obtained in Production Example 2 is applied to the inner surface of a cylindrical mold, and is subjected to heat treatment at 320 ° C. for 3 hours in a nitrogen atmosphere with a hot air drier to peel off the semiconductive resin. A belt can be obtained. The obtained semiconductive resin belt is seamless, and in view of the volume resistivity of the sheet-like molded body B, it becomes a good semiconductive one.

Claims (8)

A solution comprising the following component (A), component (B) and component (C), wherein component (B) is 1 to 100 parts by weight with respect to 100 parts by weight of component (A) Composition.
(A) Solvent-soluble liquid crystal polyester (B) Conductive substance (C) Solvent The component (A) has a structural unit represented by the following formula (1), a structural unit represented by the formula (2), and a structural unit represented by the formula (3), and has a total structure. The structural unit represented by the formula (1) is 30 to 80 mol%, the structural unit represented by the formula (2) is 35 to 10 mol%, and the structural unit represented by the formula (3) with respect to the total of the units. The solution composition according to claim 1, wherein the liquid crystal polyester comprises 35 to 10 mol%.
⁽¹⁾ -O-Ar 1 -CO-
(2) —CO—Ar ² —CO—
⁽³⁾ -X-Ar 3 -Y-
(In the formula, Ar ¹ is phenylene, naphthylene; Ar ² is phenylene, naphthylene, or a group represented by the following formula (4); Ar ³ is phenylene or a group represented by the following formula (4); X and Y each independently represent O or NH, wherein the hydrogen atom bonded to the aromatic ring of Ar ¹ , Ar ² and Ar ³ may be substituted with a halogen atom, an alkyl group or an aryl group. .)
^{(4) -Ar 11 -Z-Ar} 12 -
(In the formula, Ar ¹¹ and Ar ¹² each independently represent phenylene or naphthylene. Z represents O, CO, or SO _2. )   The solution composition according to claim 1 or 2, wherein the component (B) is carbon black.   The solution composition according to claim 1, wherein the component (C) is an aprotic solvent.   A molded product obtained from the solution composition according to claim 1. 6. The molded body according to claim 5, wherein the volume resistivity is 1 × 10 ⁷ to 1 × 10 ¹⁰ Ω · cm.   The molded article according to claim 5 or 6, wherein the molded article is used as a semiconductive resin belt.   The molded article according to claim 5 or 6, wherein the molded article is used as a semiconductive resin belt selected from the group consisting of a transfer belt, an intermediate transfer belt, and a transfer fixing belt.