JP2008031567A - Aliphatic polyester fiber and fiber product made thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aliphatic polyester fiber having high electrical conductivity, uniform conductivity on the fiber surface and extremely excellent stability of the conductivity in the case of varying the humidity and provide an aliphatic polyester fiber product such as clothes, carpet and brush produced by using the fiber. <P>SOLUTION: The aliphatic polyester fiber contains an aliphatic polyester containing a conductive agent and an aromatic polyester and has an average resistivity P of ≤1.0×10<SP>12</SP>[Ω/cm]. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an aliphatic polyester fiber excellent in conductivity and a fiber product comprising the same. More specifically, an aliphatic polyester fiber having a conductivity excellent in conductivity stability when the humidity changes, and an aliphatic polyester fiber product such as clothing, rug or brush using the fiber. It is about.

  In general, a fiber whose main repeating structural unit is an aliphatic polyester is generally a raw material derived from a natural product (e.g., polyethylene terephthalate or polybutylene terephthalate). In recent years, it has attracted attention from the viewpoint of protecting the global environment and is being developed rapidly.

  By the way, “conductivity” is one of the important functions in imparting the functionality of conventional and future fibers. For example, as a textile fiber for clean rooms or as a fiber mixture for carpets, There is a great demand in a wide range of fields such as clothing and industrial use, such as removal or application of charges in the apparatus. In recent years, the exposure of electromagnetic waves has increased in daily environments due to the spread of electronic information devices, especially wireless terminals such as mobile phones, and there are concerns about the impact on health. Increasingly, it is used as an electromagnetic shielding material.

For example, a technique related to antistatic fibers using a block copolymer of polylactic acid and polyalkylene ether as an antistatic agent has been proposed (see, for example, Patent Document 1). In this technique, although fibers having excellent antistatic properties can be obtained, polyethylene glycol is used as a copolymerization component, so that the conductivity level is at most about 10 ⁸ [Ω · cm] and high conductivity. In addition, since the conductivity of the antistatic agent changes depending on the presence or absence of moisture, the fiber obtained by the technique has high conductivity or any atmosphere (change in humidity). However, stable conductivity and the like were not ensured.

  Moreover, the technique regarding the conductive fiber which employ | adopted the polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) used conventionally as a structural component of a conductive fiber is proposed (for example, refer patent document 2). In this technique, conductive fine particles are contained in PET or PBT, and high-speed spinning is performed as a core-sheath composite fiber using PET having a high intrinsic viscosity as a core component, so that a fiber having excellent strength and elongation characteristics can be obtained. However, as is conventionally known, PET and PBT are very difficult to melt-spin by containing conductive fine particles at a high concentration. Even if PET with a high intrinsic viscosity is used as a core component, Even when composite spinning was performed, conductive fibers having high conductivity were not obtained.

On the other hand, a fiber-forming polymer containing aliphatic polyester as a main component and a conductive polymer obtained by mixing conductive particles and a polymer containing aliphatic polyester as a main component are combined in a single fiber. Techniques related to conductive fibers have been proposed (see, for example, Patent Document 3). In this technology, the aliphatic polyester containing conductive particles and the aliphatic polyester containing no conductive particles are combined in a single fiber, so that it has electrical conductivity. On the other hand, the fibers obtained by this technique are mainly focused on utilizing the excellent biodegradability of aliphatic polyesters, and since only aliphatic polyesters are used, However, even if the shape is maintained, the physical properties of the yarn such as strength are significantly deteriorated, and the application is limited, and the rigidity of the fiber properties is also halfway, so high rigidity is required for cleaning. It was not used very often in brush applications and in applications that require flexibility. Of course, there was no disclosure of a specific application that was conscious of high rigidity or low rigidity, and there were no guidelines or ideas for fiber design aimed at the application.
JP-A-8-253665 (claims, paragraph numbers [0008], [0013], [0014], etc.) JP-A-63-85114 (Claims) Japanese Patent Laid-Open No. 9-155793 (claims, paragraph number [0025])

  An object of the present invention is to solve the above-mentioned problems of the prior art, have high conductivity without depending on temperature / humidity change, and have shape stability under a high temperature atmosphere and rigidity according to the application. It is an object of the present invention to provide an aliphatic polyester fiber having various aliphatic polyester fiber products using the aliphatic polyester fiber.

  The present invention has been intensively studied in order to obtain fibers having excellent conductivity and weather resistance, and it has been made into a fiber having a specific composition and has specific physical properties, thereby eliminating the drawbacks of the above prior art. It has been found that it is possible to provide further merits that cannot be achieved by the prior art, and the present invention has been achieved.

The present invention adopts the following configuration in order to solve the above problems. That is,
(1) An aliphatic polyester fiber comprising an aliphatic polyester and an aromatic polyester containing a conductive agent, and having an average resistivity P of 1.0 × 10 ¹² [Ω / cm] or less. .

  (2) The aliphatic polyester fiber according to (1), wherein the aliphatic polyester has lactic acid as a main repeating structural unit.

  (3) The aliphatic polyester fiber as described in (1) or (2) above, wherein the initial tensile elastic modulus is 15 cN / dtex to 80 cN / dtex.

  (4) The ratio R (R = Q / P) between the average resistivity P and the standard deviation Q of the resistivity is 0.5 or less, any one of (1) to (3) above The aliphatic polyester fiber described.

  (5) Ratio Z (Z = Y / X) of the average resistivity X [Ω / cm] at 23 ° C. and 55% humidity and the average resistivity Y [Ω / cm] at 10 ° C. and 15% humidity ) Is in the range of 1 to 5, aliphatic polyester fiber according to any one of (1) to (4).

  (6) An aliphatic polyester fiber product comprising the aliphatic polyester fiber according to any one of (1) to (5) as at least a part thereof.

  (7) An aliphatic polyester fiber brush characterized by using the aliphatic polyester fiber according to any one of (1) to (5) as at least a part thereof.

  Since the aliphatic polyester containing a high concentration conductive agent for high conductivity is an aliphatic polyester, the fiber of the present invention is a PET having a conventional repeating unit such as ethylene terephthalate as a main repeating structural unit. Unlike PBT polymers and PBT polymers with butylene terephthalate as the main repeating structural unit, fibers can be formed even if they contain a conductive agent at a high concentration, which has been difficult until now. It becomes an electrically conductive fiber, and can be used for non-clothing applications such as garment applications such as dust-proof clothing, interior materials such as vehicle interior materials and building wall materials, carpets and flooring materials. In addition, since it is a polyester, there is almost no water absorption or hygroscopicity. As a result, the conductivity is very stable because the humidity dependency of the conductivity is small. For these reasons, in applications that require high conductivity and conductivity stability in environmental changes, such as in wiring objects and electrophotographic apparatuses that use electricity that is used by applying voltage constantly or frequently as described below. It is suitably used for various brush rollers.

  In addition, since the fiber of the present invention is composed of an aromatic polyester, it has excellent shape stability of a fiber product using a fiber or fiber at a high temperature, and therefore, compared with a fiber made only of an aliphatic polyester. In addition to being able to be used for various purposes, it is possible to impart desired rigidity (initial tensile elastic modulus) to the fiber by selecting the type of aromatic polyester. Compared to a fiber having conductivity only, it has an excellent effect of being excellent in handleability while having equivalent conductive performance, and the use is greatly expanded.

  The fiber in the present invention refers to a thin and long shape, and the length may be a long fiber (filament) generally referred to or a short fiber (staple). In the case of a short fiber, it may be a desired length depending on the use, but it is preferably 0.05 to 150 mm in length considering that it is used in a spinning process or an electric flocking process as described later, More preferably, it is 0.1-120 mm. Moreover, when using especially for electric flocking, it is more preferable that it is 0.1-10 mm in length, and it is especially preferable that it is 0.2-5 mm. Here, the length of the short fiber is determined in accordance with Example I. described later. It is measured by the method in the section.

  The single yarn (single fiber) fineness of the fiber of the present invention is not particularly limited, but the single yarn fineness is 50 dtex (decitex) or less in that it can be used for various applications as described later. In addition, it is preferably 0.01 dtex or more, more preferably 0.01 to 20 dtex, and particularly preferably 0.1 to 10 dtex. For example, when used for a brush roller incorporated in an electrophotographic apparatus to be described later and used for an application incorporated in a cleaning apparatus or a charging apparatus, the single yarn fineness is 0.1 to 8 dtex in that the cleaning performance or charging performance is excellent. It is particularly preferred that it is 0.1 to 4 dtex. Moreover, when using for at least one part of the lining of clothing or other various clothing, it is especially preferable that it is 0.1-6 dtex. When used for at least part of non-clothing applications such as interior materials such as vehicle interior materials, building wall materials, carpets, flooring materials, etc., other than clothing applications, it may be 0.1 to 6 dtex. Particularly preferred. Further, the cross-sectional shape of the fiber is not particularly limited, and a round shape is preferable because it has uniform fiber properties and isotropic conductivity within the fiber cross-section, and the fiber is used for a brush roller. Incorporated in the form of short fibers, woven fabrics, knitted fabrics or non-woven fabrics, and depending on the application or purpose of use, for example, anisotropy is given in the direction of bending of the fibers to increase rigidity, or used in an electrophotographic apparatus to be described later In this case, a flat type, a polygonal shape, a multi-leaf type, a hollow type, an indeterminate type, or the like is preferable for the purpose of obtaining a good contact property with the toner and expressing a superior cleaning performance. Here, regarding the single yarn fineness, Example A. described later. Determined by measuring by the method in the paragraph. Further, the cross-sectional shape or single fiber diameter of the fiber is determined by measuring with a scanning electron microscope (SEM) at a magnification at which all the fiber outer diameters are within the field of view. For details, see Example K. below. Measure using the method in the section.

  As for the fiber of this invention, aliphatic polyester contains a electrically conductive agent. Since the conductivity of the fiber itself is determined by the aliphatic polyester containing this conductive agent, the desired conductivity can be freely controlled, and the fiber has very excellent conductivity. The reason why aliphatic polyester can achieve the phenomenon that “melt spinning is possible even when containing a high concentration of a conductive agent”, which could not be achieved with PET-based polymers and PBT-based polymers, which are polyesters, is completely clear. However, one is that “aliphatic polyesters have less interaction between molecular chains than PET-based polymers and PBT-based polymers, and there are gaps that can contain a conductive agent between the molecular chains. The gap is wider than the gap between molecular chains of PET polymers and PBT polymers, and the other is that the molecular chain alignment is smaller due to the alignment of the molecular chains in the orientation behavior of the molecular chains during melt spinning. In the phenomenon that the aliphatic polyester is, the two points that the degree to which the gap is smaller is smaller than that of the PET-based polymer or the PBT-based polymer. I have speculated that it is the reason.

  Moreover, as a structure of the aliphatic polyester fiber of this invention, the aliphatic polyester containing a conductive agent (henceforth abbreviated as "conductive agent containing APE") and aromatic polyester are comprised. That is, in the fiber of the present invention, the conductive agent-containing APE and the aromatic polyester have a fiber cross section perpendicular to the fiber axis direction, (1) the aromatic polyester is a sheath or sea, and the conductive agent-containing APE is a core or a plurality of Composite fibers forming islands (here, the core or the plurality of islands may be partially or entirely exposed on the fiber surface or included in the fibers), (2) the conductive agent-containing APE is a sheath or sea, A composite fiber in which an aromatic polyester forms a core or an island (here, the core or the plurality of islands may be partially or entirely exposed on the fiber surface or included in the fiber), (3) the above (1 ), (2) composite type (aromatic polyester and conductive agent-containing APE each form a sheath, sea, core, or a plurality of islands are preferred, but not particularly limited. Here The number of islands to be arranged is preferably at most 100. In addition, when islands are arranged at two or more places, fiber properties (bending rigidity, tensile strength, or tensile strength) It is preferable that they are equally arranged so as to be symmetric with respect to the fiber center point in the fiber cross section perpendicular to the fiber axis direction in terms of uniform elasticity. The shape of the core or island in the cross section of the fiber perpendicular to the fiber axis direction of the component may be a circle or an ellipse, or a wide variety of shapes such as a triangle, a quadrangle, or a larger polygon. Polygons that are more than triangles usually have rounded corners due to the melting behavior of the polymer itself. However, a shape other than a circle, such as an ellipse or a triangle, may behave differently in the bending direction, particularly as described later. For example, when used for a brush, the core or island can be shaped like a triangle, quadrangle, or a polygon larger than the circle, so that the rigidity of the fiber itself can be controlled to be high. The arrangement of the conductive agent-containing APE and the aromatic polyester may be appropriately selected depending on the use, but the fiber itself maintains the high conductivity and has the abrasion resistance as described above. In the application where the surface electrical resistance of the fiber needs to be low, the conductive agent-containing APE is at least on the fiber surface as a core or island. A form that is partially exposed or the form (2) described above is preferable. It is particularly preferable that the conductive agent-containing APE is exposed as a core or an island on at least a part of the fiber surface as a material capable of expressing high conductive performance on the fiber surface. In addition, the aromatic polyester excellent in abrasion resistance on the fiber surface does not contain a conductive agent or does not impair the physical properties of the fiber (for example, strength, residual elongation, initial tensile elastic modulus, abrasion resistance). A small amount of a conductive agent may be contained, and further, for example, the aromatic polyester itself may have a different function or may have a different function by containing a functional component.

  In the aliphatic polyester fiber of the present invention, the proportion of the aliphatic polyester containing the conductive agent in the fiber cross section perpendicular to the fiber axis direction (in other words, in the fiber) can be appropriately set according to the intended use. Although it is good, the aliphatic polyester is generally an environmentally friendly material, and particularly in the case of an aliphatic polyester having lactic acid as a main repeating structural unit, it is an excellent environmentally-adapted material having biodegradability. The fiber obtained in (1) can also be used in an amount of 5% by volume or more in that it has environmental adaptability. And the ratio of the aliphatic polyester containing the conductive agent in the fiber in that the desired fiber properties (for example, strength, residual elongation, initial tensile elastic modulus, etc.) can be achieved while maintaining excellent conductivity. It is more preferably 7% by volume or more, and particularly preferably 10% by volume or more in consideration of the fact that it can be produced more stably. In addition, the higher the proportion of the aliphatic polyester containing the conductive agent is, the more preferable from the viewpoint of environmental adaptability described above. However, the upper limit of the proportion is 95% by volume or less in view of having high temperature heat resistance. Preferably, it is 90% by volume or less, more preferably 80% by volume or less, considering that it can be produced more stably. The ratio of the aliphatic polyester containing the conductive agent in the fiber can be determined from the area ratio of the aliphatic polyester part containing the conductive agent in the single fiber cross section to the single fiber cross-sectional area. Use the value measured by the method in the section.

  As the aliphatic polyester in the fiber of the present invention, a polyester in which the main repeating structural unit is composed of an aliphatic ester can be used. The “main repeating structural unit” is an aliphatic polyester constituting the aliphatic polyester as a polymerization raw material in a fraction of 50 mol% or more, preferably 80 mol% or more, particularly preferably 95 mol% or more, a) a homopolymer of an aliphatic polyester composed of a single type of repeating structural unit, and (b) an aliphatic polyester copolymer polymer composed of a plurality of types of repeating structural units. In the aliphatic polyester copolymer, other components other than the aliphatic polyester, for example, aromatic polyester, polyalkylene oxide, polycarbonate, polyamide, polyurea, polyurethane, polyorganosiloxane and the like are contained in less than 50 mol%, preferably Less than 20 mol%, more preferably less than 5 mol%, may be copolymerized, and particularly preferably an aliphatic polyester that is not copolymerized at all, that is, a homopolymer of the above-mentioned (a) aliphatic polyester. . The copolymerization mode may be any of block copolymerization and / or graft copolymerization and / or random copolymerization. Particularly preferred are (a) homopolymers of aliphatic polyesters. Conventionally used aromatic polyesters, for example, a polyester component in which the main repeating structural unit is composed of ethylene terephthalate (hereinafter may be abbreviated as PET polymer) and the main repeating structural unit is composed of tetramethylene terephthalate. The polyester component (hereinafter sometimes abbreviated as PBT-based polymer) usually contains no more than about 10% by weight or more of a conductive agent, and yarn breakage during melt spinning no longer occurs. Although it was not possible to take up the aliphatic polyester, even in the case where a large amount of a conductive agent is contained, the aliphatic polyester is a normal process that does not contain a conductive agent in a process for forming fibers, for example, melt spinning. Melt spinning can be achieved just like melt spinning aliphatic polyesters The door present inventors have found that it was heading. As a result, the production of highly conductive fibers, which was previously possible with polyamide-based polymers, contains high-concentration conductive agents in the same way, even with polyester-based polymers, to form highly conductive fibers. It became possible to do.

  Specific examples of the aliphatic polyester in the present invention include (A) aliphatic hydroxycarboxylic acid such as glycolic acid, lactic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 6-hydroxycaproic acid and the like. Examples thereof include aliphatic polyesters (polyhydroxycarboxylic acids) such as polyglycolic acid and polylactic acid, which are polymerized from a single monomer, such as acids and aliphatic lactones such as glycolide, lactide, butyrolactone, and caprolactone. In (A), only a single monomer may be employed, a plurality of types may be used, or a diol monomer or dicarboxylic acid monomer described in (B) below may be copolymerized.

  Specific examples of other aliphatic polyesters include (B) aliphatic diols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, neopentylglycol, or diethylene glycol, triethylene glycol, ethylpropyl. Aliphatic polyalkylene ether glycols such as ether glycol, bishydroxyethylpropane, bishydroxypropylbutane, polyethylene glycol, polypropylene glycol, polybutylene ether, etc., and succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decane Aliphatic polyester composed of aliphatic dicarboxylic acid such as dicarboxylic acid, that is, composed of diol (glycol) monomer and dicarboxylic acid monomer And the like. Also in (B), only a single diol monomer and a single dicarboxylic acid monomer may be used, or a plurality of types of diol monomers and / or a plurality of types of dicarboxylic acid monomers may be used. The copolymer components include aliphatic polycarbonate glycols such as dihydroxybutyl carbonate, dihydroxyhexyl carbonate, polybutylene carbonate (glycol), polyhexane carbonate (glycol), polyoctane carbonate (glycol), and copolymers and oligomers thereof. May be used.

  In addition, the aliphatic polyester classified as (a) or (b) in the present invention is melted almost the same as a normal aliphatic polyester not containing a conductive agent even if a high concentration conductive agent is contained. The polyester is used in such a range that does not impair the advantage that spinning can be achieved, and the repeating structural unit constituting the aliphatic polyester is less than 50 mol%, preferably less than 20 mol%, more preferably less than 5 mol%. You may copolymerize other components other than the aliphatic which can be comprised. Specifically, an aromatic or alicyclic dicarboxylic acid compound can be copolymerized, such as terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, anthracene dicarboxylic acid, phenanthrene dicarboxylic acid, diphenyl ether. Dicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenylethanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium isophthalic acid, azelaic acid, dodecanedioic acid, hexahydroterephthalic acid, etc. Aromatic, alicyclic dicarboxylic acids and their derivatives such as alkyl, alkoxy, allyl, aryl, amino, imino, halides, adducts, structural isomers and optical isomers. , It may be used one kind of these dicarboxylic acid compounds alone or object may be used in combination of two or more in a range that does not impair the present invention.

  In addition, the aliphatic polyester classified as (a) or (b) in the present invention can copolymerize an aromatic or alicyclic diol compound, and examples of the diol compound include 1,4, Aromatics such as cyclohexanedimethanol, hydroquinone, resorcin, dihydroxybiphenyl, naphthalenediol, anthracenediol, phenanthrenediol, 2,2-bis (4-hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl ether, bisphenol S, and fats Examples thereof include cyclic diol compounds and their derivatives such as alkyl, alkoxy, allyl, aryl, amino, imino, halide, adducts, structural isomers, and optical isomers. One of these diol compounds is used alone. Used in Good to, or object may be used in combination of two or more in a range that does not impair the present invention.

  Examples of the copolymer component include aromatic or alicyclic hydroxycarboxylic acids such as hydroxybenzoic acid, hydroxynaphthoic acid, hydroxyanthracenecarboxylic acid, hydroxyphenanthrenecarboxylic acid, (hydroxyphenyl) vinyl. Aromatic or alicyclic hydroxycarboxylic acids such as carboxylic acids and their derivatives such as alkyl, alkoxy, allyl, aryl, amino, imino, halides, adducts, structural isomers and optical isomers Of these aromatic or alicyclic hydroxycarboxylic acids, one kind may be used alone, or two or more kinds may be used in combination as long as the object of the present invention is not impaired.

  As described above, the aliphatic polyester in the present invention can be used in a wide variety, but the gist of the present invention, that is, a normal aliphatic that does not contain a conductive agent even if it contains a high concentration of a conductive agent. The aliphatic polyester in the present invention includes lactic acid, glycolic acid, and 3-hydroxypropionate from the viewpoint of satisfying the point that melt spinning can be achieved almost the same as polyester and having a high melting point and low refractive index as described later. Aliphatic polyesters mainly composed of hydroxycarboxylic acids such as 3-hydroxybutyrate and 3-hydroxybutyrate valerate are preferred, and aliphatic polyesters comprising lactic acid as the main repeating structural units (hereinafter referred to as “polylactic acid”). Are generally preferred). Polylactic acid includes poly (L-lactic acid) containing L-lactic acid as a main component and poly (D-lactic acid) containing D-lactic acid as a main component. Since poly (L-lactic acid) and poly (D-lactic acid) usually contain a small amount of each racemate, for example, even poly (L-lactic acid) contains a small amount of D-lactic acid. . In this case, since D-lactic acid becomes a copolymer in poly (L-lactic acid), if excessive D-lactic acid is present in poly (L-lactic acid), the melting point as polylactic acid is lowered. Therefore, in the case of poly (L-lactic acid) having L-lactic acid as a main component, it means that 60 mol% or more of the repeating structural units are composed of L-lactic acid, and D does not exceed 40 wt%. -Polyester containing lactic acid may be sufficient. At this time, since it is preferable that the fraction of L-lactic acid is large, 80 mol% or more of the repeating structural units are preferably composed of L-lactic acid, and particularly preferably 90 mol%. The polylactic acid may be one containing both poly (L-lactic acid) and poly (D-lactic acid) (sometimes referred to as “stereocomplex”). The fraction of lactic acid) and poly (D-lactic acid) is not particularly limited, but the closer the ratio of poly (L-lactic acid) and poly (D-lactic acid) is, the higher the melting point of polylactic acid itself is. It is most preferred that the ratio of -lactic acid) and poly (D-lactic acid) is equal, that is, the weight fraction of poly (L-lactic acid): weight fraction of poly (D-lactic acid) = 50: 50.

  The aliphatic polyester in the present invention preferably has a melting point of 130 ° C. or higher. As will be described later, the fibers of the present invention are used in various applications such as clothing, rugs, and brushes. In these applications, when the melting point of the aliphatic polyester is lower than 130 ° C, Melting defects may occur during dyeing processing, heat setting, or friction heating, and the quality of the product may be lowered. The melting point of the aliphatic polyester in the present invention is preferably 150 ° C. or higher, and particularly preferably the melting point is 170 ° C. or higher. Here, the melting point (Tm) is the value of Example H. described later. Refers to the endothermic peak temperature observed by the method in the section.

  Further, the aliphatic polyester in the present invention preferably has a refractive index of 1.50 or less, and more preferably 1.45 or less. When the refractive index is 1.50 or less, the color developability of the fabric during dyeing is excellent, and as a result, an excellent color tone is obtained. The lower the refractive index, the better. The lower limit is 1.00. The refractive index referred to here is based on the method described in JIS-K7105 using an Abbe refractometer equipped with a prism, which is installed in a room where natural light can be taken and adjusted to 23 ° C. by means of circulating constant temperature water. Means the value to be measured.

  The number average molecular weight of the aliphatic polyester in the present invention is preferably as high as possible, preferably 50,000 or more, and more preferably 100,000 or more. Moreover, although it is so preferable that this number average molecular weight is high, considering that it is stably produced at the time of production, it is 400,000 at most, and it is preferable that it is 300,000 or less. When the average molecular weight is lower than 50,000, the strength properties of the fiber may be lowered. Here, the number average molecular weight is the value of Example L. described later. The value obtained by the measurement according to the method of item is used.

  In addition, the manufacturing method of the polylactic acid made especially preferable in the aliphatic polyester in this invention is not specifically limited. Specifically, the method disclosed in JP-A-6-65360 is exemplified. That is, it is a direct dehydration condensation method in which lactic acid is dehydrated and condensed as it is in the presence of an organic solvent and a catalyst. Further, there is a method of copolymerizing and transesterifying at least two kinds of homopolymers disclosed in JP-A-7-173266 in the presence of a polymerization catalyst. Furthermore, the method currently disclosed by US Patent 2,703,316 is mentioned. That is, an indirect polymerization method in which lactic acid is once dehydrated to form a cyclic dimer and then subjected to ring-opening polymerization.

  The aliphatic polyester fiber of the present invention comprises an aromatic polyester. As the aromatic polyester, a polyester having at least one aromatic ring structure in a main repeating structural unit which is an ester formed by an esterification reaction of a carboxylic acid and an alcohol can be used. Specifically, examples of the aromatic polyester-based polymer used in the present invention include a polymer formed from an ester bond of an aromatic dicarboxylic acid compound and a diol compound. Terephthalate (PET), polytrimethylene terephthalate (sometimes called polypropylene terephthalate; PTT), polytetramethylene terephthalate (PBT), polyethylene naphthalate (PEN), polypropylene naphthalate (PPN) and polycyclohexanedimethanol terephthalate Aromatic polyesters such as (PCMT) are preferred. And although it does not restrict | limit in particular, the other component may be copolymerized in the range which does not impair the objective of this invention, For example, a dicarboxylic acid compound can be copolymerized. Examples of the dicarboxylic acid compound include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, anthracene dicarboxylic acid, phenanthrene dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenylethanedicarboxylic acid, adipic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium isophthalic acid, azelaic acid, dodecanedioic acid, hexahydroterephthalic acid, aromatic, aliphatic, alicyclic dicarboxylic acids and their Derivatives, adducts, structural isomers and optical isomers such as alkyl, alkoxy, allyl, aryl, amino, imino, halide, etc. It may be used one kind alone of, or object may be used in combination of two or more in a range that does not impair the present invention.

  Moreover, as a copolymerization component of the aromatic polyester, a diol compound can be copolymerized. Examples of the diol compound include ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, and 1,4-cyclohexanediene. Methanol, neopentyl glycol, hydroquinone, resorcin, dihydroxybiphenyl, naphthalenediol, anthracenediol, phenanthrenediol, 2,2-bis (4-hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl ether, bisphenol S, polyethylene glycol, polypropylene Aromatic, aliphatic and alicyclic diol compounds such as glycol and polybutylene ether and their alkyl, alkoxy, allyl, Derivatives, adducts, structural isomers and optical isomers, and one of these diol compounds may be used alone, or the object of the present invention Two or more kinds may be used in combination as long as they do not impair.

  Examples of the copolymerization component of the aromatic polyester include a compound having a hydroxyl group and a carboxylic acid in one compound, that is, a hydroxycarboxylic acid. Examples of the hydroxycarboxylic acid include lactic acid, 3- Aromatic, aliphatic such as hydroxypropionate, 3-hydroxybutyrate, 3-hydroxybutyrate valerate, hydroxybenzoic acid, hydroxynaphthoic acid, hydroxyanthracenecarboxylic acid, hydroxyphenanthrenecarboxylic acid, (hydroxyphenyl) vinylcarboxylic acid , Alicyclic diol compounds and derivatives thereof such as alkyl, alkoxy, allyl, aryl, amino, imino, halides, adducts, structural isomers and optical isomers. Among these hydroxycarboxylic acids seed It may be used alone or may be used in combination of two or more in a range that does not impair the object of the present invention.

  In addition, the aromatic polyester may be an aromatic polyester having an aromatic ring structure mainly composed of an aromatic hydroxycarboxylic acid compound having both a carboxylic acid and a hydroxyl group, and examples thereof include polyhydroxybenzoic acid. In addition, these poly (aromatic hydroxycarboxylic acids) can be aromatic, aliphatic, alicyclic dicarboxylic acids, or aromatic, aliphatic, alicyclic as long as the object of the present invention is not impaired. A group diol component may be used, or a plurality of hydroxycarboxylic acids may be copolymerized.

  As these aromatic polyesters, ethylene terephthalate is the main repeating structural unit in that the interfacial adhesion to the conductive agent-containing APE is good and peeling is difficult to occur, and the polymer melting temperature in melt spinning is close to that of aliphatic polyesters. PET-based polymer, trimethylene terephthalate-based polymer having trimethylene terephthalate as the main repeating structural unit (hereinafter sometimes referred to as “PTT-based polymer”), PBT-based having tetramethylene terephthalate as the main repeating structural unit Polymer, ethylene naphthalate polymer having ethylene naphthalate as the main repeating structural unit (these may be collectively referred to as “PEN polymer” hereinafter), and cyclohexanedimethanol terephthalate as the main repeating structure Cyclohexanedimethanol terephthalate polymer (hereinafter sometimes referred to as “PCMT polymer”), propylene naphthalate polymer having propylene naphthalate as the main repeating structural unit (hereinafter referred to as “PPN polymer”) May be collectively referred to as a particularly preferable one. Individually, in applications where high rigidity is desired, such as when used as a member of a cleaning device incorporated in an electrophotographic apparatus as described below, generally rigid fibers are preferred, The aromatic polyester is preferably higher in rigidity than the conductive agent-containing APE, and is preferably a PET-based polymer or a PEN-based polymer. In particular, the third component (or more) A PET polymer obtained by copolymerizing the above plural components) is preferred. Alternatively, in applications where low rigidity is desired, for example when used as a member of a charging device incorporated in an electrophotographic apparatus as will be described later, fibers with low rigidity are generally preferred. The group polyester is preferably one having lower rigidity than the conductive agent-containing APE, and particularly preferably a PTT polymer or a PBT polymer.

  The structure of the fiber of the present invention is not particularly limited as long as it comprises an aliphatic polyester containing a conductive agent (conductive agent-containing APE) and an aromatic polyester. That is, in the fiber of the present invention, one or more kinds of polymers other than the conductive agent-containing APE and the aromatic polyester may be contained. In the fiber of the present invention, components other than aliphatic polyesters and aromatic polyesters containing a conductive agent (aromatic polyesters may be used alone or in combination of two or more) (other polymers) When (component) is arrange | positioned (included), it is preferable that this other polymer component consists of a polymer which has a fiber formation ability as a main component. Examples of the other polymer components include aliphatic polyester polymers, polyamide polymers, polyimide polymers, polyolefin polymers and other vinyl polymers such as polyacrylonitrile polymers synthesized by addition polymerization of vinyl groups, fluorine Polymer, cellulose polymer, silicone polymer, aromatic or aliphatic ketone polymer, elastomers such as natural rubber and synthetic rubber, and other various engineering plastics.

  More specifically, as the other polymer component, for example, a polyolefin-based polymer synthesized by a mechanism in which a monomer having a vinyl group is formed by an addition polymerization reaction such as radical polymerization, anion polymerization, or cation polymerization As vinyl polymers, polyethylene, polypropylene, polybutylene, polymethylpentene, polystyrene, polyacrylic acid, polymethacrylic acid, polymethyl methacrylate, polyacrylonitrile, polytetrafluoroethylene, polyvinylidene fluoride, polyvinylidene chloride, polycyanation Vinylidene and the like can be mentioned, but these may be a polymer by homopolymerization, such as polyethylene alone or polypropylene alone, or by conducting a polymerization reaction in the presence of a plurality of monomers. For example, when polymerization is carried out in the presence of styrene and methyl methacrylate, a copolymerized polymer called poly (styrene-methacrylate) is produced, but within the range not impairing the object of the present invention. A polymer which is such a copolymer may be used.

  Examples of the other polymer component include polyamide polymers formed by the reaction of carboxylic acid or carboxylic acid chloride and amine. Specifically, nylon 6, nylon 7, nylon 9, nylon 11, Nylon 12, Nylon 6,6, Nylon 4,6, Nylon 6,9, Nylon 6,12, Nylon 5,7, Nylon 5,6 and the like, and others within the range not impairing the gist of the present invention Aromatic, aliphatic, alicyclic dicarboxylic acid and aromatic, aliphatic, alicyclic diamine component, or one compound such as aromatic, aliphatic, alicyclic has both carboxylic acid and amino group The aminocarboxylic acid compound may be used alone, or may be a polyamide polymer in which the third and fourth copolymerization components are copolymerized. .

  Examples of the other polymer component include an aliphatic polyester polymer formed by an esterification reaction of a carboxylic acid and an alcohol. Although the aliphatic polyester specifically mentioned above is mentioned above, it means that the aliphatic polyester which does not contain a conductive agent may be contained in the fiber.

  Other polymer components include polycarbonate polymers formed by transesterification of alcohol and carbonic acid derivatives, polyimide polymers formed by cyclization polycondensation of carboxylic acid anhydrides and diamines, dicarboxylic acid esters and diamines. Polybenzimidazole polymers formed by this reaction, and other polymers such as polysulfone polymers, polyether polymers, polyphenylene sulfide polymers, polyether ether ketone polymers, polyether ketone ketone polymers, aliphatic polyketones In addition, cellulose-based polymers and polymers derived from natural polymers such as chitin, chitosan and derivatives thereof are also included.

  As the other polymer component, one kind of polymer selected from the above may be used alone, or a plurality of kinds of polymers may be used in combination as long as the object of the present invention is not impaired.

As the conductive agent contained in the aliphatic polyester in the present invention, a wide variety of conductive agents can be adopted, and conductive carbon black, metal oxides, and the like can be appropriately employed depending on the required use. Specifically, conductive carbon black can be mentioned as a preferable example. For example, conductive furnace black, conductive ketjen black, conductive acetylene black, carbon nanotube (hereinafter sometimes abbreviated as CNT), gas, Phase-grown carbon fibers (hereinafter sometimes abbreviated as VGCF) and the like are preferably used. Among these, the conductive furnace black has a good interaction with the aliphatic polyester in the preferred melt spinning as will be described later, so it is excellent while being contained in the aliphatic polyester at a high concentration. It is used as a more preferred component in that the spinnability can be maintained. Further, CNTs having a diameter of 50 nm or less have high conductivity, and since they have high conductivity as a conductive agent-containing APE when added in a small amount as described later, they are used as very preferable conductive agents. The conductivity of these conductive carbon blacks is preferably 5000 [Ω · cm] or less as a specific resistance value, and a particularly preferred range is from 1.0 × 10 ⁻⁶ [Ω · cm] to 500 [500]. Ω · cm]. Here, the specific resistance value is the value of Example E. below. Measured by the method in the section.

In addition, when the conductive carbon black described above is used as the conductive agent in the present invention, the resulting fiber may become black and may not be used depending on the application. Therefore, in that case, a conductive agent other than black may be used, and examples thereof include metals, metal oxides and metal compounds, or particles coated with metals and metal oxides. Examples of the metal include gold, silver, copper, nickel, iron, aluminum, or an alloy containing at least one selected from these metals. In particular, for iron, pure iron particles having a high purity and a small particle diameter can be easily obtained, and the specific resistance value is as small as 10 ⁻⁵ [Ω · cm] or less, and can be suitably used. Examples of the metal compound include copper sulfide, copper iodide, zinc sulfide, cadmium sulfide and the like. In addition, preferred examples of the metal oxide include tin oxide, zinc oxide, indium oxide, zirconium oxide, tungsten oxide, antimony oxide, and aluminum oxide. More preferably, particles formed by coating a metal oxide are used. Examples of the particles include titanium oxide, magnesium oxide, silicon oxide, and aluminum oxide. Also, as the metal oxide to be coated, Tin oxide, aluminum oxide, antimony oxide, zinc oxide, indium oxide and the like can be mentioned. These metal oxides may be used alone or in combination with a plurality of different elements. good. Among the particles formed by coating these metal oxides, titanium oxide particles formed by coating a tin oxide containing (doped) antimony oxide, or containing (doped) antimony oxide. Examples thereof include aluminum oxide particles formed by coating indium oxide and silicon oxide particles formed by coating tin oxide containing (doped) antimony oxide. The average particle size of the particles is small, and even if added to the fiber, there is little adverse effect on physical properties such as strength and elongation, and the specific resistance value of the particles themselves is high and not black (the brightness L * is high). In view of the above, particles formed by coating metal oxides selected from at least two elements derived from different elements among tin oxide, zinc oxide, indium oxide, antimony oxide, and aluminum oxide are preferable. Titanium oxide particles formed by coating tin oxide containing (doped) oxide are particularly preferable.

  When the conductive agent in the present invention is contained in an aliphatic polyester, it is preferable not to impair the physical properties of the fiber, and since it is preferable that the conductive agent does not easily aggregate, the particle size of the conductive agent is an average particle size. The thing of the range of 0.1-500 nm is preferable. In the case of the conductive furnace black that is preferable as described above, the one in the range of 5 to 100 nm is more preferable, and the one in the range of 5 to 50 nm is particularly preferable. Moreover, if it is the carbon nanotube (CNT) made preferable in the above-mentioned, the diameter of the range of 0.1-100 nm is preferable on the average, and the range of 0.5-50 nm is more preferable. In addition, the ratio (aspect ratio) L / D of the diameter D and the length L of the CNTs has an appropriate size so that the CNTs hardly aggregate in the aliphatic polyester of the present invention, or fibers are formed. In some cases, L / D is preferably 10 to 10,000, and preferably 15 to 5,000 because it has a preferable characteristic that the conductivity in the longitudinal direction of the fiber is substantially oriented and the electrical conductivity in the longitudinal direction of the fiber becomes uniform. More preferably, it is 20-3000. Here, the average particle diameter of the conductive agent and the L / D of CNT are shown in Examples J. It is measured by the method.

  In addition, the content of the conductive agent in the aliphatic polyester is such that the conductive furnace black and the conductive cable are used because the fiber has high conductivity and the physical properties such as strength and elongation of the fiber are stable. In the case of chain black or conductive acetylene black, it is preferably 10% by weight to 40% by weight, more preferably 15% by weight to 35% by weight, and more preferably 16% by weight to 30% by weight. It is particularly preferred. When the conductive agent is CNT or VGCF, it is preferably 0.1 wt% or more and 20 wt% or less, more preferably 0.5 wt% or more and 15 wt% or less, and 1.0 wt% or more and 10 wt% or less. It is particularly preferable that the amount is not more than% by weight. When the conductive agent is a metal, a metal oxide or a metal compound, or particles coated with a metal or a metal oxide, it is preferably 10% by weight or more and 90% by weight or less, and 20% by weight or more and 85% by weight or less. More preferably, it is 40 to 80% by weight. The content of the conductive agent in the aliphatic polyester is N. It is measured by the method of item.

  In the present invention, any method can be employed as a method for causing the aliphatic polyester to contain a conductive agent. Specifically, (A) the aliphatic polyester is melted in an inert gas atmosphere, and the conductive agent is added. A method of kneading under normal pressure or reduced pressure by a kneader such as an extruder or a stationary kneader. (B) In a normal aliphatic polyester polymerization reaction, a conductive agent is contained at any stage before the polymerization reaction stops. Kneading and kneading, (C) Powder or granular aliphatic polyester and powder or granular conductive agent are mixed in a predetermined amount and stirred in an arbitrary stage before melting the aliphatic polyester. These can be melted and kneaded under normal pressure or reduced pressure using a kneader such as an extruder or a stationary kneader. And since the conductive agent and an aliphatic polyester component is kneaded more finely, it is preferably employed a method (A) or (C). In particular, with regard to the extruder, a uniaxial or biaxial or more multiaxial extruder can be suitably used. However, when the aliphatic polyester component and the conductive agent are kneaded, the conductive agent is finely kneaded. It is preferable to employ a multi-axis extruder. The ratio l / w between the length (l) of the extruder shaft and the thickness (w) of the shaft is not particularly limited, but l / w may be 10 or more in terms of improving kneadability. Preferably, it is 20 or more, more preferably 30 or more. In view of the residence time of the polymer in the apparatus, the l / w is preferably 200 or less. At this time, as described above, the conductive agent may be dry blended before being supplied to the extruder, or mixed in the extruder with the melted aliphatic polyester using the side feeder provided in the extruder. You may do it. In particular, with regard to the stationary kneading element, for example, the operation of dividing the flow path of the melted aliphatic polyester into two or more and reuniting (one operation from this division to unity is 1 The number of stages of the stationary kneading element is preferably 5 or more from the viewpoint that the kneading property is more excellent. It is still more preferable that it is above. Moreover, it is preferable that it is 50 steps or less depending on the required length of the flow path.

  Since the fiber of the present invention may be exposed to high temperature depending on the environment at the time of use, it has excellent heat resistance, so that it has a shrinkage rate when held in the atmosphere at 160 ° C. for 15 minutes (“dry heat shrinkage rate”). Is preferably 20% or less, more preferably 10% or less, and particularly preferably 7% or less. The lower the value, the more preferably up to 0%. Here, the dry heat shrinkage rate is the same as that of Example G. below. Use the value measured by the method in the section.

  The fiber of the present invention preferably has a residual elongation of 5 to 100%, and 5 to 60%, in that the deformation during use in various applications such as clothing and brush rollers described later is small. It is particularly preferred. Here, the residual elongation is measured according to Example B. below. Use the value measured by the method in the section.

  The fiber of the present invention has an initial tensile elastic modulus of 15 cN / dtex to 80 cN / dtex in that it can be appropriately applied to various uses although the physical properties of the fiber may be appropriately controlled according to various uses. In addition, it can be stably produced in this range. Depending on the specific application, there is an initial tensile elastic modulus that is more preferable. For example, when it is used as a member of a cleaning device incorporated in an electrophotographic apparatus as described later, it is generally rigid (initial It is more preferable that the initial tensile elastic modulus is 45 cN / dtex to 80 cN / dtex in that the fiber having a high correlation with the tensile elastic modulus is preferred and the scraping property is good. Particularly preferred is 80 cN / dtex. Here, in order to make the initial tensile elastic modulus 45 cN / dtex or more, which is preferable for use as a member of a cleaning device incorporated in an electrophotographic apparatus, aliphatic polyester containing a conductive agent (conductive APE polymer containing ethylene terephthalate as a main repeating structural unit as an aromatic polyester in that a higher initial tensile elastic modulus can be achieved when forming a fiber comprising a combination of an agent-containing APE) and an aromatic polyester. It is preferable that the fiber is formed using a PEN polymer having ethylene naphthalate as a main repeating structural unit. Alternatively, when used as a member of a charging device incorporated in an electrophotographic apparatus as will be described later, fibers having low rigidity (which has a high correlation with the initial tensile elastic modulus) are generally preferred. The initial tensile elastic modulus is more preferably from 15 cN / dtex to 45 cN / dtex, even more preferably from 15 cN / dtex to 40 cN / dtex, in that abnormal charging during charging is reduced as much as possible. It is particularly preferred to be -35 cN / dtex. And it is so preferable that it is low. In order to reduce the initial tensile elastic modulus to 45 cN / dtex or less, which is preferable for use as a member of a charging device incorporated in an electrophotographic apparatus, an aliphatic polyester containing a conductive agent (conductive Agent-containing APE) and an aromatic polyester to form a fiber, a PTT polymer having trimethylene terephthalate as a main repeating structural unit in view of achieving a lower initial tensile elastic modulus, It is preferable to form a fiber by using a PBT polymer having methylene terephthalate as a main repeating structural unit as an aromatic polyester. Here, the initial tensile elastic modulus is the value of Example B. below. Use the value measured by the method in the section.

  The fiber of the present invention preferably has a breaking strength of 1.0 cN / dtex or more in order to stably satisfy the shape or characteristics for various uses such as clothing and brush rollers described later. It is more preferably dtex or more, and even more preferably 2.0 cN / dtex or more. Normally, aromatic polyesters that have been used for general purposes such as the aforementioned PET-based polymers and PBT-based polymers that contain a conductive agent at a high concentration to produce highly conductive fibers are used when fibers are formed. Has a very low breaking strength (approximately less than 1.0 cN / dtex), and it was difficult to increase the breaking strength by any means. However, the present inventors have found that when an aliphatic polyester is used as the polyester, even if the conductive conductive agent is contained at a high concentration, there is almost no decrease in breaking strength. The higher the breaking strength, the better. However, in consideration of productivity, a material having a strength of 7.0 cN / dtex or less is preferably manufactured. Here, the breaking strength was measured according to Example B. below. Use the value measured by the method in the section.

The fibers of the present invention have an average resistivity P of 1.0 × 10 ¹² [Ω / cm] or less. In the range of the average resistivity, desired conductivity is imparted in various uses as described later, for example, clothing, actuators, brush rollers, heating elements, or various products incorporating these. The smaller the average resistivity P is, the higher the conductivity is, that is, the easier it is for electricity to flow. Therefore, although the average resistivity P needs to have a low average resistivity depending on the application, it is the maximum for the aliphatic polyester in the aliphatic polyester fiber of the present invention. In view of the amount of the conductive agent that can be contained, the lower limit of the average resistivity P is preferably 1.0 × 10 ⁻² [Ω / cm]. A range of 1.0 × 10 ⁻¹ [Ω / cm] to 1.0 × 10 ¹² [Ω / cm] is preferable because it can be stably controlled. In particular, when the aliphatic polyester fiber of the present invention is used in a brush roller incorporated in an electrophotographic apparatus as described later, an average resistivity in the range of 1.0 × 10 ^{3 to} 1.0 × 10 ¹² [Ω / cm]. It is preferable that fibers having an average resistivity in a range as described later are employed depending on the characteristics of the member and apparatus used for the brush roller. Further, even when used in a heating element as will be described later, the average resistivity may be appropriately set according to the target calorific value, but 1.0 × 10 ^{−2 to} 1.0 × 10 ⁷ [Ω / The average resistivity in the range of cm] is preferable. Here, the average resistivity P is the value of Example C. below. Use the value measured by the method in the section.

In addition, since the aliphatic polyester fiber of the present invention preferably has stable, spotless conductivity for various uses as described later, the ratio between the average resistivity P and the standard deviation Q of resistivity. R (R = Q / P) is preferably 0.5 or less. A ratio R of 0.5 or less means that the conductive spots are small, and the smaller the value, the better the conductivity is without spots. And it is more preferable that it is 0.4 or less, and it is especially preferable that it is 0.3 or less. When the average resistivity of the fiber of the present invention is less than 1.0 × 10 ⁹ [Ω / cm], the ratio R is particularly preferably 0.2 or less. For example, when used as a member of a charging device incorporated in an electrophotographic apparatus as described later, the ratio R is particularly preferably 0.1 or less. Although the ratio R is preferably as small as possible, R is 0.001 or more as a normally achievable value. Here, the ratio R is the value of Example C. below. Use the value measured and calculated by the method in the section.

  Furthermore, the aliphatic polyester fiber of the present invention has a change in temperature and humidity, specifically, even in a wet climate such as in the rainy season or even in a dry climate such as winter. It is preferable that the conductive performance does not change at all. Therefore, the average resistivity X [Ω / cm] at medium temperature and medium humidity (23 ° C. and 55% humidity) and the average resistivity Y [Ω / cm] at low temperature and low humidity (10 ° C. and humidity 15%) The ratio Z (= Y / X) is preferably in the range of 1-5, more preferably in the range of 1-4, and particularly preferably in the range of 1-2. As Z takes a value close to 1, the difference between the intermediate temperature medium humidity and the low temperature and low humidity is small, that is, the temperature is less dependent on temperature and humidity and is an excellent fiber. Here, the ratio of the average resistivity is shown in Example D. below. Use the value measured by the method in the section.

  Since the aliphatic polyester fiber of the present invention comprises an aromatic polyester, it is excellent in high temperature heat resistance while being excellent in conductivity. As in the prior art (for example, Patent Document 3), when the conductive fiber made of only aliphatic polyester is at most 140 ° C., the strength or form stability of the fiber is greatly deteriorated to form a fiber structure such as a woven fabric. In addition, shrinkage and melting were observed, and there were many cases where it was not useful. However, since the aliphatic polyester fiber of the present invention comprises an aromatic polyester, it has excellent shape stability at a high temperature of 160 ° C. or higher. The high temperature heat resistance is preferable when the change in the shape (appearance change) of the fiber structure is observed at 160 ° C or higher, more preferably 180 ° C or higher, even more preferably 200 ° C or higher, It is particularly preferable that no change in appearance is observed even at 200 ° C. About this high temperature heat resistance, the following Example P.I. Use the value measured by the method in the section.

The fiber of the present invention preferably has a specific resistance value of 10 ⁶ to 10 ⁹ [Ω · cm] in that the fiber can be processed more efficiently when it is made into a short fiber and electroflocking. More preferably, it is 10 ⁷ to 10 ⁸ [Ω · cm]. And in order to make these short fibers which have the value of the specific resistance value considered preferable, it is preferable to process with a conductive preparation agent etc. Examples of the conductive preparation agent include an aqueous solvent or an organic solvent mixed with silica-based particles, and the particle size of the silica-based particles at that time is usually 1 nm to 200 μm. A particle size of 3 nm to 100 μm is preferred. Here, the specific resistance value is the value of Example E. below. Use the value measured by the method in the section.

  The fiber of the present invention does not detract from the gist of the present invention, i.e., it is free from spots, and has a matte agent, a flame retardant, a lubricant, a reducing agent within a range that does not impair the property of exhibiting excellent melt spinning properties while maintaining high conductivity. A small amount of additives such as a sticking agent, an antioxidant, an ultraviolet absorber, an infrared absorber, a crystal nucleating agent, a fluorescent brightener, and an end group blocking agent may be retained. In particular, for polylactic acid, which is particularly preferable among the aliphatic polyesters used in the present invention, a lactam-based thinning agent or a carbodiimide-based end group blocking agent, which is a cyclic amide compound or a derivative thereof, can be preferably used. . In addition, as described above, when the fiber of the present invention is a composite fiber, these additives are aliphatic polyesters containing a conductive agent (conductive agent-containing APE) and / or aliphatic polyesters containing a conductive agent. It may be held in any of the components.

  Hereinafter, the preferable manufacturing method of the aliphatic polyester fiber of this invention is illustrated.

  The aliphatic polyester fiber of the present invention can be produced by employing various synthetic fiber spinning methods such as melt spinning, dry spinning, wet spinning, or solution spinning such as dry and wet spinning, but is disposed in the fiber. It is easy and possible to contain the conductive agent in the aliphatic polyester at a high concentration, and since the fiber shape can be precisely controlled, it is preferably produced by melt spinning. And fiber is obtained by carrying out the composite spinning of aliphatic polyester (conductive agent containing APE) containing a conductive agent, and aromatic polyester (and other polymer components) together. The melt-discharged fiber (undrawn yarn) is cooled to a glass transition temperature (Tg) or lower, and after the treatment agent is not adhered or after the treatment agent is adhered, the take-up speed is preferably from 100 to 10,000 m / min. Is a take-up speed of 7000 m / min or less, more preferably 5000 m / min or less, particularly preferably 3000 m / min or less, and the lower limit may be 10 m / min or more. Take over at a take-up speed of at least / min. Here, the number of bundles of fibers ejected from the cap hole (the number of fibers in the yarn) may be appropriately selected according to the intended use or application, and 3000 even in the state of one monofilament. Although multifilaments composed of the following plural yarns may be used, 4 to 500 are preferable, and 10 to 150 are particularly preferable in that a fiber having stable physical properties can be obtained and suitably used for various applications. Further, the treatment agent to be adhered can be used as appropriate depending on the use of the fiber, and although a water-containing or non-water-containing treatment agent can be adopted here, among the uses using the fiber of the present invention, When used as a member of an electrophotographic apparatus, it may be used in contact with a photoreceptor, but it does not contain a compound that can degrade the photoreceptor in order to prevent the photoreceptor from being degraded. preferable.

  After winding, without winding or once winding, the polymer constituting the fiber is heated to a glass transition temperature (Tg) + 100 ° C. or lower, more preferably glass transition temperature Tg−20 ° C. to Tg + 80 ° C. To a temperature at which the residual elongation of the drawn yarn becomes 5 to 60%, and preferably at a magnification at which the residual elongation of the drawn yarn becomes 10 to 50%. Here, after stretching once (that is, after finishing the first stage stretching), the second stage stretching may be performed at a magnification of 1 to 2 times.

  After stretching, the fiber is preferably heat-treated at a temperature not lower than the final stretching temperature and not higher than the melting point (Tm). By performing a heat treatment at a high temperature after stretching, it is possible to obtain a fiber having excellent heat resistance and small conductive spots as described above. Here, the Tg and Tm are the same as those in Example H. below. Use the value measured by the method in the section.

  The stretching method or the heat treatment method after stretching is not particularly limited, and is a contact type heater using a contact heater such as a heated pin-shaped object, a roller object, or a plate object, or a heated liquid, or Although it is possible to employ non-contact heating media using heated gas, heated steam, electromagnetic waves, etc., contact type heaters such as heated pin-shaped objects, roller-shaped objects, plate-shaped objects, and heated liquids A contact type bath using a metal is preferable because the apparatus is simple and heating efficiency is high, and a heated roller is particularly preferable. Although the heat-treated fiber is cooled while traveling in the air, it is preferably cooled by a cooling medium in the range of −50 ° C. to 50 ° C. downstream of the heat treatment means. Here, as the cooling medium, a contact-type medium such as a pin-like object, a roller-like object, or a plate-like object, a contact-type bath using liquid, or a non-contact-type medium using gas, steam, or the like is adopted. However, a contact medium such as a pin-shaped object, a roller-shaped object, or a plate-shaped object, or a contact bath using a liquid is preferable because the apparatus is simple and has high cooling efficiency, and a roller-shaped object is particularly preferable. Adopted. And between the heat treatment means and the cooling medium, depending on the intended use, the average resistivity to be set, or the ratio R (R = Q / P) of the average resistivity P and the standard deviation Q of the resistivity, the fiber May be stretched (stretched) or contracted (relaxed). Here, as a ratio of stretching or relaxing, the ratio (SH / SC) of the yarn speed (SH) on the heat treatment means and the yarn speed (SC) on the cooling medium is 0.90 ≦ SH / SC ≦ 1. 1 is preferable, and 0.95 ≦ SH / SC ≦ 1.05 is more preferable. Of course, when there is no need to stretch or relax, SH / SC = 1, that is, SH = SC may be used. Finally, after passing through the cooling medium, it is wound up to obtain fibers.

  The aliphatic polyester fiber of the present invention may be subjected to false twisting after the above-mentioned stretching or instead of stretching when used for woven fabrics or knitted fabrics and various clothing applications. In the false twisting process, the fiber is heated without heating the drawn yarn or undrawn yarn or with a heated pin-like product, roller-like product, plate-like product, non-contact type heater, etc. It is false twisted with a belt-like material. The drawn false twisted fiber is preferably wound as it is or after being heat set, although not particularly limited. Moreover, the aliphatic polyester fiber of the present invention may be subjected to twisting processing instead of the above-described false twisting processing.

  The aliphatic polyester fiber of the present invention can be made into a woven fabric that is used at least in part or in whole, depending on the intended use or shape. Here, for example, single woven fabrics such as broad, voile, lone, gingham, tropical, taffeta, shantung, desin and other plain weaves, denim, surge, gabardine and other twill weaves, satin and doskin and other satin weaves, baskets, panama, mats, Hopsacks, Oxfords and other Nanako weaves, Grosgrain, Ottoman, Hair cords and other woven fabrics, French twills, herringbones, broken twills, etc. Examples include oblique text, decorative text, irregular vermilion, stacked vermilion, spread vermilion, vermilion vermillion, day / night vermilion, honeycomb weaving, hack weaving, pear weaving, Niagara, etc. Double woven fabrics such as pique and puffer weaves, double weft fabrics such as Bedford cord, double weft fabrics such as air-woven fabrics and bag weaves. In addition, examples of pile fabrics include weft pile weaves such as benji and corten, warp pile weaves such as towels, velvet, velvet, etc. Examples of the woven fabric include a jacquard woven fabric, and a pile woven fabric is preferable when a woven fabric is used for a brush roller described later. The fibers of the present invention used for producing the woven fabric are not particularly limited with respect to the form of fibers such as raw yarns, twisted yarns, false twisted yarns, and long fibers (filaments) or short fibers (staples). Absent.

  In addition, the aliphatic polyester fiber of the present invention can be made into a knitted fabric that is used at least in part or in whole, in accordance with the intended use or shape. Here, flat knitting such as tengu and single, rib knitting such as rubber knitting and milling, pearl knitting such as links, kanoko, pear fabric, accordion knitting, small pattern, lace knitting, fleece knitting, single knitting knitting , Weft knitting such as Ripple, Milan Rib, Double Picket, etc., or warp knitting such as Tricot, Russell, Miranese, etc. Alternatively, a knitted fabric that has been subjected to raising treatment for protruding pile-like fibers on the knitted surface is preferable. The aliphatic polyester fiber of the present invention used for producing the knitted fabric is a raw fiber, a twisted yarn, a false-twisted yarn, etc., and a fiber form such as a long fiber (filament) or a short fiber (staple). There is no limit.

  Moreover, the aliphatic polyester fiber of the present invention can be made into a non-woven fabric that is used at least in part or in whole according to the use or shape that can be used. Here, examples of the nonwoven fabric include those formed by bonding or adhesion methods such as a chemical bond method, a thermal bond method, a needle punch method, a water jet punch (spun lace) method, a stitch bond method, and a felt method. The aliphatic polyester fiber of the present invention used for producing the fiber is not particularly limited with respect to the form of fiber such as raw yarn, twisted yarn, false twisted yarn, long fiber (filament), short fiber (staple), etc. .

  The above-mentioned woven fabric or knitted fabric in which the aliphatic polyester fiber of the present invention is used at least in part may be subjected to processing such as conventional scouring, dyeing, heat setting, etc. Physical processing such as attaching press, embossing press, compact processing, flexible processing, heat setting, bonding processing, laminating processing, coating processing, antifouling processing, water repellent processing, antistatic processing, flameproofing processing, insectproofing processing, Chemical processing such as sanitary processing and foam resin processing, and other application processing such as microwave application, ultrasonic application, far-infrared application, ultraviolet application, and low-temperature plasma application may be performed.

  Further, as the above-mentioned woven fabric, knitted fabric or non-woven fabric in which the aliphatic polyester fiber of the present invention is used at least in part, the aliphatic polyester fiber of the present invention, synthetic fibers different from the present invention, semi-synthetic fibers, For example, a natural fiber such as cellulose fiber, wool, silk, stretch fiber, or at least one fiber selected from acetate fiber may be used. Specific examples include cellulose fibers such as natural fibers such as cotton and hemp, or copper ammonia rayon, rayon, polynosic, etc. The content of the aliphatic polyester fiber of the present invention mixed with these cellulose fibers. Is not particularly limited, but in order to make use of the texture, hygroscopicity, water absorption, antistatic property, etc. of the cellulose fiber and make use of the conductivity of the aliphatic polyester fiber of the present invention, 0.1 to 50% by weight preferable. In addition, the wool and silk used for the mixture can be used as they are, and the content of the aliphatic polyester fiber of the present invention mixed with the wool or silk is about the texture of the wool, warmth, bulkiness, Moreover, 0.1-50 weight% is preferable in order to make use of the texture of silk, a squeak sound, and the conductivity of the aliphatic polyester fiber of the present invention. In addition, the stretch fiber used for mixing is not particularly limited, and polyester-based elastic typified by dry-spun or melt-spun polyurethane fiber, polybutylene terephthalate fiber, or polytetramethylene glycol copolymer polybutylene terephthalate fiber. In the mixed fabric using stretch fibers, the content of the aliphatic polyester fiber of the present invention is preferably about 0.1 to 50% by weight. The acetate fiber used for mixing is not particularly limited, and may be a diacetate fiber or a triacetate fiber. The content of the aliphatic polyester fiber of the present invention mixed with these acetate fibers is the texture of the acetate fiber, In order to make use of sharpness and gloss, and to make use of the conductivity of the aliphatic polyester fiber of the present invention, 0.1 to 50% by weight is preferable.

  With respect to these various mixed woven fabrics, knitted fabrics, and nonwoven fabrics, the form of the aliphatic polyester fiber of the present invention and the mixing method are not particularly limited, and known methods can be used. For example, mixed methods include woven fabrics such as union woven fabrics and reversible fabrics used for warp or weft yarns, knitted fabrics such as tricot and russell, and other knitting, doubling, and entanglement may be performed.

  The woven fabric, knitted fabric or non-woven fabric using the aliphatic polyester fiber of the present invention at least partly or entirely may be dyed, including those mixed as described above. For example, in the case of knitting, post-weaving or non-woven fabric After the web is formed and formed by the above-described joining or adhesion method, it is preferable to take the steps of scouring, pre-setting, dyeing, and final setting by a conventional method. The aliphatic polyester fiber of the present invention comprises an aliphatic polyester and an aromatic polyester containing a conductive agent, but may be subjected to alkali weight reduction treatment by a conventional method after scouring and before dyeing depending on the required range. . The present invention contains an aliphatic polyester as a component of the fiber, but the aliphatic polyester has a weight reduction rate in the alkali weight loss treatment which is much higher than that of a PET polymer or PBT polymer as used conventionally. Because of its large size, it is necessary to pay close attention to the time required for the weight loss treatment and the aqueous solution concentration of alkali components (sodium hydroxide, potassium hydroxide, etc.). The scouring is preferably performed in a temperature range of 40 to 98 ° C. In particular, in the case of mixed use with stretch fibers, it is more preferable to scour the fabric while relaxing because it improves elasticity. One or both of the heat sets before and after dyeing can be omitted, but it is preferable to carry out both in order to improve the form stability and dyeability of the woven fabric, knitted fabric or nonwoven fabric. The heat setting temperature needs to be 120 to 190 ° C., preferably 140 to 180 ° C., which does not detract from the spirit of the present invention, but the heat setting time is 10 seconds to 5 minutes, preferably 20 seconds. ~ 3 minutes.

  The aliphatic polyester fiber of the present invention is very useful as a fiber itself because of its excellent conductivity, and the fiber can be used as a long fiber as it is. It is used as a short fiber of the length. The short fiber is formed by cutting the filament into a single yarn or a tow in which a plurality of yarns are bundled. Particularly, the short fiber having a length of 0.1 to 10 mm is, for example, By a variety of methods such as electric flocking and spraying, it is possible to obtain a flocked body that is bonded to the base and planted. More than 50% of the fibers planted by the electric flocking process are bonded in a generally upright state from 10 degrees to the base (that is, 90 degrees). Here, in addition to the short fiber made of the aliphatic polyester fiber of the present invention, the short fiber made of another fiber that is not the fiber of the present invention is mixed and planted in the short fiber used for forming the flocked body. May be. The flocked body is formed by adhering a short fiber to a base and planting, and when adhering, for example, an acrylic, urethane, or ester adhesive may be used for adhesion. Is preferred. Here, the thickness of the adhesive layer is preferably 1 to 500 μm, and a single layer or, if necessary, a plurality of types of adhesives may be mixed or divided into a plurality of layers. In addition, the base to be planted is not particularly limited, and may be appropriately selected according to the apparatus for incorporating the flocked body and the adhesive to be used. Synthetic resin, natural resin, synthetic fiber, natural fiber, wood Films, sheets, paper, boards, fabrics, etc. made of minerals or metals can be suitably employed, or directly implanted on the base of a metal processed body, synthetic or natural resin processed body or molded body that is a member for various applications. Also good. In particular, in order to increase the affinity with the adhesive, a sheet made of a synthetic or natural resin or metal subjected to a hydrophilic treatment is preferable. And if this base | substrate is the raw material which forms the front and back, such as the said film, sheet | seat, paper, board, cloth, according to a use or the objective, it can plant on both surfaces of the surface and a back surface. The flocked body can be used as a conductive brush roller because of its conductivity, for example, as its usage or application.

  The above-mentioned woven fabric, knitted fabric or non-woven fabric using at least a part of the aliphatic polyester fiber of the present invention can be a fabric composite formed by bonding to a base. In this case, in the case of a woven fabric, there are piled or threaded ends on the surface of the fabric by pile weaving or treatment, and in the case of a knitted fabric, there are pile-shaped fiber raised or raised and the pile or yarn ends are on the knitted surface. Some are preferable because the functions of the brush roller described later may be further enhanced. When adhering, it is preferable to adhere using, for example, an acrylic, urethane, or ester adhesive. Here, the thickness of the adhesive layer is preferably 1 to 500 μm, and a single layer or, if necessary, a plurality of types of adhesives may be mixed or divided into a plurality of layers. Further, the substrate to be bonded is not particularly limited, and may be appropriately selected according to the apparatus incorporating the fabric composite and the adhesive used. However, synthetic resin, natural resin, synthetic fiber, natural fiber, wood Films, sheets, paper, boards, fabrics, etc. made of minerals or metals can be suitably used, or directly bonded to the base of a metal processed body, synthetic or natural resin processed body or molded body, which is a member for various applications. Also good. In particular, in order to increase the affinity with the adhesive, a sheet made of a synthetic or natural resin or metal subjected to a hydrophilic treatment is preferable. If the substrate is a material forming the front and back surfaces, such as the film, sheet, paper, board, or fabric, the fabric is formed by adhering the woven fabric, knitted fabric, or nonwoven fabric to both the front and back surfaces according to the purpose or purpose. Can be a composite. The fabric composite can be used as a conductive brush roller because of its electrical conductivity, for example, because of its electrical conductivity.

  Since the aliphatic polyester fiber of the present invention has stable conductivity and can be controlled to a desired resistivity, a weak current can flow when a constant voltage is applied. . Utilizing this, an actuator that is controlled and driven by a signal sent with a weak current is formed. The actuator can be designed to use the aliphatic polyester fiber of the present invention in the drive part so that it can move, or it can carry another. At this time, the length of the fibers may be long fibers (filaments) or short fibers as described above. In the actuator, the aliphatic polyester fiber of the present invention can be used as a part of an actuator circuit because it can transmit a weak current as a signal, for example, the same as human muscle.

  The aliphatic polyester fiber of the present invention is a garment that is used at least in part or in whole. At this time, the length of the fibers may be long fibers (filaments) or short fibers as described above. For example, when it is made into clothing, it is more comfortable to wear, such as being able to suppress the generation of static electricity in winter or when dry due to its excellent conductivity, or it is difficult to get dust close to it, so when manufacturing surgical clothing or semiconductors It can form dust-proof clothing such as work clothes. In that case, the aliphatic polyester fiber of the present invention may be used as a garment, or it may be used as warp yarn and / or weft yarn at least for some of the woven fabrics constituting the garment. Is preferred. In addition, as a secondary effect, for example, carbon black and metal oxides improve the thermal conductivity of fibers by containing a conductive agent. It can also be used as a warm material that warms your body as soon as you enter a warm room from the cold.

  The aliphatic polyester fiber of the present invention is a heating element used for at least part or all of it. At this time, the length of the fiber may be long fiber (filament) or short fiber as described above. Since the aliphatic polyester fiber of the present invention is excellent in electrical conductivity when it becomes a heating element and can be designed to have the required average resistivity [Ω / cm], the applied voltage, the target temperature, It can be a heating element according to the above. By applying a certain voltage, the aliphatic polyester fiber of the present invention functions as a resistor and generates heat. When designing the heating element, it is preferable to use the fibers of the present invention as warp yarns and / or weft yarns for every few fibers, for example, when only a small amount of temperature increase is required. Alternatively, when the area to be heated needs to be planar, when the aliphatic polyester fiber of the present invention is used for warp or weft, increasing the number of fibers tends to increase the surface temperature, and in the limit, warp and What is necessary is just to form a textile fabric using the aliphatic polyester fiber of this invention for all the wefts. A knitted fabric may be used instead of the woven fabric. The heating element can be used as a heating element as long as it has a heating rate of 0.1 ° C./min or more when a voltage of 100 V is applied to both ends of the fiber or both ends of the fabric. It is preferably at least ° C / min, and those that are heated at a rate of temperature rise of at least 1 ° C / min are particularly preferred and can be used as a heating element.

The woven fabric and / or the knitted fabric and / or the non-woven fabric using the aliphatic polyester fiber of the present invention can be used for at least a part of the woven fabric and / or the knitted fabric and / or the non-woven fabric to adhere to a rod-like object to form a brush roller. The woven fabric and / or knitted fabric and / or non-woven fabric used here are wound and bonded in one round by cutting the length of the rod-like object that is functionally required (ie, the winding width) when adhering to the rod-like object. Alternatively, a rod-shaped object cut in a slit shape with a width of a fraction of one-tenth to one-tenth of the length of the rod-shaped object may be wound around and adhered to the rod-shaped object. The adhesive used here may be appropriately employed depending on the intended use or purpose, and various types such as acrylic, ester or urethane can be employed, and if necessary, the adhesive is conductive. Carbon black, carbon nanotube, VGCF, or a conductive agent such as metal or metal oxide, or a magnetic control agent may be added. Here, the thickness of the adhesive layer is preferably 1 to 500 μm, and a single layer or, if necessary, a plurality of types of adhesives may be mixed or divided into a plurality of layers. Further, the woven fabric and / or the knitted fabric and / or the non-woven fabric are made of a material such as a conductive treatment agent or a conductive sheet or a conductive film having a specific resistance of 10 ² to 10 ¹⁰ Ω · cm on the bonding surface before bonding. You may stick together.

The short fiber using the aliphatic polyester fiber of the present invention can be used for at least a part or all of the short fiber and can be planted by being adhered to a rod-like object to form a brush roller. The short fiber used here may be sprayed with a short fiber by electric gas or may be subjected to electric flocking when it is planted by adhering to a rod-like object, but it is generally upright on the surface of the rod-like object. Since it can be obtained efficiently, it is preferably obtained by electric flocking. At this time, 50% or more of the short fibers are bonded in a generally upright state from 10 degrees to the vertical (that is, 90 degrees) on the surface of the rod-like object. Here, as long as the object of the present invention is not impaired, the short fibers made of other fibers that are not the aliphatic polyester fibers of the present invention are mixed with the short fibers made of the aliphatic polyester fibers of the present invention. And may be planted. In addition, the adhesive when planted by adhesion is not particularly limited, and for example, acrylic, urethane, or ester adhesives are selected and used depending on the application or purpose. The thickness of the adhesive layer is preferably 1 to 500 μm, and a single layer or, if necessary, a plurality of types of adhesives may be mixed or divided into a plurality of layers. Moreover, the specific resistance value of the brush roller itself of the brush roller formed by using at least a part of the short fiber made of the aliphatic polyester fiber of the present invention and adhering to a rod-like object is 10 ² to 10 ¹¹ [Ω. · Cm] is preferable.

  The main material used for the core of the rod-shaped object described above may be any material suitable for the intended use or purpose, and may be selected from metals, synthetic resins, natural resins, wood, minerals, etc., alone or in combination. However, when used as a member to be incorporated in an electrophotographic apparatus described later, it is preferably made mainly of metal. Further, when the rod-shaped object is a metal, an intermediate layer covers the entire surface of at least a part of the metal or a necessary part, and the woven fabric and / or knitted fabric and / or the nonwoven fabric is adhered thereon, Or it is preferable that a short fiber adheres and is planted. The material used as the intermediate layer mainly provides cushioning properties to the rod-like object, or bears auxiliary elasticity / rigidity when it cannot be achieved only by the elasticity / rigidity of the brush-like fibers, which will be described later. For example, the toner removal performance in the cleaning device or the toner application performance in the developing device is significantly improved. Although not particularly limited, for example, a urethane material, an elastomer material, a rubber material, or an ethylene-vinyl alcohol material is preferably used for the intermediate layer. And it is preferable that the thickness of this intermediate | middle layer is 0.05-10 mm, Furthermore, the above-mentioned electrically conductive agent or a magnetic control agent may be added as needed.

The woven fabric and / or knitted fabric and / or non-woven fabric using the aliphatic polyester fiber of the present invention is used at least in part, and a brush roller formed by adhering to a rod-shaped object, or the short fiber is used at least in part, The brush roller formed by being adhered to an object is preferably used as a member of a cleaning device incorporated in an electrophotographic apparatus, for example, derived from the conductivity of the aliphatic polyester fiber of the present invention used. Used. Here, the average resistivity P of the fibers for the brush roller used in the cleaning device is 1.0 × 10 ³ [Ω / cm] or more and 1.0 × 10 ⁸ [Ω / cm] or less, or 1.0 ×. A material in the range of 10 ⁹ [Ω / cm] to 1.0 × 10 ¹² [Ω / cm] is preferably used according to the mechanism of the cleaning device. While the brush roller rotates in the cleaning device, electricity is applied if necessary, and unnecessary matter (for example, residual colorant that has not been transferred in the electrophotographic device) is captured and removed. However, when the aliphatic polyester fiber of the present invention is used, as described above, it is a fiber having stable conductive performance even when there is a change in temperature and humidity, so this removal performance is remarkably excellent. is there. In addition, as described above, the brush roller is used in the cleaning device, as described above, in addition to cleaning the photosensitive member by directly contacting the photosensitive member with the brush roller (in the case of the brush roller as described above). As a brush roller for cleaning the cleaning device itself, or as a brush roller for transferring the collected unnecessary toner to another place. Is also used. Further, in the cleaning device of the present invention, one brush roller may be used or a plurality of two or more brush rollers may be used depending on the purpose and the cleaning mechanism.

The woven fabric and / or knitted fabric and / or non-woven fabric using the aliphatic polyester fiber of the present invention is used at least in part, and a brush roller formed by adhering to a rod-shaped object, or the short fiber is used at least in part, The brush roller formed by being bonded to an object is derived from the conductivity of the fiber of the present invention used, and is preferably incorporated and used in a charging device that can be used in an electrophotographic apparatus described later. The average resistivity of the fibers of the brush roller incorporated in the charging device is preferably in the range of 1.0 × 10 ⁶ [Ω / cm] to 1.0 × 10 ¹⁰ [Ω / cm], more preferably 1. Those in the range of 0 × 10 ⁷ [Ω / cm] to 1.0 × 10 ¹⁰ [Ω / cm] are preferably used. The performance of the charging device using the brush roller depends on the conductive performance of the brush roller, that is, the performance of the aliphatic polyester fiber of the present invention. It is required that the conductivity of the brush roller does not change at all with respect to environmental changes in the apparatus, that is, changes in temperature and humidity that gradually change during operation of the electrophotographic apparatus, or changes in temperature and humidity due to the season. On the other hand, the aliphatic polyester fiber of the present invention hardly changes in conductivity with respect to the above-mentioned environmental change, and thus hardly causes charging spots on the photoconductor, and becomes a very excellent charging device. In addition, even when there is residual toner on the surface of the photoreceptor of the electrophotographic apparatus due to insufficient cleaning, the brush roller is brush-like and can also serve as a cleaning roller. In the case of downsizing the electrophotographic apparatus, it is possible to save space as a cleaning device and a charging device without separately installing the cleaning device and the charging device. It is also possible to do so, and that is also much better. In the charging device of the present invention, one brush roller or a plurality of brush rollers may be used depending on the purpose and mechanism.

  The woven fabric and / or knitted fabric and / or non-woven fabric using the aliphatic polyester fiber of the present invention is used at least in part, and a brush roller formed by adhering to a rod-shaped object, or the short fiber is used at least in part, The brush roller formed by adhering to an object is derived from the conductivity of the aliphatic polyester fiber of the present invention used, and is preferably incorporated and used in a developing device. In the later-described electrophotographic apparatus, the developing apparatus visualizes a latent image drawn by a laser on the surface of the photosensitive member uniformly charged by the charging apparatus. Since the resistivity of the brush roller does not change even when the environment changes, the toner for image formation is uniformly supplied to the photoconductor and the image is developed. Because it is beautiful with little or no, it is much better.

The woven fabric and / or knitted fabric and / or non-woven fabric made of the aliphatic polyester fiber of the present invention is used at least in part, and a brush roller formed by adhering to a rod-like object or the short fiber is used at least in part to adhere to the rod-like object. The brush roller thus implanted is derived from the conductivity of the aliphatic polyester fiber of the present invention used, and is suitably incorporated and used in a static eliminator that can be used in an electrophotographic apparatus described later. The average resistivity of the fibers for the brush roller incorporated in the static eliminator is preferably in the range of 1.0 × 10 ³ [Ω / cm] to 1.0 × 10 ¹² [Ω / cm]. In particular, when used in an electrophotographic apparatus to be described later, the aliphatic polyester fiber of the present invention used for a brush roller expresses a stable and uneven discharge effect, and is usually disposed after the discharge apparatus. In addition, the electrophotographic apparatus can be incorporated as a static eliminator and a cleaning apparatus by using the brush roller when the electrophotographic apparatus is downsized.

An electrophotographic apparatus, specifically a laser beam monochrome printer, a laser beam color printer, using the cleaning device and / or the charging device and / or the developing device and / or the discharging device using the aliphatic polyester fiber of the present invention. , Monochrome copiers, color copiers, monochrome or color facsimiles, multifunctional multifunction machines, word processors, etc., but with a mechanism that draws a latent image with a laser on a charged photoreceptor and visualizes it with toner. As described above, the developing or printing apparatus uses the aliphatic polyester fiber of the present invention, so that it can be stably cleaned, charged, developed, and developed regardless of environmental changes in the electrophotographic apparatus, particularly temperature and humidity. It has static elimination performance, and the obtained print or developed product is Further, in the case of a color that uses a large amount of a plurality of types of toner, the color becomes particularly beautiful, and further, the driving speed of the electrophotographic apparatus is further increased, that is, the printing or developing speed (number of sheets) per unit time is increased. It becomes possible. Further, as described above, an electrophotographic apparatus using the aliphatic polyester fiber of the present invention can be further reduced in size, space and power, and is very preferable.
[Fibers and fiber products of the present invention]
As described above, the woven fabric using the aliphatic polyester fiber of the present invention at least partly uses a fiber having very excellent conductivity. Even if this fiber is used for the part, it becomes a fabric having excellent conductive performance or performance capable of escaping electricity (in other words, electrostatic performance), so that it can be used for various materials such as curtains, curtains, and human bodies. It is excellent in that it can be used for seats of vehicles such as automobiles, railways, and airplanes that are prone to generate static electricity, wall materials and rugs, futons, blankets, and bedding.

  The knitted fabric using at least a part of the aliphatic polyester fiber of the present invention becomes a knitted fabric having conductive performance or electrostatic performance similar to the above-mentioned woven fabric, and therefore is used for various materials, for example, rugs such as building wall materials and carpets. It can be used for vehicle seats such as automobiles and railway aircraft, wall materials, rug vehicle seats or beddings such as futons, blankets and mattresses.

  Since the nonwoven fabric comprising the aliphatic polyester fiber of the present invention at least in part is a nonwoven fabric having electrical conductivity or electrostatic performance similar to the above-described woven fabric or knitted fabric, the same material as that for the above-described woven fabric or knitted fabric is used. In addition, it can be widely used as a material that requires a thickness, for example, a partition material, a package, a cushion, etc.

  Further, as yet another use of the short fiber made of the aliphatic polyester fiber of the present invention, woven fabric, particularly pile woven fabric, knitted fabric or non-woven fabric, by using these, the planted on the base, Can be made. Since these flocks or fabric composites are excellent in electrical conductivity or antistatic properties, they can be used as various interior materials with excellent touch.

  Since the aliphatic polyester fiber of the present invention or the short fiber made of the aliphatic polyester fiber of the present invention is excellent in electrical conductivity, it can form a wiring object, for example, various operations such as artificially reacting with weak electricity. It can also be used as part of an actuator circuit such as a muscle. Alternatively, a heating element can be formed from a wiring object, and since this uses the fiber of the present invention having excellent conductivity and small conductive spots, only using one that is controlled to a desired conductive performance, A heating element with good heat generation efficiency is obtained and is excellent. In addition, although the heat generating element will be used mainly at low temperature and low humidity in winter, the aliphatic polyester fiber of the present invention has no dependency on temperature and humidity or is very small, so it is stable even in winter. Demonstrates conductive performance and becomes a very excellent heating element.

  The apparel comprising at least a portion of the aliphatic polyester fiber of the present invention uses a fiber having excellent conductivity, so that it can suppress the generation of static electricity during clothing and escape from the body. It is useful when used as a dust proof clothing because it is hard to generate dust because it is hard to generate static electricity, and when the conductive agent is carbon black, metal, or metal oxide, for example. Because of its excellent thermal conductivity, contact cold sensation clothing that can dissipate heat outside the body, or conversely, contact sensation clothing that can quickly absorb heat from outside the body into a cold body, such as these Sports clothing that requires functionality (golf wear, gateball, baseball, tennis, soccer table tennis, volleyball, basketball, rugby, American Football, hockey, athletics, triathlon, speed skating, ice hockey and other uniforms) and infants, ladies, seniors, and other outdoor clothing (shoes, bags, supporters, socks, climbing clothes) Can be used.

  The brush roller formed by adhering at least a part of the woven fabric and / or the knitted fabric and / or the non-woven fabric made of the aliphatic polyester fiber according to the present invention uses an electrically conductive fiber at least in part. It is excellent because it has a function of efficiently removing unnecessary substances or imparting a necessary substance by utilizing a mechanical action.

  The brush roller using the short fiber made of the aliphatic polyester fiber of the present invention uses an electrically conductive fiber for at least a part thereof, so that it is not required efficiently by utilizing the electrical action as described above. In addition to having the function of removing substances or adding necessary substances, the fiber length of the short fibers can be controlled to control the fiber planting density of the brush rollers or the removal performance or application performance of the brush rollers depending on the purpose. Excellent because it can be easily controlled. In particular, when the rod-shaped object to be implanted is mainly made of metal, the conductivity (specific resistance value) of the brush roller itself can be controlled by controlling the conductivity of the aliphatic polyester fiber of the present invention. When the rod-shaped object is composed of metal and an intermediate layer covering at least a part of the metal, cushioning can be imparted by controlling the material and thickness of the intermediate layer. The performance can be greatly improved and it is excellent.

  The cleaning device using the brush roller of the present invention is very excellent in removal performance when the brush roller itself rotates to remove unnecessary substances and clean them. For example, in the electrophotographic apparatus to be described later, when the toner can be electrically removed, the conductive performance of the brush roller does not fluctuate even when there is an environmental change in the electrophotographic apparatus, particularly a humidity change. It has excellent removal performance at all times. Further, the brush roller of the present invention is not limited to the cleaning material itself, for example, in the electrophotographic apparatus described later, in addition to performing cleaning by directly contacting the photoconductor, the cleaning roller itself can also be used. It is also useful as a member for removing unnecessary materials and cleaning the cleaning device itself, resulting in a high-performance cleaning device.

  The charging device using the brush roller of the present invention is used by controlling the conductivity (specific resistance value) of the brush roller itself. For example, the photoconductor is uniformly charged by an electrophotographic apparatus described later. In addition to being able to charge the photoreceptor uniformly when used as a brush roller, the specific resistance value of the brush roller itself changes even when the environment in the electrophotographic apparatus changes, for example, when the electrophotographic apparatus is operating or when the humidity changes due to seasonal changes. No change or very small change, so that charging spots on the photoconductor hardly appear, which is very good. In addition, even when there is residual toner due to insufficient cleaning on the photoreceptor of the electrophotographic apparatus, the brush roller can also function as a cleaning roller, so that contamination during development or printing can be avoided. In addition to being excellent, there is little or no improvement, and when the electrophotographic apparatus is downsized, the cleaning apparatus and the charging apparatus are not installed separately, but are used only as the cleaning apparatus and charging apparatus with the brush roller alone. It is very good because

  The developing device using the brush roller of the present invention is used by making full use of the conductivity of the brush roller itself in the same way as the effect of the charging device described above. When the toner is attached to the drawn electrostatic latent image, the toner is uniformly exposed because there is no or almost no unevenness in the specific resistance value of the brush roller itself during environmental changes such as humidity changes as described above. The developed product or printed product supplied to the body and visualized is excellent because it is very beautiful with little or no contamination.

  The static eliminator using the brush roller according to the present invention controls the content of the conductive agent contained in the fiber to reduce the electrical conductivity (specific resistance value) of the brush roller, so that the excellent static eliminator. It is useful because it becomes a brush roller having performance. In particular, when used in an electrophotographic apparatus described later, since the brush roller made of countless hairs (fibers) has a stable and uniform neutralizing effect, the cleaning apparatus disposed after the neutralizing apparatus In addition to being able to enhance the cleaning effect, the electrophotographic apparatus is excellent because it can be incorporated as a static eliminator and a cleaning apparatus by using the brush roller when the electrophotographic apparatus is downsized.

  An electrophotographic apparatus, specifically a laser, using the cleaning device and / or charging device and / or developing device and / or static eliminator incorporating the brush (roller) using the aliphatic polyester fiber of the present invention. As described above, a device that develops or prints a latent image with a laser on a charged photoconductor such as a beam printer, copying machine, facsimile machine, multifunctional multifunction machine, or word processor, and visualizes it with toner. Since it has stable cleaning, charging, developing, and charge removal performance regardless of environmental changes in the electrophotographic apparatus, the obtained print or developed product becomes very beautiful. Further, by optimizing the fiber length of the brush roller or the content of the conductive agent to be contained, it has more stable cleaning / electricity resistance / development / static elimination performance, so that the driving speed of the electrophotographic apparatus is further increased. This is preferable because the printing or developing speed (number of sheets) per unit time can be increased.

  EXAMPLES Hereinafter, the present invention will be described specifically and in detail with reference to examples, but the present invention is not limited only to these examples. In addition, the physical-property value in an Example was measured with the following method.

A. Measurement of Fineness [dtex] and Single Yarn Fineness [dtex] The fiber (multifilament) is crushed by 100 m in length, and the weight (g) of the crushed fiber is measured and multiplied by 100. The average value of three measurements obtained in the same manner was defined as the fineness of the fiber. Regarding the single yarn fineness, a value obtained by dividing the fineness by the number of single fibers constituting the filament was defined as a single yarn fineness [dtex].

B. Measurement of initial tensile elastic modulus, residual elongation, and breaking strength of fiber Tensilon tensile tester (TENSIRON UCT-100) manufactured by Orientec Co., Ltd., if it is an undrawn yarn, the initial sample length is 50 mm, and the tensile speed is 400 mm / min. In the case of drawn yarn, the initial tensile modulus (stretched yarn only), strength, and residual elongation were measured at an initial sample length of 200 mm and a tensile speed of 200 mm / min, and the average value measured five times was used as the measured value. The initial tensile elastic modulus was recorded on chart paper as a chart speed of 100 cm / min and a stress full range of 500 g, and was determined from the slope of the initial tensile curve.

C. Measurement of average resistivity P and calculation of resistivity standard deviation Q and ratio R (R = Q / P) of average resistivity P and resistivity standard deviation Q Medium temperature and medium humidity (23 ° C humidity 55%) The sample to be measured was measured for at least 1 hour in the atmosphere and then measured. A probe consisting of two rod terminals connected to an insulation resistance meter SM-8220 manufactured by Toa DKK Co., Ltd. between the rollers when running the yarn with a pair of mirror rollers consisting of a yarn feeding roller and a winding roller Installed with the running yarn in contact with the rod, the thickness of the rod φ5mm, the measured length of the yarn contacted between the rod terminals is 2.0cm, the applied voltage is 100V, the yarn feeding speed is 100cm / min, and the yarn tension between the rollers is The resistance value is set to the range of 0.05 to 0.1 cN / dtex (there is no difference in the measured value within this range), and the length is 200 cm at a sampling rate of 0.2 seconds with an insulation resistance meter. And the average resistance value [Ω] of the obtained value divided by the distance (2.0 cm) of the yarn contacting between the bar terminals was defined as the average resistivity P [Ω / cm]. Further, the standard deviation Q for all the values obtained at the same time was calculated, and the ratio R (R = Q / P) between the average resistivity P and the standard deviation Q of the resistivity was calculated.

D. Ratio Z (Z = Y / X) of average resistivity between average resistivity X at medium temperature and medium humidity (23 ° C. humidity 55%) and average resistivity Y at low temperature and low humidity (10 ° C. humidity 15%) (temperature Humidity change Z)
For medium temperature and medium humidity, C.I. The measurement method of the item is adopted, and C.I. The average resistivity was obtained by measurement in the same manner as in the item, and the ratio Z (Z = Y / X) of the obtained average resistivity X and Y was obtained.

E. Measuring method of specific resistance value The measurement was carried out after holding the sample to be measured at the medium temperature and humidity for at least 1 hour in the atmosphere. When the object to be measured is a fiber having a length of 100 mm or more, the fiber bundle is made into a bundle of 1000 dtex and cut to a length of 50 mm (at this time, the fiber end face is cut obliquely), and the end face is electrically conductive. After applying the paste, an electrode was attached and measurement was performed at 500V. When the object to be measured is a fibrous or powdery material having a length of less than 100 mm, it is 10 cm in length, 2 cm in width, 1 cm in depth, and an insulating box container having electrodes on both end faces. After filling and sealing at a pressure of 50 kgf / cm ² , measurement was performed at 500 V, and the specific resistance value per unit volume [Ω · cm] was calculated. For the gut-shaped one, two terminals of the tester are arbitrarily selected using a tester for a gut having a diameter D (with a diameter in the range of 0.2 to 0.3 cm) and a length of 12 cm in one measurement. The resistance value R [Ω] was measured at an interval of 10 cm, and the resistance value R [Ω] was measured, and the specific resistance value of the gut was obtained from the formula of (specific resistance value) = R × (D / 2) ² × π / 10. . The specific resistance value was measured once for each of the five different guts, and the average value of the five times was taken as the specific resistance value.

F. Measurement of melt viscosity Using Capillograph 1B manufactured by Toyo Seiki Co., Ltd., under a nitrogen atmosphere, with a barrel diameter of 9.55 mm, a nozzle length of 10 mm, and a nozzle inner diameter of 1 mm, a polymer extrusion piston speed of 1 mm / min (shear speed of 12.16 sec ⁻¹ ) Or 100 mm / min (shear rate of 1216 sec ⁻¹ ), and measurement was performed after 10 minutes passed immediately after sample filling. The average value of the values measured five times was taken as the melt viscosity at each shear rate.

G. Calculation of shrinkage rate (dry heat shrinkage) for 15 minutes in the atmosphere at 160 ° C. One clip is attached to a bundle obtained by scooping five rings of 1 m drawn yarn, and the length L1 of the bundle is measured (at this time, about 500 mm). Length). Next, it is slowly lowered into the atmosphere at 160 ° C. and left to stand for 15 minutes. After 15 minutes, it is taken out and air-dried for 1 hour or more. After air drying, the length L2 of the bundle is measured again. The shrinkage rate (%) is calculated by the following formula.
Dry heat shrinkage (%) = {(L1-L2) ÷ L1} × 100
H. Measurement of glass transition point (Tg) and melting point (Tm) Using a differential scanning calorimeter (DSC-2) manufactured by PerkinElmer Co., Ltd., the sample was measured at a heating rate of 16 ° C./min. The definitions of Tm and Tg are as follows. After observing the endothermic peak temperature (Tm ₁ ) observed once measured at a heating rate of 16 ° C./min, the temperature is kept at a temperature of about (Tm ₁ +20) ° C. for 5 minutes. Rapidly cool to room temperature (hold for 5 minutes by combining the quenching time and room temperature holding time) and measure the endothermic peak temperature as Tg as a stepwise baseline deviation when measured again at 16 ° C / min. The endothermic peak temperature observed as the melting temperature of the crystal was defined as Tm.

I. Measurement of fiber length of short fibers Short fibers having a length of 20 mm or more are subjected to a load of 0.1 g / dtex using a caliper, and short fibers having a length of less than 20 mm are measured using NIPPON KOGAK K.K. The length of 50 short fibers was measured 20 times using K SHADOW GRAPH Model 6 and the average value was defined as the fiber length.

J. et al. Measurement of carbon nanotube (CNT) diameter D and ratio of D to length L (aspect ratio) L / D, measurement of average particle diameter of conductive agent Block in which CNT is embedded in fiber epoxy resin as it is (CNT block), or if the CNT is present in the fiber, the block in which the fiber is embedded in an epoxy resin (hereinafter referred to as the fiber block) is cut with an ultramicrotome and the CNT block at any place. In the case of a fiber block, an ultrathin section of a CNT is cut in the vicinity of the center of the fiber in the direction parallel to the fiber axis direction to produce an ultrathin section of a single fiber longitudinal section, and a transmission electron microscope (TEM) observation device ( Observation was performed at an arbitrary magnification of 100,000 to 500,000 times with an acceleration voltage of 75 kV. Obtained as a digitized photograph in the observation, select 100 arbitrary CNTs on the photograph, measure the diameter D and length L of the CNTs by analyzing the image with WinROOF made by Mitani Corporation, D and L / D were calculated to determine the average value of 100, and the average value was used as the average diameter D and aspect ratio L / D of the CNT. Also, the average particle diameter of the conductive agent is observed with the same device and magnification as CNT, 100 conductive agent particles are selected, and the average particle diameter of these 100 particles is analyzed by WinROOF manufactured by Mitani Corporation. Sought by.

K. Measurement of single fiber diameter After performing a platinum-palladium vapor deposition (deposition film pressure: 25 to 50 angstrom) at an acceleration voltage of 2 kV using a scanning electron microscope (SEM) STRATA DB235 manufactured by FEI Company, the outer diameter of the fiber Are within the field of view (5,000 times if the single fiber diameter is 25 μm to 50 μm, 10,000 times if the single fiber diameter is 15 μm to 25 μm, and 20,000 times if it is 5 μm to 15 μm). At this time, the single fiber diameter is defined as an average value obtained by observing and measuring at least five points at an interval of 3 cm or more in the same fiber.

L. Measurement of number average molecular weight The gel permeation chromatography 2690 manufactured by Waters was used and measured under the following conditions. Column: Two Shodex GPC K-805L (8 mm ID * 300 mm L) connected and used, Solvent: Chloroform (Wako Pure Chemical Industries, Ltd., for high performance liquid chromatogram), Temperature: 40 ° C., Flow rate: 1 mL / min, Sample concentration: 10 mg / 4 mL, Filtration: Mysholy disk 0.5 μ-TOSOH, injection amount: 200 μL, detector: differential refractometer RI (Waters 2410), standard: polystyrene (concentration: sample 0.15 mg / solvent 1 mL), measurement time: 40 Min.

M.M. Calculation of the proportion of aliphatic polyester containing conductive agent in the fiber A block in which the filament of the fiber for which the proportion is to be calculated is embedded in an epoxy resin is cut with a microtome in the fiber cross-sectional direction perpendicular to the fiber axis direction. After making a thin section and observing / photographing it with a light microscope at 200 times with transmitted light, the obtained fiber cross-sectional photograph is an aliphatic polyester part containing a conductive agent and other polymers in the above-mentioned WinROOF manufactured by Mitani Corporation. The ratio with the component was calculated by image analysis of the area.

N. Content of Conductive Agent in Aliphatic Polyester To determine the content of the conductive agent with a resin composition containing a conductive agent or a fiber made of only aliphatic polyester containing a conductive agent, Hitachi High-Technologies Corporation Using a spectrophotometer U-3010, a calibration curve was prepared using five types of solutions of different concentrations (solvents for dissolving aliphatic polyesters; for example, chloroform for polylactic acid) whose concentration of the conductive agent is known in advance. After the preparation, the content of the conductive agent in the aliphatic polyester containing the conductive agent was determined. In the case of a composite fiber, the aforementioned M.M. The content of the conductive agent in the aliphatic polyester was calculated from the ratio of the aliphatic polyester obtained in the item. In the case of an aliphatic polyester that is insoluble or difficult to dissolve in a solvent, after stirring for 24 hours at 30 ° C. with a 1N aqueous sodium hydroxide solution and centrifuging, the amount of the conductive agent was measured.

O. Evaluation of high-temperature heat resistance Fabrics using the obtained fibers for both wefts and warps were prepared, and six 10 cm × 10 cm test pieces made of the fabrics were prepared, and 100 ° C., 120 ° C., 140 ° C., 160 ° C. Each of the test pieces was ironed at temperatures of 180 ° C. and 200 ° C., and the temperature at which the appearance change (shrinkage or melting) of the fabric was observed visually was determined as the heat resistant limit temperature. Shrinkage was regarded as shrinkage when shrinking by 3% or more. In the evaluation of the high temperature heat resistance, the temperature at which the appearance change occurred is 140 ° C. or less, the high temperature heat resistance is poor (×), and the high temperature heat resistance is slightly inferior at 160 ° C. (Δ; can be used) 180 Good high-temperature heat resistance at 0 ° C. (◯), first appearance change at 200 ° C., or no change in appearance at 200 ° C., high-temperature heat resistance was considered excellent (double circle).

Comparative Example 1
(Production method of polyethylene terephthalate, preparation of polyethylene terephthalate to which carbon black is added, production of fiber): coloring agent for low polymer obtained by usual esterification reaction from 166 parts by weight of terephthalic acid and 75 parts by weight of ethylene glycol As a polycondensation catalyst, 0.03 part by weight of 85% phosphoric acid aqueous solution, 0.06 part by weight of antimony trioxide as a polycondensation catalyst, and 0.06 part by weight of cobalt acetate tetrahydrate as a toning agent are added to carry out a polycondensation reaction. Polyethylene terephthalate (hereinafter referred to as PET) pellets having a commonly used IV of 0.66, a melt viscosity of 126 [Pa · sec] (measurement temperatures of 290 ° C., 12.16 sec ⁻¹ , melting point (Tm) of 256 ° C.) were obtained.
The PET pellets are vacuum dried at 150 ° C. for 10 hours, and then are granulated in a nitrogen atmosphere. Before being melt-kneaded using a biaxial extruder (axial length L / axial diameter D = 45), In addition, carbon black as furnace black (type VULCAN XC72, specific resistance 0.45 [Ω · cm], average particle size 31 nm, hereinafter referred to as FCB) manufactured by Cabot Specialty Chemicals, Inc. is mixed with powder and then melted. And kneaded with the biaxial extruder. Here, FCB was prepared so that the FCB would be 16% by weight in the resin composition of PET and FCB obtained after completion of kneading, and kneaded at 280 ° C. After kneading, the discharged gut-shaped resin composition is cooled with tap water at 15 ° C. and then cut with a cutter, and a PET having a melt viscosity of 618 [Pa · sec] (measurement temperature 290 ° C., 12.16 sec ⁻¹ ). And pellets of a resin composition of FCB (hereinafter referred to as PET-FCB) were obtained. It was 10 ^2.29 [ohm * cm] when the (average) specific resistance value was measured about the gut of the resin composition which was not made into the pellet.
This extruder-type melt spinning machine equipped with a biaxial extruder (axial length L / axial diameter D = 35) using this PET-FCB is a round shape with a spinning temperature of 290 ° C. and a pore diameter of 0.3 mm and 24 holes. A spinneret with a pore size of 20 μm and a filter with a fine mesh of 20 μm are installed and melt spinning, and an aqueous treatment agent (concentration of 20% by weight of effective component) is added as an effective component so that the amount of adhesion is 1% by weight After adhering, melt spinning was attempted at a take-up speed of 1500 m / min. However, at a take-up speed of 1500 m / min, the yarn was severely broken and could not be taken up at all, so the take-up speed was set at 500 m / min. However, the yarn was still severely cut, and as a result, the spinnability was very poor and a wound yarn could not be obtained. It was.

Comparative Example 2
(Preparation of aliphatic polyester containing carbon black, production of fiber): A lactide produced from L-lactic acid having an optical purity of 99.5% was converted into a bis (2-ethylhexanoate) tin catalyst (lactide to catalyst molar ratio). = 10000: 1) and the polymerization time was changed to 280 minutes and 415 minutes, respectively, at 180 ° C. in a nitrogen atmosphere to obtain two types of polylactic acid (hereinafter referred to as PLA-1 and PLA-2) having different molecular weights. Subsequently, delactide treatment was performed at 180 ° C. under reduced pressure. In addition, "Ultranox 626" manufactured by GE was added as a stabilizer during polymerization at 0.15% by weight relative to lactide. The number average molecular weights of the obtained PLA-1 and PLA-2 were 150,000 and 220,000, respectively, and the melting point (Tm) was 174 ° C. Subsequently, the PLA-1 pellets were vacuum-dried at 120 ° C. for 10 hours, and then the same FCB type and FCB addition amount (16% by weight) were the same in the same apparatus except for kneading at 230 ° C. in the same kneading as in Comparative Example 1. And a pellet of a resin composition of PLA and FCB (hereinafter referred to as PLA-FCB16) having a melt viscosity of 893 [Pa · sec] (measurement temperature: 230 ° C., 12.16 sec ⁻¹ ) was obtained. When the (average) specific resistance value of the gut of the resin composition not formed into pellets was measured, it was 10 ^2.21 [Ω · cm].
Using this PLA-FCB16, the same extruder type melt spinning machine used in Comparative Example 1 was used, and a spinning experiment was carried out under the same conditions except that the spinning temperature was 230 ° C. There was no problem at a take-up speed of 1500 m / min. An undrawn yarn having a total fineness of 183 dtex and 24 filaments was wound up. There was no problem in the spinnability, and no breakage was observed even during continuous spinning for 24 hours.
When the obtained multifilament is stretched, the yarn feeding speed of the yarn feeding roller is 320 m / min, the first roller is 70 ° C. and the yarn feeding speed is 320 m / min, and the second roller is 110 ° C. and the yarn feeding speed is 800 m / min. The third roller was spun at a room temperature of 800 m / min at room temperature, combined the three undrawn yarns described above, subjected to drawing and heat treatment, and then cooled to below Tg of the polyester with a cold roller. Later, it was wound up to obtain a drawn yarn having a fineness of 220 dtex and a filament cross section of 72 and having a round fiber cross section. There was no problem such as winding of a single yarn around the roller during drawing, and the drawability was excellent. Table 1 shows the yarn physical properties. However, when the high-temperature heat resistance of the obtained drawn yarn was evaluated, it was found that the fabric contracted and melted at 140 ° C. and was inferior in high-temperature heat resistance.

Comparative Example 3
This is an extruder-type composite melt spinning machine equipped with two twin-screw extruders (shaft length L / shaft diameter D = 35). The sheath component is PLA-2 synthesized in Comparative Example 2, and the core component is a comparative example. 1 is obtained by performing concentric core-sheath compound melt spinning in the same manner as in Comparative Example 2 and winding the fiber. It was. When the obtained fiber was further drawn, three undrawn yarns were drawn under the same drawing conditions as in Comparative Example 2 and drawn to obtain fibers having the physical properties shown in Table 1 and having a round fiber cross section. Obtained. The number of filaments was 72 in all cases. Although it was a fiber excellent in electroconductivity and a thread physical property similarly to the comparative example 2, shrinkage | contraction and melting | fusing of a textile fabric were seen and it turned out that it is inferior to high temperature heat resistance.

Examples 1-6 and Comparative Examples 4, 5
<Manufacture of polytrimethylene terephthalate (hereinafter PTT)>
Dimethyl terephthalate 130 parts (6.7 mole parts), 1,3-propanediol 114 parts (15 mole parts), calcium acetate monohydrate 0.24 parts (0.014 mole parts), lithium acetate dihydrate To a low polymer obtained by transesterifying 0.1 parts (0.01 mole parts) of salt and distilling off methanol, 0.065 parts of trimethyl phosphate and 0.134 parts of titanium tetrabutoxide were added. The polycondensation reaction was performed while distilling off 1,3-propanediol, and a chip-shaped prepolymer was obtained. The obtained prepolymer was further subjected to solid phase polymerization at 220 ° C. under a nitrogen stream, IV 1.16, melt viscosity 497 [Pa · sec] (measurement temperature 260 ° C., 12.16 sec ⁻¹ ), melting point (Tm). PTT pellets at 229 ° C. were obtained. When this PTT pellet was used for melt spinning, it was vacuum-dried at 150 ° C. for 10 hours.
<Composite spinning>
When performing core-sheath composite spinning in the same manner as in Comparative Example 3, PLA-1 containing FCB as the core component was placed in the amount of FCB (Tables 1 to 6 and Comparative Example 4) as shown in Table 1. 5) was changed and the same discharge rate (unit time) was used in the spinning process under the same spinning conditions as in Comparative Example 3, except that melt spinning was performed at a spinning temperature of 265 ° C. using the PTT as a sheath component. The same volume (cc / min)) and the stretching conditions were the same as in Comparative Example 3 except that the first roller was 80 ° C. and the second roller was 130 ° C. Got. As the content of the conductive agent increases, the physical properties of the resulting fiber tend to improve the electrical conductivity, while other physical properties tend to decrease, and before melt spinning at an excessive FCB high concentration (Comparative Example 4). The specific resistance of the resin composition was very low, and although it had high electrical conductivity, it could not be taken up by melt spinning. Moreover, when the density | concentration of FCB in a core component is small (comparative example 5), the average resistivity was high and it was inferior to electroconductivity. Table 1 shows the yarn physical properties.

Examples 7 to 14 and Comparative Example 6
As in Comparative Example 3, the core-sheath composite yarn as shown in FIG. 1 is obtained. When performing core-sheath composite spinning, the FCB is 25% by weight (Examples 9 to 14) or 35% by weight as the core component. % (Examples 7 and 8, Comparative Example 6) Changed the composite ratio of the core component (PLA-FCB) and the sheath component (PTT) as shown in Table 2 with PLA-FCB composed of PLA-1 contained. In the spinning process, the same discharge amount (the same volume amount [cc / min] per unit time) is obtained under the same spinning conditions as in Comparative Example 3 except that melt spinning is performed at a spinning temperature of 265 ° C. Thus, regarding the stretching conditions, fibers were obtained in the same manner as in Comparative Example 3 except that the first roller was set to 80 ° C. and the second roller was set to 130 ° C. As the proportion of the core component increased, the physical properties of the resulting fiber tended to improve the conductivity while decreasing the high-temperature heat resistance. When the core component was excessively low (Comparative Example 6), the average resistivity was high and the conductivity was inferior. Table 2 shows the yarn physical properties.

Examples 15-20
<Production of isophthalic acid copolymerized polyethylene terephthalate (hereinafter referred to as PET / I)>
In Comparative Example 1, in place of 166 parts by weight of terephthalic acid, 150 parts by weight of terephthalic acid and 16 parts by weight of isophthalic acid were used in the same manner as in Comparative Example 1, with an IV of 0.65 and a melt viscosity of 119 [Pa · sec]. PET / I pellets (measurement temperature 290 ° C., 12.16 sec ⁻¹ , melting point (Tm) 222 ° C.) were obtained. When this PET / I pellet was used for melt spinning, it was vacuum-dried at 130 ° C. for 24 hours.
<Composite spinning>
As in Comparative Example 3, a core-sheath composite yarn as shown in FIG. 1 is obtained. When performing core-sheath composite spinning, 35% by weight of FCB (Examples 15 and 18) or 30% by weight is disposed as the core component. (Examples 16, 17, 19, 20) PLA-FCB composed of PLA-1 contained therein, as shown in Table 3, core component (PLA-FCB) and sheath component (Examples 15 to 17: Toray Industries, Inc.) The composite ratio of polybutylene terephthalate (type 1300S, melting point (Tm) 225 ° C., hereinafter referred to as PBT), Examples 18 to 20: PET / I) was changed, and Examples 15 to 17 had a spinning temperature of 265 ° C. In Examples 18 to 20, except that melt spinning was performed at a spinning temperature of 275 ° C., the same discharge amount (the same volume per unit time [cc / Min]) and Thus, with respect to the stretching conditions, fibers were obtained in the same manner as in Comparative Example 3 except that the first roller was set to 80 ° C. and the second roller was set to 130 ° C. at all levels in Examples 15 to 20. . The physical properties of the obtained fiber were excellent in electrical conductivity and excellent in high temperature heat resistance. Table 3 shows the yarn physical properties.

Examples 21-25
In the same manner as in Comparative Example 3, the core-sheath composite yarn as shown in FIG. 1 is obtained. When performing core-sheath composite spinning, the composite spinning method as shown in Table 4 (Examples 21 and 23 are sea-island composite spinning as shown in FIG. 2). Examples 22 and 24 are sea-island composite spinning, in which island components are partially exposed on the fiber surface), conductive agent species and content (Example 23: Ketjen Black EC manufactured by Ketjen Black International Co., Ltd.) Specific resistance value 0.2 [Ω · cm], average particle diameter 31 nm, hereinafter KCB, Example 24: carbon nanotube, hereinafter CNT, Example 25: tin oxide containing (doped) antimony oxide The same as in Comparative Example 3 except that the composite ratio of the core and the sheath (or the sea and the island) and the content of each conductive agent in the aliphatic polyester were changed. Thus, at a spinning temperature of 265 ° C., the same discharge amount (the same volume amount [cc / min] per unit time) is used in the spinning process, and the stretching conditions are the same as in Example 1. Fibers were obtained at the (rolling roller speed and roller temperature). Here, the production of CNTs was obtained by supplying titanosilicate powder treated with ferrous acetate and cobalt acetate as a zeolite catalyst and supplying ultrapure acetylene gas at 10 ml / min in an argon gas atmosphere at 900 ° C. . Even if the type and composite form of the conductive agent were changed, there was no problem with the yarn forming property, conductivity, and high temperature heat resistance. Table 4 shows the yarn physical properties.

Examples 26-28
0.1% by weight of triphenyl phosphite and 0.01% by weight of antimony trioxide were added to glycolic acid, and dehydrated by heating at 200 ° C. for about 1.5 hours in a nitrogen gas atmosphere. Subsequently, it heated up to 220 degreeC, reducing pressure to 0.1-0.6 kPa, stirring over 45 minutes. After reaching 220 ° C., the degree of vacuum was increased as much as possible and continued for 10 hours. Meanwhile, when the polymer solidified, it was heated to 245 ° C. and melted. The obtained polymer is once cooled and pulverized, heated and remelted, and heated under stirring at 220 ° C. for 24 hours to remove residual glycolide to obtain polyglycolic acid (hereinafter PGA). It was. In preparing the conductive agent-containing PGA by the same method as in Example 2, the same equipment such as the same FCB type and FCB addition amount (20% by weight) was used in the same apparatus except for kneading at 250 ° C. Pellets of a resin composition of PGA and FCB (hereinafter referred to as PGA-FCB) having a viscosity of 1625 [Pa · sec] (measurement temperature: 250 ° C., 12.16 sec ⁻¹ ) were obtained. When the (average) specific resistance value of the gut of the resin composition not formed into pellets was measured, it was 10 ^2.31 [Ω · cm].
Then, when performing composite spinning similar to Comparative Example 3, using this PGA-FCB as an island component, Examples 26 and 27 were set at a spinning temperature of 260 ° C., Example 28 was set at a spinning temperature of 270 ° C. Except for the ratios as shown in Table 4, respectively, under the same spinning conditions as in Comparative Example 3, in the spinning process, the same discharge amount (the same volume amount [cc / min] per unit time) was obtained. Regarding the stretching conditions, fibers were obtained under the same conditions as in Example 1 (stretching roller speed and roller temperature). Even if the type of the aliphatic polyester was changed, there was no problem in the spinning property, conductivity, and high temperature heat resistance. Table 4 shows the yarn physical properties.

Example 29
The fibers obtained in Examples 1 to 28 were cut into short fibers having average fiber lengths of 0.5, 1.0, and 2.0 mm, respectively, and then colloidal silica manufactured by Nissan Chemical Industries, Ltd. “ After processing with “Snowtex OS (registered trademark)”, a polyester film “Lumirror (registered trademark) QT33 (thickness: 100 μm)” manufactured by Toray Industries, Inc., acrylic ester adhesive DICNAL K- manufactured by Dainippon Ink & Chemicals, Inc. 1500 (100% by weight of K-1500 using 2% by weight of DICNAL VS-20 as a thickener; hereinafter referred to as “adhesive A”) is applied to one side of the film at a thickness of about 100 μm. Then, electric flocking was applied to one side of the film to which the adhesive was applied to produce a flocked body. About flocking property (degree of success of flocking), it is almost upright (double circle), some sleeping fibers are seen (○), about half of the fibers are sleeping (△), upright As a result of visually judging that there were few things (x) and evaluating them, both were excellent as double circles.
Moreover, after performing twisting using each of the fibers obtained in Examples 1 to 28, a pile woven fabric was prepared, followed by raising treatment, and using the adhesive A as described above, the polyester film described above The fabric composites were prepared respectively. All the raising properties were excellent.

Example 30
Fabrics were produced at a weaving density of 150 yarns / inch using the fibers produced in Examples 6, 12, 13, 14, and 22 as warps and wefts, and electrodes were provided at both ends so as to have a length of 20 cm and a width of 5 cm. When a fabric object having a length of 20 cm is regarded as a wiring object and a voltage of 100 V is applied to both electrodes, 1.1 ° C./min, 1.9 ° C./min, 3.6 ° C./min, and 5.1 ° C., respectively. The heating element increased in temperature at a heating rate of 0.9 ° C./min.

Example 31
Using the fibers obtained in Examples 1 to 28, short fibers having an average fiber length of 2 mm were prepared, and using the adhesive A of Example 29, a metal rod-like object A made of SUS304 and a urethane made of SUS304 Each of the metal rod-like objects B provided with an intermediate layer (thickness of 1.5 mm and covered with 2 cm of the metal rod end) is subjected to electric flocking (the metal rod-like object B is applied only to the intermediate layer portion). ) After sweeping unbonded short fibers from the rod-like objects, brush rollers were obtained (A1 to A28, B1 to B28). Moreover, a pile woven fabric was produced using what twisted like Example 29 using Examples 1-4, 7-10, 15, 16, 18, 19, 23, 25-27, and pile was made. The raised pile fabric made into a 1 cm wide slit was wound around the metal rod-like object A, and brush rollers (C1 to C4, C7 to C10, C15, C16, C18, C19, C23). , C25-C27).

Example 32
Among the brush rollers obtained in Example 31, C1, C2, C3, C7 to C10, C15, C18, and C25 were each printed continuously for a long time by a monochrome laser printer installed in a cleaning device (10 per minute). When the printability was confirmed along with the humidity change in the printer, the humidity in the printer dropped from the initial 65% to 31% and about 10,000 sheets were printed. However, even when the number of printed sheets exceeded 20000, the sharpness of printing and the toner cleaning performance were all excellent. Further, among the brush rollers, C4, C16, C19, C23, C26, and C27 were each incorporated into a charging device and examined in the same manner. As a result, even when all the printed sheets exceeded 30,000, the sharpness of printing was high. It was excellent.

Example 33
Using each of the fibers obtained in Examples 1, 4-6, 11-14, 16, 17, 19, 20, 22, using these fibers for all the warp and weft yarns (1 for one Y-shirt) Y-shirts (with various types of fibers used for warp and weft) were made, and 10 men selected at random were tested for monitor clothing. Especially for the Y-shirts made of the fibers obtained in Examples 12, 13, 14, and 22, all responded “I feel very cold when I wear them (I feel a strong feeling of cold contact)” did.

Example 34
Using the fibers obtained in Examples 1, 4 to 6, 11 to 14, 16, 17, 19, 20, and 22, carpets mainly formed from nylon 6 containing 10% by weight of these fibers (size 1 m × 1m), wearing leather shoes made of synthetic leather that is not subjected to conductive processing, etc., and stepping 100 times in an atmosphere of 23 ° C and 55% humidity. The experiment of touching the doorknob showed no electrostatic discharge.

It is a cross-sectional view of the fiber obtained by Examples 1-20 of this invention and Comparative Examples 3-6. It is a cross-sectional view of the fiber obtained by Example 21,23,26,27 of this invention. It is a cross-sectional view of the fiber obtained by Example 22, 24, 28 of this invention.

Explanation of symbols

1: Aliphatic polyester containing conductive agent 2: Aromatic polyester

Claims (7)

An aliphatic polyester fiber comprising an aliphatic polyester and an aromatic polyester containing a conductive agent, and an average resistivity P of 1.0 × 10 ¹² [Ω / cm] or less.   2. The aliphatic polyester fiber according to claim 1, wherein the aliphatic polyester contains lactic acid as a main repeating structural unit.   The aliphatic polyester fiber according to claim 1 or 2, wherein an initial tensile elastic modulus is 15 cN / dtex to 80 cN / dtex.   4. The aliphatic polyester fiber according to claim 1, wherein a ratio R (R = Q / P) of the average resistivity P to the standard deviation Q of the resistivity is 0.5 or less. .   The ratio Z (Z = Y / X) of the average resistivity X [Ω / cm] at 23 ° C. and 55% humidity to the average resistivity Y [Ω / cm] at 10 ° C. and 15% humidity is 1 It is the range of -5, The aliphatic polyester fiber of any one of Claims 1-4 characterized by the above-mentioned.   An aliphatic polyester fiber product comprising the aliphatic polyester fiber according to any one of claims 1 to 5 at least in part.   An aliphatic polyester fiber brush comprising at least a part of the aliphatic polyester fiber according to any one of claims 1 to 5.

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