Classifications

• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H5/00—Special paper or cardboard not otherwise provided for
  • D21H5/12—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
  • D21H13/10—Organic non-cellulose fibres
  • D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D21H13/26—Polyamides; Polyimides
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
  • D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
  • D21H15/08—Flakes
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
  • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/20—Conductive material dispersed in non-conductive organic material
  • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
• • H—ELECTRICITY
  • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
  • H02K—DYNAMO-ELECTRIC MACHINES
  • H02K3/00—Details of windings
  • H02K3/32—Windings characterised by the shape, form or construction of the insulation
  • H02K3/40—Windings characterised by the shape, form or construction of the insulation for high voltage, e.g. affording protection against corona discharges
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
  • D21H13/36—Inorganic fibres or flakes
  • D21H13/46—Non-siliceous fibres, e.g. from metal oxides
  • D21H13/50—Carbon fibres
• • H—ELECTRICITY
  • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
  • H02K—DYNAMO-ELECTRIC MACHINES
  • H02K3/00—Details of windings
  • H02K3/30—Windings characterised by the insulating material

Definitions

• the present invention relates to a conductive aramid useful as a rotating machine (generator, motor), in the field of transformers and in electrical and electronic equipment antistatic materials, in particular, as a corona generation preventing material of rotating machines, antistatic parts for electrical and electronic equipment, etc.
• the present invention relates to paper and a method of manufacturing the same.
• a material capable of alleviating the electric field generated between the coil and the insulating material is extremely important in order to ensure the reliability of the insulating system capable of suppressing corona generation.
• a method of reducing the electric field of a rotating machine to which a high voltage is applied a method of applying and impregnating a conductive paint on the outermost surface of an insulating layer is widely used.
• the properties are not necessarily good, the influence of solvent volatilization on the working environment can not be ignored, the operation takes a long time, and the reproducibility of the conductivity (resistance value).
• a method of winding or inserting a conductive thin film material for example, paper, film, tape, etc.
• a conductive thin film material for example, paper, film, tape, etc.
• the temperature rise of the devices is also large, and therefore, materials having high heat resistance are required.
• highly heat-resistant aramid paper is widely used as an electrical insulator or a thin leaf structure material, as an electric insulating material for the above-mentioned rotating machine (generator, motor), transformer field and electric / electronic equipment.
• the use of paper as an electric field relaxation material by imparting a certain degree of conductivity has also been considered.
• Patent Document 1 and Patent Document 2 disclose papers using aramid fibrids and carbon fibers or metal fibers. However, none of them are aimed at conductivity and mechanical strength because they do not aim at the above-mentioned electric field relaxation material. Further, Patent Document 3 discloses a low density and high strength conductive aramid paper which is composed of aramid short fibers, aramid fibrids, and conductive fillers such as carbon fibers.
• the present invention provides a corona suppressing material of a rotating machine, and further, an antistatic component for electric and electronic equipment and a conductive aramid paper having an electric field relaxation function and an antistatic function that can be favorably used as auxiliary materials during processing and assembly thereof.
• the purpose is
• the present invention also aims to provide a conductive aramid paper with good antistatic properties, improved mechanical properties and improved fuzziness.
• Another object of the present invention is to provide a method for efficiently producing the conductive aramid paper.
• the inventor appropriately combined an aramid staple fiber, an aramid fibrid and a conductive filler to obtain a density of 0.45 to 1.10 g / cm 3 and a tensile strength of 2.
• the conductive aramid paper has 5 kN / m or more and a surface resistivity of 1.0 ⁇ 10 1 to 5.0 ⁇ 10 2 ⁇ / ⁇
• the conductive aramid paper shows a sufficient effect for electric field relaxation. It has been found that the above problems can be solved by having a good antistatic function and improved mechanical properties, and the present invention has been accomplished.
• the first invention of the present application is a conductive aramid paper comprising aramid staple fibers, aramid fibrids and a conductive filler, wherein the density is 0.45 to 1.10 g / cm 3 and the tensile strength is 2 kN / m.
• the conductive aramid paper described above and having a surface resistivity of 1.0 ⁇ 10 1 to 5.0 ⁇ 10 2 ⁇ / ⁇ are provided.
• a second invention of the present application provides the conductive aramid paper according to the first invention, wherein the conductive aramid paper has a thickness of 20 to 100 ⁇ m.
• a third invention of the present application provides the conductive aramid paper according to the first or second invention, wherein the aramid short fiber and the aramid constituting the aramid fibrid are polymetaphenylene isophthalamides. It is.
• a fourth invention of the present application provides the conductive aramid paper according to any of the first to third inventions, wherein the conductive filler is a carbon fiber.
• a fifth invention of the present application relates to the conductive aramid paper according to any one of the first to fourth inventions, wherein aramid short fibers, aramid fibrids, and a conductive filler are mixed in water to form a sheet by a wet paper-making method Then, the resulting sheet is heated and pressed at a temperature of 330 ° C. or higher between a pair of metal rolls to provide a method for producing a conductive aramid paper.
• aramid means a linear polymer compound in which 60% or more of amide bonds are directly bonded to an aromatic ring.
• examples of such aramids include polymetaphenylene isophthalamide and copolymers thereof, polyparaphenylene terephthalamide and copolymers thereof, copolyparaphenylene 3,4'-diphenylether terephthalamide and the like.
• These aramids are industrially produced by, for example, a solution polymerization method by condensation reaction with an aromatic acid dichloride and an aromatic diamine, a two-step interfacial polymerization method, and the like.
• the form of the aramid used in the present invention is not particularly limited, but the form such as aramid fibrid, aramid short fiber, fibrillated aramid and the like is preferable.
• Examples of the aramid short fibers used in the present invention include those obtained by cutting a fiber made of aramid into a predetermined length, and examples of such fibers include “Teijin Conex (Teijin Techno Products Co., Ltd.) Acquired under the trade name of "registered trademark", “Technola (registered trademark)", “Nomex (registered trademark)” of DuPont, "Kevlar (registered trademark)", “Twallon (registered trademark)” of Teijin Aramid, etc. Although what can be mentioned is mentioned, it is not limited to these.
• Aramid staple fibers can preferably have a fineness in the range of not less than 0.05 dtex and less than 25 dtex. Fibers having a fineness of less than 0.05 dtex are not preferable because they tend to cause aggregation in the wet process (described later), and fibers having a fineness of 25 dtex or more have an excessively large fiber diameter, for example, Assuming that the density is 1.4 g / cm 3 in shape, if the diameter is 45 microns or more, disadvantages such as reduction in aspect ratio, reduction in mechanical reinforcement effect, and poor uniformity of conductive aramid paper may occur. .
• the length of the aramid short fiber can be selected from the range of 1 mm or more and less than 25 mm. If the length of the short fibers is smaller than 1 mm, the mechanical properties of the conductive aramid paper are deteriorated, while those having a length of 25 mm or more are "entangled" and "bonded” in the production of the conductive aramid paper by the wet method described later. It is not preferable because it is likely to occur and cause defects.
• the aramid fibrid used in the present invention is a film-like fine particle made of aramid and may be referred to as aramid pulp.
• aramid pulp As the manufacturing method, for example, the methods described in JP-B-35-11851, JP-B-37-5732, etc. are exemplified.
• Fibrids have the same papermaking properties as ordinary wood (cellulose) pulps, so after being dispersed in water, they can be formed into a sheet by a paper machine. In this case, so-called refining treatment can be performed in order to maintain the quality suitable for papermaking.
• This refining process can be carried out by means of a disc refiner, a beater, or any other paper cutting material processing device that exerts a mechanical cutting action.
• the morphological change of the fibrid can be monitored by the freeness as defined in JIS P8121.
• the freeness of the fibrid of the organic compound after being subjected to beating treatment is preferably in the range of 10 to 300 cm 3 (Canadian Standard Freeness). With a fibrid having a freeness larger than this range, the strength of the non-woven sheet formed therefrom may be reduced.
• the conductive filler used in the present invention has a wide range of conductivity from a conductor having a volume resistance of about 10 ⁇ 1 ⁇ ⁇ cm or less to a semiconductor having a volume resistance of about 10 ⁇ 1 to 10 8 ⁇ ⁇ cm.
• a fibrous or fine particle is mentioned.
• conductive fillers for example, materials having homogeneous conductivity such as metal fibers, carbon fibers, carbon black, or metal plated fibers, metal powder mixed fibers, carbon black mixed fibers, etc. conductive materials and non-conductive materials And materials which are mixed to exhibit conductivity as a whole, but are not limited thereto. Among these, in the present invention, it is preferable to use carbon fiber.
• the carbon fiber to be used in the present invention is preferably carbonized by firing a fibrous organic substance at high temperature in an inert atmosphere.
• carbon fibers are roughly classified into those obtained by firing polyacrylonitrile (PAN) fibers and those obtained by spinning and spinning pitch, but besides this, resins such as rayon and phenol are spun and then produced by firing. And they can also be used in the present invention. It is also possible to carry out an oxidation crosslinking treatment using oxygen etc. prior to firing to prevent fusion at the time of firing.
• the fineness of the carbon fiber used in the present invention is preferably in the range of 0.5 to 10 dtex.
• the fiber length is selected from the range of 1 mm to 20 mm.
• the conductive filler it is more preferable to use a material having high conductivity and exhibiting good dispersion in the wet sheet-forming method described later. Moreover, when selecting a carbon fiber, it is preferable to select the thing which is further high intensity
• the conductive aramid paper of the present invention is characterized by being composed of the above-mentioned aramid staple fibers, aramid fibrids, and a conductive filler.
• the content of aramid staple fibers in the total weight of the conductive aramid paper of the present invention is 5 to 60 wt%, preferably 10 to 55 wt%, more preferably 20 to 50 wt%, but is limited thereto It is not a thing.
• the content of aramid staple fiber is less than 5% by weight, the mechanical strength of the conductive aramid paper tends to decrease, and when it exceeds 60% by weight, the content of aramid fibrids decreases and the mechanical strength also decreases.
• the content of the aramid fibrid in the total weight of the conductive aramid paper of the present invention is 30 to 80 wt%, preferably 35 to 70 wt%, more preferably 40 to 65 wt%, but is limited thereto It is not a thing. In general, when the content of aramid fibrids is less than 30% by weight, the mechanical strength of the conductive aramid paper tends to decrease, and when it exceeds 80% by weight, the freeness decreases in the manufacture by a wet method (described later). And uniformity defects of the conductive aramid paper.
• the paper having a surface resistivity of 1.0 ⁇ 10 1 to 5.0 ⁇ 10 2 ⁇ / ⁇ which is the feature of the present invention
• the content of the conductive filler is 1 to 30% by weight, more preferably 2 to 20% by weight, and still more preferably 3 to 10% by weight.
• the content of the conductive filler is less than 1% by weight, it is difficult to obtain the surface resistance value in the above range, and generally, when it exceeds 30% by weight, the mechanical strength of the conductive aramid paper tends to decrease. And, it becomes difficult to produce homogeneous paper without using complicated methods.
• the density of the conductive aramid paper of the present invention is a value calculated from (basis weight / thickness) specified by JIS C 2300-2 and is a value within the range of 0.45 to 1.10 g / cm 3 It is characterized by taking If the density is less than 0.45 g / cm 3 , it is necessary to increase the basis weight to increase mechanical strength, which is not preferable because the thickness is increased, and if it exceeds 1.10 g / cm 3 , the paper Since the amount of voids inside is reduced, for example, it is not suitable for applications where resin is impregnated and used, and it is not preferable because it becomes difficult to manufacture.
• the density of the conductive aramid paper of the present invention is preferably 0.50 to 1.00 g / cm 3 .
• the tensile strength of the conductive aramid paper of the present invention is characterized by being 2.5 kN / m or more, preferably 3.0 kN / m or more. When the tensile strength is less than 2.5 kN / m, for example, when a tape produced using the paper of the present invention is wound around a coil conductor or the like using an automatic tape winding machine, tears, tears, etc. Can happen.
• the tensile strength of the conductive aramid paper of the present invention is more preferably 3.5 to 10.0 kN / m.
• the conductive aramid paper of the present invention is characterized by having a surface resistivity of 1.0 ⁇ 10 1 to 5.0 ⁇ 10 2 ⁇ / ⁇ , preferably 5.0 ⁇ 10 1 to 5.0 ⁇ 10 It is 2 ⁇ / ⁇ , more preferably 5.0 ⁇ 10 1 to 4.0 ⁇ 10 2 ⁇ / ⁇ . If the surface resistivity is less than 1.0 ⁇ 10 1 ⁇ , it is necessary to increase the content of the conductive filler in order to obtain the surface resistivity, which makes it difficult to obtain sufficient mechanical strength.
• the thickness of the conductive aramid paper is not particularly limited, but generally, the thickness is preferably in the range of 20 ⁇ m to 100 ⁇ m, and more preferably 30 to 80 ⁇ m. If the thickness is smaller than 20 ⁇ m, the mechanical properties are deteriorated, which tends to cause problems in handling such as transportation in the manufacturing process. On the other hand, if it exceeds 100 ⁇ m, space saving, for example, when installing in an electric device or conductor Is an obstacle to The basis weight of the conductive aramid paper is preferably 10 to 110 g / m 2 .
• the conductive aramid paper of the present invention having the performance as described above can generally be produced by mixing the above-mentioned aramid staple fiber, aramid fibrid and conductive filler and then forming a sheet.
• a method of forming a sheet using air flow, aramid short fibers, aramid fibrids and conductive filler After dispersion and mixing in a liquid medium, it is possible to apply a method in which the sheet is discharged onto a liquid-permeable support, such as a net or belt, to form a sheet, and the liquid is removed and dried.
• a liquid-permeable support such as a net or belt
• the aqueous slurry of a single or a mixture of at least aramid staple fibers, aramid fibrids, and conductive fillers is sent to a paper machine and dispersed, and then subjected to dehydration, water squeezing and drying operations.
• As the papermaking for example, a Fourdrinier paper machine, a cylinder paper machine, an inclined paper machine, a combination paper machine combining these, etc. can be used.
• a composite sheet comprising a plurality of paper layers by sheet-forming and uniting aqueous slurries of different blending ratios.
• additives such as a dispersibility improver, an antifoaming agent, a paper strengthening agent and the like may be used as needed, and when the conductive filler is a particulate matter, it is acrylic Although resins, fixing agents, polymer flocculants and the like may be added, care should be taken in their use so as not to hinder the purpose of the present invention.
• conductive aramid paper of the present invention other fibrous components other than the above components, for example, polyphenylene sulfide fiber, polyether ether ketone fiber, cellulose fiber, polyvinyl, as long as the object of the present invention is not impaired.
• Organic fibers such as alcohol fibers, polyester fibers, polyarylate fibers, liquid crystal polyester fibers, polyimide fibers, polyamideimide fibers, polyparaphenylene benzobisoxazole fibers, and inorganic fibers such as glass fibers, rock wool and boron fibers may also be added. it can.
• the mechanical strength of the conductive aramid paper thus obtained can be improved, for example, by hot-pressing at a high temperature and a high pressure between a pair of flat plates or between metal rolls.
• the conditions of the hot-pressing process can be exemplified by a temperature of 100 to 400 ° C. and a linear pressure of 50 to 1000 kg / cm in the case of using a metal roll, for example, but the characteristics of the conductive aramid paper of the present invention
• the roll temperature is preferably 330 ° C. or higher, more preferably 330 ° C. to 380 ° C., in order to obtain high tensile strength and surface smoothness.
• the linear pressure is preferably 50 to 500 kg / cm.
• this temperature is higher than the glass transition temperature of meta-aramid and close to the crystallization temperature of meta-aramid, not only mechanical strength is improved by heat-pressing at this temperature, but also conductive aramid paper
• conductive aramid paper By firmly adhering the constituent materials to each other, for example, when the conductive filler is a carbon fiber, scattering thereof can be prevented, and direct contact with the fiber or a site where the conductive aramid paper is used or used.
• the adhesion to the skin due to the scattering of fibers and the skin irritation such as itching and pain due to it can be suppressed, and the deterioration of the working environment can be prevented.
• the above-mentioned hot-pressing process may be performed several times, and depending on the application, it may not be necessary to save the space excessively and may sometimes need a thickness exceeding 100 ⁇ m.
• a plurality of sheets obtained by the above-mentioned method may be stacked to perform heat and pressure processing.
• the conductive aramid paper of the present invention has (1) appropriate conductivity, (2) heat resistance and flame retardancy, and (3) sufficient application to automatic tape winding machines and the like. It has excellent properties such as high tensile strength that can be used, (4) low skin irritation, etc., and in particular, corona generation preventing materials such as high-voltage large-sized rotating machines, electric and electronic It can be suitably used as an antistatic component or the like of equipment.
• the portion 10 cm was rubbed only 10 times in one direction at a reciprocating speed of 30 times per minute 30 times a minute, and the state of the sheet after the friction was visually determined in the following manner.
• ⁇ no fuzz
• ⁇ slight fuzzing
• ⁇ fuzzing
• a polymethaphenylene isophthalamide fibrid was produced by a method using a wet precipitator composed of a combination of a stator and a rotor as described in Japanese Patent Publication No. 52-15621. This was treated with a beating machine to adjust the length-weighted average fiber length to 0.9 mm (freeness 200 cm 3 ). On the other hand, a Dupont meta-aramid fiber (Nomex (registered trademark), single yarn fineness 2.2 dtex) was cut into a length of 6 mm to be used as a material for papermaking.
• Nomex registered trademark
• Examples 1 to 4 Meta-aramid fibrids, meta-aramid staple fibers, and carbon fibers prepared as described above (manufactured by Toho Tenax Co., fiber length 3 mm, single fiber diameter 7 ⁇ m, fineness 0.67 dtex, volume resistivity 1.6 ⁇ 10 ⁇ 3 ⁇ ⁇ Each slurry was dispersed in water to prepare a slurry. The slurry is mixed with meta-aramid fibrids, meta-aramid staple fibers, and carbon fibers so as to obtain the mixing ratio shown in Table 1, and treated with a tappy-type hand paper machine (cross-sectional area 325 cm 2 ) to give a sheet Was produced.
• Example 5 The sheet obtained in the same manner as in Example 1 was hot-pressed at a temperature of 350 ° C. and a linear pressure of 150 kg / cm by a pair of metal calender rolls to obtain a conductive aramid paper.
• the main characteristic values of the conductive aramid paper thus obtained are shown in Table 1.
• Comparative Example 1 A slurry of the meta-aramid fibrid, meta-aramid staple fiber, and carbon fiber ("Torayca (registered trademark)" chopped fiber (fiber length 6 mm, single fiber diameter 7 ⁇ m) prepared as described above dispersed in water) was produced. Using this slurry, in the same manner as in Reference Example 2 described in JP-A-11-20083, it was treated with a tappy type hand-made machine (cross-sectional area 325 cm 2 ) to prepare a sheet. Next, the obtained sheet was hot-pressed at a temperature of 330 ° C. and a linear pressure of 150 kg / cm by a pair of metal calender rolls to obtain a conductive aramid paper.
• Torayca (registered trademark) chopped fiber (fiber length 6 mm, single fiber diameter 7 ⁇ m) prepared as described above dispersed in water
• the main characteristic values of the conductive aramid paper thus obtained are shown in Table 2.
• Comparative Example 2 The sheet obtained in the same manner as in Example 1 was brought into contact with a metal roll heated to 320 ° C. for 7 seconds to obtain a conductive aramid paper. The main characteristic values of the conductive aramid paper thus obtained are shown in Table 2.
• Comparative Example 3 A sheet obtained in the same manner as in Example 1 was hot-pressed at a temperature of 250 ° C. and a linear pressure of 150 kg / cm by a pair of metal calender rolls to obtain a conductive aramid paper. The main characteristic values of the conductive aramid paper thus obtained are shown in Table 2.
• a conductive aramid which has suitable conductivity and is excellent in heat resistance, flame retardancy and mechanical strength, which is useful as a corona generation preventing material such as a large rotating machine of high voltage, an antistatic component of electric and electronic equipment, etc.
• a corona generation preventing material such as a large rotating machine of high voltage, an antistatic component of electric and electronic equipment, etc.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Power Engineering (AREA)
• Physics & Mathematics (AREA)
• Dispersion Chemistry (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Inorganic Chemistry (AREA)
• Paper (AREA)
• Insulation, Fastening Of Motor, Generator Windings (AREA)

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• 2011
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