WO2001007713A1 - Papier de fibres de polyamide entierement aromatique, son procede de fabrication et feuilles laminees en etant faites - Google Patents

Papier de fibres de polyamide entierement aromatique, son procede de fabrication et feuilles laminees en etant faites Download PDF

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Publication number
WO2001007713A1
WO2001007713A1 PCT/US2000/017891 US0017891W WO0107713A1 WO 2001007713 A1 WO2001007713 A1 WO 2001007713A1 US 0017891 W US0017891 W US 0017891W WO 0107713 A1 WO0107713 A1 WO 0107713A1
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WO
WIPO (PCT)
Prior art keywords
paper
aromatic polyamide
fiber
fiber paper
polyamide fiber
Prior art date
Application number
PCT/US2000/017891
Other languages
English (en)
Inventor
Hiroyuki Suzuki
Lee James Hessler
Christopher Roger Whitfield
Original Assignee
E. I. Du Pont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by E. I. Du Pont De Nemours And Company filed Critical E. I. Du Pont De Nemours And Company
Priority to KR1020027000302A priority Critical patent/KR20020047088A/ko
Priority to AU58990/00A priority patent/AU5899000A/en
Priority to EP00944985A priority patent/EP1208267A1/fr
Publication of WO2001007713A1 publication Critical patent/WO2001007713A1/fr

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0275—Fibers and reinforcement materials
    • H05K2201/0278—Polymeric fibers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0275—Fibers and reinforcement materials
    • H05K2201/0293—Non-woven fibrous reinforcement

Definitions

  • the present invention pertains to a completely aromatic polyamide fiber paper that comprises completely aromatic polyamide fiber.
  • the paper can be used to manufacture the substrate of an electric circuit.
  • the fiber paper of the present invention is useful in the fields, which have high requirements for electric insulation reliability under high humidity, dimensional stability, soldering heat resistance, and strength.
  • a base material made of completely aromatic polyamide fiber paper characterized by the following facts: the fiber paper is mainly composed of completely aromatic polyamide fiber formed by spinning from an anisotropic polymer solution and which is capable of deionization; the crystallinity of the fiber paper is 45% or higher; and the crystal size (ACS: Apparent Crystallinity Size (plane 110) is 50 A or larger.
  • Completely aromatic polyamide fiber is widely used in industry and daily life because of its high strength, high modulus, high heat resistance, and other excellent mechanical and thermal properties.
  • Typical examples of such synthetic fiber include polyparaphenylene terephthalamide fiber and polyparaphenylene benzobisoxazole fiber.
  • para-aromatic polyamide fiber is the aromatic polyamide fiber paper disclosed in Japanese Kokai Patent Application No. Hei 1 [1989] -281790 which is composed of an organic resin binder and a para-aromatic polyamide fiber, such as the paraphenylene/oxydiphenylene/terephthalamide copolymer fiber spun from an isotropic solution (Technora, product of Teijin Ltd.) and polyparaphenylene/terephthalamide fiber formed by air gap spinning from an anisotropic polymer solution (Kevlar, product of Toray DuPont Co., Ltd.).
  • a manufacturing method for aromatic polyamide fiber paper was disclosed in Japanese Kokai Patent Application No. Hei 2 [1990] -203589) .
  • the fiber paper made of the former fiber has a low heat resistance because the fiber starts to show thermal shrinkage at a temperature as low as about 200°C.
  • the substrate will be deformed when parts are installed on the substrate by means of reflow soldering performed at a high temperature.
  • the former fiber has a larger coefficient of thermal expansion in the radial direction than the latter fiber formed by spinning from anisotropic polymer solutions.
  • the fiber paper made from the former fiber is used as the base material of a circuit substrate, the dimensional change percentage in the thickness direction of the substrate increases, causing a problem in the reliability of through-hole connections for realizing electric conduction in the thickness direction in the substrate.
  • an organic thermosetting resin binder is used together with the aforementioned fibers to manufacture paper.
  • a para-aromatic polyamide fiber with high heat resistance and small dimensional change and spun from anisotropic polymer solution such as a homopolymer-type para-aromatic polyamide fiber (polyparaphenylene/terephthalamide fiber (Kevlar, product of Toray DuPont Co., Ltd.)), in this case.
  • the fiber paper formed using the aforementioned polyamide fibrids has high heat resistance and excellent post-heating dimensional stability.
  • the aforementioned fiber is manufactured using a spinning method, in which the polymer is spun in an acidic anisotropic polymer solution, followed by neutralization.
  • the ionic substances in the fibers are changed into salts.
  • the content of the salt is usually in the range of 0.5-1 wt% after the spinning operation, and the content of the salt is maintained on that same level even when the fibers are processed into paper.
  • the purpose of the present invention is to provide a type of completely aromatic polyamide fiber paper characterized by the following facts: the paper is made of completely aromatic polyamide fiber formed by spinning an anistropic polymer solution; the paper can be used as the base material for an electric circuit substrate; the fiber paper contains a small amount of ionic substance with little deposition of ionic substance; the fiber paper shows excellent electric insulation at high humidity and has high heat resistance and high post-heating stability; and the inflection point temperature of dimensional change percentage of the fiber paper is high.
  • the present invention uses a type of completely aromatic polyamide fiber formed by spinning an anisotropic polymer solution and having high heat resistance and excellent dimensional stability.
  • the ionic substance contained in the fibers can be washed out with water, and the fiber can be deionized if spinning is carried out under such a condition that the crystal size of the fiber is smaller than a certain level.
  • the deionized fiber of this invention can be processed into a pulp consisting of short fibers or fibrils, which are combined with a binder having high heat resistance. In this way, it is possible to perform a heat treatment for the obtained fiber paper at a high temperature. Also, the crystallinity, heat resistance, dimensional stability, and moisture resistance of the fiber paper can be improved. The content of the ionic substance and deposition of the ionic substance can be reduced.
  • the fiber paper of the present invention shows excellent electric insulation in an environment with high humidity. Any completely aromatic polyamide fiber formed by spinning an anistropic polymer solution can be used in the present invention.
  • the aromatic polyamide fiber used in the present invention is aromatic polyamide obtained by spinning an anistropic polymer solution. It is preferable to manufacture the fiber from a polymer with a number- average molecular weight in the range of 20,000-25,000 and formed by condensation polymerization of paraphenylenediamine and terephthalic dichloride.
  • the conventional air gap spinning of an anisotropic solution can be used to form the fiber from the polymer.
  • a viscous solution prepared by dissolving the polymer in a concentrated sulfuric acid solvent, is spun from a spinning nozzle through an air gap and into a coagulating bath.
  • the shearing speed is preferably in the range of 25,000-50,000 sec "1 .
  • the fiber is washed with water after the sulfuric acid used as the solvent is neutralized with an aqueous solution of sodium hydroxide immediately after the spinning operation. Subsequently, the fiber is wound after it is dried/heat treated at
  • the crystal size of the obtained fiber is usually larger than 50 A and in the range of 55-75 A.
  • sodium sulfate is contained in the fiber during the neutralization treatment, and its content is in the range of 0.5-1.0 wt% in this stage.
  • the fiber in the present invention it is necessary to spin the fiber under appropriate drying/heat treating conditions so that the crystal size is smaller than 50 A, preferably in the range of 35-45 A. If the fiber has a crystal size in the aforementioned range, although the ionic substance is still contained in the fiber, it can be almost completely washed out of the fiber when the fiber is brought into contact with water or other liquids. As a result, when the obtained fiber is used for an electric circuit substrate, the electric insulation at high humidity is improved.
  • the size of the aromatic polyamide fiber used in the present invention should be in the range of 0.1-5 denier, or preferably in the range of 0.3-3 denier from the viewpoint of spinnability, cost effectiveness, and papermaking properties during the papermaking operation. If the fiber size is too large, papermaking properties and texture are poor. On the other hand, if the fiber size is too small, it is difficult to spin the fiber, leading to poor cost effectiveness.
  • the length of the short fiber used to manufacture the aromatic polyamide fiber paper of the present invention is preferably in the range of 1-50 mm, or in the range of 2-14 mm when the paper is manufactured using a wet method.
  • the fiber is too long, it is difficult to disperse the fibers during the papermaking operation, and the texture surface is not good enough to make the fiber paper a qualified base material for a circuit board substrate. On the other hand, if the fiber is too short, the fibers cannot be sufficiently interwoven. As a result, the paper strength and other mechanical properties are poor.
  • meta-aromatic polyamide fibrids As the binder in the present invention from the viewpoint of heat resistance and dimensional stability.
  • An example of meta-aromatic polyamide fibrids is polymetaphenylene isophthalamide or a copolymer or mixed polymer mainly composed of polymetaphenylene isophthalamide.
  • copolymerize terephthalic acid, paraphenylenediamine, and the like as a third component with the meta-aromatic polyamide the content of the third component should be 20 mol% or lower.
  • thermosetting resin such as epoxy resins, phenol resins, and melamine resins
  • the binder component in addition to the meta-aromatic polyamide fibrids as long as the purpose of the present invention is not affected by this resin.
  • the mixing ratio should be such that the amount of the para-aromatic polyamide short fiber is in the range of 60-97 wt%, and the amount of the meta-aromatic polyamide fibrids is in the range of 3-40 wt% with respect to the total weight of the aromatic polyamide fiber paper. If the content of the meta-aromatic polyamide fibrids is too low, the paper strength will be low during the papermaking process and the heat treatment, and the paper will be difficult to wind up.
  • the para-aromatic polyamide short fibers will fall off, and fuzz will occur on the surface of the paper, leading to a problem in quality.
  • the content of the binder be at least 5 wt%.
  • the meta-aromatic polyamide fibrids are softened and thus expand at high temperature during the heat treatment, to bond the para-aromatic polyamide fibers together.
  • the content of the binder should be 30 wt% or less.
  • para-aromatic polyamide short fiber In addition to the para-aromatic polyamide short fiber, it is also possible to add copolymer-type para-aromatic polyamide short fibers such as paraphenylene/3, 4-diphenylene copolymer ether terephthalamide short fiber (Technora, product of Teijin Ltd.) and polyparaphenylene benzobisoxazole short fiber, glass short fibers, ceramic short fibers and the like as long as the purpose of the present invention is not affected by these fibers. In this case, the content of the aforementioned materials should be 45 wt% or lower, or preferably 35 wt% or lower. In the following, the method used for manufacturing paper made of completely aromatic polyamide fiber formed by spinning an anisotropic polymer solution will be explained.
  • copolymer-type para-aromatic polyamide short fibers such as paraphenylene/3, 4-diphenylene copolymer ether terephthalamide short fiber (Technora, product of Teijin Ltd.)
  • para-aromatic polyamide short fibers and meta-aromatic polyamide fibrids are dispersed in water in an aforementioned ratio to obtain a homogeneous papermaking slurry.
  • the concentration of fiber in the dispersion is kept in the range of 0.1-1.0 wt% . If the concentration of fiber is too high, the fiber may not be well dispersed.
  • Paper is manufactured from the obtained dispersion using a flat wire type papermaking machine, cylinder wire type papermaking machine, inclined wire type papermaking machine, and the like.
  • the ionic substance contained in the para-aromatic polyamide short fiber used in the present invention is ionized when it contacts water and is then extracted from the fiber.
  • the ionic substance is discharged together with the water used in the papermaking process and the fiber is deionized.
  • the content of the ionic substance in the short fiber can be reduced to a level lower than 0.5 wt%.
  • the obtained fiber paper can display excellent electric insulation even at high humidity when it is used for an electric circuit substrate .
  • the paper has the following properties including density and strength, which have influence on the operation for manufacturing the substrate and the properties of the substrate.
  • the density of the paper is preferably in the range of 0.40-0.85 g/cm 3 . If the density is too low, it is difficult to obtain a high strength. Also, the dimensional stability is poor. Therefore, it is preferable that the density of the paper be 0.50 g/cm 3 or higher. On the other hand, if the density is too high, when the resin-impregnated pre-preg is manufactured, the resin enters the interior of the paper with difficulty, which adversely affects the properties of the substrate.
  • the density of the paper is preferably 0.75 g/cm 3 or lower. It is preferable that the strength of the paper be 1.5 kg/cm or higher so that the paper will not tear easily in the resin-impregnating operation to be described later.
  • the aromatic polyamide fiber paper with the aforementioned composition is used as an electric circuit substrate, in order to fully display heat resistance, post-heating dimensional stability, and post-humidification stability, it is necessary to perform a heat treatment after the paper is manufactured and to process the paper appropriately so that the characteristics of the paper are in the aforementioned ranges, respectively. For example, it is possible to use a calender machine to process the paper and control the temperature and pressure.
  • the paper is passed between calender rolls made from one-stage or multistage metal rolls under heat and pressure.
  • the temperature and pressure for softening the binder are in the range of 140-400°C and 30 kg/cm or higher, respectively. If the temperature and pressure are not kept in the aforementioned ranges, a fine paper structure cannot be obtained, and the strength of the paper reaches the aforementioned level with difficulty.
  • the conditions of the heat treatment should be set appropriately so that the crystallinity of the aromatic polyamide fiber paper of the present invention is 45 or higher, and the crystal size (ACS: Apparent Crystallinity Size (plane 110)) is 50 A or larger.
  • the fiber paper By promoting crystallization of the fiber paper, it is possible to restrain ionization of a small amount of the ionic substance left in the aromatic polyamide fiber at high humidity when the paper is used as an electric circuit substrate. Also, the heat resistance, dimensional stability, and moisture resistance of the fiber paper used as the base material for a circuit substrate can be improved significantly by forming a fine aromatic polyamide fiber crystal structure.
  • TEST METHODS Crystallinity and crystal size.
  • the diffraction intensity of a paper sample cut in a size of about 3 cm x 4 cm is measured using an X-ray diffraction device (PW1075/00, product of Philips Co.) under the conditions of 40 kv and 40 mA in a reflection mode.
  • the crystal size (ACS: Apparent Crystallinity Size) is equivalent to the diffraction intensity at a scanning angle of 20-21°. It is calculated from the following equation using the half-value width of the diffraction peak of plane (110).
  • the crystal size and crystallinity are calculated in the same way using the aforementioned method except that a paper sample with a length of 4 cm and a weight of 20 mg is fixed with a collodion solution before measurement is carried out.
  • the paper sample is incinerated with a gas burner or an electric oven.
  • the obtained incinerated substance is pyrolyzed in sulfuric acid, nitric acid, or hydrofluoride acid and is then dissolved in diluted nitric acid to obtain a solution.
  • the amount of cationic substance in the obtained solution is measured using the atomic absorption method.
  • the density of the paper is measured according to JIS P-8118.
  • the change in the length of a paper sample with a length of 200 mm and a width of 30 mm is measured.
  • the length of the paper sample is measured with an X-Y coordinate measuring device before the sample is heated and after the sample is heated at 300°C for 10 min .
  • the dimensional change percentage (%) of both MD and CD are calculated.
  • Dimensional change percentage (%) 100 x (length measured after heating - length measured before heating) / (length measured before heating)
  • the temperature at which the dimensional change of a paper sample with a length of 5 mm and a width of 2 mm increases significantly is measured.
  • the measurement is carried out using TMA (thermomechanical analysis device: product of TA Instrument Co.).
  • the temperature is raised from room temperature to 150°C at a heating rate of 10°C/min under a load of 2 g, it is then dropped and then raised again at a rate of 10°C/min.
  • the paper sample is heated to 350°C.
  • the temperature at which the constant dimensional change rate varies significantly is taken as the inflection point temperature of dimensional change.
  • the insulation reliability of the fiber paper used as an electric circuit substrate at high humidity is determined by evaluating the extraction state of the ionic substance as ions.
  • the ionic substance is extracted using the following method. About 5 g of paper sample are cut out and weighed accurately. After the paper sample is loaded in a flask, about 180 mL of ion exchange water are added. The flask is heated for 24 h, and the ions are extracted into the water. After cooling, the electroconductivity of the extracted liquid is measured with a conductivity meter and calculated as the value for every 5 g of sample.
  • An epoxy resin composition is prepared by adding dicyandiamide as curing agent and benzyl methyl amine as curing promoter in cresol novolac epoxy resin and bisphenol A epoxy resin used as the epoxy resin with which the aromatic polyamide fiber paper is impregnated. After the aromatic polyamide fiber paper is impregnated with a varnish prepared by dissolving the aforementioned epoxy resin composition in a methyl ethyl ketone solution, the paper is dried to obtain a B-stage pre-preg containing 53 wt% of resin.
  • the pre-preg is pressed by a vacuum heating press machine at 170°C under a pressure of 30 kg/cm 2 for 60 min to obtain a laminate.
  • a comb electrode pattern is formed by means of etching at a line width and interval of 200 ⁇ m on one side of the laminate.
  • B-stage pre-pregs impregnated with the aforementioned resin are arranged on both sides of the laminate, followed by pressing at 170°C under a pressure of 30 kg/cm 2 for 60 min using a vacuum heating press machine to obtain another laminate.
  • the substrate is allowed to stand at 110°C and 85%RH for 500 h and 1000 h while a DC voltage of 20 V is applied to the substrate. After the substrate is removed from the aforementioned high-temperature and high-humidity environment, it is allowed to stand at 20°C and 60%RH to recover to a normal state. Then, a DC voltage of 35 V is applied between the comb electrodes for 60 sec, and the insulating resistance of the substrate after treatment in the high-humidity environment is measured. The lowest resistance of each comb electrode is taken as the measured value.
  • soldering heat resistance of the copper foil laminate obtained in item 9, above is measured according to JIS C-6481.
  • a sample with a size of 10 mm x 10 mm is cut out from the substrate after the copper foil on each side of the copper foil laminate obtained in item 9, above, is removed by means of etching.
  • the coefficient of thermal expansion in the thickness direction is measured using TMA (thermomechanical analysis device: product of TA Instrument Co.). The temperature is raised from room temperature to 150°C at a heating rate of 10°C/min under a load of 2 g, then it is dropped and then raised again to 300°C at a rate of 10°C/min. The average coefficient of thermal expansion in the range from room temperature to 250°C is calculated.
  • the para-aromatic polyamide short fiber used for the completely aromatic polyamide fiber formed by spinning an anisotropic polymer solution was made of polyparaphenylene terephthalamide.
  • the content of the ionic substance in the short fiber was 0.36 wt% after spinning, and the short fiber was processed appropriately so that the crystal size on plane (110) was 40 A.
  • the size and length of the short fiber were 1.5 denier and 3 mm, respectively.
  • a polymetaphenylene isophthalamide solution was precipitated in a coagulating solution under high shear to obtain meta-aromatic polyamide fibrids.
  • the short fibers and the fibrids were dispersed homogeneously together with a dispersant in water to obtain a papermaking slurry with a fiber concentration of 0.2 wt%.
  • the short fiber was 90 wt% of the total short fibers and fibrids.
  • the slurry was processed with a TAPPI type square sheet machine, followed by dehydration to obtain a type of aromatic polyamide fiber paper with a basis weight of 70 g/cm 2 .
  • the fiber paper was subject to calender processing carried out under a linear pressure of 60 kg/cm 2 using a calender machine made of a pair of metal rolls heated to 300°C. Then, the paper was heated in a hot blast stove at 300°C for about 2 min.
  • a resin-impregnated pre-preg was formed using the obtained fiber paper following the method described above.
  • a substrate for an electric circuit was formed using the obtained pre-preg.
  • the characteristics of the completely aromatic, synthetic fiber paper and the characteristics of the substrate used for an electric circuit are listed in Table I.
  • the para-aromatic polyamide short fiber used for the completely aromatic polyamide fiber formed by means of liquid crystal spinning was made of polyparaphenylene terephthalamide.
  • the content of the ionic substance in the short fiber was 0.36 wt% after spinning, and the short fiber was processed appropriately so that the crystal size on plane (110) was 40 A.
  • the size and length of the short fiber were 1.5 denier and 3 mm, respectively.
  • Para-aromatic polyamide fiber paper was manufactured in the same way as described in Application Example 1 except instead of meta-aromatic polyamide fibrids, that the paper was coated with an aqueous solution of bisphenol-type water dispersible epoxy resin and processed appropriately so that the amount of the attached epoxy resin was 10 wt%.
  • the content of the short fiber in the coated paper system was 90 wt%.
  • a resin-impregnated pre-preg was formed using the obtained fiber paper following the method described above.
  • a substrate for an electric circuit was formed using the obtained pre-preg.
  • the characteristics of the completely aromatic polyamide fiber paper and the characteristics of the substrate used for an electric circuit are listed in Table I.
  • a type of para-aromatic polyamide fiber paper was manufactured in the same way as described in Application Example 1 except for using a different type of short fiber.
  • the para-aromatic polyamide short fiber (Kevlar, product of Toray DuPont Ltd.) used for the completely aromatic polyamide fiber formed by spinning an anisotropic polymer solution was made of polyparaphenylene terephthalamide.
  • the content of the ionic substance that had gone through drying heat treatment after spinning was 0.5 wt% .
  • the crystal size on plane (110) was 55 A.
  • the size and length of the short fiber were 1.5 denier and 3 mm, respectively.
  • the content of the short fibers in the resulting paper was 90 wt% of the total short fibers and fibrids.
  • a resin-impregnated pre-preg was formed using the fiber paper following the method described above.
  • a substrate for an electric circuit was formed using the obtained pre-preg.
  • the characteristics of the completely aromatic polyamide fiber paper and the characteristics of the substrate used for an electric circuit are listed in Table I. Comparative Example 2
  • a type of para-aromatic polyamide fiber paper was manufactured in the same way as described in Application Example 1 except for using a different type of short fiber.
  • the para-aromatic polyamide short fiber used in this case was manufactured using a method other than by spinning an anisotropic polymer solution.
  • the short fiber was made of paraphenylene/3, 4-oxydiphenylene/terephthalamide copolymer (Technora, product of Teijin Ltd.).
  • the size and length of the short fiber were 1.5 denier and 3 mm, respectively.
  • the content of the short fiber in the resulting paper was 90 wt% of the total short fibers and fibrids.
  • a resin-impregnated pre-preg was formed using the obtained fiber paper following the method described above.
  • a substrate for an electric circuit was formed using the obtained pre-preg.
  • the characteristics of the completely aromatic polyamide fiber paper and the characteristics of the substrate used for an electric circuit are listed in Table I .
  • a type of para-aromatic polyamide fiber paper was manufactured in the same way as described in Application Example 1 except for the following facts.
  • the para-aromatic polyamide short fiber used in this case was manufactured using a method other by spinning an anisotropic polymer solution.
  • the short fiber was made of paraphenylene/3, 4-oxydiphenylene/terephthalamide copolymer (Technora, product of Teijin Ltd.).
  • the size and length of the short fiber were 1.5 denier and 3 mm, respectively.
  • the content of the short fiber in the resulting paper was 90 wt% of the total short fibers and fibrids.
  • the paper was coated with an aqueous solution of bisphenol-type water dispersible epoxy resin and processed appropriately so that the amount of the attached epoxy resin was 10 wt% .
  • a resin-impregnated pre-preg was formed using the obtained fiber paper following the method described above.
  • a substrate for an electric circuit was formed using the obtained pre-preg.
  • the characteristics of the completely aromatic polyamide fiber paper and the characteristics of the substrate used for an electric circuit are listed in Table I.

Abstract

L'invention porte sur un type de papier de fibres consistant en fibres de polyamide entièrement aromatique obtenues par centrifugation de cristaux liquides. Ledit papier, qui peut servir de substrat de circuits électriques, est un isolant très fiable en présence de forte humidité présentant une excellente stabilité dimensionnelle après chauffage, et une résistance élevée à la chaleur.
PCT/US2000/017891 1999-07-22 2000-06-29 Papier de fibres de polyamide entierement aromatique, son procede de fabrication et feuilles laminees en etant faites WO2001007713A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020027000302A KR20020047088A (ko) 1999-07-22 2000-06-29 전방향족 폴리아미드 섬유지 및 이로부터 제조된 적층시이트
AU58990/00A AU5899000A (en) 1999-07-22 2000-06-29 Wholly aromatic polyamide fiber paper and laminated sheet therefrom
EP00944985A EP1208267A1 (fr) 1999-07-22 2000-06-29 Papier de fibres de polyamide entierement aromatique, son procede de fabrication et feuilles laminees en etant faites

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP11208033A JP2001049593A (ja) 1999-07-22 1999-07-22 全芳香族合成繊維からなる繊維紙及びその製造方法及び積層板
JP11/208033 1999-07-22

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WO2001007713A1 true WO2001007713A1 (fr) 2001-02-01

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EP (1) EP1208267A1 (fr)
JP (1) JP2001049593A (fr)
KR (1) KR20020047088A (fr)
CN (1) CN1364208A (fr)
AU (1) AU5899000A (fr)
WO (1) WO2001007713A1 (fr)

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US20110174452A1 (en) * 2008-07-22 2011-07-21 Peizhi Heng Base paper of aramid fiber honeycomb core and manufacturing method thereof

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ES2668652T3 (es) * 2011-01-04 2018-05-21 Teijin Aramid B.V. Papel aislante eléctrico
CN103897389A (zh) * 2012-12-26 2014-07-02 钦焕宇 一种芳纶纤维阻燃板及其制备方法
CN108570877A (zh) * 2017-03-14 2018-09-25 南京新莱尔材料科技有限公司 一种高频高速电路板用对位芳纶基半固化片的制造方法
CN107498952B (zh) * 2017-08-01 2019-10-18 华南理工大学 间位芳纶纤维/玻璃纤维纸基覆铜箔层压板及其制造方法
CN110154464A (zh) * 2019-06-14 2019-08-23 赣州龙邦材料科技有限公司 芳纶纸基挠性覆铜板及其制造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4511623A (en) * 1982-08-30 1985-04-16 Korea Advanced Institute of Science and Technology, 200-43 Highly oriented aromatic polyamide short fiber
EP0348996A2 (fr) * 1988-06-30 1990-01-03 E.I. Du Pont De Nemours And Company Procédé et dispositif pour la fabrication de pulpe de para-aramide et pulpe produite par ce procédé
WO1999013140A1 (fr) * 1997-09-09 1999-03-18 E.I. Du Pont De Nemours And Company Fibre entierement synthetique et aromatique produite par filage des cristaux liquides, procede de production et d'utilisation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4511623A (en) * 1982-08-30 1985-04-16 Korea Advanced Institute of Science and Technology, 200-43 Highly oriented aromatic polyamide short fiber
EP0348996A2 (fr) * 1988-06-30 1990-01-03 E.I. Du Pont De Nemours And Company Procédé et dispositif pour la fabrication de pulpe de para-aramide et pulpe produite par ce procédé
WO1999013140A1 (fr) * 1997-09-09 1999-03-18 E.I. Du Pont De Nemours And Company Fibre entierement synthetique et aromatique produite par filage des cristaux liquides, procede de production et d'utilisation
EP1020547A1 (fr) * 1997-09-09 2000-07-19 E.I. Du Pont De Nemours And Company Fibre entierement synthetique et aromatique produite par filage des cristaux liquides, procede de production et d'utilisation

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7015159B2 (en) 2001-07-24 2006-03-21 E. I. Du Pont De Nemours And Company Nonwoven material for low friction bearing surfaces
US7247587B2 (en) 2001-07-24 2007-07-24 E. I. Du Pont De Nemours And Company Nonwoven material for low friction bearing surfaces
US7718691B2 (en) 2004-02-27 2010-05-18 Schering Corporation Compounds as inhibitors of hepatitis C virus NS3 serine protease
US20110174452A1 (en) * 2008-07-22 2011-07-21 Peizhi Heng Base paper of aramid fiber honeycomb core and manufacturing method thereof
US8764941B2 (en) * 2008-07-22 2014-07-01 Longpoint Co., Ltd. Base paper of aramid fiber honeycomb core and manufacturing method thereof

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EP1208267A1 (fr) 2002-05-29
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JP2001049593A (ja) 2001-02-20
AU5899000A (en) 2001-02-13

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