WO2009093412A1 - Article en feuille à module à résistance et à élasticité élevées - Google Patents

Article en feuille à module à résistance et à élasticité élevées Download PDF

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Publication number
WO2009093412A1
WO2009093412A1 PCT/JP2009/000081 JP2009000081W WO2009093412A1 WO 2009093412 A1 WO2009093412 A1 WO 2009093412A1 JP 2009000081 W JP2009000081 W JP 2009000081W WO 2009093412 A1 WO2009093412 A1 WO 2009093412A1
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WO
WIPO (PCT)
Prior art keywords
fabric
strength
unit
resin
sheet
Prior art date
Application number
PCT/JP2009/000081
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English (en)
Japanese (ja)
Inventor
Takashi Katayama
Shinya Inada
Yoshinori Hitomi
Ushio Suzuki
Original Assignee
Kuraray Co., Ltd.
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Filing date
Publication date
Application filed by Kuraray Co., Ltd. filed Critical Kuraray Co., Ltd.
Priority to JP2009550447A priority Critical patent/JP5571963B2/ja
Publication of WO2009093412A1 publication Critical patent/WO2009093412A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
    • B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
    • B29B15/10—Coating or impregnating independently of the moulding or shaping step
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/283—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads synthetic polymer-based, e.g. polyamide or polyester fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
    • B29C70/22—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in at least two directions forming a two dimensional structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/246—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using polymer based synthetic fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/248—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using pre-treated fibres
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D1/00—Woven fabrics designed to make specified articles
    • D03D1/0082—Fabrics for printed circuit boards
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/40—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads
    • D03D15/41—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads with specific twist
    • 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
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
    • D10B2331/042—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET] aromatic polyesters, e.g. vectran
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/06—Load-responsive characteristics
    • D10B2401/063—Load-responsive characteristics high strength
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00—Industrial
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00—Industrial
    • D10B2505/02—Reinforcing materials; Prepregs
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00—Industrial
    • D10B2505/12—Vehicles
    • 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
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0141—Liquid crystal polymer [LCP]
    • 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
    • H05K2201/029—Woven fibrous reinforcement or textile

Definitions

  • the present invention relates to a sheet-like material used in a field where rigidity is required even though it is thin and lightweight and has high strength, little dimensional change, and rigidity.
  • the object of the present invention has been made in view of such problems, and is a sheet-like fabric (or sheet-like product) that is high in strength despite being lightweight, excellent in dimensional stability, and excellent in rigidity. Reinforcing material), a sheet-like material, and a resin molded product obtained by singly or laminating the sheet-like material.
  • Another object of the present invention is to provide a sheet-like reinforcing material having a low dielectric constant, a sheet-like material, and a resin molded product obtained by singly or laminating the sheet-like material, in addition to the excellent characteristics described above. It is to be.
  • Still another object of the present invention is to provide a sheet-like reinforcing material having a high strength and a high elastic modulus even when the thickness is small, a sheet-like material, and a resin molded product formed by laminating the sheet-like material alone. That is.
  • Another object of the present invention is to provide a method for easily producing a sheet-like material having the above-described excellent characteristics.
  • the present inventors have found the following points and completed the present invention.
  • the multifilament yarns constituting the fabric are specified.
  • the ratio of fabric weight per unit area, thickness, and tensile strength at break has a specific relationship, the sheet-like product and the resin molded product using this fabric have rigidity despite being thin. I found it excellent.
  • the multifilament yarns constituting the fabric In the case where the diameter and the thickness of the fabric show a predetermined relationship, they are found to be excellent in rigidity despite being thin, and when the ratio between the tensile strength of the fabric and the fabric weight satisfies the predetermined relationship, it is lightweight.
  • the present invention A preparation step of preparing a fabric made of melt anisotropic aromatic polyester fiber; An impregnation or adhesion step of impregnating or adhering a matrix resin to the fabric, and a method for producing a high-strength sheet material,
  • the fabric is a multifilament yarn-like woven or knitted fabric, and the multifilament yarn-like fineness is 20 to 300 dtex,
  • the fabric weight W (unit: g / m 2 ), thickness D (unit: mm), and tensile strength at break Sb (unit: N / cm) are expressed by the following formula Sb / W in both the vertical and horizontal directions of the fabric.
  • / D ⁇ 30 Is a method for producing a high-strength sheet.
  • the fabric weight W may be about 15 to 200 g / m 2 , and the fabric has a tensile strength at break Sb (unit: N / cm) and an intermediate elongation (1/2 of the cutting elongation).
  • the relationship with the strength Sc (unit: N / cm) of the fabric is the following formula Sc / Sb ⁇ 0.25 in both the warp direction and the horizontal direction of the fabric. May be satisfied.
  • the relationship between the fabric thickness D (unit: mm) and the converted filament RD (unit: mm) of the multifilament yarn constituting the fabric is expressed by the following formula: D / RD ⁇ 1.2 May be satisfied.
  • the fabric may be subjected to physical treatment, chemical treatment, or both physical treatment and chemical treatment.
  • the present invention also includes a high-strength sheet-like fabric made of melt-anisotropic aromatic polyester fibers.
  • This fabric may have the above-described characteristics, and further, the melt-differentiating material constituting the fabric.
  • the ratio of the major axis to the minor axis (major axis / minor axis) of the fiber cross section of the isotropic aromatic polyester fiber may be 1.1 to 3.0.
  • the present invention also includes a high strength sheet-like material in which such a fabric is impregnated or adhered with a matrix resin.
  • the resin content may be about 10 to 95% by mass.
  • the present invention includes a resin molded product obtained by singly or laminating the high-strength sheet material.
  • the dielectric constant may be 3.2 or less.
  • a plurality of high-strength sheet-like materials may be laminated, and the thickness T of the resin molded product may be about 0.02 to 8 mm.
  • the woven or knitted fabric is used as a generic term including both woven fabrics and knitted fabrics, and the woven fabric is a layer in which yarns made of fused anisotropic aromatic polyester fibers are arranged in parallel to each other.
  • the woven or knitted fabric of the present invention does not include a nonwoven fabric in which melt anisotropic aromatic polyester fibers are randomly oriented.
  • the sheet-like material of the present invention is thin and lightweight, it has high strength and excellent rigidity, so it can be used as a substrate for printed circuit boards, prepregs, high-strength film materials, and various building materials. Furthermore, since molding by thermal compression is also possible, it can also be used as automobile parts, parts for electrical products, and structural materials. In addition, when the resin molded product of the present invention has a low dielectric constant, such a resin molded product can be usefully used as a printed board or the like by making use of dielectric characteristics.
  • the thread A is a fiber made of a melt anisotropic aromatic polyester polymer
  • the thread B is a general-purpose fiber such as polyester or nylon.
  • a first layer in which the thread-like A is arranged in parallel to each other and a second layer in which the thread-like A is arranged in parallel to each other in a direction perpendicular to the thread-like A constituting the first layer are provided.
  • the thread A is a fiber made of a melt anisotropic aromatic polyester polymer
  • the thread B is a general-purpose fiber such as polyester or nylon.
  • a first layer in which the thread-like A is arranged in parallel to each other and a second layer in which the thread-like A is arranged in parallel to each other in a direction perpendicular to the thread-like A constituting the first layer are provided.
  • the high-strength sheet material of the present invention includes a fabric made of melt anisotropic aromatic polyester fibers as a reinforcing material for sheet material, and a thermoplastic resin or a thermosetting resin is used for the reinforcing material (or fabric). Impregnated or adhered.
  • a high-strength sheet-like product obtained by impregnating or adhering a thermoplastic resin or a thermosetting resin to a cloth made of melt anisotropic aromatic polyester fibers.
  • the fabric constituting the sheet-like material is mainly composed of fibers made of melt anisotropic aromatic polyester.
  • the melt-anisotropic aromatic polyester referred to in the present invention is an aromatic polyester or polyester amide capable of forming an anisotropic melt phase, from aromatic diol, aromatic dicarboxylic acid, aromatic hydroxycarboxylic acid, aromatic acin, etc. The resulting polymer.
  • melt phase exhibits optical anisotropy (liquid crystallinity). This property is obtained by heating and heating a sample on a hot stage in a nitrogen atmosphere. It can be easily recognized by observing the transmitted light.
  • melt-anisotropic aromatic polyester of the present invention include those composed of combinations of the following repeating components.
  • components of 10 mol% or less may be copolymerized with the above repetitive components.
  • the component (B) is more preferably an aromatic polyester that is, for example, 4 to 45 mol% (preferably 10 to 35 mol%) of the whole.
  • the above component may contain other polymers such as polyolefins, polyamides, polyesters, polyarylates, polycarbonates, polyphenylene sulfides, polyester ether ketones and the like having a fiber-forming ability within a range that does not substantially impair liquid crystallinity. It doesn't matter. Furthermore, various additives such as pigments, carbon, heat stabilizers, ultraviolet absorbers, lubricants, fluorescent brighteners and the like may be included.
  • the fiber comprising the melt anisotropic aromatic polyester constituting the present invention can be obtained by an ordinary melt spinning method.
  • the melting point of the polymer is MP (° C.)
  • spinning is usually performed at a temperature 10 to 50 ° C. higher than MP. Since the fiber after spinning does not have sufficient performance, heat treatment is performed.
  • the heat treatment causes solid-state polymerization (sometimes accompanied by a cross-linking reaction), improving strength and elastic modulus, and further increasing the melting point.
  • the melting point (MP) referred to in the present invention is an endothermic peak temperature measured using a TA-3000 DSC manufactured by METTLER under the condition of a temperature increase rate of 20 ° C./min.
  • the heat treatment can be performed in an inert atmosphere such as nitrogen, an active atmosphere containing oxygen such as air, or under reduced pressure.
  • the heat treatment atmosphere is preferably a gas having a dew point of ⁇ 40 ° C. or lower.
  • Preferable temperature conditions include a pattern in which the temperature is raised sequentially from the fiber melting point or lower.
  • the processing time can be several seconds to several tens of hours depending on the target performance.
  • the heat treatment is performed in a fiber state, but may be performed in a woven or knitted state as necessary.
  • the fabric of the present invention is a multifilament yarn-like woven or knitted fabric, and the multifilament yarn-like fineness is required to be 20 to 300 dtex. If the fineness is less than 20 dtex, high-density weaving and knitting for obtaining the desired strength is difficult, and a product having high rigidity cannot be obtained. On the other hand, if it exceeds 300 dtex, it is out of the object of the present invention of being thin and lightweight. Preferably it is 25 to 250 dtex, and more preferably 30 to 230 dtex.
  • the relationship between the thickness D (unit: mm) of the fabric and the converted diameter RD (unit: mm) of the multifilament yarns constituting the fabric may be D / RD ⁇ 1.2. . If the ratio of D / RD is too high, there is a possibility that the balance between thinness and rigidity, which is an important object of the present invention, cannot be exhibited.
  • the converted diameter RD (unit: mm) referred to in the present invention is a diameter obtained by regarding the multifilament thread shape as a monofilament having a round cross section, and is a value calculated by the following equation.
  • RD 0.0113 (T / ⁇ ) 1/2
  • T is the fineness (unit; dtex) of the multifilament thread
  • (rho) is the specific gravity (unit: g / cc) of the fiber which comprises a fiber.
  • the RD can be appropriately selected according to the fineness and specific gravity of the fiber.
  • the RD may be about 0.03 to 0.3, preferably about 0.05 to 0.25.
  • the fabric thickness D (unit: mm) referred to in the present invention is a value measured using a digital measuring instrument B-2 manufactured by Toyo Seiki Seisakusho Co., Ltd., and D is, for example, 0.01 to 0 About 0.3, preferably about 0.02 to 0.2.
  • the fabric weight is W (unit: g / m 2 )
  • the fabric weight W (unit: g / m 2 )
  • thickness D (unit: mm)
  • tensile breaking strength Sb (unit: N) / Cm) is the following formula Sb / W / D ⁇ 30 for both the vertical and horizontal directions of the fabric. It is necessary to satisfy
  • Sb / W / D is less than 30, it is not possible to obtain a lightweight and high-strength fabric that is the object of the present invention.
  • Sb / W / D ⁇ 40 more preferably 400 ⁇ Sb / W / D ⁇ 50.
  • W and tensile breaking strength Sb may satisfy the following formulas in both the warp direction and the horizontal direction of the fabric.
  • Sb / W is too low, there is a possibility that the lightweight and high-strength fabric intended by the present invention cannot be obtained.
  • the relationship between Sb and the strength Sc (N / cm) at the time of intermediate (1/2 of the cut elongation) may satisfy the following formula in both the vertical direction and the horizontal direction of the fabric.
  • the tensile strength Sb referred to in the present invention is a strip-shaped test piece having a width of 3 cm prepared from a fabric, subjected to a tensile test at a test length of 10 cm, and determining the cutting strength (unit: N). 1 cm). Further, the strength Sc at the time of intermediate extension in the present invention is the strength at the time of extension which is half of the cut elongation obtained at the time of the tensile test.
  • the fabric weight W may be about 15 to 200 g / m 2 , preferably about 20 to 180 g / m 2 , more preferably about 20 to 150 g / m 2.
  • both the vertical and horizontal Sb values may be about 200 to 800 N / cm, and preferably about 300 to 600 N / cm.
  • both the vertical and horizontal Scs may be about 50 to 300 N / cm, and preferably about 80 to 200 N / cm.
  • Such a fabric having high strength and high elastic modulus can be produced, for example, by the following method. That is, the fiber constituting the fabric is a fiber made of melt-anisotropic aromatic polyester, and a multifilament yarn shape of 20 to 300 dtex made of the fiber (for example, a single yarn fineness of about 1 to 10 dtex) is used. it can.
  • the multifilament yarn may have a sweet twist, but is preferably substantially untwisted. Furthermore, the multifilament thread form once formed may be formed into a multifilament thread form by performing a fiber opening process and / or a smoothing process. From the viewpoint of thinning the fabric, it is preferable to form the fabric with a multifilament yarn that has been subjected to such a fiber opening treatment and / or a smoothing treatment.
  • the fabric is formed of a woven or knitted fabric, and preferably a woven fabric.
  • a woven fabric there is a fabric structure (I) in which yarns made of molten anisotropic aromatic polyester fibers are interlaced as warps and wefts, and layers in which yarns made of molten anisotropic aromatic polyester fibers are arranged in parallel to each other.
  • Examples include a woven fabric structure (II) that has at least one layer but is not interlaced with each other and is connected by an auxiliary yarn.
  • Examples of the woven structure (I) include plain weave, twill, satin and the like.
  • the amplitude of the woven wave formed by the multifilament yarn is made as small as possible for both warp and weft. preferable.
  • the amplitude of the woven wave may be reduced by using a multifilament yarn that has been subjected to a fiber opening process and / or a smoothing process, as described above. It may be reduced by thinning the fabric using a roller or the like.
  • the woven fabric structure (II) includes, for example, a unidirectional woven fabric (for example, a weave fabric) having a single layer of a thread-like layer composed of melt-anisotropic aromatic polyester fibers arranged in parallel to each other;
  • a multi-woven fabric for example, a bi-directional woven fabric, a tri-directional woven fabric, etc.
  • the yarns made of the melt-anisotropic aromatic polyester fibers do not cross each other, but these yarns are integrated by the auxiliary yarns.
  • the auxiliary yarn is not particularly limited as long as it can connect the filaments made of melt-anisotropic aromatic polyester fibers, and examples thereof include polyester, nylon, acrylic, polyolefin, polyurethane and the like.
  • the crossing state of the auxiliary yarn with respect to the yarn shape made of the melt anisotropic aromatic polyester fiber is not particularly limited as long as the yarn shape can be integrated, and may have a woven structure as shown in FIG.
  • the interval between adjacent multifilament yarns is in a range where the fabric does not slip.
  • one of the warp and the weft constituting the fabric for example, the wider one of the warp and the weft
  • the width of both the warp and the weft is 3RD or more (for example, about 3RD to 7RD, preferably Is preferably about 3.5 RD to 6.5 RD, more preferably about 4 RD to 6 RD).
  • RD is the above-described converted diameter of the multifilament thread.
  • a structure in which fibers made of melt-anisotropic aromatic polyester are not mixed with warp and weft is preferable, for example, a cloth having a woven structure (II) as shown in FIGS. 1 and 2 is particularly preferable. .
  • the obtained fabric is thinned by, for example, the methods shown in 1) and 2) below.
  • 1) Tension treatment is performed between rollers that rotate the fabric or between heated rollers.
  • 2) The fabric is pressed between the heating roller and the nip roller (including calendar processing).
  • the woven wave or the like expands, for example, as shown in FIG. 3, the Sc value is improved in the tensile test of the fabric, the elastic modulus after resin impregnation is increased, and the rigidity is improved.
  • the ratio of the major axis to the minor axis is less than 1.1, the thinning effect may not be obtained.
  • the ratio of the major axis to the minor axis exceeds 3.0, tearing or breakage may occur, and a sheet-like material excellent in strength and elastic modulus, which is the object of the present invention, may not be obtained. More preferably, it is 1.3 to 2.8.
  • the ratio of the major axis to the minor axis in the present invention means that the cross section of the fabric of the present invention is taken with a scanning electron microscope (SEM), and the major axis and the short axis of the melt-anisotropic aromatic polyester fiber are taken from the cross-sectional photograph. It is an average value of the ratios obtained by measuring the diameter, and specifically, a value measured by the method described in Examples described later.
  • SEM scanning electron microscope
  • the matrix resin referred to in the present invention may be either a thermoplastic resin or a thermosetting resin.
  • thermoplastic resins include polyethylene terephthalate, modified polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and other polyesters, polypropylene, modified polypropylene, polyolefins such as polyethylene, polyamide 6, polyamide 66, polyamide 12, polyamide 6-12, and polyamide 9T.
  • polyamides such as polyamide 66IT, polycarbonate, polyarylate, polyimide, polyphenylene sulfide, polyetheresterketone, fluororesin, and thermoplastic elastomers such as polyurethane, styrene-based elastomer, and olefin-based elastomer.
  • These resins may be used alone or in combination of two or more.
  • semi-aromatic and wholly aromatic polyesters, polypropylene, polyamide 6, polyamide 66, thermoplastic elastomer and the like are preferable.
  • thermosetting resin according to the present invention examples include one or more thermosetting resins selected from, for example, phenol resins, epoxy resins, unsaturated polyester resins, cyanate resins, maleimide resins, polyimide resins and the like. Resin. Furthermore, one or two of the above-mentioned thermosetting resins are modified by adding polyvinyl butyral, acrylonitrile-butadiene rubber, polyfunctional acrylate compound, etc., crosslinked polyethylene, bismaleide-triazine resin, crosslinked polyethylene modified epoxy.
  • thermosetting resin IPM type or semi-IPM type polymer alloy
  • a thermoplastic resin such as a resin, a crosslinked polyethylene-modified cyanate resin, or a polyphenylene ether-modified cyanate resin
  • epoxy resin polyimide resin, unsaturated polyester resin, cyanate resin, and the like are suitable as the matrix resin.
  • a bismaleide-triazine resin that is excellent in adhesiveness to the fabric and that is excellent in insulation and heat resistance is preferably used as the matrix resin.
  • the method for producing a high-strength sheet material of the present invention includes a preparation step of preparing a fabric made of melt anisotropic aromatic polyester fibers, and an impregnation or adhesion step of impregnating or adhering a matrix resin to the fabric. It has.
  • the impregnation or adhesion method of the resin to the fabric in the impregnation or adhesion process is not particularly limited, and a conventionally known method may be used.
  • an impregnation method, a coating method, a transfer method or the like may be employed.
  • a method of impregnating a fiber base material prepared by dissolving a matrix resin in a solvent and drying the fiber base material do not use a solvent.
  • a method of impregnating a fabric with a liquid matrix resin in a normal temperature state or a heated state, a method of fixing a powdery matrix resin to a fabric, and forming a matrix resin layer on a film or sheet having releasability A method of transferring to a fabric can be employed.
  • the preparation step for preparing the fabric physical and / or chemical treatment may be performed on the fabric as necessary in order to improve the adhesion with the resin to be impregnated or adhered.
  • Examples of physical treatment include corona discharge treatment, glow discharge treatment, plasma treatment, electron beam treatment, ultraviolet treatment, heat treatment in an oxygen-containing atmosphere, heat treatment in a moisture-containing atmosphere, and the like.
  • Examples include acid treatment, alkali treatment, and treatment using an oxidizing agent.
  • the chemical treatment may be performed at room temperature or may be performed under heating, but is preferably performed under heating. These treatments may be performed alone or in combination of two or more. Of these post-treatments, physical treatments such as ultraviolet treatment and heat treatment are preferable because they can be produced efficiently.
  • an ultraviolet lamp such as a low pressure mercury lamp or an excimer lamp may be used.
  • the energy density of the UV treatment from the viewpoint of improving adhesion without degrading the fabric, for example, may be about 0.1 ⁇ 50mW / cm 2, preferably a 1 ⁇ 40mW / cm 2 of about Also good.
  • the irradiation time can be appropriately set according to the energy density and the like, but may be, for example, about 10 seconds to 10 minutes, and preferably about 20 seconds to 5 minutes.
  • the heat treatment in an oxygen-containing atmosphere, for example, may be performed at about 230 to 350 ° C. or about 250 to 330 ° C.
  • the heating time may be, for example, about 1 to 100 hours, or about 10 to 80 hours.
  • the high-strength sheet material (or prepreg) of the present invention is formed by impregnating or adhering the above-described matrix resin to the fabric obtained by the above-described method. And to obtain an excellent sheet-like product of the present invention, as described above, by using a high-strength fiber made of a melt-anisotropic aromatic polyester, it is made into a fabric so as to satisfy the above-mentioned predetermined conditions. This is possible for the first time.
  • the content of the matrix resin in the sheet-like material suppresses delamination and molding defects and makes the mechanical performance, dimensional stability, and thermal stability good, so that the total mass of the sheet-like material is It is preferably 10 to 95% by mass, particularly 15 to 80% by mass.
  • this invention also includes the resin molded product formed by laminating
  • the dielectric constant is 3 GHz at a frequency of 1 GHz or more (for example, 1 to 10 GHz, for example). .2 or less, and preferably about 2.5 to 3.15.
  • the “dielectric constant” referred to in the present specification is a relative dielectric constant when the dielectric constant of vacuum is 1, and is a value measured by the method described in the examples described later.
  • the shape of the resin molded product may be either a planar shape or a curved surface shape.
  • the thickness T of the resin molded product (Unit: mm) may be about 0.02 to 8 mm, preferably about 0.03 to 6 mm, and more preferably about 0.05 to 4 mm.
  • the sheet-like product and resin molded product of the present invention can be used as a substrate for printed circuit boards, prepreg applications, high-strength membrane materials (such as tents), and various building materials (such as cloth and mats). Since molding by heat compression is also possible, it can also be used as parts for automobiles, parts for electrical products, and structural materials.
  • the logarithmic viscosity, fiber strength, and elastic modulus of the melt-anisotropic aromatic polyester polymer mean those measured by the following measuring methods.
  • the flexural modulus F (unit: N / mm) was measured in accordance with JIS K 7017 test method with a distance between fulcrums of 60 mm for a sample piece of length 120 mm ⁇ width 25 mm.
  • Example 2 A plain fabric having a warp density of 56 / 2.5 cm and a warp density of 56 / 2.5 cm was produced from this filament by a conventional method. In addition, 150 times / m twisted yarn was used for the warp yarn. Further, this plain woven fabric was placed between stainless steel mirror surfaces and calendered at a linear pressure of 40 kg / cm 2 and a temperature of 190 ° C. to obtain a plain woven fabric of Example 1. Further, a plain woven fabric in which both warp and weft yarns were untwisted was produced in the same manner as in Example 1, and designated as Example 2. Table 1 shows the physical properties of the obtained plain woven fabric.
  • a fabric having the structure shown in FIG. 1 was obtained using a multi-loom using the multifilament (yarn A) of (1) and a 28 dtex polyethylene terephthalate false twisted yarn (yarn B).
  • the densities of the filaments A and B were 24 / 2.5 cm for both vertical and horizontal.
  • This fabric was impregnated with the matrix resin liquid (varnish) produced in Reference Example 1 and dried at 150 ° C. to produce a sheet (prepreg) having a resin content of 60% by mass. Thereafter, in the same manner as in Example 1, a prepreg was laminated and hot-pressed to produce a laminate. Table 1 shows the evaluation results of the obtained fabric and laminate.
  • Example 4 The fabric of Example 3 was passed through an electrostatic fiber opening device, then placed between stainless steel mirror surfaces, and calendered at a linear pressure of 50 kg / cm 2 and a temperature of 180 ° C. Thereafter, resin impregnation was carried out in the same manner as in Example 3 to produce a sheet (prepreg). Thereafter, in the same manner as in Example 1, a prepreg was laminated and hot-pressed to produce a laminate. Table 1 shows the evaluation results of the obtained fabric and laminate.
  • Example 5 Using the same melt anisotropic aromatic polyester polymer as in Example 3, a 56 dtex / 30 filament multifilament was obtained. This multifilament was treated in a nitrogen atmosphere at 280 ° C. for 20 hours. The obtained multifilament had a strength of 30.1 cN / dtex, an elongation of 4.5%, and an initial elastic modulus of 720 cN / dtex.
  • a plain woven fabric having a warp density of 72 / 2.5 cm and a horizontal density of 72 / 2.5 cm was produced by a normal method. The plain fabric was impregnated with resin in the same manner as in Example 2 and calendered. The results are shown in Table 1. The thickness of the sheet-like material after impregnation with the resin was 40 ⁇ m, and a sheet-like material having excellent rigidity was obtained despite this thinness.
  • Example 6 In Example 2, the temperature condition and linear pressure condition of the calendar were changed as shown in Table 2 to produce a plain woven fabric, and a sheet-like material was produced in the same manner as in Example 2. The results are shown in Table 1, and a cross-sectional photograph of Example 6 is shown in FIG. Although these sheet-like materials were very thin, they were highly strong, and the laminate obtained by the same production method as in Example 1 had excellent rigidity.
  • Example 8 The plain fabric obtained in Example 2 was further heat-treated in the air by being left in a 290 ° C. hot air drying oven for 24 hours. The obtained fabric was impregnated with resin in the same manner as in Example 2 to produce a sheet (prepreg). Thereafter, in the same manner as in Example 2, a prepreg was laminated and hot-pressed to produce a laminate. Table 1 shows the evaluation results of the obtained fabric and laminate.
  • Example 9 The plain fabric obtained in Example 2 was further processed using an 110 mW low-pressure mercury lamp manufactured by Sen Engineering Co., Ltd. at an energy density of 17 mW / cm 2 so that the irradiation time was 1 minute.
  • the obtained fabric was impregnated with resin in the same manner as in Example 2 to produce a sheet (prepreg). Thereafter, in the same manner as in Example 2, a prepreg was laminated and hot-pressed to produce a laminate.
  • Table 1 shows the evaluation results of the obtained fabric and laminate.
  • Example 1 A laminated body was produced in the same manner as in Example 1 except that a nonwoven fabric of melt anisotropic aromatic polyester polymer having a basis weight of 39 g / m 2 and an average fiber diameter of 5 ⁇ m was used instead of the plain fabric obtained in Example 1. did.
  • the melt blown nonwoven fabric manufacturing apparatus having a nozzle having a width of 1 m and a hole number of 1000 was supplied to manufacture. Table 1 shows the evaluation results of the obtained fabric and laminate.
  • Example 2 A laminate was produced in the same manner as in Example 1 except that a plain woven fabric of melt anisotropic aromatic polyester polymer having a basis weight of 168 g / m 2 was used instead of the plain woven fabric obtained in Example 1.
  • a multi-filament having a fineness of 1650 dtex / 300 filaments was obtained by melt spinning, and a plain fabric produced from the filaments at a warp density of 56 / 2.5 cm and a horizontal density of 56 / 2.5 cm. Table 1 shows the evaluation results of the obtained fabric and laminate.
  • Example 1 was used except that instead of the plain woven fabric obtained in Example 1, a plain woven fabric (glass cloth manufactured by Nittobo Co., Ltd., thickness 0.095 mm) formed of glass fibers having a basis weight of 104 g / m 2 was used. A laminate was produced in the same manner as described above. Table 1 shows the evaluation results of the obtained fabric and laminate.
  • the fabrics of Examples 1 to 9 satisfied Sb / W / D ⁇ 30 in both the warp direction and the horizontal direction of the fabric, although the fineness of the multifilament yarn was 56 to 220 dtex. And the laminated body using these plain fabrics was excellent in rigidity even if it was thin. That is, the ratio of the flexural modulus F to the thickness showed a high value in the examples.
  • the fabrics of Examples 1 to 9 satisfy D / RD ⁇ 1.2, and satisfy the conditions of Sb / W ⁇ 5 and Sc / Sb ⁇ 0.25 in both the vertical and horizontal directions of the fabric. .
  • Comparative Example 3 using a plain woven fabric formed of glass fibers, the plain woven fabric does not satisfy Sb / W / D ⁇ 30, but the laminate using this plain woven fabric has excellent rigidity. The weight of the laminate was high and weight reduction could not be achieved. In Comparative Example 3, the dielectric constant also showed a high value.
  • the sheet-like material of the present invention can be used as a substrate for printed circuit boards, prepreg applications, high-strength film materials, various building materials, and can also be molded by heat compression. It can also be used as a structural component or structural material.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Textile Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Composite Materials (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)
  • Woven Fabrics (AREA)

Abstract

La présente invention concerne un article en feuille qui est fin, léger, résistant et qui présente une bonne stabilité dimensionnelle. Ledit article est utilisé dans des domaines nécessitant de la rigidité. Il est formé en imprégnant ou en fixant une résine matricielle dans un tissu, comprenant des fibres polyesters aromatiques ayant une anisotropie en fusion, ou sur celui-ci, le tissu étant un tissu tissé avec plusieurs filaments avec une finesse de 20-300 dtex et un poids W (g/m2), une épaisseur D (mm), et une résistance au cisaillement par traction Sb (N/cm) du tissu satisfaisant Sb/W/D ≥ 30.
PCT/JP2009/000081 2008-01-25 2009-01-09 Article en feuille à module à résistance et à élasticité élevées WO2009093412A1 (fr)

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JP2011063636A (ja) * 2009-09-15 2011-03-31 Kuraray Co Ltd 耐衝撃性複合体
WO2013021587A1 (fr) * 2011-08-09 2013-02-14 住友ベークライト株式会社 Préimprégné, plaque laminée, carte imprimée, conditionnement de semi-conducteurs et dispositif à semi-conducteurs
JP2015536853A (ja) * 2012-12-07 2015-12-24 ハンファ アズデル インコーポレイテッド 無撚繊維を含む物品およびその使用方法
WO2018092708A1 (fr) * 2016-11-15 2018-05-24 日本バルカー工業株式会社 Feuille d'élément piézoélectrique et procédé permettant de fabriquer cette dernière
JP2020090089A (ja) * 2018-10-23 2020-06-11 株式会社クラレ 複合シート
CN114214770A (zh) * 2021-11-23 2022-03-22 山东东岳高分子材料有限公司 一种用于离子交换膜的高平整增强网及其应用

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JPH0544146A (ja) * 1991-08-06 1993-02-23 Kuraray Co Ltd 高強力シート状物およびその製造法
JP2001064845A (ja) * 1999-08-18 2001-03-13 Kuraray Co Ltd 基 布
JP2001089953A (ja) * 1999-09-22 2001-04-03 Unitika Glass Fiber Co Ltd 多層プリント配線基板用絶縁補強材ならびにそれから形成されたプリプレグおよび積層板

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011063636A (ja) * 2009-09-15 2011-03-31 Kuraray Co Ltd 耐衝撃性複合体
WO2013021587A1 (fr) * 2011-08-09 2013-02-14 住友ベークライト株式会社 Préimprégné, plaque laminée, carte imprimée, conditionnement de semi-conducteurs et dispositif à semi-conducteurs
JP2015536853A (ja) * 2012-12-07 2015-12-24 ハンファ アズデル インコーポレイテッド 無撚繊維を含む物品およびその使用方法
WO2018092708A1 (fr) * 2016-11-15 2018-05-24 日本バルカー工業株式会社 Feuille d'élément piézoélectrique et procédé permettant de fabriquer cette dernière
JPWO2018092708A1 (ja) * 2016-11-15 2019-10-17 株式会社バルカー 圧電素子シートおよびその製造方法
JP2020090089A (ja) * 2018-10-23 2020-06-11 株式会社クラレ 複合シート
JP7333910B2 (ja) 2018-10-23 2023-08-28 株式会社クラレ 複合シート
CN114214770A (zh) * 2021-11-23 2022-03-22 山东东岳高分子材料有限公司 一种用于离子交换膜的高平整增强网及其应用

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