WO1994022941A1 - Resin-impregnated fiber sheet - Google Patents
Resin-impregnated fiber sheet Download PDFInfo
- Publication number
- WO1994022941A1 WO1994022941A1 PCT/JP1994/000511 JP9400511W WO9422941A1 WO 1994022941 A1 WO1994022941 A1 WO 1994022941A1 JP 9400511 W JP9400511 W JP 9400511W WO 9422941 A1 WO9422941 A1 WO 9422941A1
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- WIPO (PCT)
- Prior art keywords
- resin
- impregnated
- sheet
- fiber sheet
- pps
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Classifications
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- 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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- 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
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0333—Organic insulating material consisting of one material containing S
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- 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
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/02—Polythioethers; Polythioether-ethers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/901—Printed circuit
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the present invention relates to a resin-impregnated fiber sheet in which a fiber sheet is impregnated with a poly-p-phenylene sulfide resin. More specifically, the present invention relates to a resin-impregnated fiber sheet having excellent heat resistance, thermal dimensional stability, high frequency characteristics, mechanical characteristics, and the like, and particularly suitable for thin-walled circuit boards.
- an insulating base material in this field a base material in which glass cloth is impregnated with an epoxy resin (hereinafter sometimes abbreviated as an epoxy resin-impregnated base material), a polyimide film, a fluorine-based film Films and the like are generally known.
- epoxy resin-impregnated base materials have low moisture absorption and poor high-frequency characteristics, making it difficult to make them thinner.
- Polyimide film has high heat resistance, but easily absorbs moisture and has poor high frequency characteristics.
- fluorine-based films have poor adhesion, and have problems such as difficulty in mounting the conductive paste when machining through holes. o
- PPS sheet an unstretched sheet of poly (p-phenylene sulfide) (hereinafter sometimes abbreviated as PPS) (hereinafter sometimes abbreviated as PPS sheet) is disclosed in JP-A-56-3444.
- a biaxially oriented film hereinafter sometimes abbreviated as a PPS film
- PPS film may be used as an insulating material of a circuit board.
- the PPS sheet alone satisfies various characteristics such as thermal dimensional stability, low moisture absorption, flame retardancy, and high-frequency characteristics, but has a lower heat resistance temperature than the biaxially oriented film (glass transition). Beyond the point, thermal deformation tends to occur.) However, as the number of heating steps increases, crystallization progresses and the material becomes brittle. When used as a printed substrate, the crystal size is controlled to satisfy the heat resistance and brittleness to some extent.However, there is a problem that heat is easily deformed when sudden heat is applied. Was.
- the PPS film itself undergoes dimensional changes due to thermal shrinkage, for example, if heat is applied in the process of manufacturing a circuit board, a circuit shift is likely to occur.
- it has problems such as easy tearing of the laminated circuit board during through-hole processing, and its application range was limited in fields requiring high-precision thermal dimensional stability.
- Aromatic polyamide fiber sheet and adhesive The laminated structure is disclosed in Japanese Patent Publication No. 60-63158.
- each of the laminate and the glass fiber sheet has the following problems.
- the laminate of item (1) is laminated via an adhesive, and the heat resistance of the adhesive adversely affects the base material (that is, the heat resistance of the adhesive decreases the heat resistance of the entire base material). Dominates) but cannot take full advantage of the excellent properties of PPS.
- resin is applied to the fiber sheet. Since it is not impregnated, it has problems such as infiltration of the conductive paste during through-hole processing and the inability to apply metal plating (fiber burrs are generated and it is difficult to ride). .
- the laminate of item (2) is obtained by laminating a PPS film and a fiber sheet by heat fusion, and has excellent heat resistance, but has poor adhesion and is subjected to stress such as bending. And the fiber sheet layer easily peels off. In addition, the workability of through-holes is lacking for the same reason as in the laminate of (1).
- Sheets in which glass fiber impregnated with PPS resin in section (3) tends to crack when subjected to stresses such as bending or punching, and has a problem with circuit board workability.
- the required fields had limited applications.
- the laminate of the item (4) also had a problem in mechanical properties as in the sheet of the item (3). Also, since the impregnation rate of the glass fiber with the PPS resin is low, there is a problem with the workability of through holes.
- the laminate of item (5) also had a low impregnation ratio of the PPS resin with the glass fiber, and had a problem in the workability of the through-hole.
- the adhesive strength between the PPS sheet layer and the PPS film layer was not strong, For example, when a strong impact force is applied, as in the case of punching, it may peel off, and the range of use has been limited.
- the present invention solves such disadvantages of the prior art, and has heat resistance, It balances various characteristics such as thermal dimensional stability, low moisture absorption, flame retardancy, high frequency characteristics, etc. at a high level, and is excellent in processability of circuit boards such as mechanical characteristics and through-hole addition, especially thinner.
- An object is to provide an insulating base material suitable for a circuit board.
- the present invention provides a sheet in which a fiber sheet (A) is impregnated with a resin composition (B) containing poly (p-phenylene sulfide) as a main component, wherein the resin composition (B)
- the present invention relates to a resin-impregnated fiber sheet characterized by having a degree of orientation of 0.3 to 0.9.
- the resin-impregnated fiber sheet of the present invention having the above-described structure, is required to maintain various properties such as heat resistance, thermal dimensional stability, and dielectric properties, and to be used as an insulating base material of a circuit board. It has the effect of greatly improving the mechanical properties when bending o
- the fiber sheet (A) in the present invention is a thin sheet composed of an aggregate of fibers, and has a thickness of 10 to 700 as a generic name of cloth, cloth, filter, nonwoven fabric, paper, and the like. / zm (especially preferably 100 to 500 m), such as glass fiber sheets, liquid crystal fiber sheets, carbon fiber sheets, fluorine fiber sheets, and aramide. Fiber sheets can be used.
- the fiber sheet may be processed such as easy adhesion and coloring, or may be a mixture or a laminate of two or more materials.
- the ratio of rn (K / L) in the range of 0.3 to 1.2 is dimensionally stable It is preferable to improve the sexual orientation.
- glass fiber sheets are preferred in terms of electrical properties and thermal dimensional stability, and glass fiber cloths are particularly preferred in terms of heat resistance, dimensional stability and workability.
- the average density of the warp and the weft is preferably in the range of 0.7 to 1.4 in terms of thermal dimensional stability.
- the fiber sheet does not have a melting point up to a temperature of 400 ° C, and this fiber sheet is a fiber sheet that is infusible at a temperature of 400 ° C.
- infusible means a state in which it does not melt or soften when exposed to a temperature of 400 ° C. If the fiber sheet used in the present invention does not have the above characteristics, the thermal dimensional stability when the circuit board of the present invention is exposed to a temperature around 300 ° C. is insufficient.
- poly-p-phenylene sulfide means that at least 80 mol% (preferably at least 90 mol%) of the repeating unit has the structural formula ⁇ ⁇ ⁇ . ⁇ S) — means a polymer consisting of the structural units represented by. If the content of such a component is less than 80 mol%, the crystallinity of the polymer, the heat transition temperature, and the like are low, and the heat resistance, dimensional stability, mechanical properties, and the like, which are characteristics of the resin composition containing PPS as a main component, are impaired.
- a copolymerizable sulfonate is less than 20 mol%, preferably less than 10 mol% of the repeating unit.
- a unit containing an amide bond may be contained, and the copolymerization method of the polymer may be random or block type.
- a resin composition containing poly (p-phenylene sulfide) as a main component (hereinafter sometimes abbreviated as a PPS composition) (B) refers to poly (p-phenylene sulfide) A composition containing 60% by weight or more of sulfide. If the content of PPS is less than 60% by weight, the mechanical properties, heat resistance, heat fusibility and the like of the impregnated sheet comprising the composition are impaired. The remaining less than 40% by weight of the composition may contain additives other than PPS, such as polymers other than PPS. Inorganic or organic fillers, lubricants, and coloring agents.
- the melt viscosity of the PPS composition is 100 to 500 000 voids (more preferably 500 000) at a temperature of 300 ° C. and a shear rate of 200 seconds. ⁇ 200 000 voise) is preferable in view of the workability of lamination.
- the resin-impregnated fiber sheet of the present invention is a sheet obtained by impregnating the above fiber sheet with a PPs-based resin composition, and the sheet has a thickness of 20 to 100 m (more preferably). Or 50 to 700 m).
- impregnation means that the resin enters around the elementary fibers constituting the fiber sheet and is adhered and solidified to the elementary fibers.
- the ratio of the PPS resin layer to the fiber sheet of the resin-impregnated fiber sheet of the present invention is determined by observing the thickness (b) of the layer made of PPS alone and the PPS impregnation when each layer is observed with an electron microscope from the cross section of the sheet.
- the ratio of the thickness (a) (b / It is particularly preferred that a) is in the range of 0.25 to 2.5 in view of the mechanical properties, impregnation rate, thermal dimensional stability and surface smoothness of the sheet.
- (B / a) is more preferably between 0.4 and 2.3, most preferably between 0.5 and 2.0.
- the layer (a) does not necessarily need to be located at the center in the thickness direction of the resin-impregnated fiber sheet, and may be located at a shifted position.
- the degree of orientation of the layer (b) must be 0.3 to 0.9. More preferably 0.5 to 0.9, most preferably 0.6 to 0.85.
- the degree of orientation referred to here means the degree of orientation (hereinafter abbreviated as 0 F) measured from the edge and end directions, respectively, measured by the wide-angle X-ray diffraction method. It is an essential requirement that it be in the range of 0.3 to 0.9.
- the degree of orientation measured from the edge direction is defined by the X-ray incidence from a direction parallel to the resin surface of the resin-impregnated fiber sheet and also parallel to the width direction (or longitudinal direction). X-ray plate photos are taken and the PPS crystal
- the intensity of the diffraction from the (200) plane is calculated as follows:
- the resin-impregnated fiber sheet of the present invention appears when the angle dependence of the degree of molecular orientation of the PPS resin layer of the impregnated sheet is determined using a certain direction in the same plane of the sheet as a reference axis.
- the ratio (xZy) of the maximum value (X) to the minimum value (y) should be 4.0 or less, more preferably 3.5 or less. It is preferred in terms of.
- the term “isotropic” as used herein means that the directionality of the properties of the resin-impregnated fiber sheet is small, and when the above (X ny) exceeds 4.0, the dimensions of the sheet of the present invention are reduced.
- the directionality of the rate of change, mechanical characteristics, etc. has increased, and it has become more difficult to manufacture high-density circuit boards.
- the impregnation referred to in the present invention means a state in which the resin enters around the elementary fibers constituting the fiber sheet and is adhered and solidified to the elementary fibers.
- the resin impregnation rate of the resin-impregnated fiber sheet of the present invention refers to the fact that the cross section of the sheet is photographed with an electron microscope, and the cross section photograph shows the fiber impregnated with respect to the sum of the circumferences of the fiber fibers of the fiber sheet.
- the value calculated from the ratio of the sum of the arc lengths of the element fibers in contact with the resin or adjacent element fibers is expressed in%.
- the impregnation rate is preferably at least 85%, more preferably at least 90%.
- the impregnation rate is less than 85%, it is difficult to apply the circuit board to a circuit board that requires a high precision due to a large thermal dimensional change rate.
- the conductive paste seeps into the sheet, and the metal plating layer is difficult to adhere to. Becomes difficult.
- the average surface roughness (R a) of the resin-impregnated fiber sheet of the present invention is preferably 0.8 / m or less in order to increase the density of electric circuits on the circuit board. More preferably, it is less than 0.65; um.
- another substrate (metal, sheet) is laminated on at least one surface of the resin-impregnated fiber sheet of the present invention, and another resin or a coating agent is coated or molded. There may be. Further, the resin-impregnated fiber sheet of the present invention may be oxidatively cross-linked by heat, ultraviolet light or the like.
- the PPS used in the present invention is obtained by reacting aluminum sulfide and paradihalobenzene in a polar solvent at high temperature and high pressure.
- a polar solvent such as N-methylpyrrolidone.
- a so-called polymerization aid such as caustic alkali or alkali metal carboxylate is added, and the reaction is carried out at 230 to 280 ° C. I like it.
- the polymerization system pressure and polymerization time are appropriately determined depending on the type and amount of the auxiliary agent used, the desired degree of polymerization, and the like.
- the obtained powdery or granular polymer is washed with water or Z and a solvent to separate by-product salts, polymerization aids, unreacted monomers and the like. Needed for the polymer obtained above Accordingly, an inorganic or organic additive or the like is added to such an extent that the object of the present invention is not hindered, thereby obtaining a PPS resin composition.
- the resin-impregnated fiber sheet of the present invention is a sheet in which the fiber sheet (A) is impregnated with the above-mentioned PPS resin composition (B).
- a method of thermocompression bonding to a fiber sheet using a stretched (oriented) film made of the resin composition is most preferred.
- a method for obtaining a stretched film of the PPS resin composition is as follows. First, the resin composition is vacuum-dried at a temperature of 150 to 180 ° C for 1 to 3 hours, and a melt extruder typified by an extruder is used. The mixture is heated to a temperature not lower than the melting point of the polymer composition (preferably in the range of 290 to 350 ° C.) and sufficiently kneaded, and then continuously extruded from a slit die. Form a sheet and rapidly cool to a temperature below the glass transition temperature of the polymer to obtain a substantially non-oriented PPS sheet o
- the obtained PPS sheet is uniaxially or biaxially stretched using a known stretching method such as a sequential biaxial stretching method, a simultaneous biaxial stretching method, a tubular method, or a rolling method.
- a film stretcher can be used.
- a sequential biaxial stretching method a uniaxially stretched film is first obtained by stretching in the longitudinal direction of the film with a stretching machine composed of rolls.
- the stretching temperature at this time is preferably in the range of 90 to 120 ° C, and the stretching ratio is preferably in the range of 1.3 to 4.5.
- the film is stretched in the width direction by a tenter.
- the biaxially stretched film can be obtained by using the same stretching conditions as in the above-described stretching in the longitudinal direction.
- heat treatment is performed in a heat treatment chamber following the tenter, as necessary, with a fixed length or a limited shrinkage of 15% or less.
- the heat treatment is preferably performed at a temperature of 200 to 285 ° C. for 1 to 90 seconds.
- the film may be subjected to an annealing treatment under a limited shrinkage or free in order to reduce the heat shrinkage of the film.
- the degree of orientation (OF) of the stretched film obtained above is preferably in the range of 0.1 to 0.75 in order to achieve the object of the present invention. It is particularly preferable to use a biaxially stretched film.
- thermocompression bonding the fiber sheet and the above-mentioned PP s stretched film is performed by laminating the film on both sides of the fiber sheet, hot plate pressing, heating, and the like.
- a roll pressing method, a method of pressing between heated metal belts, or the like can be used.
- the temperature 2 9 0 ⁇ 3 5 0 ° C , the pressure l ⁇ 3 0 k gZ cm 2 also time is 0.5 to 3 hours impregnation ratio at the temperatures required for the impregnation,
- the degree of orientation (OF) of the resin layer of the resin-impregnated fiber sheet obtained unless the above conditions are appropriately determined according to the degree of orientation (OF) of the film used in the present invention. Therefore, the object of the present invention cannot be achieved.
- the thickness ratio (BZA) between the fiber sheet (A) and the PPS film (B) before thermocompression bonding is in the range of 0.3 to 3.0. It is preferable for achieving the object of the present invention.
- the distance between the sample and the film was 41 mm, and the multiple exposure method (15 minutes and 30 minutes) was adopted using a Kodak non-screen screen film.
- the intensity of the (200) peak on the plate photograph is set to 0 ° (on the equator line), and the densitometer is radially shifted from the center of the photograph at the positions of 10 °, 20 °, and 30 °.
- Scan read the degree of blackening, and determine the degree of orientation (OF) of each sample by k.
- the equipment is Sakura Mike Rodenshi Tomeichi manufactured by Konishi Roku Kogyo. Evening model PDM— 5 Evening-Eve A is used, and the measurement concentration range is
- the cross section of the resin-impregnated fiber sheet is photographed with an electron microscope, and the sum of the arc lengths of the elementary fibers in contact with the resin or adjacent elementary fibers is the sum of the circumferences of the elementary fibers of the fiber sheet.
- the measurement visual field was randomly set to be 20 visual fields, and the average value was taken as the impregnation rate (%) (however, the magnification of the electron microscope was set to 300000).
- a 2 cm square sample was floated in a solder bath set at a temperature of 280 ° C for 30 seconds and evaluated according to the following criteria.
- the entire surface is deformed or peeled such as waving or bending, and the dimensional change rate of each layer is large.
- X is at a level that cannot be used as a circuit board.
- the direction where the circuit board is located is set as the reference direction, and 90 Cut out each 1 Q-O mm x O mm in the direction of the angle, mark the conductor part of the circuit, and read the distance between the marks in the longitudinal direction accurately with a microscope (p mm).
- p mm a microscope
- the above distance is accurately measured (r mm).
- the heat shrinkage rate (%) in each direction was calculated by the following formula, and the average heat shrinkage rate was shown.
- the circuit board was passed through a furnace (far-infrared ray method) set at a temperature of 250 ° C for 5 seconds, and the circuit was displaced compared to a circuit not passing through the furnace.
- a furnace far-infrared ray method
- the level of circuit deviation is so large that it cannot be corrected when manufacturing the circuit board.
- Ink penetration length is less than l mm.
- Ink penetration length is l mm to 5 mm.
- Ink penetration length is 5 mm or more.
- the circuit When the workability is at the level of X, the circuit is short with another circuit in the insulating base material and cannot be used as a circuit board.
- the resin-impregnated fiber sheet was repeatedly bent at an angle of 90 degrees, and the number of bendings at which the cracks occurred in the resin layer was measured.
- the measurement value (// m) measured by the stylus type surface roughness meter specified in JIS-B-0601 (ISO4686-1982) is shown (cut off 0.08 mm, Measurement value at 4 mm)
- the resin impregnated sheet is converted to molecules by microwave (4 GHz).
- an orientation meter MOA-2A, 1A, manufactured by KS System Co., Ltd.
- determine the angle dependence of the microwave transmission intensity read the maximum (X) and minimum (y) values, and The ratio (x / y) was determined.
- the orientation pattern of the molecules can be known from the angle dependence of the microwave transmission intensity, which reflects the interaction between the microwaves and the polar molecules constituting the resin.
- composition pellets were vacuum dried at a temperature of 180 ° C. for 3 hours. Furthermore, it was melted at 310 ° C by an extruder with a diameter of 40 mm, filtered with a 95% cut hole diameter of 10 m using a wire mesh fiber, and then filtered to a length of 400 mm with a gap of 400 mm. Extruded from a T-die having a linear rip of 0.5 mm, cast on a metal drum maintained at a surface temperature of 25 ° C, and unstretched sheet (PPS sheet) with a thickness of 350 zm — 1) was obtained.
- PPS sheet unstretched sheet
- the PPS sheet-1 is stretched in a longitudinal direction at a temperature of 95 ° C and a magnification of 3.5 times with a longitudinal stretching device consisting of rolls.
- the subsequent tenter is at a temperature of 100 and a magnification of 3.5.
- the film was stretched in the width direction under the same conditions.
- a temperature of 270 T a temperature of 270 T; a heat treatment under a limited shrinkage of 5%, and a biaxially stretched (oriented) film of PPS having a thickness of 25 ⁇ m (PPS film). I got 1).
- the OF of the finolem was 0.25 in both the EdgeEnd direction.
- the glass cloth used had a density ratio between the warp and the weft of 1.1, a basis weight of 47 gZm 2 , and a thickness of 55 / m (EPC 050: manufactured by Arisawa Seisakusho Co., Ltd.) (fiber sheet 1). ).
- the three-layer base material with the fiber sheet — 1 sandwiched between the two layers of the PPS film 1-1 is sandwiched between two SUS plates with a thickness of 3 mm, and the heat-resistant thickness 5 mm fiber web — Placed on a SUS plate and thermocompressed by hot plate press method.
- the press temperature at this time is 320 ° C.
- the pressure is 10 kg / cm 2 .
- the press time at a temperature of 320 ° C is 60 minutes. After pressing, it was cooled to a temperature of 60 ° C at a cooling rate of 2 CZ by a water cooling method to obtain a PPS resin-impregnated fiber sheet (impregnation sheet 1) having a thickness of 78 / m.
- the evaluation results of this resin-impregnated sheet are shown in Tables 1 and 2.
- a PPS sheet was obtained by the method of Example 1, and the PPS sheet was simultaneously biaxially stretched at 95 ° C. using a film stresser (manufactured by TM Long, USA). For stretching, 1.5, 2.0, 2.5, 3.0. 3.5.4.5 times 6 types of PPS biaxially stretched films (PPS films—2 to 7 in order) were obtained. Was. The thickness of the film was adjusted to 25 ⁇ m. Furthermore, the film is sandwiched between two aluminum frames and fixed. Heat treatment was performed at 60 ° C for 60 ° C.
- the fiber sheet 1 and the PPS films 1 to 7 were thermocompressed under the conditions and method of Example 1 to obtain six types of resin-impregnated fiber sheets (impregnated sheets 1 to 9 respectively).
- Tables 1 and 2 show the evaluation results of this resin-impregnated sheet.
- Example 2 The PPS film-1 and the fiber sheet-1 obtained in Example 1 were subjected to the same method as in Example 1 except that the thermocompression bonding was performed at a temperature of 310 ° C and the press time was set at 20 minutes. (Impregnated sheet: 10) was obtained. Tables 1 and 2 show the evaluation results of this resin-impregnated sheet.
- the resin has a plane orientation ratio (xZy) of 4.10 in the impregnated sheet, and the heat shrinkage tends to be large in directionality, which tends to deteriorate the circuit misalignment and the heat resistance.
- xZy plane orientation ratio
- the PPS film-1 and the fiber sheet 1-1 obtained in Example 1 were subjected to the same method as in Example 1 except that the thermocompression bonding temperature was changed to 310 ° (, 320 ° C) and the pressing time was changed to 30 ° C. In this way, two types of resin-impregnated fiber sheets (impregnated sheets 11 and 12) were obtained, and the evaluation results of the resin-impregnated sheets are shown in Tables 3 and 4.
- a PPS unstretched sheet having a thickness of 25 // m was obtained by the method of Example 1, and a fiber sheet 1 and a press temperature of 280 ° C, 295 ° C, and 320 were obtained by the method of Example 1.
- Thermocompression bonding was performed at each temperature of ° C to obtain three types of resin-impregnated fiber sheets (impregnation sheets 13 to 15 respectively). Evaluation results of this resin impregnated sheet Tables 3 and 4 show the results.
- a PPS film—11 having a thickness of 75 / zm in Example 4 was prepared. Tables 3 and 4 show the evaluation results of this film.
- Example 1 0.25 0.25 1.2 0.71 0.70 95 0.31 impregnated sheet - 1 Comparative Example 1 0. 25 0. o 25 1. 2 0. 29 0. 29 86 0. 58 impregnated Site 2
- Example 1 0. 05 0. 06 1.20 ⁇ 8 ⁇ ⁇ 0.0020 Impregnated sheet-1 Comparative Example 1 0.25 0.55 3.84 ⁇ 15 X ⁇ 0.0021 Impregnated sheet-2
- Impregnated sheet 12 Comparative example 2 0.93 0.93 1.2 0.91 0.92 78 0.37 Impregnated sheet—13
- the resin-impregnated fiber sheet according to the present invention has significantly improved heat resistance, thermal dimensional stability, dielectric properties, and mechanical properties during bending, and has a high resin impregnation rate into the fiber sheet. Since it has excellent workability in the thickness direction of the sheet due to conductive paste and metal plating, it is an insulating base material for circuit boards and multilayer wiring boards that require high-density and thinner circuits. This is optimal.
- heat-resistant insulating materials such as transformers and motors, cable coating materials used for high-temperature and high-pressure parts, heat-resistant adhesive tapes, prepreg materials, heat-resistant labels, speaker cones, shielded materials, and washers It can also be applied to insulation spacer materials.
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/338,629 US5639544A (en) | 1993-03-31 | 1994-03-29 | Resin-impregnated fabric sheet |
EP94910562A EP0645416B1 (en) | 1993-03-31 | 1994-03-29 | Resin-impregnated fiber sheet |
DE69427258T DE69427258T2 (de) | 1993-03-31 | 1994-03-29 | Mit harz imprägnierte faserplatte |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7377993A JP3152002B2 (ja) | 1993-03-31 | 1993-03-31 | 樹脂含浸繊維シート |
JP7377893A JP3339098B2 (ja) | 1993-03-31 | 1993-03-31 | 樹脂含浸繊維シート |
JP5/73779 | 1993-03-31 | ||
JP5/73778 | 1993-03-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994022941A1 true WO1994022941A1 (en) | 1994-10-13 |
Family
ID=26414929
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1994/000511 WO1994022941A1 (en) | 1993-03-31 | 1994-03-29 | Resin-impregnated fiber sheet |
Country Status (4)
Country | Link |
---|---|
US (1) | US5639544A (ja) |
EP (1) | EP0645416B1 (ja) |
DE (1) | DE69427258T2 (ja) |
WO (1) | WO1994022941A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7970656B2 (en) | 1999-07-12 | 2011-06-28 | Meyer Cordless Llc | Methods for determining customer motivations in purchasing decisions |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6952041B2 (en) * | 2003-07-25 | 2005-10-04 | Robert Bosch Gmbh | Anchors for microelectromechanical systems having an SOI substrate, and method of fabricating same |
KR102621342B1 (ko) * | 2017-12-22 | 2024-01-08 | 도레이 카부시키가이샤 | 테이프형 프리프레그 및 그의 제조 방법 |
US20220162408A1 (en) * | 2019-03-26 | 2022-05-26 | Toray Industries, Inc. | Fiber-reinforced resin base material |
CN118124220A (zh) * | 2019-05-17 | 2024-06-04 | 大日本印刷株式会社 | 蓄电装置用外包装材料、其制造方法、蓄电装置和聚酰胺膜 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0539370A (ja) * | 1991-05-29 | 1993-02-19 | Dainippon Ink & Chem Inc | ポリアリーレンスルフイド系樹脂プリプレーグ及びその成形品 |
JPH0598042A (ja) * | 1991-10-03 | 1993-04-20 | Toray Ind Inc | ポリ−フエニレンスルフイド樹脂含浸繊維シート |
JPH05310957A (ja) * | 1992-05-13 | 1993-11-22 | Toray Ind Inc | 繊維シートおよびそれを用いた回路基板 |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5796024A (en) * | 1980-12-08 | 1982-06-15 | Toray Ind Inc | Polyphenylene sulfide resin moldings |
JPS6052943B2 (ja) * | 1980-12-08 | 1985-11-22 | 東レ株式会社 | プリント配線板 |
JPS6050146B2 (ja) * | 1981-01-21 | 1985-11-07 | 東レ株式会社 | スタンピング成形用シ−ト |
US4389453A (en) * | 1982-06-07 | 1983-06-21 | Toray Industries, Inc. | Reinforced polyphenylene sulfide molded board, printed circuit board including this molded board and process for preparation thereof |
JPS593991A (ja) * | 1982-06-29 | 1984-01-10 | 東レ株式会社 | プリント配線板 |
JPS6052943A (ja) * | 1983-09-02 | 1985-03-26 | Victor Co Of Japan Ltd | ドロツプアウト持続検出装置 |
CA1277188C (en) * | 1984-11-19 | 1990-12-04 | James E. O'connor | Fiber reinforced thermoplastic articles and process for the preparationthereof |
JP2615604B2 (ja) * | 1987-03-26 | 1997-06-04 | 東レ株式会社 | 積層体 |
JPH0634434B2 (ja) * | 1987-10-07 | 1994-05-02 | 東レ株式会社 | 回路基板 |
EP0524343A1 (en) * | 1991-07-26 | 1993-01-27 | Phillips Petroleum Company | Poly(arylene sulfide) resins reinforced with glass fibers |
JPH0569504A (ja) * | 1991-09-11 | 1993-03-23 | Toyobo Co Ltd | 熱可塑性繊維強化複合成形体 |
-
1994
- 1994-03-29 DE DE69427258T patent/DE69427258T2/de not_active Expired - Lifetime
- 1994-03-29 US US08/338,629 patent/US5639544A/en not_active Expired - Lifetime
- 1994-03-29 EP EP94910562A patent/EP0645416B1/en not_active Expired - Lifetime
- 1994-03-29 WO PCT/JP1994/000511 patent/WO1994022941A1/ja active IP Right Grant
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0539370A (ja) * | 1991-05-29 | 1993-02-19 | Dainippon Ink & Chem Inc | ポリアリーレンスルフイド系樹脂プリプレーグ及びその成形品 |
JPH0598042A (ja) * | 1991-10-03 | 1993-04-20 | Toray Ind Inc | ポリ−フエニレンスルフイド樹脂含浸繊維シート |
JPH05310957A (ja) * | 1992-05-13 | 1993-11-22 | Toray Ind Inc | 繊維シートおよびそれを用いた回路基板 |
Non-Patent Citations (1)
Title |
---|
See also references of EP0645416A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7970656B2 (en) | 1999-07-12 | 2011-06-28 | Meyer Cordless Llc | Methods for determining customer motivations in purchasing decisions |
Also Published As
Publication number | Publication date |
---|---|
EP0645416B1 (en) | 2001-05-23 |
EP0645416A1 (en) | 1995-03-29 |
US5639544A (en) | 1997-06-17 |
DE69427258T2 (de) | 2001-12-06 |
DE69427258D1 (de) | 2001-06-28 |
EP0645416A4 (en) | 1996-02-21 |
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