CN1364208A - Wholly aromatic polyamide fiber paper and laminated sheet therefrom - Google Patents

Wholly aromatic polyamide fiber paper and laminated sheet therefrom Download PDF

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Publication number
CN1364208A
CN1364208A CN00810718A CN00810718A CN1364208A CN 1364208 A CN1364208 A CN 1364208A CN 00810718 A CN00810718 A CN 00810718A CN 00810718 A CN00810718 A CN 00810718A CN 1364208 A CN1364208 A CN 1364208A
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CN
China
Prior art keywords
paper
aromatic polyamide
polyamide fiber
wholly aromatic
fiber
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CN00810718A
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Chinese (zh)
Inventor
H·苏祖基
L·J·赫斯勒
C·R·怀特菲尔德
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EIDP Inc
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EI Du Pont de Nemours and Co
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Publication of CN1364208A publication Critical patent/CN1364208A/en
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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
    • H05K1/0353—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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Paper (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

A type of fiber paper is provided that is made of completely aromatic polyamide fiber formed by means of liquid crystal spinning. The fiber paper can be used as the base material of a substrate for electric circuit, and it can display high reliability in electric insulation under a high humidity, excellent post-heating dimensional stability, and high heat resistance.

Description

Wholly aromatic polyamide fiber paper and the laminated plate material that makes from it
Background of the present invention
The present invention relates to comprise the Wholly aromatic polyamide fiber paper of Wholly aromatic polyamide fiber.This paper can be used for making the substrate of circuit.Fibrous paper of the present invention is used under the high humility to be had in the field of high request electrical insulation reliability, DIMENSIONAL STABILITY, anti-sweating heat performance and intensity.
General introduction of the present invention
The base material of being made by Wholly aromatic polyamide fiber paper embodies feature in the following fact: this fibrous paper mainly can be removed ion by forming from the formed Wholly aromatic polyamide fiber of anisotropic polymer solution spinning with it; The degree of crystallinity of this fibrous paper is more than 45% or 45%; And crystalline size (ACS: apparent crystalline size (plane 110) is 50 dusts or bigger.
Detailed description of the present invention
Wholly aromatic polyamide fiber is widely used in industry and the daily life, because its high strength, high-modulus, highly heat-resistant and other excellent mechanical performance and hot property.The representative instance of these type of synthetic fiber comprises Fanglun 1414 and polyparaphenylene benzo-dioxazole fiber.
The example that uses right-aramid fibre is to be disclosed in the flat 1[1989 of Japanese Laid-Open Patent Application No.] aromatic polyamide fiber paper in-281790, it is as from isotropic aqueous solution (Technora by organic resin binding agent and right-aramid fibre, the product of Teijin Ltd.) paraphenylene terephthalamide of spinning right-phenylenediamine/oxo diphenylene diamines fibres and from anisotropic polymer solution (Keviar, Toray DuPont Co., the product of Ltd.) the formed poly-paraphenylene terephthalamide's P-pHENYLENE dI AMINE of air gap spinning is fibrous.The manufacture method of aromatic polyamide fiber paper is disclosed in the flat 2[1990 of Japanese Laid-Open Patent Application No.] in-203589.Though last right-content that aramid fibre promptly has an ionic species ehter bond and the-aramid fibre right from the formed copolymer of non-anisotropic polymer solvent spinning less than from anisotropic polymer solution spinning formed back a pair of-ionic species content aramid fibre, but, the fibrous paper of being made by last fiber has low heat resistant because fiber fiber begins to show thermal contraction under about 200 ℃ temperature being low to moderate.As a result, when this fibrous paper is used as the basic material of circuit substrate, this substrate will deform when each parts utilizes the reflow soldering of carrying out under the high temperature to be installed on the substrate.Simultaneously, last fiber radially has than having bigger thermal coefficient of expansion from the formed back of anisotropic polymer solution spinning one fiber.When the fibrous paper that makes from last fiber was used as the basic material of circuit substrate, the change in size percentage of substrate on thickness direction improved, and will be used for causing problem on the reliability that the through hole of realizing conduction on the substrate thickness direction connects.Simultaneously, as mentioned above, organic thermosetting resin binding agent and above-mentioned fiber one are used from manufacturing paper.Because the glass transition temperature of the glass transition temperature comparison-aramid fibre of resin is much lower, when the prepreg of this paper is being heated and is adding when depressing tegillum and pressing as the basic material of circuit substrate, resinoid bond in substrate can melt again, causes unsettled bonding in the fiber that forms this paper.As a result, significant change in size takes place in the substrate of lamination.
In order to reduce above-mentioned change in size, clear and the 61[1986 of Japanese Laid-Open Patent Application No.]-160500 and US patent No.4,729,921 disclose one type fibrous paper, it is with having between high-fire resistance-aromatic polyamides fibrid (US patent No.3,018,091) replaces the right-aramid fibre manufacturing that bonds of above-mentioned resin binder.The preferred use in this case has high-fire resistance and little change in size and from the right-aramid fibre of anisotropic polymer solution spinning, as the homopolymers type right-aramid fibre (poly-paraphenylene terephthalamide's P-pHENYLENE dI AMINE fiber (Kevlar, Toray DuPont Co., the product of Ltd.)).Use above-mentioned polyamide-based fibroplastic fibrous paper to have high heat resistance and excellent back dimensional stability under heat.Yet above-mentioned fiber is by using spinning process manufacturing, and wherein this polymer is spinning in the anisotropic polymer solution of acidity, neutralizes then.In N-process, the ionic species in the fiber becomes salt.After the spinning operation content of salt normally in the 0.5-1wt% scope and even when fiber is processed to paper, the content of salt is maintained at same level.As a result, when this fibrous paper during as the basic material of the substrate of circuit, electrical insulation capability can become problem under high humility.This is the problem that must solve.
The purpose of this invention is to provide a kind of Wholly aromatic polyamide fiber paper, it is characterized in that the following fact: this paper is by making by the formed Wholly aromatic polyamide fiber of spinning anisotropic polymer solution; This paper can be as the basic material of circuit substrate; This fibrous paper contains a small amount of ionic species, and the deposition of ionic species is less; This fibrous paper under high humility, demonstrate excellent electrical insulation capability and have high heat resistance and high after add heat endurance; And the inflection temperature of the change in size percentage of this fibrous paper is high.
To achieve these goals, the present invention uses by anisotropic polymer solution being carried out a kind of Wholly aromatic polyamide fiber that spinning is formed and have high heat resistance and excellent size stability.In this case, the ionic species that contains in fiber can wash with water out, and if carry out spinning under the crystalline size of fiber is less than the condition of certain level making, then fiber can be removed ion.The fiber that removes deionization of the present invention can be processed into by staple fibre or fibrillated paper pulp, it then with have high stable on heating binding agent and combine.Like this, might at high temperature heat-treat the fibrous paper that is obtained.Simultaneously, the degree of crystallinity of fibrous paper, heat resistance, DIMENSIONAL STABILITY and heat-resisting property access improvement.The content of ionic species and the deposition of ionic species can reduce.Fibrous paper of the present invention demonstrates excellent electrical insulation capability in the environment of high humility.
Can be used in the present invention by anisotropic polymer solution being carried out the formed any Wholly aromatic polyamide fiber of spinning.
The aramid fibre that is used for the present invention is by anisotropic polymer solution is carried out the aromatic polyamides that spinning obtained.Preferably from number-average molecular weight 20,000-25 makes fiber in 000 scope and by the formed polymer of the polycondensation reaction of P-pHENYLENE dI AMINE and tere-phthaloyl dichloride.The common air gap spin processes of anisotropic solution can be used in from this polymer and forms fiber.For right-aramid fibre, by with polymer dissolution in concentrated sulfuric acid solvent prepared viscous solution from the spinnerets spinning by air gap and enter into coagulating bath.In this case, when fiber sprayed from spinnerets, shear rate was preferably 25,000-50,000 second -1In the scope.After and then will neutralizing with sodium hydrate aqueous solution as the sulfuric acid of solvent after spinning operation, this fiber washes with water.Subsequently, this fiber reeled (US patent No.3,767,756) after 150-500 ℃ of down dry and heat treatment.The crystal size of the fiber that obtains is usually greater than 50 dusts and in 55-75 dust scope.In addition, as ionic species, sodium sulphate is included in the fiber in the neutralisation treatment process, and its content is in the 0.5-1.0wt% scope in this stage.
In order to use this fiber in the present invention, be necessary this fiber of spinning under suitable drying and heat-treat condition, so that crystalline size is less than 50 dusts, preferably in 35-45 dust scope.If this fiber has the crystalline size in above-mentioned scope, though ionic species still is contained in the fiber, this material almost can wash out from fiber fully when fiber contacts with water or other liquid.As a result, when the fiber that is obtained was used for circuit substrate, the electrical insulation capability under high humility was improved.
From spinnability, cost effectiveness and Papermaking Performance consideration the papermaking operation, the size of the aramid fibre of Shi Yonging should be in 0.1-5 DENIER scope or preferably in 0.3-3 DENIER scope in the present invention.If fiber size is too big, Papermaking Performance and texture are poor.On the other hand, if fiber size is too little, this fiber is difficult to spinning, causes the cost effectiveness of difference.
The length of staple fibre that is used to make aromatic polyamide fiber paper of the present invention is in the 2-14mm scope when using wet papermaking maybe preferably in the 1-50mm scope.If this fiber is oversize, be difficult in and disperse this fiber in the papermaking operation, and this fabric face is unlikely and must be enough to make this fibrous paper to become the high-quality basic material that the power circuit board substrate is used.On the other hand, if this fiber is too short, then fiber can not interweave fully.As a result, paper intensity and other mechanical performance variation.
Consider from heat resistance and DIMENSIONAL STABILITY, between preferably using-the aromatic polyamides fibrid is as the binding agent among the present invention.Between-example of aromatic polyamides fibrid be poly-between phenyl-diformyl m-phenylenediamine or copolymer or the mixed polymer mainly formed by phenyl-diformyl m-phenylenediamine between poly-.Though also might with terephthalic acid (TPA), P-pHENYLENE dI AMINE and analog as the 3rd component and-the aromatic polyamides combined polymerization, the 3rd components contents should be 20mol% or lower.And, also might be added with the machine resin, thermosetting resin especially, as epoxy resin, phenol resin, and melamine resin, as except-binder component the aromatic polyamides fibrid, as long as purpose of the present invention is not subjected to the influence of this resin.
When right-aramid staple fiber and-when the aromatic polyamides fibrid is used to make aromatic polyamide fiber paper of the present invention, the amount of right-aramid staple fiber that this mixing ratio should make is in the 60-97wt% scope, with-amount of aromatic polyamides fibrid is in the 3-40wt% scope, with respect to the gross weight of aromatic polyamide fiber paper.If-content of aromatic polyamides fibrid is too low, and paper intensity seems too low and paper is difficult to reel in paper-making process and heat treatment.And right-aramid staple fiber will drop, and can fluff on the surface of paper, causes quality problems.Preferably the content of binding agent is 5wt% at least.Between-the softening and therefore expansion at high temperature in heat treatment of aromatic polyamides fibrid, bond together with right-aramid fibre.Yet if the content of binding agent is too high, the porosity of paper is too low, causes the poor maceration of this resin impregnant and obtains poor quality.Therefore, the content of binding agent should be 30wt% or below the 30wt%.
Except right-aramid staple fiber, also might add the right-aramid staple fiber such as paraphenylene terephthalamide's P-pHENYLENE dI AMINE/3 of copolymer type, 4-diphenylene diamine copolymer ether staple fibre (Technora, the product of Teijin Ltd.) and polyparaphenylene benzo-dioxazole staple fibre, staple glass fibre, ceramic short fibers etc. are not as long as purpose of the present invention is subjected to the influence of these fibers.In this case, the content of above-mentioned material should be 45wt% or below the 45wt%, or preferred 35wt% or below the 35wt%.
To explain the method for making paper hereinafter, this paper is by forming by the formed Wholly aromatic polyamide fiber of the anisotropic polymer solution of spinning.At first, right-aramid staple fiber and-the aromatic polyamides fibrid is dispersed in the water by above-mentioned ratio and obtains the papermaking slurry of homogeneous.At this moment, the concentration of fiber is maintained in the 0.1-1.0wt% scope in dispersion.Concentration as fruit fiber is too high, and then this fiber can't fully be disperseed.By using flat line style paper machine, cylinder type paper machine, the dispersion manufacturing paper from being obtained such as oblique net type paper machine.Ionization can take place and extracts from fiber then in contained ionic species in the right-aramid staple fiber of Shi Yonging when this fiber contact water in the present invention.As a result, this ionic species is discharged from employed water in paper-making process and this fiber is removed ion.In this stage, can be reduced to the level that is lower than 0.5wt% at the content of staple fibre intermediate ion material.Especially, when the content of ionic species was reduced to the level that is lower than 0.2wt%, the fibrous paper that is obtained can even demonstrate excellent electrical insulation capability under high humility, when it is used for circuit substrate.
When aromatic polyamide fiber paper of the present invention when the circuit substrate, preferably this paper has the following performance that comprises density and intensity, these performances are influential to the performance of the operation of making substrate and substrate.The density of paper is preferably at 0.40-0.85g/cm 3In the scope.If this density is too low, be difficult to obtain high strength.In addition, this DIMENSIONAL STABILITY is poor.So preferably the density of paper is 0.50g/cm 3Or it is higher.On the other hand, if this density is too high, when making the prepreg of this resin-dipping, this resin is difficult to enter the inside of paper, has influenced the performance of substrate unfriendly.Therefore, the density of paper 0.75g/cm preferably 3Or it is lower.Preferably, the intensity of paper is 1.5kg/cm or higher, so that this paper will be difficult for tearing in the resin impregnation operation of describing below.
When the aromatic polyamide fiber paper with above-mentioned composition is used as circuit substrate, in order fully to show heat resistance, back dimensional stability under heat and back humidification stability, be necessary after this paper is manufactured, to heat-treat and suitably handle this paper, so that every characteristic of paper is respectively in above-mentioned scope.For example, might use calender to come treatment paper and this temperature of control and pressure.In this case, in heating with add to depress and allow paper between the stack of making from one or more levels metallic roll, pass through.When-the aromatic polyamides fibrid is when this binding agent, the temperature and pressure of softening this binding agent is respectively in 140-400 ℃ and 30kg/cm or higher scope.If this temperature and pressure does not remain in the above-mentioned scope, then can not obtain meticulousr paper structure, the intensity of paper is difficult to reach above-mentioned level.In addition, heat treated condition should suitably be set, so that the degree of crystallinity of aromatic polyamide fiber paper of the present invention is 45 or higher, and crystalline size (ACS: be 50 dusts or bigger apparent crystalline size (110 face)).By promoting the crystallization of fibrous paper, when this paper is used as circuit substrate, might under high humility, limit the ionization that is retained in a small amount of ionic species in the aramid fibre.Simultaneously, heat resistance, DIMENSIONAL STABILITY and the moisture resistance as the fibrous paper of the basic material of circuit substrate can be significantly improved by forming meticulous aramid fibre crystal structure.
Hereinafter, will explain the present invention in more detail with reference to Application Example.
Yet the present invention is not limited to these Application Examples.
Test method
1. degree of crystallinity and crystalline size.
Under 40kv and 40mA condition, measure the diffracted intensity of the pattern product of the size that cuts into about 3cm * 4cm by using X-ray diffraction device (PW 1075/00, the product of Philips Co.) by reflective-mode.This crystalline size (ACS: apparent crystalline size) corresponding to the diffracted intensity under 20-21 ° scan angle.It is that half breadth by the diffraction maximum of using plane (110) calculates from following formula.
ACS＝(Kx)/βcosTH)
K＝1
X=X beam wavelength (1.5418 dusts under this situation)
β=correction factor
TH=is from the Bragg angle on the plane (110) that diffraction pattern obtains half (half of angle of scattering)
This degree of crystallinity (CI: be to calculate crystallinity index) by following formula.
CI＝[(A-C)×100]/A
A=is at the diffraction peak intensity of about 23 ° of lower planes (200)
C=is in about 22 ° of following minimum diffraction intensity
With regard to fiber, this crystalline size and degree of crystallinity are calculated by the same manner by using said method, and just before measuring, the pattern product with 4cm length and 20mg weight formalize with collodion solution.
2. the content of paper intermediate ion material
The paper of about 0.3g is placed in the platinum dish.
After being dissolved in sulfuric acid, the pattern product are calcined with gas burner or electric dry oven.The calcined material that is obtained thermal decomposition in sulfuric acid, nitric acid or hydrofluoric acid is dissolved in rare nitric acid then and obtains solution.
The amount of cationic substance is measured by using atomic absorption method in the solution that is obtained.
3. the density of paper
The density of paper is to measure according to JIS P-8118.
4. the change in size percentage of paper during heating
The variation of the length of the pattern product of measurement 200mm length and 30mm width.Before sample is heated and this sample heats 10min under 300 ℃ after, the length of pattern product is measured with the X-Y coordinate measuring set.After the pattern product are heated, calculate the change in size percentage (%) of MD and CD.Change in size percentage (%)=100 * (length measured before heating back length measured-heating)/(length measured before the heating).
5. the inflection temperature of the change in size of paper during heating
The temperature of measurement when the change in size of the pattern product of 5mm length and 2mm width enlarges markedly.Use TMA (thermo-mechanical analysis device: the product of TA Instrument Co.) measure.This temperature is that the rate of heat addition with 10 ℃/min is elevated to 150 ℃ from room temperature under the load of 2g, and it reduces then and the speed followed again with 10 ℃/min raises.The pattern product are heated to 350 ℃.Along with the rising of temperature, the temperature when constant change in size speed marked change is got the inflection temperature of making change in size.
6. the thermal coefficient of expansion on the paper thickness direction
Measurement is cut into the thermal coefficient of expansion of the pattern product of 10mm * 10mm size.Use TMA (thermo-mechanical analysis device: the product of TA Instrument Co.) measure.This temperature is that the rate of heat addition with 10 ℃/min is elevated to 150 ℃ from room temperature under the load of 2g, and it reduces then and the speed followed again with 10 ℃/min is increased to 350 ℃.The mean thermal expansion coefficients of calculating in room temperature to 250 ℃ scope.
7. the TENSILE STRENGTH of paper (paper power),
The TENSILE STRENGTH of paper can be measured according to JIS P-8113.
8. the extracting electrical conductivity of paper
The insulating reliability of fibrous paper under high humility as circuit substrate is to measure as the extracting state of this ionic species of ionic species by evaluation.Ionic species makes and comes extracting in the following method.Cut about 5g pattern product and accurately weigh.After the pattern product are installed in the flask, add the ion exchange water of about 180ml.This flask is heated 24 hours, ion by extracting in water.After cooling, the electrical conductivity of extracting liquid is with electrical conductivity instrumentation amount, and calculates as the value of every 5g sample.
The characterisitic parameter of circuit substrate
9. the insulating reliability after moisture absorption
Prepare composition epoxy resin by in as the cresol novolak epoxy of epoxy resin (flooding aromatic polyamide fiber paper) and bisphenol A epoxide resin, adding as the dicyandiamide of curing agent with as the benzyl methylamine of curing accelerator with it.Use by after above-mentioned composition epoxy resin is dissolved in varnish impregnation prepared in the butanone solution at this aromatic polyamide fiber paper, this paper is dried, and obtains to contain the B rank prepreg of 53wt% resin.Arrange on the both sides of prepreg after the 18 micron thickness Copper Foils, this prepreg passes through at 170 ℃ and 30kg/cm 2Pressure down with pressurize 60min and obtain laminated material of heating in vacuum press.Live width and spacing with 200 microns on a side of laminated material are carried out etching, form the comb poles pattern.Then, the B-rank prepreg of crossing with above-mentioned resin impregnation is arranged on the both sides of laminated material, subsequently by using the heating in vacuum press at 170 ℃ and 30kg/cm 2The following pressurization 60min and obtain another laminate of pressure.This substrate is placed under 500h and the 1000h under 110 ℃ and 85%RH, meanwhile substrate is applied direct current (DC) voltage of 20V.Take out substrate from above-mentioned high temperature and high temperature environment after, it is placed to return to normal condition under 20 ℃ and 60%RH.Then, the DC voltage that applies 35V between comb poles reaches 60 seconds, measures the insulaion resistance of the substrate after handling in high humidity environment.The most low-resistance of each comb poles is got and is made measured value.
10. DIMENSIONAL STABILITY
With 5 impregnated prepregs of B b stage resin b that in above 9, obtain manufacturing sheet material that overlaps.The Copper Foil of applying 18 micron thickness on each side of this sheet material, it uses the heating in vacuum press at 180 ℃ and 30kg/cm then 2Pressure down pressurization 60min obtain laminate.This copper-clad laminate is cut into the size of 250mm * 250mm.Prepare four above-mentioned laminated board samples.Size on the vertical and horizontal of each substrate is to measure at interval with the measurement of 200mm * 200mm.Under normal circumstances (measure 1), after the Copper Foil etch processes, (measure 2) and after heat treatment, (measure 3), measure.Change in size percentage from minimum and maximum change calculations normal condition.
11. anti-sweating heat performance
The anti-sweating heat performance of the copper-clad laminate that obtains in above 9 is to measure according to JIS C-6481.
12. the thermal coefficient of expansion on thickness direction
Copper Foil on each side of the copper-clad laminate that obtains in above 9 utilizes after etching removes, and downcuts the sample of 10mm * 10mm size from substrate.Use TMA (thermo-mechanical analysis device: the thermal coefficient of expansion of measurement on the thickness direction product of TA Instrument Co.).This temperature is that the rate of heat addition with 10 ℃/min is elevated to 150 ℃ from room temperature under the load of 2g, and it reduces then and the speed followed again with 10 ℃/min is increased to 300 ℃.The mean thermal expansion coefficients of calculating in room temperature to 250 ℃ scope.
The narration of preferred embodiment
Application Example 1
This right-aramid staple fiber that is used for by anisotropic polymer solution being carried out the formed Wholly aromatic polyamide fiber of spinning is to be made of PPTA.After spinning, be 0.36wt% and this staple fibre carries out suitable processing so that the crystalline size on plane (110) is 40 dusts at the content of staple fibre intermediate ion material.The size of staple fibre and length are respectively 1.5 DENIER and 3mm.Phenyl-diformyl m-phenylenediamine solution is deposited under high shear and solidifies in the solution between poly-, between acquisition-and the aromatic polyamides fibrid.Staple fibre and fibrid are dispersed in the water with dispersant, obtain to have the paper making pulp of 0.2wt% fibre concentration.This staple fibre is the 90wt% of the total amount of staple fibre and fibrid.This paper pulp is handled with the square tablet press machine of TAPPI type, and subsequent dewatering obtains to have 70g/cm 2A kind of aromatic polyamide fiber paper of basis weight.Subsequently, by using the calender of forming by a pair of metallic roll that is heated to 300 ℃, at 60kg/cm 2Line pressure under allow this fibrous paper roll processing.Then, paper heats about 2min in 300 ℃ hot-blast stove.By using the fibrous paper that obtains according to the above method, formed the prepreg of resin impregnation.By using the prepreg that is obtained to form the substrate of circuit.The characteristic of full aromatics synthetic fibre paper is listed in Table I with the characteristic that is used for the substrate of circuit.
Application Example 2
This right-aramid staple fiber that is used for by the formed Wholly aromatic polyamide fiber of fiber spinning from crystalline state is to be made of PPTA.After spinning, be 0.36wt% and this staple fibre carries out suitable processing so that the crystalline size on plane (110) is 40 dusts at the content of staple fibre intermediate ion material.The size of staple fibre and length are respectively 1.5 DENIER and 3mm.According to making right-aromatic polyamide fiber paper with the same manner described in the Application Example 1, between just replacing-the aromatic polyamides fibrid, this paper applies and suitably handles with the aqueous solution of the dispersible epoxy resin of bisphenol type water, so that the amount of the epoxy resin that adheres to is 10wt%.Content at coated paper system middle short fiber is 90wt%.By using the fibrous paper that obtains according to the above method, formed the prepreg of resin impregnation.By using the prepreg that is obtained to form the substrate of circuit.The characteristic of Wholly aromatic polyamide fiber paper is listed in Table I with the characteristic that is used for the substrate of circuit.
The comparative example 1
According to Application Example 1 in same mode, only be to use dissimilar staple fibres, make a kind of right-aromatic polyamide fiber paper.In this case, this right-aramid staple fiber (Kevlar, the product of Toray DuPont Ltd.) that is used for by the formed Wholly aromatic polyamide fiber of spinning anisotropic polymer solution is made of PPTA.The content of the ionic species of process dry heat treatment is 0.5wt% after spinning.Crystalline size on plane (110) is 55 dusts.The size of staple fibre and length are respectively 1.5 DENIER and 3mm.Content at the paper middle short fiber that is obtained is the 90wt% of the total amount of staple fibre and fibrid.By using the fibrous paper that obtains according to the above method, formed the prepreg of resin impregnation.By using the prepreg that is obtained to form the substrate of circuit.The characteristic of Wholly aromatic polyamide fiber paper is listed in Table I with the characteristic that is used for the substrate of circuit.
The comparative example 2
According to Application Example 1 in same mode, only be to use dissimilar staple fibres, make a kind of right-aromatic polyamide fiber paper.Right-the aramid staple fiber of Shi Yonging is or not to make by other method of the anisotropic polymer solution of spinning by using a kind of in this case.This staple fibre is by paraphenylene terephthalamide's P-pHENYLENE dI AMINE/3, and 4-oxygen base diphenylene diamine copolymer (Technora, the product of Teijin Ltd.) is formed.The size of staple fibre and length are respectively 1.5 DENIER and 3mm.Content at the paper middle short fiber that is obtained is the 90wt% of the total amount of staple fibre and fibrid.By using the fibrous paper that obtains according to the above method, formed the prepreg of resin impregnation.By using the prepreg that is obtained to form the substrate of circuit.The characteristic of Wholly aromatic polyamide fiber paper is listed in Table I with the characteristic that is used for the substrate of circuit.
The comparative example 3
According to Application Example 1 in same mode, just except the following fact, make a kind of right-aromatic polyamide fiber paper.Right-the aramid staple fiber of Shi Yonging is or not to make by other method of the anisotropic polymer solution of spinning by using a kind of in this case.This staple fibre is by paraphenylene terephthalamide's P-pHENYLENE dI AMINE/3, and 4-oxygen base diphenylene diamine copolymer (Technora, the product of Teijin Ltd.) is formed.The size of staple fibre and length are respectively 1.5 DENIER and 3mm.Content at the paper middle short fiber that is obtained is the 90wt% of the total amount of staple fibre and fibrid.Between replacement-and aromatic polyamides, this paper applies and suitably handles with the aqueous solution of the dispersible epoxy resin of bisphenol type water, so that the amount of the epoxy resin that adheres to is 10wt%.By using the fibrous paper that obtains according to the above method, formed the prepreg of resin impregnation.By using the prepreg that is obtained to form the substrate of circuit.The characteristic of Wholly aromatic polyamide fiber paper is listed in Table I with the characteristic that is used for the substrate of circuit.
Table I
The characteristic of paper The characteristic of circuit substrate
Degree of crystallinity % Crystalline size (110 plane) dust The content of ionic species (wt%) Density g/cm 3 Change in size % in heating process The inflection temperature of change in size ℃ Ppm/ ℃ of thickness direction thermal coefficient of expansion The intensity Kg/cm of paper Extracting electrical conductivity μ s/cm Insulating reliability under high humility (minimum) DIMENSIONAL STABILITY Anti-sweating heat performance sec On the thickness direction thermal coefficient of expansion ppm/ ℃
??500h ??0 ???1000h ???0 % behind molding % after etching
Application examples 1 application examples 2 Comparative Examples 1 Comparative Examples 2 Comparative Examples 3 52.9 53.0 54.0 can't measure and can't measure 73.0 70.0 74.0 50 or lower 50 or lower ????0.03 ????0.03 ????0.50 ????0.02 ????0.02 ???0.63 ???0.53 ???0.53 ???0.47 ???0.47 ????0.030 ????0.030 ????0.036 ????0.046 ????0.046 ????275 ????170 ????275 ????255 ????170 ????140 ????340 ????150 ????170 ????1200 ????4.4 ????8.0 ????4.2 ????6.0 ????9.7 ????3 ????3 ????40 ????4 ????5 ??3.7×10 -??3.7×10 -??7.3×10 -??6.4×10 -??1.0×10 - ???6.7×10 -???6.7×10 -Short circuit 2.2 * 10 10???3.5×10 - ????0.08 ????0.08 ????0.07 ????0.12 ????0.15 ????0.15 ????0.15 ????0.17 ????0.35 ????0.33 ????1500 ????1500 ????1400 ????500 ????500 ????160 ????180 ????160 ????230 ????250

Claims (9)

1. Wholly aromatic polyamide fiber paper, be characterised in that: this Wholly aromatic polyamide fiber paper comprises the Wholly aromatic polyamide fiber of 60-97wt% and the binding agent of 3-40wt%; Content at above-mentioned fibrous paper intermediate ion material is to be lower than 0.5wt%; The degree of crystallinity of this aramid fibre is 45% or higher; Crystalline size (ACS: be 50 dusts or bigger apparent crystalline size (110 plane)) with this aramid fibre.
2. according to the Wholly aromatic polyamide fiber paper of claim 1, be characterised in that the following fact: this Wholly aromatic polyamide fiber is a PPTA.
3. according to the fibrous paper of claim 1, be characterised in that the following fact: the length of this Wholly aromatic polyamide fiber is 2-14mm.
4. according to the Wholly aromatic polyamide fiber paper of claim 1, be characterised in that the following fact: the density of this paper is 0.45-0.85g/cm 3
5. according to the Wholly aromatic polyamide fiber paper of claim 1, be characterised in that the following fact: 300 ℃ down after these paper of heating 10 minutes the change in size in paper be 0.03% or lower.
6. according to the Wholly aromatic polyamide fiber paper of claim 1, be characterised in that the following fact: the thermal coefficient of expansion at this paper on the thickness direction is in 50-400ppm/ ℃ of scope.
7. according to the Wholly aromatic polyamide fiber paper of claim 1, be characterised in that the following fact: the extracting conductance of this paper is 10 μ S/cm or lower.
8. according to the Wholly aromatic polyamide fiber paper of claim 1, be characterised in that the following fact: this TENSILE STRENGTH is 1.5kg/cm or higher.
9. one kind comprises that wherein the thermal coefficient of expansion of laminated board is 200ppm/ ℃ or lower with the laminated board of the fibrous paper of the claim 1 of one deck at least of thermosetting resin dipping.
CN00810718A 1999-07-22 2000-06-29 Wholly aromatic polyamide fiber paper and laminated sheet therefrom Pending CN1364208A (en)

Applications Claiming Priority (2)

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JP11208033A JP2001049593A (en) 1999-07-22 1999-07-22 Fiber paper comprising wholly aromatic synthetic fiber and method for producing the same and laminate
JP208033/99 1999-07-22

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CN1364208A true CN1364208A (en) 2002-08-14

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WO2010009613A1 (en) * 2008-07-22 2010-01-28 成都龙邦新材料有限公司 Base paper of aramid fiber honeycomb core and preparing method thereof
CN103282412A (en) * 2011-01-04 2013-09-04 帝人芳纶有限公司 Electrical insulating paper
CN103897389A (en) * 2012-12-26 2014-07-02 钦焕宇 Aramid fiber fire retardation plate and preparation method thereof
CN107498952A (en) * 2017-08-01 2017-12-22 华南理工大学 Meta-aramid fibers/all-glass paper base copper-clad laminate and its manufacture method
CN108570877A (en) * 2017-03-14 2018-09-25 南京新莱尔材料科技有限公司 A kind of manufacturing method of high-frequency high-speed circuit board p-aramid fiber base prepreg
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US5028372A (en) * 1988-06-30 1991-07-02 E. I. Du Pont De Nemours And Company Method for producing para-aramid pulp
KR100526727B1 (en) * 1997-09-09 2005-11-09 이 아이 듀폰 디 네모아 앤드 캄파니 Wholly Aromatic Synthetic Fiber Produced by Liquid-crystal Spinning, Process for Producing the Same, And Use Thereof

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CN1300413C (en) * 2004-03-23 2007-02-14 华南理工大学 Amide aramid fiber paper, preparation method and application
WO2010009613A1 (en) * 2008-07-22 2010-01-28 成都龙邦新材料有限公司 Base paper of aramid fiber honeycomb core and preparing method thereof
US8764941B2 (en) 2008-07-22 2014-07-01 Longpoint Co., Ltd. Base paper of aramid fiber honeycomb core and manufacturing method thereof
CN103282412A (en) * 2011-01-04 2013-09-04 帝人芳纶有限公司 Electrical insulating paper
CN103282412B (en) * 2011-01-04 2018-04-10 帝人芳纶有限公司 Electrically-insulating paper
CN103897389A (en) * 2012-12-26 2014-07-02 钦焕宇 Aramid fiber fire retardation plate and preparation method thereof
CN108570877A (en) * 2017-03-14 2018-09-25 南京新莱尔材料科技有限公司 A kind of manufacturing method of high-frequency high-speed circuit board p-aramid fiber base prepreg
CN107498952A (en) * 2017-08-01 2017-12-22 华南理工大学 Meta-aramid fibers/all-glass paper base copper-clad laminate and its manufacture method
CN107498952B (en) * 2017-08-01 2019-10-18 华南理工大学 Meta-aramid fibers/all-glass paper base copper-clad laminate and its manufacturing method
CN110154464A (en) * 2019-06-14 2019-08-23 赣州龙邦材料科技有限公司 Aramid fiber paper base flexibility coat copper plate and its manufacturing method

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WO2001007713A1 (en) 2001-02-01
KR20020047088A (en) 2002-06-21

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