CN102333735A - Glass composition for glass fiber, glass fiber, and sheet-shaped material of glass fiber - Google Patents

Abstract

A glass composition for glass fiber, characterized by comprising, in terms of oxide contents by mass, 45 to 65% of SiO2, 10 to 20% of Al2O3, 13 to 25% of B2O3, 5.5 to 9% of MgO, 0 to 10% of CaO, 0 to 1% of (Li2O+Na2O+K2O), SrO, and BaO; a glass fiber which consists of the glass composition and which has an average fiber diameter of 3 to 7.2[mu]m; and a sheet-shaped material of the glass fiber, which is to be combined with an organic resin and thus form an organic resin composite material.

Description

Spun glass is with glass composition, spun glass and spun glass sheet thing

Technical field

The glass composition that the employed meltbilities such as PC board that need high-density installation that the present invention relates in electronic unit etc., to use, the spun glass that spinnability is good are used, the spun glass that constitutes by this glass composition and the spun glass sheet thing that constitutes by this spun glass.

Background technology

Development along with mobile phone, personal digital assistant device various information equipments such as (PDA); Be in the trend of background with the high-density installation technology, the situation that the electronic unit of One's name is legions such as resistor, electrical condenser, unicircuit is installed on the PC board (being also referred to as printed substrate, rigid substrates, printed base plate or PC board) with the high-density that did not have in the past increases.PC board is with an amount of matrix material that has the chip shape that forms that mixes such as resin, spun glass and properties-correcting agent; Has the form that is provided with through hole of being used to carry various electronic units etc.; According to its function, purposes, also use another names such as module, plate, unit or package to show sometimes.

In the spun glass that uses in this PC board purposes, use to have the glass composition that is called E glass that existing non-alkali glass is formed.The electrical insulating property of this E glass is good, is the also good materials of processibility such as, cutting processing good as the spinnability of spun glass when molten state begins to make, and therefore, has multiple use actual effect, is that the spun glass of knowing is the most used glass material.And E glass is for example represented with the quality percentage that oxide compound converts, is to comprise SiO ₂52～56%, Al ₂O ₃12～16%, B ₂O ₃5～10%, CaO 16～25%, MgO 0～5%, alkalimetal oxide (R ₂O) 0～2%, Fe ₂O ₃0.05 the glass material of F20～1.0%～0.4%.

On the other hand, in the purposes of PC board, need to use high frequency in recent years in order to realize the high speed electronic circuit, but attention this moment is the electrical characteristic of PC board.Because the square root of transmission speed and specific inductivity is inversely proportional to, therefore, need lower specific inductivity in order to improve transmission speed.In addition, require dielectric loss little, therefore need dielectric loss angle tangent less.Need to prove that the specific inductivity described in the present invention (ε) is that the ratio of specific inductivity and the specific inductivity of vacuum of expression medium is the dimentionless quantity of relative permittivity exactly, but is expressed as specific inductivity (ε) by convention.Generally speaking, when in glass, feeding alternating current, glass carries out energy absorption to alternating current, absorbs as heat.The dielectric loss energy that is absorbed is used W=kfv with proportional by the specific inductivity and the dielectric loss angle tangent of the composition of glass and structures shape ²* ε tan δ representes.At this, W representes the dielectric loss energy, and k representes constant, and f representes frequency, v ²The expression potential gradient, ε representes specific inductivity, tan δ representes dielectric loss angle tangent.Can be known that by this formula specific inductivity and dielectric loss angle tangent are big more, and frequency is high more, then dielectric loss is big more.Therefore, in order to reduce dielectric loss, require to set specific inductivity and dielectric loss angle tangent less.

Therefore; Require specific inductivity and the low spun glass of dielectric loss angle tangent to use material for the spun glass that uses in the PC board; Disclose a kind of glass material of the D of being called glass in the patent documentation 1, it is used to realize under the room temperature, the specific inductivity during frequency 1MHz is 6.7, dielectric loss angle tangent is 12 * 10 ^-4Specific inductivity that is lower than E glass and dielectric loss angle tangent.This D glass is that the quality percentage that for example converts with oxide compound is represented, comprises SiO ₂74.5%, Al ₂O ₃0.3%, B ₂O ₃21.7%, CaO 0.5%, Li ₂O 0.5%, Na ₂O 1.0%, K ₂The glass material of O 1.5%, the specific inductivity of the 1MHz of this glass are about 4.3, dielectric loss angle tangent is about 10～20 * 10 ^-4

But,, pointed out variety of issue aspect first-class in the manufacturing process of PC board, spun glass though D glass is good aspect electric property.For example D glass is poorer than glass melting property with the E glassy phase, and easy multiple fracture of wire etc. is difficult to carry out the manufacturing of spun glass during spinning.In addition, D glass is structurally more crisp, and therefore, poor in the weaving property that is used to form to obtaining in the weaving process that cloth form that PC board uses carries out, the result causes product percent of pass to descend.In addition, use the PC board of D glass, also exist: forming what do not embed the electronic unit lead-in wire is that the through hole of purpose is that the abrasion to drill bit increases the problem that the positional precision of through hole reduces in the drilling operating of via hole (Via Hole) with the interlayer conduction.

In order to solve above-described problem, a lot of inventions have been carried out up to now.For example disclose a kind of glass fiber with low dielectric constant in the patent documentation 2, it is characterized in that,, had SiO in quality % ₂50～60%, Al ₂O ₃10～18%, B ₂O ₃18～25%, CaO 0～10%, MgO 1～10%, Li ₂O+Na ₂O+K ₂O 0～1.0%, Fe ₂O ₃0.1～1% glass is formed.

Disclose a kind of glass fiber with low dielectric constant in the patent documentation 3, it is characterized in that,, had SiO in quality % ₂50～60%, Al ₂O ₃10～20%, B ₂O ₃20～30%, CaO 0～5%, MgO 0～4%, Li ₂O+Na ₂O+K ₂O 0～0.5%, TiO ₂0.5～5% composition.

In addition, disclose a kind of low-k low dielectric loss angle tangent glass in the patent documentation 4, it is characterized in that, having SiO in quality % ₂48～80%, Al ₂O ₃0～18%, B ₂O ₃11～35%, MgO 0～10%, CaO 0～10%, Li ₂O+Na ₂O+K ₂O 0～7%, TiO ₂The composition of less than 3%, and H ₂Specific inductivity under the O＜800ppm, 1MHz is below 5.0, dielectric loss angle tangent is 7 * 10 ^-4Below.

The prior art document

Patent documentation

Patent documentation 1: japanese kokai publication sho 63-2831 communique

Patent documentation 2: japanese kokai publication hei 10-167759 communique

Patent documentation 3: japanese kokai publication hei 8-333137 communique

Patent documentation 4: TOHKEMY 2003-137590 communique

Summary of the invention

But; Only with invention disclosed so far; Realize generation that has sufficient mechanical property and suppress glass defects such as devitrification easily and the glass material of realizing low-k and low dielectric loss angle tangent; Obtain the spun glass of low-k and low dielectric loss angle tangent, also existence needs the further problem of solution.

The glass composition of patent documentation 2 for example; Though successfully reduced the specific inductivity and the dielectric loss angle tangent of spun glass; But the meltbility at glass melting initial stage existing problems, easy residual bubble in the melten glass is not claimed fully for the melten glass that obtains homogeneous during glass melting.

In addition, PC board is carried in many electronic installations, and the peripheral environment of the electronic installation that is carried is various.For example, be equipped with many unicircuit on the present automobile.These electronic units are installed on the PC board to high-density, thereby the parts that require to use in the automobile are from guaranteeing safety to going on the road in the north extremely under the hot weather in midsummer.In addition, passenger car in recent years is in order fully to guarantee by bus space, how electronic circuit etc. is provided in around engine room or the engine room periphery etc. that envrionment temperature is high, temperature variation compared in the violent in the past environment.And the substrate size of lift-launch also requires miniaturized.

In view of so multiple situation changes, the printed substrate that begins the vehicle-mounted purposes of requirement has existing degree above hear resistance and high through hole reliability.This is because the thermal linear expansion coefficient of PC board and installation parts there are differences, thereby therefore must definitely avoid braze welding joint generation thermal stresses under hot environment and the generation of the fault that to cause that the soldering crackle can't obtain to be electrically connected etc. big.That is, the electronic unit that uses in the vehicle-mounted purposes does not allow to break down because of bigger temperature variation causes electronic circuit, but and requires its safety long term maintenance.Therefore, in order to satisfy such requirement, therefore the PC board that reduce to use in the environment of vehicle-mounted purposes and the thermal linear expansion coefficient of installation parts poor require to reduce thermal linear expansion coefficient.Therefore, require to be lower than the spun glass that the glass material of E glass forms by thermal linear expansion coefficient.

In addition; Along with of the propelling of reflection electronics to the slimming of the printed base plate of the requirement of compactization; The spun glass that uses in the PC board tends to require the littler spun glass kind in fiber footpath; But under the viscosity of spinning temperature height and glass as D glass can the situation with temperature variation generation noticeable change, what is called " long property " glass; Be difficult under limited manufacturing environment, make the little high-quality spun glass in fiber footpath with flawless stable quality, therefore, what is called " short " glass that the changes viscosity with temperature of requirement manufacturing glass sharply changes.The glass composition of patent documentation 3 has 10 ^3.0The tendency that the spinning temperature of dPas is high, " long property " glass that is that the temperature dependency of viscosity is little is inappropriate for and makes the little spun glass in fiber footpath.Therefore in addition, under the high situation of spinning temperature, can apply big load, also have the problem of the life expectancy shortening of bushing (bushing) producing apparatus of etc.ing that uses when spun glass pulled out producing apparatus.There are the problem of the life expectancy shortening of device for spinning in the glass composition of patent documentation 4, spinning temperature up to more than 1300 ℃.

In addition, make the little spun glass in fiber footpath aspect, be included in bubble in the melten glass sometimes as defective and become easily the reason of breakout in the spinning of spun glass.In addition, sneak into as tubular fibre under the situation in the PC board at the spun glass that contains bubble, through hole plating material can invade in the tubular fibre, thereby has the danger of poor flow, makes the reliability decrease of PC board thereby has problems.As D glass as 10 of melt temperature standard ^2.0Under the high situation of the temperature of dPas, need huge energy during fusion, thereby and see during fusion more bubble fully come-up produce the situation of a large amount of tubular fibres.In order to reduce the number of bubbles in the melten glass, it is effective using finingss such as arsenus acid, ANTIMONY TRIOXIDE SB 203 99.8 PCT.But these finingss also are the carrying capacity of environment materials, contain these elemental compositions in the employed member of electronics and are regarded as problem.

Problem of the present invention is to provide solution above-mentioned variety of issue; Melt temperature is low thereby obtain the melten glass of homogeneous easily; The spinnability of spun glass is good; Has high chemical durability; Can realize the desired low-k of PC board and the low dielectric loss angle tangent of high-density installation; And the spun glass with low coefficient of linear thermal expansion is used compsn; With through this spun glass is carried out spun glass that spinning obtains and the spun glass sheet thing that is formed by this spun glass with the glass of compsn.

The inventor etc. have carried out a large amount of research repeatedly for the glass fiber compound of the problem of desired many difficulties in the purposes that can overcome the PC board that can carry out high-density installation effectively and can stably manufactured fiber footpath little spun glass; Wherein, Particularly pay close attention to the effect of the alkali earth metal in the glass composition; The result finds, through adding these compositions of specified amount, can solve above-mentioned variety of issue; Can access the glass fiber compound of the premium properties that performance do not have so far and this glass fiber compound is configured as the little spun glass in fiber footpath, thereby propose the present invention at this.

Spun glass of the present invention is used glass composition, it is characterized in that, representes with the quality percentage that oxide compound converts, and contains SiO ₂45～65%, Al ₂O ₃10～20%, B ₂O ₃13～25%, MgO5.5～9%, CaO 0～10%, Li ₂O+Na ₂O+K ₂O 0～1%, SrO, BaO.

At this, represent with the quality percentage that oxide compound converts, contain SiO ₂45～65%, Al ₂O ₃10～20%, B ₂O ₃13～25%, MgO 5.5～9%, CaO 0～10%, Li ₂O+Na ₂O+K ₂O0～1%, SrO, BaO are meant following implication.

That is, when representing with the oxide compound conversion through the elemental composition of using various analysis means such as chemical analysis, device analysis will constitute glass, during glass is formed, SiO ₂Composition in the scope of 45 quality % to 65 quality %, Al ₂O ₃Composition in the scope of 10 quality % to 20 quality %, B ₂O ₃Composition is in the scope of 13 quality % to 25 quality %, and the MgO composition is in the scope of 5.5 quality % to 9 quality %, and the CaO composition is below the 10 quality %, Li ₂O composition, Na ₂O composition and K ₂The total amount of O composition is below the 1 quality %, and contains SrO composition, BaO composition.

In addition, spun glass of the present invention, is represented with the quality percentage that oxide compound converts, if also contain 0.01～5.0% CeO except that mentioned component with in the glass composition ₂, then can reduce the number of bubbles in the melten glass, the generation of tubular fibre reduces, and can access the high spun glass of uniformity.

In addition, spun glass of the present invention is with in the glass composition, except that mentioned component; Quality percentage so that oxide compound converts is represented; If also contain SrO 0.1～10%, BaO 0.1～10%, therefore the glass composition of the crystallization property separated out in the time of then accessing glass melting, the state that so-called increased devitrification resistance is low can easily carry out glass melting; And the water tolerance of glass, acid resistance can not reduce yet, thereby preferred.

Promptly; With likewise above-mentioned; Quality percentage so that oxide compound converts representes to contain SrO 0.1～10%, BaO 0.1～10% is meant, when constituting the elemental composition of glass with oxide compound conversion expression, except that the formation that above-mentioned glass is formed; The SrO composition is 0.1 quality % to 10 quality %, and the BaO composition is 0.1 quality % to 10 quality %.

Below, the qualification reason of above formation spun glass of the present invention with the content of each composition of glass composition specified.

SiO ₂Composition is the composition that constitutes its cancellated skeleton in the glass structure, is the staple of glass composition of the present invention, the SiO in the glass composition ₂The content of composition increases the big more tendency of structural strength that glass is then arranged more.When the structural strength of glass increased, chemical durability also correspondingly improved, and particularly aspect acid resistance, has high-performance.For the sufficient state of the strength maintenance that makes glass structure, obtain having the glass of stabilizing quality, need be with SiO ₂The content of composition is set at more than the 45 quality % at least, more preferably is set at more than the 48 quality %.On the other hand, the SiO in the glass composition ₂When the content of composition increased, the high temperature viscosity value of melten glass increased, and the result then needs the equipment of high price if will make such glass composition in heterogeneity with high-level efficiency through scorification.Forming temperature when in addition, being configured as spun glass also raises.Restriction is considered also to exist sometimes in aspects such as equipment control during therefore, from manufacturing.In addition, melten glass, the glass melting of the homogeneous of bubble of generation etc. do not need excessive heat energy and the high spinning property when guaranteeing to make spun glass when obtaining not residual glass reaction easily when making glass melting etc., need be with SiO ₂The content of composition is set at the content below 65%.

Al ₂O ₃Composition is to be used to realize the chemistry of glass, the effective constituent of mechanical stability, through in glass, containing in right amount, have the effect that the crystallization that suppresses in the melten glass is separated out, phase-splitting generates sometimes, but volume contains the viscosity that increases melten glass sometimes.Al during glass is formed ₂O ₃Composition contain quantity not sufficient 10 quality % the time, fusion time-division phasic property variation, thereby not preferred.Branch phasic property variation in the melten glass can cause the acid resistance variation of the spun glass of gained, thereby not preferred.Here, phase-splitting is meant that melten glass is separated into the phenomenon of two or more multiple glassy phases.On the other hand, the Al during glass is formed ₂O ₃When the content of composition excessively increases, other composition, particularly SiO ₂The content of composition reduces relatively, and above-mentioned acid resistance is shown detrimentally affect, so Al ₂O ₃The content of composition need be set at below the 20 quality %, more preferably below the 18 quality %, further be preferably below the 17 quality %, further be preferably below the 16 quality %, most preferably be below the 15 quality %.

B ₂O ₃Composition and SiO ₂Composition is same, is in the glass reticulated structure, to constitute the composition of its skeleton, but can look like SiO ₂The composition that kind increases the high temperature viscosity of melten glass, has the effect that high temperature viscosity is descended on the contrary.Therefore, B ₂O ₃The specific inductivity that composition has the glass of the shaping of making simultaneously keeps lowlyer and suppresses the effect that the high temperature viscosity of melten glass increases.B during glass is formed ₂O ₃The content of composition when less than 13 quality %, is difficult to when the specific inductivity that makes glass keeps below 6.0, make as 10 of spinning temperature sometimes ^3.0The temperature of the melten glass during dPas is for guaranteeing 1300 ℃ the temperature of being lower than of abundant spinnability.On the other hand, B ₂O ₃When the content of composition in glass is formed is too much, B in the melting process ₂O ₃The steam output of composition increases, and is difficult to make melten glass to keep the state of homogeneous sometimes.In addition, B ₂O ₃When the content of composition is too much, the easy variation of acid resistance, thus cause the branch phasic property variation in the melten glass.Consider the B during glass is formed from such viewpoint ₂O ₃When composition surpasses 25 quality %, the acid resistance of glass, branch phasic property variation, thereby not preferred.

The MgO composition is the composition with the effect that makes the easy fused fusing assistant of frit, simultaneously for reducing by 10 ^2.0The pairing high temperature viscosity of the temperature of dPas is very effective, and the bubble of glass is eliminated well when making fusion, helps to make the glass of homogeneous.In addition, has reduction by 10 ^3.0The temperature of dPas, make glass become the effect of short-nature glass, therefore, productivity is very good, helps the little spun glass in producd fibers footpath effectively.But, be 10 in order in this glass composition, to make spinning temperature ^3.0Near the dPas high temperature viscosity descends, and the MgO composition will reach effective acting state and need be set at more than the 5.5 quality %.On the other hand, when the content of MgO composition in glass is formed was too much, the branch phasic property of melten glass raise, the acid resistance variation.In addition, specific inductivity also rises, and therefore considers from such viewpoint, does not preferably surpass 9 quality %.

The CaO composition is likewise to have with the MgO composition to make 10 ^2.0The composition of the effect that the viscosity of the pairing melten glass of temperature of dPas descends, minimum in the increase ratio of the composition medium dielectric constant microwave medium that constitutes by alkali earth metal.But, when containing the CaO composition in a large number during glass is formed, divide phasic property to uprise, the acid resistance of glass descends.In addition, the specific inductivity of glass also increases along with the increase of CaO composition.Therefore, the CaO composition does not preferably surpass 10 quality %.

For with Li ₂O composition, Na ₂O composition or K ₂The alkalimetal oxide composition that oxide compound during the glass that the form of O composition is represented is formed converts and representes; When multiple frit is processed glass melt with the admixture heating; Performance is easy to generate glass melt, is the effect of so-called fusing assistant, and has the effect that reduces high temperature viscosity.But, Li ₂O composition, Na ₂O composition or K ₂When the content of O composition in glass is formed increases, the dielectric loss angle tangent of glass is increased, so the higher limit of its total amount is till the 1 quality %.

The SrO composition is to have to make 10 ^2.0The viscosity of the pairing melten glass of temperature of dPas descends and makes 10 of melten glass ^3.0The composition of the effect that near the spinning temperature the dPas descends, but its effect is not as good as MgO, CaO composition.But therefore branch phasic property variation when the SrO composition is the glass melting that causes for the increase because of MgO, CaO composition and the glass acid resistance that accompanies the with it inhibited composition that descends is essential composition in the present invention.Like this contain the SrO composition various act on glass form in content be that 0.1 quality % is more obvious when above.On the other hand, when the glass composition that the making spun glass is used,, then can obtain slow-setting glass, be difficult to make the little spun glass in fiber footpath if the SrO component content is too much.Consider that from such viewpoint the upper content limit of SrO composition is preferably till the 10 quality %.During glass melting, if divide the phasic property variation, then melten glass can be separated into the good phase of acid resistance and acid resistance difference mutually, this moment the acid resistance difference the acid resistance that determines spun glass mutually, so as the acid resistance variation of spun glass, thereby not preferred.

The BaO composition is to have equally with the SrO composition to make 10 ^2.0The viscosity of the pairing melten glass of temperature of dPas descends and makes 10 of melten glass ^3.0The composition of the effect that near the spinning temperature the dPas descends, but its effect is not as good as MgO, CaO composition.But the BaO composition is the inhibited composition that descends branch phasic property variation that causes for the increase because of MgO, CaO composition and the glass acid resistance that accompanies with it, likewise is to realize the necessary composition of the object of the invention with the SrO composition.For the BaO composition, also with the SrO composition likewise, in glass is formed content be 0.1 quality % when above its contain produce effect more obvious.On the other hand, when making the glass composition that spun glass uses, if the content of BaO composition is too much, liquidus temperature variation then, and can become slow-setting glass, be difficult to make the little spun glass in fiber footpath.Consider that from such viewpoint the content of BaO composition is preferably the scope till the 10 quality %.Slow-setting glass is meant the glass that viscosity is little to the dependency of temperature variation, is difficult to be cured as fiber through cooling.

In addition, SrO composition and BaO composition are easy and SiO ₂Form crystallization, if comprising SiO ₂Glass contain the SrO composition in forming, then separate out SrOSiO easily ₂Crystallization in addition, if contain the BaO composition, is then separated out BaO2SiO easily ₂Crystallization, the tendency that the result has the liquidus temperature of glass to raise.If liquidus temperature is high during the spun glass spinning, then the bushing nozzle can stop up because of the crystallization that separate out at bushing nozzle place, thereby the problem that spun glass cuts off in spinning occurs.But when in glass is formed, having SrO composition and BaO composition simultaneously, the glass composition falls into SrOSiO ₂With BaO2SiO ₂Eutectic regions, the liquidus temperature of glass descends, and is difficult for separating out crystallization in the spinning, therefore, preferred glass contains SrO composition and BaO composition in forming simultaneously, promptly coexisting has SrO composition and BaO composition.

CeO ₂Make the bubble floating that exists as defective in the melten glass make the effect of glass clarifying easily thereby composition has, add in right amount as the finings of non-ambient load substances, in order to show CeO more significantly ₂The clarification of composition, the quality percentage that converts with oxide compound is expressed as more than 0.01%, more preferably more than 0.02%.But, add CeO too in large quantities ₂During composition, influence the increased devitrification resistance of melten glass sometimes.Consider from such viewpoint, represent should not surpass 5% with the quality percentage that oxide compound converts.In order to obtain more stable quality, its higher limit is preferably till 4%, more preferably till 2%.If be the righttest addition, then can realize non-hollowization of spun glass thus.

Spun glass of the present invention in the scope of not remarkably influenced spun glass of the present invention with the performance of glass composition, can add various compositions with in the glass composition as required except that mentioned component.Illustration can be used as the material of spun glass of the present invention with the constituent use of glass composition particularly, can contain ZrO with the content that quality % is expressed as below 3% ₂, P ₂O ₅, Fe ₂O ₃, SO ₂, Cl ₂, F ₂, La ₂O ₃, WO ₃, Nb ₂O ₅And Y ₂O ₃Deng rare-earth oxide or MoO ₃Deng.

In addition, except that mentioned component, can contain with quality % and represent the trace ingredients till 0.1%.For example, Cr ₂O ₃, H ₂O, OH, H ₂, CO ₂, CO, He, Ne, Ar and N ₂Belong to such composition etc. various trace ingredientss.

In addition, spun glass of the present invention under the situation of not remarkably influenced spun glass with the performance of glass composition, can contain the precious metal element of trace with in the glass composition in glass.For example, can contain till the 1000ppm, belong to element for the platinum such as Pt, Rh and Os till 0.1% when promptly representing the content of metallic element with quality percentage.

In addition, spun glass of the present invention is with in the glass composition, except that mentioned component; When the quality percentage that converts with oxide compound is represented; The value that the total amount that the total amount that the alkaline earth metal oxide of MgO, CaO, SrO and BaO converts is 10～25%, the total amount of SrO and BaO converts divided by alkaline earth metal oxide obtains is in 0.15 to 0.50 the scope time, the phase-splitting of glass in the time of can suppressing fusion, thus avoid the caused acid proof decline of phase-splitting; And spinning temperature reduces; Can obtain short-nature glass, therefore can improve the productivity of non-hollow glass, thus preferred.In addition; Crystalline is separated out or phase-splitting causes melten glass to be the dangerous little of heterogeneity state during glass melting, and near the temperature dependency of viscosity spinning temperature is big, obtains having the melten glass of short viscosity; And it is can access specific inductivity, the dielectric loss angle tangent of regulation, thereby preferred.

Quality percentage so that oxide compound converts is represented; The value that the total amount that the total amount that the alkaline earth metal oxide of MgO, CaO, SrO and BaO converts is 10～25%, the total amount of SrO and BaO converts divided by alkaline earth metal oxide obtains is to be meant in 0.15 to 0.50 the scope, and the value that the total amount value that the total amount value that the quality percentage that the oxide compound of Sr and Ba converts is represented is represented divided by the quality percentage of the oxide compound conversion of alkaline-earth oxide element M g, Ca, Sr, Ba obtains is in 0.15～0.50 the scope.

When the quality percentage that converts with oxide compound is represented; During insufficient total amount 10 quality % that the alkaline earth metal oxide of MgO, CaO, SrO and BaO converts; The glass melting initial stage is difficult to obtain sufficient homogeneous state; And the viscosity of the glass of molten state increases, so forming temperature too raises the spinnability decline of spun glass.On the other hand, represent that with the quality percentage that oxide compound converts the total amount that the alkaline earth metal oxide of MgO, CaO, SrO and BaO converts surpasses at 25% o'clock, can have problems aspect acid resistance, the branch phasic property.

In addition, during value less than 0.15 that the total amount that the total amount of SrO and BaO converts divided by alkaline earth metal oxide obtains, the content of MgO, CaO is than increasing, and the tendency that raises of the branch phasic property of melten glass increases thus, and specific inductivity also raises, thereby not preferred.On the other hand, the value that the total amount that the total amount of SrO and BaO converts divided by alkaline earth metal oxide obtains surpasses at 0.50 o'clock, and it is too high that specific inductivity possibly become.In addition, spinning temperature Ty raises, and glass becomes the direction of long property, so spinnability descends, and is difficult to make the little spun glass in fiber footpath.

Spun glass of the present invention is used glass composition, except that above-mentioned, if the specific inductivity under the frequency 1MHz is below 6.0 and dielectric loss angle tangent is 20 * 10 ^-4Below, then the dielectric loss of PC board reduces, thereby preferred.

In addition, spun glass of the present invention is used glass composition, except that above-mentioned, if the specific inductivity under the frequency 10GHz is below 6.0 and dielectric loss angle tangent is 100 * 10 ^-4Below, then using the loss of high-frequency PC board medium further to reduce, thus preferred.

Spun glass of the present invention is used glass composition, except that above-mentioned, if the volume specific resistance log ρ under 150 ℃ is that then resistance is fully big more than the 13 Ω cm, and the performance that can play stably during therefore as uses such as PC boards.

In addition, spun glass of the present invention is used glass composition, except that above-mentioned, if 10 ^3.01300 ℃ of the temperature T y less thaies of dPas and Ty deduct 10 ^7.6The value that the temperature T x of dPas obtains is in 300～450 ℃ scope, and the device for spinning, the spinning processes that then need not spun glass carry out bigger change, can make spun glass effectively, thereby preferred.

10 ^3.0The temperature T y of dPas deducts 10 ^7.6The value that the temperature T x of dPas obtains is more than 450 ℃ the time; The viscosity of glass becomes long property; When being spun into the little spun glass in fiber footpath; The curve form that the melten glass of pulling out from the spray nozzle front end that is disposed on the bushing forms in nozzle, to be that meniscus becomes unstable, produces the problem that can not get the neat stable spinnability in fiber footpath.On the other hand, 10 ^3.0The temperature T y of dPas deducts 10 ^7.6The value that the temperature T x of dPas obtains is below 300 ℃ the time; It is too short that the viscosity of glass becomes; Therefore, set that other that be used to obtain the specific fibre footpath are created conditions, for example drawing speed, the isochronous proper range of cooling conditions narrow down, and produces the problem that is difficult to manage the fiber footpath.

Spun glass of the present invention is formed with glass composition by spun glass of the present invention; The MV of the diameter of spun glass is 3～7.2 μ m; Therefore; Need particularly to be applied to through using so little spun glass in fiber footpath, can significantly improve the performance of composites of the PC board purposes of formation under the situation of purposes of PC board etc. of high-density and slimming.

When the MV less than 3 μ m of the diameter of spun glass, it is too small that fiber directly becomes, and therefore the manufacturing yield of spun glass descends sometimes.In addition, can occur environment for use because of the spun glass processed cause through the time deterioration the disperse problem of in the atmosphere isochronous environment aspect of spun glass, perhaps need make up the processing environment that human body etc. is not produced dysgenic high price during recycling etc.Because it is not bring the problems of such environment aspect, thereby preferred.

On the other hand; When the MV of the diameter of spun glass surpasses 7.2 μ m; The spun glass that is to use used all the time glass composition to form even do not use the spun glass that forms by glass composition of the present invention by low-k; Also can access the spun glass of few stay in grade such as glass defect, so the advantage of economic aspect is poor.

Consider from above viewpoint; Spun glass of the present invention is formed with glass composition by spun glass of the present invention; More preferably the MV of its diameter is the scope of 3.1～6.5 μ m, further is preferably the scope of 3.2～6.2 μ m, further is preferably the scope of 3.3～5.5 μ m; And further be preferably 3.4～5.2 μ m, most preferably be 3.8～4.8 μ m.

In addition, spun glass of the present invention except that above-mentioned, if tubular fibre is below 2/100,000 filaments (filament), when then in the purposes that constitutes PC board, using, can obtain the high PC board of safety.

Tubular fibre is to be meant below 2/100,000 filaments, and the tubular fibre number in per 100,000 filaments is below 2.The metering of tubular fibre number can easily be obtained through following method: woven fiber glass impregnated in the steeping fluid that specific refractory power is adjusted to spun glass equates; Under transmission microscopy (50 times), observe then; The radical of the tubular fibre in the organizine of reflex glass cloth, with this value divided by the filament radical of observing and multiply by 100,000.

In addition; Spun glass of the present invention; Except that above-mentioned, if the bubble containing ratio were below 0.01, particularly 0.001/below the m, when then in the purposes that constitutes PC board, using; Can obtain the high composite structure of homogeneity that defective reduces, thus can be according to the design specification performance performance of PC board.

The bubble containing ratio be 0.001/be meant below the m that the number of bubbles in every 1000m filaments of glass is below 1, the counting of this number of bubbles is to be that all bubbles more than the 1mm carry out to bubble length.The counting of number of bubbles, through in microscope with glass fiber impregnated in the steeping fluid that specific refractory power is adjusted to glass equates, can easily measure.

In addition, spun glass of the present invention except that above-mentioned, is below the 50/100g glass if bubble contains proportional, then can realize higher quality, more preferably below the 20/100g glass, further is preferably below the 5/100g glass.Bubble contains ratio representes the number of bubbles in the glass of 100g quality.

For spun glass, can be coated with the coating agent that is used to give desired physicochemical property in its surface.Particularly, can apply collecting agent, antistatic agent, tensio-active agent, inhibitor, tunicle formation agent, coupling agent or lubricant.

If want spendable silane coupling agent in the illustration surface treatment; Have: γ-An Jibingjisanyiyangjiguiwan, N-phenyl-gamma-amino propyl trimethoxy silicane, γ-glycidoxypropyltrime,hoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-(2-amino-ethyl) TSL 8330, β-(3; 4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane, N-β-(N-vinyl benzyl amino-ethyl)-gamma-amino propyl trimethoxy silicane hydrochloride, γ-r-chloropropyl trimethoxyl silane, γ-Qiu Jibingjisanjiayangjiguiwan, vinyltriethoxysilane etc. can suitably be selected according to the kind of the resin of employed and compoundization of spun glass.

Spun glass of the present invention; Except that mentioned component; If is the form that many filaments of glass below 10% are processed chopped strand, yarn or rove with the standard deviation of Fibre diameter divided by the CV value of the glass fiber diameter that obtains with 100 on duty of the MV gained of Fibre diameter; Then except the PC board purposes, in other purposes beyond the PC board, need also can be used to the various occasions of the little spun glass in fiber footpath.The CV value of spun glass surpasses at 10% o'clock, can hinder the plasticity that requires precise shape etc., thereby not preferred.

With the CV value of glass fiber diameter is that the form that many filaments of glass below 10% are processed chopped strand, yarn or rove is meant; By melten glass above-mentioned spun glass of the present invention is carried out spinning; The diameter of each filament in the glass strand that mensuration obtains (glass strand); Making its standard deviation is below 10 divided by MV and the value that multiply by 100 gained; Regulate each condition of spun glass manufacturing installation in the above described manner and carry out spinning, the spun glass that obtains cut off process the glass chopped strand, or add and be twisted into yarn, or will many filaments of glass draw together and be wound as reeling condition and process rove.Explanation is in passing, and the standard deviation of Fibre diameter and MV are the values by the variable calculating of 200 spun glass.

For the CV value of feed glass Fibre diameter is below 10%; For example under the situation of using the glass forming apparatus that is equipped with a plurality of thermotolerance nozzles on the bushing, nozzle bore diameter, nozzle length, nozzle temperature, nozzle free air temperature, injector head pressure, air supply velocity and filaments of glass are pulled out each condition of speed confirm as and be suitable for spun glass of the present invention most and get final product with the condition of compsn.

For spun glass of the present invention; If with the CV value of glass fiber diameter is the form that many spun glass below 10% are processed chopped strand, yarn or rove; Then can the spun glass of homogeneous diameter be shaped with various forms, the woven fiber glass after obtaining shredding, expanding when in the purposes of PC board, using and handling suppresses the change of the hole site that the skew because of chisel edge produces thus in the drilling operating that forms through hole; Thereby it is improve the positional precision in hole, thereby preferred.

In addition, spun glass of the present invention as long as can realize desired performance, can be made through any method of manufacture.The marble hot melt process) for example, can adopt direct forming method (DM method: directly hot melt process), moulding method (MM method: various method of manufacture such as indirectly according to purposes, manufacture.That is, spun glass of the present invention except that aforesaid method, thereby as long as carries out spinning through from the bushing that possesses the thermotolerance nozzle, pulling out the spun glass that spun glass obtains specified diameter.

Spun glass of the present invention; Except that above-mentioned; Use if after processing woven fiber glass or zellglas, form in the purposes of organic resin composite materials, then can access the spun glass that is suitable for constituting high density printed circuit board most with compoundization of organic resin material, thus preferred.

Promptly; After processing woven fiber glass or zellglas, form to use in the purposes of organic resin composite materials and be meant with compoundization of organic resin material; With spun glass as organizine and tram, be made into fabric with the employed various Weaving methods of woven fiber glass through PC board; Perhaps chopped strand is processed zellglas through damp process, drying process, they and compoundization of organic resin material are formed in the purposes of organic resin composite materials thus use again.

Constitute the spun glass of the woven fiber glass that uses spun glass of the present invention and obtain; Be 1～50tex for example, be preferably 1.5～23tex, further be preferably 1.5～15tex, the cross-sectional shape of the filaments of glass of the glass strand of formation boundling etc. need not special qualification.The cross-sectional shape of spun glass can be circle, can be ellipse, also can be Long Circle.Glass fiber bundle add twisting count more preferably 2 times/below the 25mm.

In addition, the woven fiber glass that uses spun glass of the present invention to obtain, more preferably to be respectively 30～100, preferred organizine be that 45～90, tram are the woven fiber glass of 35～90 formation to the radical of throwing a spear of the organizine of every 25mm and tram.

The fabric products that uses spun glass of the present invention to obtain, when the constituent material as PC board used, its manufacturing process particularly was described below.Promptly; To on the bobbin of spun glass of the present invention formed Glass yarn coiling body or Glass yarn folded yarn coiling body, separate easypro Glass yarn or Glass yarn folded yarn with warper warping in addition with compsn; After the starching of starching machine secondary, from the beam winding to the loom beam on it as organizine.It is easypro that the bobbin of Glass yarn coiling body or Glass yarn folded yarn coiling body is separated, and it is used as tram, utilizes air-jet loom etc. to knit the system woven fiber glass.Through to carrying out heating flame and be removed (heating de-oiling) knitting the organic composition that adheres on the woven fiber glass of processing; After in containing the treatment solution of silane coupling agent, flooding also dry (surface treatment); Infiltration resin, range upon range of and make resin solidification is made the plywood that PC board is used thus.

In addition, the zellglas that uses spun glass of the present invention to obtain, under the situation of zellglas that is the use chopped strand, unqualified to the length dimension of this chopped strand.The length dimension of fiber can be selected based on purposes.In addition, the method for manufacture of chopped strand also can adopt arbitrary method.Can the precursor that be spun in the fusion operation be carried out cutting processing immediately after spinning, carry out cutting processing according to purposes with cutting unit again after also can reeling as continuous fibre earlier.At this moment, cutting method also can adopt arbitrary method.For example, can use peripheral edge cutting unit, interior all sword cutting units, beater grinder etc.In addition, do not limit the set form of chopped strand is also special.

In addition, use in the woven fiber glass or zellglas that spun glass of the present invention obtains, according to purposes can and with spun glass of the present invention filamentary material, solid additive, liquid additive in addition.In addition; When constituting woven fiber glass or zellglas; As with filamentary material beyond the spun glass of the present invention of glass fiber material of the present invention and usefulness; Can use spun glass or organic fibrous material, ceramic fiber, thomel of D glass fibre or other compositions etc.; Add material as solid; Ceramic powder, organic resin powder, organosilicon powder etc. are arranged,, can use polymerization promotor, stopper, inhibitor, decomposition reaction suppressor factor, thinner, antistatic agent, anticoalescent, properties-correcting agent, wetting agent, siccative, mould inhibitor, dispersion agent, curing catalyst, reaction promotor, tackifier or reaction promotor etc. in right amount as liquid additive.

Glass fiber sheets of the present invention is characterized in that, with spun glass of the present invention and compoundization of organic resin material and form in the purposes of organic resin composite materials and use.

At this, with spun glass of the present invention and compoundization of organic resin material and form to use in the purposes of organic resin composite materials and be meant, will representing with the quality percentage that oxide compound converts and containing SiO ₂45～65%, Al ₂O ₃10～20%, B ₂O ₃13～25%, MgO 5.5～9%, CaO 0～10%, Li ₂O+Na ₂O+K ₂It is the spun glass sheet thing below the 1mm that the spun glass of O 0～1%, SrO, BaO is processed thickness, and infiltration has the organic resin material of Thermocurable and obtains using in the purposes of organic resin matrix material.

As organic resin material, for example, can use resins such as resol, epoxy resin, polyimide resin or bimaleimide resin with Thermocurable.

In addition, glass fiber sheets of the present invention except that above-mentioned, if the glass flap is woven fiber glass or zellglas, then can be made the PC board of the various performances of performance according to purposes.

As woven fiber glass, can adopt weaving cotton cloth of various structures.For example, can use from weaving cotton cloth to of weaving structures such as plain weave, twill weave and have more weaving cotton cloth of complex construction.In addition, for zellglas, can use chopped strand, in plain boiled water, make it be separated into monofilament after, drain, use organic bond to be configured as flap.For example; Under the situation of using chopped strand; With the melten glass that above-mentioned spun glass of the present invention obtains with the compsn fusion, from the heat-resisting system nozzle that shaping apptss such as bushing set, pull out continuously, and coat collecting agent etc. around it and be configured as long glass fiber.Then, with the long glass fiber that obtains be wound up into paper tube etc. around process yarn cake (perhaps being also referred to as cheese) after, from the yarn cake, pull out required radical in the lump and use the size of spun glass cut as specified length.After being dispersed in the chopped strand that obtains thus in the plain boiled water; Drain on the net, become under the flaky state random be stacked on the travelling belt, the side scatters liquid wedding agent from it; And this wedding agent is solidified; Each glass chopped strand is bonded with each other,, obtains containing the spun glass sheet thing of glass chopped strand through above-mentioned operation.

The effect of invention

(1) spun glass of the present invention is used compsn, representes with the quality percentage that oxide compound converts, and contains SiO ₂45～65%, Al ₂O ₃10～20%, B ₂O ₃13～25%, MgO 5～9%, CaO0～10%, Li ₂O+Na ₂O+K ₂O 0～1%, SrO, BaO, therefore, the spinnability during with the spun glass spinning is good, can easily carry out the shaping of the little spun glass in fiber footpath, and electrical properties such as the specific inductivity of the spun glass of gained, dielectric loss angle tangent are good.

(2) spun glass of the present invention is used compsn, contains 0.01～5.0% CeO if the quality percentage that converts with oxide compound is represented ₂, then can obtain the high spun glass of uniformity by the melten glass that number of bubbles is suppressed, therefore can improve the performance of the spun glass of making efficient, manufacturing, thereby preferred.

(3) spun glass of the present invention is used compsn, if the quality percentage that converts with oxide compound is represented and contained SrO 0.1～10%, BaO 0.1～10%, the increased devitrification resistance due to branch phasic property in the time of then can avoiding glass melting and crystallization are separated out.

(4) spun glass of the present invention is used compsn; The total amount that the alkaline earth metal oxide of MgO, CaO, SrO and BaO converts if the quality percentage that converts with oxide compound is represented be 10～25% and the value that obtains of the total amount that converts divided by alkaline earth metal oxide of the total amount of SrO and BaO be in 0.15 to 0.50 the scope, then be fit to obtain to realize to be suitable for carrying out the high temperature viscosity of spinning operation and the temperature dependency of high temperature viscosity and the acid resistance of glass, the also good spun glass of quality of increased devitrification resistance aspect.

(5) spun glass of the present invention is used compsn, if the specific inductivity under the frequency 1MHz is below 6.0 and dielectric loss angle tangent is 20 * 10 ^-4Below, then can access the little PC board of high speed, dielectric loss that can tackle electrical signal, therefore have the performance that is fit to be applied to PC board.And, if the specific inductivity under the frequency 10GHz is below 6.0 and dielectric loss angle tangent is 100 * 10 ^-4Below, then have the character that is more suitable for being applied to utilizing the PC board of high frequency.

(6) spun glass of the present invention is formed with glass composition by spun glass of the present invention, and the MV of the diameter of spun glass is 3～7.2 μ m, therefore, is particularly suitable for as the PC board of realizing high-density installation.

(7) spun glass of the present invention; Use if after forming woven fiber glass or zellglas, form in the purposes of organic resin composite materials with compoundization of organic resin material; Then can have high performance spun glass with optimal form supply, can improve dielectric characteristics, the thermotolerance of the PC board of using in the various electronic circuits according to purposes.

(8) spun glass sheet thing of the present invention; If in the purposes that spun glass of the present invention and compoundization of organic resin material is formed organic resin composite materials, use, then be fit to make the PC board that need not to change the high-quality and performance of playing stably that existing operation can make.

(9) spun glass sheet thing of the present invention is woven fiber glass or zellglas; Therefore; During the pre-formed articles (prepreg) that in making PC board manufacturing process, uses; Can make not changing under the situation such as create conditions, therefore can not become the obstacle of the manufacturing process of PC board, even be fit to obtain the PC board that in the violent environment of temperature variation, also can use.

Embodiment

Below, carry out bright specifically based on embodiment with compsn, spun glass and method of manufacture thereof to spun glass of the present invention.

Embodiment

The spun glass of embodiments of the invention is shown in table 1 with the composition and the evaluation result of compsn.The glass of the oxide compound conversion expression shown in the table 1 is formed and is all represented with quality %.

[table 1]

For as the sample No.1 of embodiment each glass specimen, prepare glass specimen according to the order of the following stated to sample No.10.

At first, form according to the glass of table 1 respectively, with g unit's multiple frit kinds such as natural mineral frit, chemosynthesis frit of weighing specified amount respectively of 3 behind the radix point.Then, these plurality of raw materials are mixed into the state of homogeneous, preparation frit compound drops into having in the 500cc volumetrical crucible of platinum rhodium system with this frit compound.Then, the platinum rhodium system crucible that this input is had a raw materials mix material makes the frit compound that chemical reaction at high temperature take place in the indirect heating electric furnace, in air atmosphere, 1550 ℃ of heating 5 hours down, obtains melten glass.In order to make this melten glass become the state of homogeneous, in the process of heating and melting, use the thermotolerance stirring rod to carry out the stirring of melten glass.

The melten glass that becomes homogeneous state like this is poured in the resistivity against fire mold of regulation, carries out casting forming, and in lehre, carry out anneal, the glass shaping body that obtains being used to test etc. until reaching room temperature with the regulation shape.

Use the glass shaping body obtain like this, each glass compositions of embodiments of the invention is carried out the metering of various physical propertys etc. according to following order.The result of metering concludes and is shown in table 1.

Metering about thermal linear expansion coefficient; The SRM-731, SRM-738 that are to use NIST are as the known standard test specimen of thermal linear expansion coefficient; Utilize through gauged known linear thermal expansion metering outfit the average thermal linear expansion coefficient that in 30 ℃ to 380 ℃ TR, measures.The value of this thermal linear expansion coefficient is low more, and under the big situation of temperature variation, the expansion of spun glass is more little, the relevant safety of temperature variation that the result can improve the PC board that uses spun glass when carrying in electronics.

10 of the high temperature viscosity of metering expression melten glass ^3.0During the temperature of dPas (Ty); Each glass specimen of pulverizing in advance to appropriate size is dropped in the oxidation aluminum crucible; Carry out reheat, be heated to the liquation state after, through the interior value of calculating respectively separately of inserting of repeatedly measuring the viscosity curve that obtains based on each viscosity value of falling ball method metering.In addition, about the value of the Ty-Tx in the table, be from 10 ^3.0The value of the pairing temperature of dPas deducts 10 ^7.6The pairing temperature of dPas is the value of softening temperature and the value that obtains.In addition, the metering of softening temperature is meant the value of measuring through the method for ASTM C338 regulation.The value of Ty-Tx is little value more, and then the temperature dependency of viscosity is big more, and this glass becomes short-nature glass.Glass for short, then reaches solid state from this molten state through cooling, therefore more more easily; With melten glass from the nozzle that bushing is set up after the spinning; Even under identical cooling conditions, meniscus is also stable, can under situation about can not cut off, produce spun glass.The temperature dependency of the viscosity of spun glass is got over and is long property, becomes unstable thereby then meniscus is longer, therefore, and the auxiliary facility when reinforced glass fibers such as necessary reinforcement cooling conditions are made.

In addition, about liquidus temperature T _LBe shape and the granularity of grinding and processing that each glass shaping body is cut into regulation for stipulating; After removing micro mist and mincing, the granularity that is adjusted to 300 μ m to 500 mu m ranges makes its surface-area that reaches specialized range, under this state, is filled in the container of platinum system with the state with suitable tap density; Put into the indirect heating type temperature gradient furnace that top temperature is set at 1250 ℃ and leave standstill, in air atmosphere, carry out 16 hours heating operations.Then, each platinum container made and test body are taken out, naturally cool to room temperature after, confirm liquidus temperature T with polarizing microscope _LAbout the Ty-T in the table _LValue, be from 10 ^3.0The value of the pairing temperature of dPas deducts liquidus temperature T _LValue and the value that obtains.Ty-T _LValue big more, then near spinning temperature, be not easy more to separate out to hinder and spin the crystallization of operation, thereby can guarantee stable spinning state.In order to increase this Ty-T _LValue, rising spinning temperature pairing 10 ^3.0The temperature T y of dPas gets final product, but can increase the required energy of glass melting like this, thereby produces the problem of the life expectancy that causes auxiliary facilitys such as making original cost raises, shortening bushing device.

About the volume specific resistance under 150 ℃, be based on ASTM C657-78 150 ℃ of values of measuring down.The value of volume resistance is high more, even then carry out the PC board of high-density installation, the electrical insulation capability that also can play stably.

About the metering of specific inductivity (ε) and the dielectric loss angle tangent (tan δ) of frequency 1MHz, the material that two surfaces of thickness 3mm of glass specimen sheet of size that use will be processed as 50mm * 50mm * 3mm obtain after with No. 1200 sand paper grinding.Mensuration is carried out based on ASTM D150-87, at room temperature measures through the 4192A electric impedance analyzer that uses Yokogawa Hewlett-Packard to make to obtain.About the metering of specific inductivity (ε) and the dielectric loss angle tangent (tan δ) of frequency 10GHz, through the two ends short circuit type dielectric resonator method based on JIS R1627:1996, the network analyzer that uses Aglient to make is at room temperature measured and is obtained.Specific inductivity and dielectric loss angle tangent are more little value, and the dielectric loss of PC board is more little when then spun glass being used for constituting the purposes of PC board.

About acid resistance,, will be equivalent to 1cm removing under the granularity that is adjusted to 300 μ m to 500 mu m ranges after micro mist minces the state with the surface-area that reaches specialized range ³Crushed material put in the acid resistance encloses container with the aqueous hydrochloric acid 50cc that is expressed as 10% with quality percentage; Kept 16 hours being set under this state in 80 ℃ the constant-temperature shaking machine; Remove by filter liquid portion then; And in 110 ℃ drying machine, carry out drying, obtain the constant value of glass quality.Then, the mass value after stoichiometric acid is handled is with respect to the decrement of the mass value of the glass of initial input.For the decrement variable that obtains like this is more than 30% and for the sample that forms resultant of reaction in the process of confirming in the acid resisting test in the corrosion reaction of the glass surface that hydrochloric acid causes; The acid resistance of glass descends; Be judged to be " * ", be judged to be " zero " for other samples.This is because when forming resultant of reaction because of corrosion reaction, the meetings of in the manufacturing process of the PC board that uses spun glass, carrying out such as plating processing hinder the treated state of guaranteeing homogeneous when carrying out s.t., cause the dangerous high of qualification rate decline.

Can know following result by above test.That is, for as the test No.1 of embodiments of the invention to the sample of testing No.12, its glass is formed the quality % that converts with oxide compound and is represented it is SiO ₂Be in 47.4% to 54.5% the scope, Al ₂O ₃Be in 11.7% to 18.7% the scope, B ₂O ₃Be in 14.0% to 20.0% the scope, MgO is 5.5～8.7%, CaO is in 3.5～8.8% the scope, Li ₂O+Na ₂O+K ₂O is in 0.1～0.4% the scope, SrO is in 1.1～8.8% the scope, BaO is in 0.8～5.0% the scope, and the value that obtains of the total amount that the total amount that converts of the alkaline earth metal oxide of MgO, CaO, SrO and BaO is in 15.2～21.4% the scope, the total amount of SrO and BaO converts divided by alkaline earth metal oxide is in 0.20 to 0.45 the scope, CeO ₂Be in 0.1～0.9% the scope.

In addition, shown in difference in the table 1, the average coefficient of linear expansion in 30 ℃ to the 380 ℃ TRs of the embodiment of the invention is 39.2 * 10 ^-7～49.0 * 10 ^-7/ ℃ scope in, spinning temperature pairing 10 ^3.0The temperature of dPas is in 1194 ℃～1298 ℃ the scope, 10 ^7.6The temperature T x of dPas is in 828 ℃～880 ℃ the scope, the value of the temperature dependent Ty-Tx of expression viscosity is in 364 ℃ to 426 ℃ the scope.And, the liquidus temperature T of embodiments of the invention _LBe in the scope of the value to 1095 ℃ below 1000 ℃, so Ty-T _LValue be in 162 ℃ to 251 ℃ the scope.And, as 10 of the standard of melt temperature ^2.0The temperature T w of dPas is 1384 ℃ to 1502 ℃ a scope, is the temperature lower than D glass.In addition; About electrical property; Volume specific resistance log ρ under 150 ℃ of embodiments of the invention is that the specific inductivity (ε) in the scope of 13.3 Ω cm～17.9 Ω cm, under the frequency 1MHz is in 5.36～5.82 the scope; Satisfying so-called specific inductivity is the condition of the present invention below 6.0, and the dielectric loss angle tangent under the frequency 1MHz (tan δ) is that also satisfying so-called dielectric loss angle tangent is 20 * 10 in 0.0008～0.0014 the scope ^-4Following condition.In addition; Specific inductivity under the frequency 10GHz (ε) is in 5.4～5.9 the scope; Satisfying so-called specific inductivity is the condition of the present invention below 6.0; Dielectric loss angle tangent under the frequency 10GHz (tan δ) is that also satisfying so-called dielectric loss angle tangent is 100 * 10 in 0.0038～0.0096 the scope ^-4Following condition.And,, have the fine quality below 1.5/100,000 filaments about the tubular fibre number.That is, to sample No.10, has the character that is suitable as glass fiber compound of the present invention as the sample No.1 of the embodiment of the invention.

Below, particularly distinctive sample in the embodiments of the invention is described.

The glass composition of the sample No.1 of embodiment, SiO ₂Content minimum, be 47.4%, but it is by the maximum B that reaches 20.0% ₂O ₃Content replenishes, thereby the coefficient of expansion is 44.7 * 10 ^-7/ ℃, be fully low value, the value of the temperature dependent Ty-Tx of expression viscosity is 364 ℃, is no problem level, and the pairing Ty of spinning temperature be 1194 ℃, as 10 of the standard of melt temperature ^2.0The temperature T w of dPas is 1384 ℃, is abundant low value.And, liquidus temperature T _LBe below 1020 ℃, Ty-T _LValue estimate to be at least more than 190 ℃, thereby be big or small fully.And; Volume specific resistance is 17.5 Ω cm, is fully big value, and the DIELECTRIC CONSTANTS under the frequency 1MHz is 5.50, dielectric loss angle tangent is 0.0010; DIELECTRIC CONSTANTS under the frequency 10GHz is 5.6, dielectric loss angle tangent is 0.0042, all shows less value without a doubt.And about acid resistance, rate of mass reduction is low, does not also observe the formation of resultant of reaction, therefore is judged to be " zero ".In addition, contain CeO ₂, consideration can promote the clarification of melten glass and not produce tubular fibre.Hence one can see that, and the glass composition of the sample No.1 of embodiment is and the corresponding glass composition of the present invention.So; Utilize this glass shaping body to implement the evaluation of spun glassization, the result does not produce problems such as devitrification, does not have residual bubble in the spun glass yet; Tubular fibre number in the reflex glass fiber, the result can judge can spin the spun glass that satisfies the homogeneous below 2/100,000 filaments.

The glass composition of the sample No.2 of embodiment is characterized in that Al ₂O ₃Be 11.7%, be minimum content, and contain CeO ₂This sample No.2 is a typical sample of the present invention, and the coefficient of expansion also is 44.4 * 10 ^-7/ ℃, be lower value without a doubt, and represent that the value of the temperature dependent Ty-Tx of viscosity is 391 ℃ to have sufficient short viscosity.As 10 of the standard of melt temperature ^2.0The temperature of dPas is low to moderate 1436 ℃, and liquidus temperature T _LFor being low to moderate 1054 ℃ value, Ty-T _LValue be 180 ℃, show fully big value.In addition; Volume specific resistance is 17.0 Ω cm, and is fully big, and the specific inductivity under the frequency 1MHz (ε) is 5.49, dielectric loss angle tangent (tan δ) is 0.0014; DIELECTRIC CONSTANTS under the frequency 10GHz is 5.6, dielectric loss angle tangent is 0.0056, is less value.And about acid resistance, likewise rate of mass reduction is low with sample No.1, does not also observe the formation of resultant of reaction, therefore is judged to be " zero ".Also using 200 nozzles to carry out spinning to this sample No.2, to make average fiber directly be 5.0 μ m; And the evaluation of enforcement spun glassization; The result can need not the existing glass producing apparatus is carried out to carry out the stable operation that spins under the situation of bigger change, and the spun glass of gained does not produce problems such as devitrification, yet not residual bubble in the spun glass; Tubular fibre number in the reflex glass fiber, the result can judge can spin the spun glass that satisfies the homogeneous below 2/100,000 filaments.In addition, the MV of the Fibre diameter of 200 these spun glass is that 5.0 μ m, standard deviation are 0.40 μ m, the standard deviation of using Fibre diameter divided by the MV of Fibre diameter and should be on duty be 8% with 100 resulting CV values, obtain good quality.Hence one can see that, has fine qualities and performance as the spun glass of PC board purposes.Therefore, this spun glass is carried out plain weave and makes pre-formed articles, the PC board that obtains thus can be given full play to design performance.

The glass composition of the sample No.4 of embodiment is the maximum glass composition of containing ratio of BaO among the embodiment, and average coefficient of linear expansion is 40.4 * 10 ^-7/ ℃, also be very little value, and 10 ^2.0The temperature T w of dPas is 1491 ℃, 10 ^3.0The temperature of dPas is 1284 ℃, and the value of the temperature dependent Ty-Tx of expression viscosity is 409 ℃, is abundant short glass.In addition, about electrical property, the specific inductivity under the frequency 1MHz (ε) is 5.46, dielectric loss angle tangent (tan δ) is 0.0012, and the DIELECTRIC CONSTANTS under the frequency 10GHz is 5.6, dielectric loss angle tangent is 0.0038, satisfies condition of the present invention.And; About acid resistance; Low with same geology amount decrement such as sample No.1, do not observe the formation of resultant of reaction yet, therefore be judged to be " zero "; The result who implements the spun glass evaluation is, can need not the existing glass producing apparatus is carried out to carry out the stable operation that spins under the situation of bigger change.The spun glass that the glass with sample No.4 that obtains is like this formed; Do not produce problems such as phase-splitting, devitrification yet; Also not residual bubble in the spun glass, the tubular fibre number in the reflex glass fiber, the result can judge can spin the spun glass that satisfies below 2/100,000 filaments.

Use the glass composition of the sample No.2 obtain as stated, make woven fiber glass through plain weave, the result can obtain that tubular fibre is few, specific inductivity and the low woven fiber glass of dielectric loss angle tangent, can bring into play the performance that is fit to the PC board purposes.

[comparative example]

Then, will likewise be shown in Table 2 about investigation result and embodiment according to the pairing sample of comparative example that makes with the same order of embodiments of the invention.For the result of the various mensuration shown in the table 2, the method for its use, the device all identical with embodiment.

[table 2]

The glass composition of the sample No.101 of comparative example has with the glass that is commonly referred to as E glass and forms similarly composition, and thermal linear expansion coefficient is up to 62.5 * 10 ^-7/ ℃, the specific inductivity under the frequency 1MHz is also up to 7.00, and the specific inductivity under the frequency 10GHz is also up to 6.8, and is therefore different fully with the present invention.

The glass composition of the sample No.102 of comparative example does not contain SrO, BaO, but SiO ₂Content up to 76.1%, so acid resistance does not have variation.But, because SiO ₂Content high, so spinning temperature pairing 10 ^3.0The temperature of dPas becomes 1336 ℃ high value.This spun glass is carrying out under the situation of spinning for a long time, can cause the deterioration of making auxiliary facility, also has problems at economic aspect.In addition, as 10 of the standard of melt temperature ^2.0The temperature T w of dPas is more than 1600 ℃, and is very high.Therefore, bubble remains in the glass easily during glass melting, and the value of Ty-Tx is 526 ℃, is slow-setting glass, the spinnability existing problems.

The glass composition of the sample No.103 of comparative example, the total amount of SrO and BaO surpasses 0.5 with respect to the ratio of the total amount of alkaline earth metal oxide.10 ^3.0The temperature of dPas surpasses 1400 ℃, and the value of Ty-Tx is 536 ℃, is slow-setting glass, therefore is difficult to make the little spun glass in fiber footpath, and the meltbility and the spinnability of melten glass have problems.10 ^2.0The temperature T w of dPas is also higher, owing to do not contain CeO ₂, so bubble remains in the glass easily during glass melting.Therefore, form with this glass and can't make that desired to satisfy the tubular fibre number be the spun glass below 2/100,000 filaments.In addition, the dielectric loss angle tangent under the frequency 1MHz is up to 0.0025, and the dielectric loss angle tangent under the frequency 10GHz is also up to 0.0108, so the dielectric loss increase, has the slack-off problem of velocity of propagation.

The glass composition of the sample No.104 of comparative example is the glass composition that does not contain SrO, BaO, and the total amount of SrO and BaO is low to moderate 0.00 with respect to the ratio of the total amount of alkaline earth metal oxide.Therefore, 10 ^3.0The temperature of dPas is up to 1332 ℃.As 10 of the standard of melt temperature ^2.0The temperature T w of dPas is also up to more than 1568 ℃, residual more bubble during glass melting.Observe the branch phasic property during glass melting, in acid resisting test, observe the resultant of reaction that forms with hydrochloric acid reaction, may have problems in the etch processes of therefore in the manufacturing process of PC board, carrying out etc.Volume specific resistance log ρ is 12.7 Ω cm, and is low as the electric safety of PC board.

The glass composition of the sample No.105 of comparative example, the total amount of SrO and BaO is low to moderate 0.05 with respect to the ratio of the total amount of alkaline earth metal oxide.Specific inductivity under the frequency 1MHz of the glass of this sample No.105 is up to 6.10, and the specific inductivity under the frequency 10GHz is also up to 6.2.In addition, the dielectric loss angle tangent under the frequency 1MHz of this sample is also up to 0.0025, and the dielectric loss angle tangent under the frequency 10GHz is also up to 0.0127, so the dielectric loss increase, has the slack-off problem of velocity of propagation.In addition, observe significant minute phasic property during glass melting, this also produces detrimentally affect to acid resistance, is the glass composition that goes wrong.

A series of evaluations through carrying out in embodiment shown in above and the comparative example can be known; Spun glass of the present invention is used glass composition; Be suitable as the little spun glass in fiber footpath that uses in the PC board of realizing high-density installation; Spinnability is good in the manufacturing of spun glass, can make the spun glass that efficient provides stay in grade with height.

Claims (10)

1. a spun glass is used glass composition, it is characterized in that,

Represent with oxide compound reduced mass per-cent, contain SiO ₂45～65%, Al ₂O ₃10～20%, B ₂O ₃13～25%, MgO 5.5～9%, CaO 0～10%, Li ₂O+Na ₂O+K ₂O 0～1%, SrO, BaO.

2. spun glass as claimed in claim 1 is used glass composition, it is characterized in that,

Quality percentage so that oxide compound converts is represented, contains CeO ₂0.01～5.0%.

3. according to claim 1 or claim 2 spun glass is used glass composition, it is characterized in that,

Quality percentage so that oxide compound converts is represented, contains SrO 0.1～10%, BaO 0.1～10%.

4. use glass composition like each described spun glass of claim 1～3, it is characterized in that,

Quality percentage so that oxide compound converts representes that the alkaline earth metal oxide conversion total amount of MgO, CaO, SrO and BaO is 10～25%, and the value that the total amount of SrO and BaO obtains divided by alkaline earth metal oxide conversion total amount is in 0.15～0.50 the scope.

5. use glass composition like each described spun glass of claim 1～4, it is characterized in that,

Specific inductivity under the frequency 1MHz is below 6.0, and dielectric loss angle tangent is 20 * 10 ^-4Below.

6. use glass composition like each described spun glass of claim 1～5, it is characterized in that,

Specific inductivity under the frequency 10GHz is below 6.0, and dielectric loss angle tangent is 100 * 10 ^-4Below.

7. a spun glass is characterized in that,

It uses each described spun glass of claim 1～6 to form with glass composition, and the MV of the diameter of spun glass is 3～7.2 μ m.

8. spun glass as claimed in claim 7 is characterized in that,

Form making woven fiber glass or non-woven fabrics and compoundization of organic resin material in the purposes of organic resin composite materials and use.

9. a spun glass sheet thing is characterized in that,

With claim 7 or 8 described spun glass and compoundization of organic resin material and form in the purposes of organic resin composite materials and use.

10. spun glass sheet thing as claimed in claim 9 is characterized in that,

Spun glass sheet thing is woven fiber glass or glass paper.