CN104364217A - Glass substrate finish-polishing method, and alkali-free glass substrate finish-polished according to said method - Google Patents

Glass substrate finish-polishing method, and alkali-free glass substrate finish-polished according to said method Download PDF

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Publication number
CN104364217A
CN104364217A CN201380029856.5A CN201380029856A CN104364217A CN 104364217 A CN104364217 A CN 104364217A CN 201380029856 A CN201380029856 A CN 201380029856A CN 104364217 A CN104364217 A CN 104364217A
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Prior art keywords
glass substrate
glass
mgo
fluctuating
grinding
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Inventor
德永博文
辻村知之
西泽学
小池章夫
城山厚
横山哲史
金子聪
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AGC Inc
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Asahi Glass Co Ltd
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Publication of CN104364217A publication Critical patent/CN104364217A/en
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C19/00—Surface treatment of glass, not in the form of fibres or filaments, by mechanical means
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)
  • Mechanical Engineering (AREA)
  • Surface Treatment Of Glass (AREA)
  • Liquid Crystal (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)

Abstract

The present invention pertains to a glass substrate finish-polishing method, whereby a polishing slurry containing cerium oxide as abrasive grains is used to polish the main surface of a glass substrate, the composition of the glass substrate being the alkali-free glass described below. The glass substrate finish-polishing method includes a step in which polishing is conducted under conditions in which, when the amount of polishing of the glass substrate is denoted as X (mum) when the height of undulations converted to undulations having a 20 mm pitch on the main surface of the glass substrate changes from 0.14 mum to 0.10 mum, 0.04/X becomes 0.12 or higher. The alkali-free glass has: a strain point of 710 degree centigrades or higher; an average coefficient of thermal expansion at 50 to 350 degree centigrades of 30 * 10-7 to 43 * 10-7/degree centigrades; a temperature (T2) of 1710 degree centigrades or less at which the glass viscosity is 102 dPa.s; and a temperature (T4) of 1320 degree centigrades or less at which the glass viscosity is 104 dPa.s, Furthermore, the alkali-free glass contains, in terms of mol% on an oxide basis, 66 to 70% SiO2, 12 to 15% Al2O3, 0 to 1.5% B2O3, over 9.5 to 13% MgO, 4 to 9% CaO, 0.5 to 4.5% SrO, 0 to 1% BaO, and 0 to 2% of ZrO2; and MgO +CaO + SrO + BaO is 17 to 21, MgO / (MgO + CaO + SrO + BaO) is at least 0.40, MgO / (MgO + CaO) is at least 0.40, and MgO / (MgO + SrO) is at least 0.60.

Description

The smooth grinding method of glass substrate and the alkali-free glass substrate of smooth grinding that utilized the method to carry out
Technical field
The present invention relates to use as various glass substrate for display, photomask glass substrate not carrying out the method for smooth grinding and the alkali-free glass substrate of smooth grinding that utilized the method to carry out containing the alkali-free glass substrate of alkalimetal oxide in fact.
Background technology
In the past, for various glass substrate for display, the glass substrate for display particularly forming metal or sull etc. from the teeth outwards, characteristic shown below was required.
(1), time containing alkalimetal oxide, alkalimetal ion can spread and make membrane property deterioration in film, therefore, and in fact not containing alkalimetal ion.
(2), when being exposed to high temperature in film formation process, in order to suppress at bottom line by the distortion of glass with the contraction (thermal contraction) that the structure stabilization of glass produces, strain point wants high.
(3) sufficient chemical durability to be had to the various chemical that semi-conductor forms middle use.Particularly to for etching SiO x, SiN xbuffered hydrofluoric acid (BHF, the mixed solution of hydrofluoric acid and Neutral ammonium fluoride) and ITO etching in use in the etching containing the liquid of hydrochloric acid, metal electrode that uses various acid (nitric acid, sulfuric acid etc.), resist stripper alkali to have weather resistance.
(4) inner and surperficial without defect (bubble, brush line, inclusion, pockmark, scar etc.).
On the basis of above-mentioned requirements, have also appeared situation as described below in recent years.
(5) require the lightweight of indicating meter, and expect that glass itself is also the glass that density is little.
(6) require the lightweight of indicating meter, and expect the thinning of base plate glass.
(7) on the basis of existing non-crystalline silicon (a-Si) type liquid-crystal display, thermal treatment temp slightly much higher crystal silicon (p-Si) type liquid-crystal display (a-Si: about 350 DEG C → p-Si:350 ~ 550 DEG C) has also been made.
(8) boost productivity to accelerate to make the heat treated intensification of liquid-crystal display and cooling rate or improve resistance to sudden heating, requiring the glass that the mean thermal expansion coefficients of glass is little.
On the other hand, dry etching is developed, and weakens the requirement of resistance to BHF.In order to make resistance to BHF good, the many uses of existing glass contain the B of 6 ~ 10 % by mole 2o 3glass.But, B 2o 3there is the tendency that strain point is reduced.As not containing B 2o 3or B 2o 3the example of poor non-alkali glass, has glass as described below.
Patent Document 1 discloses not containing B 2o 3siO 2-Al 2o 3-SrO glass, but fusing needed for temperature high, produce difficulty in the mill.
Patent Document 2 discloses not containing B 2o 3siO 2-Al 2o 3-SrO crystal glass, but fusing needed for temperature high, produce difficulty in the mill.
Patent Document 3 discloses the B containing 0 ~ 3 % by weight 2o 3glass, but the strain point of embodiment is less than 690 DEG C.
Patent Document 4 discloses the B containing 0 ~ 5 % by mole 2o 3glass, but the mean thermal expansion coefficients at 50 ~ 300 DEG C is more than 50 × 10 -7/ DEG C.
Patent Document 5 discloses the B containing 0 ~ 5 % by mole 2o 3glass, but thermal expansion is large, and density is also large.
In order to solve the problem of the glass recorded in patent documentation 1 ~ 5, propose the non-alkali glass recorded in patent documentation 6.The strain point of the non-alkali glass recorded in patent documentation 6 is high, can be formed, be suitable for the purposes such as base plate for displaying, base board for optical mask by float glass process.
For the smooth grinding implemented for such object, the glass powder of removing from the cost that can reduce needed for smooth grinding, grinding or cullet reduce to being mixed in ground slurry thus can reducing the reasons such as the replacement frequency of ground slurry to be considered, preferably can will be present in small concavo-convex, the fluctuating removing of substrate surface with less amount of grinding.
Prior art document
Patent documentation
Patent documentation 1: Japanese Laid-Open Patent Publication 62-113735 publication
Patent documentation 2: Japanese Laid-Open Patent Publication 62-100450 publication
Patent documentation 3: Japanese Unexamined Patent Publication 4-325435 publication
Patent documentation 4: Japanese Unexamined Patent Publication 5-232458 publication
Patent documentation 5: United States Patent (USP) No. 5326730 specification sheets
Patent documentation 6: Japanese Unexamined Patent Publication 10-45422 publication
Summary of the invention
Invent problem to be solved
On the other hand, by the glass substrate of float forming exist in its surface small concavo-convex, rise and fall (fluctuating that spacing is 3 ~ 30mm, maximum height is about 0.3 μm).This small concavo-convex, rise and fall problem can not be become using when being used as the sheet glass of automobile use, building etc. by the glass substrate of float forming, but when using as various glass substrate for display, the reason making the image of manufactured indicating meter produce distortion, irregular colour can be become.Therefore, need small concavo-convex, fluctuating removing by smooth grinding.
The grinding that the smooth grinding implemented preferably adopts use to carry out as the ground slurry grinding abrasive particle containing cerium dioxide for this purpose.
But, although have solid-phase crystallization method as the manufacture method of the p-Si TFT of high-quality, in order to implement the method, require to improve strain point further.
On the other hand, based on technology for making glass, particularly melt, be shaped in requirement, need to reduce viscosity, the particularly glass viscosity of glass and reach 10 4temperature T during dPas 4.
The object of the invention is to solve above-mentioned shortcoming, be provided in high to strain point, viscosity is low, particularly glass viscosity reach 10 4temperature T during dPas 4can with few amount of grinding by the smooth grinding method of the glass substrate of small concavo-convex, the removing that rises and falls be present on substrate surface and the alkali-free glass substrate of smooth grinding that utilized the method to carry out when low alkali-free glass substrate carries out smooth grinding.
For the means of dealing with problems
The invention provides a kind of smooth grinding method (1) of glass substrate, use and grind containing the interarea of ground slurry to glass substrate of cerium dioxide as grinding abrasive particle, wherein,
Described glass substrate consist of following non-alkali glass,
Described smooth grinding method comprises the stage of carrying out under the following conditions grinding: when the amount of grinding of the described glass substrate when height that obtains rising and falling is changed to 0.10 μm from 0.14 μm the fluctuating of the interarea by described glass substrate is scaled the fluctuating of 20mm spacing is set to X (μm), 0.04/X is made to be more than 0.12
The strain point of described non-alkali glass is more than 710 DEG C, and the mean thermal expansion coefficients at 50 ~ 350 DEG C is 30 × 10 -7~ 43 × 10 -7/ DEG C, glass viscosity reaches 10 2temperature T during dPas 2be less than 1710 DEG C, glass viscosity reaches 10 4temperature T during dPas 4be less than 1320 DEG C, in based on oxide compound % by mole, contain
MgO+CaO+SrO+BaO is 17 ~ 21,
MgO/ (MgO+CaO+SrO+BaO) is more than 0.40,
MgO/ (MgO+CaO) is more than 0.40,
MgO/ (MgO+SrO) is more than 0.60.
The invention provides a kind of smooth grinding method (2) of glass substrate, use and grind containing the interarea of ground slurry to glass substrate of cerium dioxide as grinding abrasive particle, wherein,
Described glass substrate consist of following non-alkali glass,
Described smooth grinding method comprises the stage of carrying out under the following conditions grinding: when the amount of grinding of the described glass substrate when the fluctuating of the interarea by described glass substrate is scaled the fluctuating of 20mm spacing and the height of the fluctuating obtained is changed to 0.10 μm from 0.14 μm is set to X (μm), 0.04/X is made to be more than 0.12
The strain point of described non-alkali glass is more than 710 DEG C, and the mean thermal expansion coefficients at 50 ~ 350 DEG C is 30 × 10 -7~ 43 × 10 -7/ DEG C, glass viscosity reaches 10 2temperature T during dPas 2be less than 1710 DEG C, glass viscosity reaches 10 4temperature T during dPas 4be less than 1320 DEG C, in based on oxide compound % by mole, contain
MgO+CaO+SrO+BaO is greater than 18.2 and is less than 21,
MgO/ (MgO+CaO+SrO+BaO) is more than 0.25,
MgO/ (MgO+CaO) is more than 0.3,
MgO/ (MgO+SrO) is more than 0.60,
Al 2o 3× (MgO/ (MgO+CaO+SrO+BaO)) is more than 5.5.
In the smooth grinding method (1) of glass substrate of the present invention, (2), the fluctuating of the interarea of the glass substrate before preferred smooth grinding is scaled the fluctuating of 20mm spacing and the height of the fluctuating obtained is less than 0.2 μm.
In the smooth grinding method (1) of glass substrate of the present invention, (2), preferably smooth grinding is carried out to the interarea of the glass substrate obtained by float forming.
In addition, the invention provides a kind of alkali-free glass substrate, it uses the smooth grinding method (1) of glass substrate or (2) to carry out smooth grinding.
In glass substrate of the present invention, the fluctuating of the glass substrate after preferred smooth grinding is scaled the fluctuating of 20mm spacing and the height of the fluctuating obtained is less than 0.07 μm
In glass substrate of the present invention, the square surfaceness of 5 μm of the interarea of the glass substrate after preferred smooth grinding is below 0.30nm.
In glass substrate of the present invention, preferably length is at least more than 900mm.
Invention effect
According to method of the present invention, can will be present in small concavo-convex, fluctuating removing on substrate surface when carrying out smooth grinding to the alkali-free glass substrate using float forming to obtain with few amount of grinding, can realize being suitable for the high flat degree as base plate for displaying purposes.
The alkali-free glass substrate utilizing method of the present invention to carry out smooth grinding is particularly suitable for base plate for displaying, the base board for optical mask and glass substrate for disc etc. of high strain-point purposes.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the relation representing spacing and fluctuating.
Fig. 2 is the integrally-built stereographic map of the milling apparatus of the smooth grinding method of the application glass substrate representing embodiment.
Fig. 3 is the side-view of the milling apparatus 10 shown in Fig. 2.
Fig. 4 is the schematic diagram of the method for trimming of the grinding tool utilizing trimming wheel to carry out representing embodiment.
Fig. 5 is the vertical view of the grinding tool utilizing the method for trimming shown in Fig. 4 to repair.
Fig. 6 is the side-view of the method for trimming representing the grinding tool utilizing finishing water spouting nozzle to carry out.
Embodiment
Below, the smooth grinding method of glass substrate of the present invention is described.
In the smooth grinding method (1) of glass substrate of the present invention, use alkali-free glass substrate, the mode that this alkali-free glass substrate employs to reach following glass composition 1 allocates the frit obtained.
A kind of non-alkali glass, in based on oxide compound % by mole, contain:
MgO+CaO+SrO+BaO is 17 ~ 21,
MgO/ (MgO+CaO+SrO+BaO) is more than 0.40,
MgO/ (MgO+CaO) is more than 0.40,
MgO/ (MgO+SrO) is more than 0.60.
In addition, in the smooth grinding method (2) of glass substrate of the present invention, use alkali-free glass substrate, the mode that this alkali-free glass substrate employs to reach following glass composition 2 allocates the frit obtained.
A kind of non-alkali glass, in based on oxide compound % by mole, contain:
MgO+CaO+SrO+BaO is greater than 18.2 and is less than 21,
MgO/ (MgO+CaO+SrO+BaO) is more than 0.25,
MgO/ (MgO+CaO) is more than 0.3,
MgO/ (MgO+SrO) is more than 0.60,
Al 2o 3× (MgO/ (MgO+CaO+SrO+BaO)) is more than 5.5.
Then, the compositing range of each composition is described.SiO 2lower than 66% (% by mole, then identical below unless otherwise specified) time, strain point can not fully improve, and thermal expansivity increases, and density raises.In addition, the chemical durability of glass, particularly acid resistance reduce, and are difficult to obtain protuberance selectivity when grinding, are difficult to obtain smoothness.Be preferably more than 66.5%, be more preferably more than 67%.During more than 70%, the melting of glass reduces, and devitrification temperature raises.Be preferably less than 69%.
Al 2o 3improve Young's modulus, suppress the distortion during grinding of glass, and suppress point phasic property of glass, reduce thermal expansivity, improve strain point, hardness is improved, thus improve grinding time protuberance selectivity, but lower than 12% time, do not show this effect, in addition, other compositions increasing expansion can be made to increase, and result thermal expansion increases.Be preferably more than 12.2%.During more than 15%, the melting of glass may be made to be deteriorated or devitrification temperature is raised.Be preferably less than 14.5%, be more preferably less than 14%, more preferably less than 13.8%.
B 2o 3the fusing improving glass is reactive, and reduces devitrification temperature, therefore can be added into 1.5%.But time too much, photoelastic constant increases, and easily produces the problems such as irregular colour during stress application.In addition, B 2o 3time too much, Young's modulus reduces, and be difficult to obtain smoothness, and the surfaceness after grinding increases due to distortion during grinding.In addition, strain point also reduces.Therefore, be preferably less than 1.3%, be more preferably less than 1%, preferably do not contain in fact.In fact not containing referring to except inevitable impurity not containing (identical in this manual).
MgO improves Young's modulus and does not make proportion increase, therefore, it is possible to alleviate the bending of glass by improving specific modulus.In addition, in alkaline-earth metal, MgO have do not increase expansion and the feature not making strain point excessively reduce, also improve melting.
At this, in glass composition 1, content of MgO is more than 9.5% and be less than 13%.Time below 9.5%, above-mentioned add by MgO the effect brought and can not fully show.But during more than 13%, devitrification temperature may raise.Be preferably less than 12.5%, be more preferably less than 12%, more preferably less than 11.5%.
On the other hand, in glass composition 2, content of MgO is 5 ~ 9.5%.Lower than 5% time, above-mentioned add by MgO the effect brought and can not fully show.Be preferably more than 6%, be more preferably more than 7%.But during more than 9.5%, devitrification temperature may raise.Be preferably less than 9.3%, be more preferably less than 9%.
In alkaline-earth metal, CaO be only second to MgO and have improve Young's modulus and specific modulus, do not increase expand and do not make the feature that strain point excessively reduces, also improve melting.
At this, in glass composition 1, CaO content is 4 ~ 9%.Lower than 4% time, above-mentioned add by CaO the effect brought and can not fully show.But, during more than 9%, devitrification temperature may be made to raise or make the Wingdale (CaCO as CaO raw material 3) in foreign matter of phosphor be mixed in a large number.Be preferably less than 7%, be more preferably less than 6%, more preferably less than 5%.
On the other hand, in glass composition 2, CaO content is 4 ~ 11%.Lower than 4% time, above-mentioned add by CaO the effect brought and can not fully show.Be preferably more than 5%.But, during more than 11%, devitrification temperature may be made to raise or make the Wingdale (CaCO as CaO raw material 3) in foreign matter of phosphor be mixed in a large number.Be preferably less than 10%, be more preferably less than 9%, more preferably less than 7%, be particularly preferably less than 6%.
SrO improves melting and the devitrification temperature of glass can not be made to raise, but lower than 0.5% time, this effect can not fully show.Be preferably more than 1.0%, more preferably more than 2.0%.But during more than 4.5%, the coefficient of expansion may increase.Be more preferably less than 4.0%, more preferably less than 3.5%.
BaO is optional, but can contain to improve melting.But time too much, glass becomes fragile and easily produces scar, and the expansion of glass and density can be made excessively to increase, therefore be set as less than 1%.Preferably lower than 1%, be more preferably less than 0.5%, preferably do not contain in fact further.
In order to improve Young's modulus, in order to reduce glass melting temperature or in order to promote crystallization when calcining, the ZrO of less than 2% can be contained 2.During more than 2%, glass becomes relative permittivity ε that is unstable or glass and increases.Be preferably less than 1.5%, be more preferably less than 1.0%, more preferably less than 0.5%, particularly preferably do not contain in fact.
In glass composition 1, when MgO, CaO, SrO, BaO are less than 17% with total amount, Young's modulus is low, and be difficult to distortion when suppressing grinding, hardness is low, therefore, is difficult to obtain protuberance selectivity when grinding.In addition, photoelastic constant increases, and melting reduces.Be preferably more than 18%, more preferably more than 18.5%.More than 21% time, the difficulty that cannot reduce thermal expansivity may be produced.Be preferably less than 20%.
In glass composition 2, when MgO, CaO, SrO, BaO count below 18.2% with total amount, Young's modulus is low, and be difficult to distortion when suppressing grinding, hardness is low, therefore, is difficult to obtain protuberance selectivity when grinding.In addition, photoelastic constant increases, and melting reduces.More than 21% time, the difficulty that cannot reduce thermal expansivity may be produced.Be preferably less than 20%.
In glass composition 1, meet above-mentioned condition by making the total amount of MgO, CaO, SrO and BaO and meet following three conditions, Young's modulus is high, the easy distortion suppressed when grinding, specific modulus is high, can improve strain point when not making devitrification temperature raise, and viscosity, the particularly glass viscosity that can reduce glass reach 10 4temperature T during dPas 4.
MgO/ (MgO+CaO+SrO+BaO) is more than 0.4, is preferably more than 0.45.
MgO/ (MgO+CaO) is more than 0.4, is preferably more than 0.52, more preferably more than 0.55.
MgO/ (MgO+SrO) is more than 0.6, is preferably more than 0.7.
In glass composition 2, meet above-mentioned condition by making the total amount of MgO, CaO, SrO and BaO and meet following three conditions, Young's modulus is high, the easy distortion suppressed when grinding, specific modulus is high, can improve strain point when not making devitrification temperature raise, and viscosity, the particularly glass viscosity that can reduce glass reach 10 4temperature T during dPas 4.
MgO/ (MgO+CaO+SrO+BaO) is more than 0.25, is preferably more than 0.3, is more preferably more than 0.4, more preferably more than 0.45.
MgO/ (MgO+CaO) is more than 0.3, is preferably more than 0.4, is more preferably more than 0.52, more preferably more than 0.55.
MgO/ (MgO+SrO) is more than 0.6, is preferably more than 0.7.
In glass composition 2, Al 2o 3× (MgO/ (MgO+CaO+SrO+BaO)) more than 5.5 can improve Young's modulus, easily suppresses distortion during grinding, therefore preferably.Be preferably more than 5.75, be more preferably more than 6.0, more preferably more than 6.25, be particularly preferably more than 6.5.
In addition, in order to not make to arrange metal on the glass surface or sull generation deterioration in characteristics when using alkali-free glass substrate of the present invention to manufacture indicating meter, preferred glass raw material is not in fact containing P 2o 5.In addition, in order to make glass easily recycle, preferred glass raw material is not in fact containing PbO, As 2o 3, Sb 2o 3.
In order to improve the melting of glass, clarification, plasticity, ZnO, Fe that total amount is less than 5% can be added in frit 2o 3, SO 3, F, Cl, SnO 2.
The Production Example of alkali-free glass substrate of the present invention is as implemented as follows.
The raw material of each composition is allocated in the mode reaching target component (above-mentioned glass composition 1,2), it is put in smelting furnace continuously, is heated to 1500 ~ 1800 DEG C and makes its melting.Utilized by this melten glass building mortion to be configured as the plate glass band of predetermined thickness of slab, cut after this glass ribbon is annealed, can alkali-free glass substrate be obtained thus.
In the present invention, be the glass ribbon of tabular preferably by float forming.
Below, with reference to the accompanying drawings the preferred implementation of the smooth grinding method of glass substrate of the present invention is described in detail.
Fig. 2 is the stereographic map that the entirety of the milling apparatus 10 of the smooth grinding method of the application glass substrate representing embodiment is formed.Fig. 3 is the side-view of the milling apparatus 10 shown in Fig. 2.
Milling apparatus 10 shown in these figure by being manufactured by float glass process, the interarea (abrasive surface) of such as thickness is below 0.7mm, length is on one side more than 900mm, Young's modulus is more than 65GPa sheet glass G uses the milling apparatus of the Flatness needed for abrasive to FPD glass substrate.Namely, this milling apparatus 10 is for as lower device: grind the abrasive surface that the height that there is the fluctuating being scaled 20mm spacing and the fluctuating obtained is the sheet glass G of the fluctuating of less than 0.2 μm, make to be scaled the fluctuating of 20mm spacing and below the height reduction to 0.07 of the fluctuating obtained μm, thus, the sheet glass of FPD glass substrate most suitable as not making image produce distortion, irregular colour is manufactured.
In addition, in the present invention, be more than 82GPa by making the Young's modulus of sheet glass G, even such as thickness is the thin plate of below 0.5mm or length is on one side the large template of more than 1000mm, also the interarea of sheet glass G (abrasive surface) can be used the Flatness needed for abrasive to FPD glass substrate.
In addition, the measuring method of above-mentioned fluctuating is JIS B0031: ' 82 and JIS B0601: the method recorded in ' 82.Spacing and fluctuating can define as shown in Figure 1.When spacing is large, rises and falls and increase, by carrying out linear regression to the relation of spacing and fluctuating, the height of the fluctuating being scaled 20mm spacing and the fluctuating obtained can be obtained.
The fluctuating of the interarea of the glass substrate before smooth grinding is scaled the fluctuating of 20mm spacing and the height of the fluctuating obtained is more preferably less than 0.17 μm.In addition, the fluctuating of the interarea of the glass substrate after smooth grinding is scaled the fluctuating of 20mm spacing and the height of the fluctuating obtained is more preferably less than 0.05 μm.
Milling apparatus 10 is made up of grinding head 12 and platform 14.Grinding head 12 possesses and keeps the glass retaining member 16 of the non-abrasive side of sheet glass G, is provided with the glass of glass retaining member 16 keeps platform 20 and be provided with the canvas 22 that glass keeps platform 20 via sealing material 18.Turning axle 24 is fixed on canvas 22, carries out rotating and grinding head 12 is rotated by turning axle 24 centered by its axle core P1, and, carry out revolving round the sun centered by hollow shaft P2 by turning axle 24 and grinding head 12 is revolved round the sun.
In addition, supply pressurized air by the turning axle 24 of hollow in the wind box 23 of canvas 22, this compressed-air actuated pressure keeps platform 20, sealing material 18 and glass retaining member 16 to be passed to sheet glass G via glass.
Above-mentioned platform 14 possesses grinding tool 26 and is provided with the grinding tool maintenance platform 30 of grinding tool 26 via sealing material 28.Sealing material 28 is soft and the sealing material of the resin-made (such as, polyurethane) that absorption retentivity is improved.
Therefore, the milling apparatus 10 of embodiment utilizes above-mentioned compressed-air actuated pressure to be pressed on grinding tool 26 by the abrasive surface of sheet glass G, and, carry out rotation, revolution and the abrasive surface of sheet glass G is ground by making grinding head 12.
Preferably A hardness (based on ISO 7619) is more than 20, D hardness (based on ISO 7619) to grinding tool 26 is less than 99, and thickness is 1.0 ~ 2.5mm, thickness distribution is ± 0.3mm within, within more preferably ± 0.05mm.
When the A hardness of grinding tool 26 is less than 20, cannot reduce the fluctuating of sheet glass G, when D hardness is more than 99, sheet glass G easily breaks.In addition, when the thickness of grinding tool 26 is less than 1mm, slot machining cannot be carried out to grinding tool 26.Particularly for large-area grinding tool 26, if cannot carry out slot machining, then abrasive particle distribution becomes uneven, has problems in the processing of sheet glass G.On the other hand, when the thickness of grinding tool 26 is greater than 2.5mm, the deflection of grinding tool 26 increases, and the processing quality of sheet glass G reduces.In addition, the thickness distribution of grinding tool 26 is the maximum ga(u)ge-minimum thickness in region except slot machining part.This thickness distribution exceedes ± 0.3mm time, pressure distribution increases, and the processing quality of sheet glass reduces.Thickness distribution be preferably ± 0.2mm within, be more preferably ± 0.1mm within, within more preferably ± 0.05mm.
Like this, specified by the hardness to grinding tool 26 described above, thickness, thickness distribution, the sheet glass G manufactured can be ground to form the sheet glass be more suitable for as FPD glass substrate by float glass process.
On the other hand, what present inventor carried out furtheing investigate found that, in order to make to be scaled the fluctuating of 20mm spacing and the height of the fluctuating obtained is less than 0.07 μm, it is insufficient for only managing the A hardness of grinding tool 26, preferably manages the rate of compression of glass retaining member 16, compressive modulus of elasticity, A hardness, thickness and distribution.
Such as, when the A hardness of glass retaining member 16 is too low, the weather resistance of glass retaining member 16 reduces, cannot Reusability glass retaining member 16.In addition, when the A hardness appropriateness of glass retaining member 16 is low, glass retaining member 16 can absorb the fluctuating in the non-abrasive side being present in sheet glass G, therefore, it is possible to utilize grinding tool 26 to grind well the fluctuating be present on the abrasive surface of sheet glass G.On the other hand, during the A much higher hard of glass retaining member 16, then can the abrasive surface of grinding tool 26 couples of sheet glass G be utilized to grind under the state that glass retaining member 16 cannot be utilized to absorb the fluctuating be present in the non-abrasive side of sheet glass G, therefore, when sheet glass G is taken off from glass retaining member 16, there is resilience in sheet glass G, result, may remain the fluctuating of height more than 0.07 μm of the fluctuating being scaled 20mm spacing and the fluctuating obtained on the abrasive surface of sheet glass G.
In addition, thickness distribution is greater than ± 0.05mm time, can make the resiliency of glass retaining member 16 in the face of sheet glass G, produce inequality, the problem rising and falling and cannot evenly remove may be produced.
Rate of compression represents the resiliency of following initial sheet glass G, the parameter needed for recovery degree when compressive modulus of elasticity is for representing Reusability.Glass retaining member 16 is polyurathamc system.
In order to eliminate the problems referred to above, glass retaining member 16 preferred compressed rate (based on JISL1021-6: ' 07 annex 1) be 10 ~ 70%, (based on JIS L1021-6: ' 07 annex 1, wherein, initial load is 100gf/cm to compressive modulus of elasticity 2, final load is 1120gf/cm 2) be 70 ~ 98, A hardness is 2 ~ 20, thickness is 0.3 ~ 2.0mm, thickness distribution is within ± 0.05mm.
In addition, about the management of glass retaining member 16, when sheet glass G is thinning, need constriction range of management especially.Such as, when thickness of slab is the sheet glass G of below 0.5mm, glass retaining member 16 preferred compressed rate is 10 ~ 70%, compressive modulus of elasticity is 70 ~ 98, A hardness is 2 ~ 20, thickness is 0.5 ~ 1.5mm, thickness distribution is within ± 0.05mm.In addition, when thickness of slab is the sheet glass G of below 0.3mm, glass retaining member 16 preferred compressed rate is 10 ~ 70%, compressive modulus of elasticity is 70 ~ 98, A hardness is 2 ~ 20, thickness is 0.7 ~ 1.2mm, thickness distribution is within ± 0.05mm.
Specified by the rate of compression to glass retaining member 16 described above, compressive modulus of elasticity, A hardness, thickness, thickness distribution, the sheet glass G manufactured can be ground to form the sheet glass be more suitable for as FPD glass substrate by float glass process.
In addition, the glass being provided with glass retaining member 16 via sealing material 18 is kept to the surface of platform 20, the maximum cross-section height of oscillating curves when preferably making evaluation length be 30mm is less than 20 μm.
Even if manage glass retaining member 16, but when glass keeps the maximum cross-section excessive height of the oscillating curves of platform 20, also glass retaining member 16 cannot be utilized to absorb the fluctuating be present in the non-abrasive side of sheet glass G well, and being difficult to the undulated abrasive of the abrasive surface of sheet glass G to the height of the fluctuating and the fluctuating obtained that are scaled 20mm spacing is less than 0.07 μm.
The maximum cross-section height of the oscillating curves of platform 20 is kept to specify by described above to glass, glass retaining member 16 can be utilized to absorb the fluctuating be present in the non-abrasive side of sheet glass G well, therefore, it is possible to the sheet glass manufactured by float glass process is ground to form the sheet glass be more suitable for as FPD glass substrate.
The grinding tool being provided with grinding tool 26 via sealing material 28 is kept to the surface of platform 30, the maximum cross-section height of cross section curve when preferably making evaluation length be 30mm is less than 100 μm.
Even if manage grinding tool 26, but when grinding tool keeps the maximum cross-section excessive height of the cross section curve of platform 30, also can produce large fluctuating on the surface of grinding tool 26, being difficult to the undulated abrasive of the abrasive surface of sheet glass G to the height of the fluctuating and the fluctuating obtained that are scaled 20mm spacing is less than 0.07 μm.
Therefore, the maximum cross-section height of the cross section curve of platform 30 is kept to specify by described above to grinding tool, the fluctuating on the surface of grinding tool 26 can be suppressed, therefore, it is possible to the sheet glass manufactured by float glass process is ground to form the sheet glass be more suitable for as FPD glass substrate.
In addition, the maximum cross-section height of oscillating curves is recorded in JIS B0601: in ' 01.
The maximum cross-section height of oscillating curves measures by utilizing Tokyo Seimitsu Co., Ltd to manufacture サ ー Off コ system " 1400-D64 " under the condition determination of measured length 30mm, λ C=0.8mm.
In addition, the fluctuation of the load be pressed on grinding tool 26 by the abrasive surface of sheet glass G is preferably less than 10% of average load.
By described above, the load that grinding tool 26 applies to sheet glass G is specified, the sheet glass G manufactured can be ground to form the sheet glass be more suitable for as FPD glass substrate by float glass process.In addition, as the determinator of load distribution, the big area pressure-distribution measurement system " BIG-MAT " that ニ ッ タ Co., Ltd. can be used to manufacture or " HUGE-MAT ".
As mentioned above, according to the milling apparatus 10 of embodiment, with what manufactured by float glass process, thickness is below 0.7mm, length is on one side more than 900mm, Young's modulus is that the sheet glass G of more than 65GPa is as grinding object, glass retaining member 16 is utilized to keep the non-abrasive side of sheet glass G, utilize grinding tool 26 to being present on the abrasive surface of sheet glass G, be scaled the fluctuating of 20mm spacing and the fluctuating that the height of the fluctuating obtained is less than 0.2 μm is ground, thus, make to be scaled the fluctuating of 20mm spacing and the height of the fluctuating obtained is decreased to less than 0.07 μm, thus manufacture glass substrate for plane display device.Thereby, it is possible to manufacture most suitable as not making, image generation is out of shape, the sheet glass G of the FPD glass substrate of irregular colour.
In the smooth grinding method of glass substrate of the present invention, implement under the following conditions to grind: when the amount of grinding of the glass substrate when will the rise and fall fluctuating being scaled 20mm spacing and the height of fluctuating obtained are changed to 0.10 μm from 0.14 μm is set to X (μm), make 0.04/X be more than 0.12.Thereby, it is possible to the cost needed for reduction smooth grinding, the glass powder removed in grinding or cullet reduce to being mixed in ground slurry thus can reduce the replacement frequency of ground slurry.More preferably under making 0.04/X be the condition of more than 0.13, implementing grinding, preferably further under making 0.04/X be the condition of more than 0.14, implement grinding, is implement grinding under the condition of more than 0.15 particularly preferably in making 0.04/X.
In smooth grinding method of the present invention, grinding 0.14 μm is reached for the height to this fluctuating the state being greater than 0.14 μm from the height of the fluctuating and the fluctuating obtained that are scaled 20mm spacing, its grinding condition be not limited to above-mentioned make 0.04/X be more than 0.12 condition.But, preferably above-mentioned make 0.04/X be the condition of more than 0.12 under implement.
In addition, in smooth grinding method of the present invention, for make to be scaled the fluctuating of 20mm spacing and the height of the fluctuating obtained is less than 0.10 μm time grinding, its grinding condition be not limited to above-mentioned make 0.04/X be more than 0.12 condition, also can implement under making above-mentioned 0.04/X be less than the condition of 0.12.
In the smooth grinding method of glass substrate of the present invention, the fluctuating of the interarea of the glass substrate before smooth grinding is scaled the fluctuating of 20mm spacing and the height of the fluctuating obtained is preferably less than 0.2 μm.Thereby, it is possible to the milling time needed for minimizing precision work, and easily obtain excellent Flatness.Be scaled the fluctuating of 20mm spacing and the height of the fluctuating obtained is more preferably less than 0.17 μm, more preferably less than 0.15 μm.
In the smooth grinding method of glass substrate of the present invention, the fluctuating of the interarea of the glass substrate after smooth grinding is scaled the fluctuating of 20mm spacing and the height of the fluctuating obtained is preferably less than 0.07 μm.Thus, in the indicating meter employing this substrate, image is not easily made to produce distortion, irregular colour.Be scaled the fluctuating of 20mm spacing and the height of the fluctuating obtained is more preferably less than 0.05 μm, more preferably less than 0.03 μm.
In the smooth grinding method of glass substrate of the present invention, utilize AFM to obtain 5 μm of square surface roughness Ra of the interarea of the glass substrate after smooth grinding are preferably below 0.30nm.Thus, in the indicating meter employing this substrate, easily obtain stable drive characteristic.
Shown in one of lapping mode such as descends.
Grinding pressure: 2kPa ~ 25kPa
Ground slurry: the slurry supply hole supply cerium dioxide aqueous solution keeping platform from grinding tool
Grinding tool: flexibel polyurethane making herbs into wool upper leather shape, from the teeth outwards there is groove (separation 4.5mm, well width 1.5mm, groove depth 1 ~ 1.5mm) for the slurry that flows
The thickness of sheet glass: 0.2mm ~ 0.7mm
The shape of sheet glass: the rectangular glass being more than 900mm
The non-abrasive side of sheet glass: utilize glass retaining member to be close to maintenance
It is more than an example of lapping mode.
In addition, in the milling apparatus 10 of embodiment, in order to maintain the grinding rate of sheet glass G, the trimming wheel containing diamond abrasive grain is utilized regularly to carry out grinding to implement finishing to the surface of grinding tool 26.
In the milling apparatus 10 of embodiment, as shown in Figure 4, will not be arranged on glass retaining member 16 in the mode of surrounding trimming wheel 40 as shown in the vertical view of Fig. 5 containing diamond abrasive grain, the frame 42 of rectangle that do not possess grinding capacity.Further, utilize the compressed-air actuated air pressure be supplied in the wind box 23 of canvas 22 trimming wheel 40 and frame 42 to be pressed on grinding tool 26, utilize the surface of trimming wheel 40 pairs of grinding tools 26 to carry out grinding.
Now, above-mentioned air pressure concentrates on the frame 42 of the periphery being positioned at trimming wheel 40, but does not possess grinding capacity due to frame 42, and therefore, the part surface contacted with frame 42 of grinding tool 26 is not ground.That is, the surface of the trimming wheel 40 pairs of grinding tools 26 providing air pressure equably is only utilized to carry out grinding.Thus, by the whole surfacing of grinding tool 26 to smooth, therefore, it is possible to improve the finishing utilizing trimming wheel 40 to carry out.
In addition, preferably not only use frame 42 when the finishing of grinding tool 26, and also use frame 42 when the grinding of sheet glass G.Thereby, it is possible to prevent the air pressure when the grinding of sheet glass G from concentrating on the edge of sheet glass G, therefore, it is possible to prevent the excessive grinding at the edge of sheet glass G.As the material of frame 42, the material that stainless steel, iron, aluminium, polyethylene, urethane etc. do not have mill capacity can be illustrated.
In addition, in the milling apparatus 10 of embodiment, in order to maintain the grinding rate of sheet glass G, implement to be washed by the regular surface to grinding tool 26 and by the finishing of the residue removings such as the cerium dioxide in the lapping liquid that is attached on the surface of grinding tool 26.
In the milling apparatus 10 of embodiment, as shown in the side-view of Fig. 6, finishing water spouting nozzle 44 is tilted, the spray angle θ of the rinse water 48 of being sprayed by jet hole 46 is set as acute angle.Further, water spouting nozzle 44 and grinding tool 26 are relatively moved back and forth in the horizontal direction, thus, by the residue removing be attached on the surface of grinding tool 26.
Thus, the residue be attached on the surface of grinding tool 26 is excavated by the pressure of the rinse water 48 tilting to spray, and therefore, is removed efficiently.In addition, the residue of removing is flushed to outside the system of grinding tool 26 efficiently by the rinse water 48 tilting to spray.Thereby, it is possible to improve the finishing utilizing water spouting nozzle 44 to carry out.
In addition, from the view point of the flush efficiency excavating efficiency and residue of residue, the spray angle θ of rinse water 48 is preferably 10 ~ 45 degree, is more preferably 30 degree.In addition, when surging force when rinse water 48 impacts grinding tool 26 is weak, the removing efficiency of residue may reduce, and when surging force when rinse water 48 impacts grinding tool 26 is strong, grinding tool 26 may be damaged, is therefore preferably 5 ~ 50kPa.In addition, when grinding tool 26 is slow with the speed of relative movement of water spouting nozzle 44, the dressing efficiency of grinding tool 26 reduces, and when grinding tool 26 is fast with the speed of relative movement of water spouting nozzle 44, the removing efficiency of residue reduces, and is therefore preferably 3 ~ 20m/ minute.
In the present invention, the strain point of the alkali-free glass substrate of above-mentioned glass composition 1,2 is more than 710 DEG C, can suppress thermal contraction when using this alkali-free glass substrate manufacture indicating meter.In addition, the manufacture method of solid-phase crystallization method as the p-Si TFT implemented in the display manufacturing operations such as LCD can be applied.Be more preferably more than 715 DEG C, more preferably more than 720 DEG C.Be particularly preferably more than 735 DEG C.When strain point is more than 735 DEG C, be suitable for high strain-point purposes (such as, the base plate for displaying of organic EL of below thickness of slab 0.7mm, preferably below 0.5mm, more preferably below 0.3mm or the thin display substrate of illumination substrate or below thickness of slab 0.3mm, preferably below 0.1mm or illumination substrate).
But, when the strain point of glass is too high, need the temperature with its correspondingly elevated device, the lost of life of building mortion.Therefore, the strain point of the alkali-free glass substrate of above-mentioned glass composition 1,2 is preferably less than 750 DEG C.
In addition, order the same reason based on strain, the second-order transition temperature of the alkali-free glass substrate of above-mentioned glass composition 1,2 is preferably more than 760 DEG C, is more preferably more than 770 DEG C, more preferably more than 780 DEG C.
In addition, the mean thermal expansion coefficients at 50 ~ 350 DEG C of alkali-free glass substrate of above-mentioned glass composition 1,2 is 30 × 10 -7~ 43 × 10 -7/ DEG C, resistance to sudden heating is strong, can improve productivity when using this alkali-free glass substrate manufacture indicating meter.In glass of the present invention, the mean thermal expansion coefficients at 50 ~ 350 DEG C is preferably 35 × 10 -7~ 40 × 10 -7/ DEG C.
In addition, the proportion of the alkali-free glass substrate of above-mentioned glass composition 1,2 is preferably less than 2.65, is more preferably less than 2.64, and more preferably less than 2.62.
In addition, the specific modulus of the alkali-free glass substrate of above-mentioned glass composition 1,2 is preferably more than 32MNm/kg.During lower than 32MNm/kg, can be difficult to obtain protuberance selectivity when grinding owing to conducting oneself with dignity bending.Be more preferably more than 33MNm/kg.
In addition, the Young's modulus of the alkali-free glass substrate of above-mentioned glass composition 1,2 is preferably more than 82GPa.During lower than 82GPa, glass substrate deforms when grinding, and is difficult to obtain smoothness, in addition, is difficult to obtain protuberance selectivity when grinding due to distortion.Be more preferably more than 84GPa, more preferably more than 86GPa, be particularly preferably more than 87GPa.
In addition, the photoelastic constant of the alkali-free glass substrate of above-mentioned glass composition 1,2 is preferably below 31nm/MPa/cm.
Make the glass substrate used in indicating meter have birefringence due to the stress produced in LCD manufacturing process or when LCD device uses, therefore observe the phenomenon that black display becomes ash, the contrast gradient of liquid-crystal display reduces sometimes.By making photoelastic constant be below 31nm/MPa/cm, this phenomenon can be suppressed in lower limit.Be more preferably below 30nm/MPa/cm, more preferably below 29nm/MPa/cm, be particularly preferably below 28nm/MPa/cm, most preferably be below 27.5nm/MPa/cm.
If consider the easiness guaranteeing other physical property, then preferred light elastic constant is more than 23nm/MPa/cm, more preferably more than 25nm/MPa/cm.
In addition, photoelastic constant can be measured under the mensuration wavelength of 546nm by disk compression method.
In addition, the relative permittivity of the alkali-free glass substrate of above-mentioned glass composition 1,2 is preferably more than 5.6.
When embedded touch control panel (being built-in with the contact panel of touch sensor in display panels) such described in Japanese Unexamined Patent Publication 2011-70092 publication, from the view point of the induction sensitivity, reduction driving voltage, the saving electric power that improve touch sensor, the relative permittivity of glass substrate is more high better.By making relative permittivity be more than 5.6, the induction sensitivity of touch sensor improves.Be preferably more than 5.8, be more preferably more than 6.0, more preferably more than 6.1.
In addition, relative permittivity can be measured by the method recorded in JIS C-2141.
In addition, the viscosities il of the alkali-free glass substrate of above-mentioned glass composition 1,2 reaches 10 2temperature T during pool (dPas) 2be less than 1710 DEG C, preferably lower than 1710 DEG C, be more preferably less than 1700 DEG C, more preferably less than 1690 DEG C, be particularly preferably less than 1260 DEG C, therefore, than being easier to fusing.
In addition, the viscosities il of the alkali-free glass substrate of above-mentioned glass composition 1,2 reaches 10 4temperature T during pool 4be less than 1320 DEG C, be preferably less than 1315 DEG C, be more preferably less than 1310 DEG C, more preferably less than 1305 DEG C, be particularly preferably less than 1295 DEG C, be suitable for float forming.
In addition, formed from the viewpoint of easy by float glass process, the devitrification temperature of the alkali-free glass substrate of above-mentioned glass composition 1,2 is preferably less than 1350 DEG C.Be preferably less than 1330 DEG C, more preferably less than 1310 DEG C, more preferably less than 1300 DEG C.
About the devitrification temperature in this specification sheets, glass particle after pulverizing is put into the plate of platinum, the thermal treatment of 17 hours is carried out in the electric furnace being controlled in certain temperature, the minimum temperature of the top temperature at the surface of glass and inner crystallization and not crystallization is obtained, using its mean value as devitrification temperature by the observation by light microscope after thermal treatment.
Embodiment
(embodiment 1 ~ 2, comparative example 1)
The raw material of each composition is allocated in the mode reaching the composition of target shown in table 1, utilizes continuous melting furnaces to melt, carry out plate forming by float glass process, obtain alkali-free glass substrate.
Keep from grinding tool the slurry supply hole of platform to have separation 4.5mm, well width 1.5mm, groove depth 1 ~ 1.5mm groove the grinding pad supply cerium dioxide aqueous solution while, obtained glass substrate (920mm × 730mm, thickness 0.5mm) is ground.Extract glass out in midway, again grind after measuring the height of the fluctuating of the interarea of amount of grinding and glass substrate, repeatedly implement aforesaid operations, obtain amount of grinding and be scaled the fluctuating of 20mm spacing and the relation of the height of fluctuating that obtains.
Obtained the amount of grinding X (μm) of the above-mentioned glass substrate when the fluctuating of the interarea of glass substrate is scaled the fluctuating of 20mm spacing and the height of the fluctuating obtained is changed to 0.10 μm from 0.14 μm by this result, obtain the value of 0.04/X.In addition, the mensuration of the square surface roughness Ra of 5 μm of the interarea of the glass substrate after the relief height of the 20mm spacing of the interarea of the glass substrate before and after smooth grinding, smooth grinding has also been carried out.About surface roughness Ra, the NanoScope IIIa utilizing Digital Instruments company to manufacture, is set as 1Hz by scanning speed, obtains 5 μm of square surfacenesses with 256 point/1 time scanning.
Show the result in following table 2.
In addition, for the alkali-free glass substrate obtained by above-mentioned steps, also measured were strain point, Young's modulus, specific modulus, photoelastic constant.Show the result in table 2.Bracket represents calculated value.
[table 1]
% by mole Embodiment 1 Embodiment 2 Comparative example 1
SiO 2 67 67.2 65.8
Al 2O 3 13.2 13.5 10.8
B 2O 3 1.1 0 7.7
MgO 9.2 9.8 5.7
CaO 5.2 5.3 4.8
SrO 4.4 4.3 5
BaO 0 0 0
ZrO 2 0 0 0
MgO+CaO+SrO+BaO 18.8 19.4 15.5
MgO/(MgO+CaO+SrO+BaO) 0.49 0.51 0.37
MgO/(MgO+CaO) 0.64 0.65 0.54
MgO/(MgO+SrO) 0.68 0.70 0.53
Al 2O 3×(MgO/(MgO+CaO+SrO+BaO)) 6.5 6.8 4.0
[table 2]
With reference to specific embodiment to invention has been detailed description, but can make various changes and modifications without departing from the spirit and scope of the present invention, this is apparent to those skilled in the art.
Its content, based on the Japanese patent application 2012-128249 proposed on June 5th, 2012, is incorporated in this specification sheets with the form of reference by the application.
Label declaration
G sheet glass
10 milling apparatuss
12 grinding heads
14 platforms
16 glass retaining members
18 sealing materials
20 glass keep platform
22 canvas
23 wind boxs
24 turning axles
26 grinding tools
28 sealing materials
30 grinding tools keep platform
40 trimming wheels
42 frames
44 water spouting nozzles
46 jet holes
48 rinse water

Claims (8)

1. a smooth grinding method for glass substrate, uses and grinds containing the interarea of ground slurry to glass substrate of cerium dioxide as grinding abrasive particle, wherein,
Described glass substrate consist of following non-alkali glass,
Described smooth grinding method comprises the stage of carrying out under the following conditions grinding: when the amount of grinding of the described glass substrate when the fluctuating of the interarea by described glass substrate is scaled the fluctuating of 20mm spacing and the height of the fluctuating obtained is changed to 0.10 μm from 0.14 μm is set to X (μm), 0.04/X is made to be more than 0.12
The strain point of described non-alkali glass is more than 710 DEG C, and the mean thermal expansion coefficients at 50 ~ 350 DEG C is 30 × 10 -7~ 43 × 10 -7/ DEG C, glass viscosity reaches 10 2temperature T during dPas 2be less than 1710 DEG C, glass viscosity reaches 10 4temperature T during dPas 4be less than 1320 DEG C, in based on oxide compound % by mole, contain
MgO+CaO+SrO+BaO is 17 ~ 21,
MgO/ (MgO+CaO+SrO+BaO) is more than 0.40,
MgO/ (MgO+CaO) is more than 0.40,
MgO/ (MgO+SrO) is more than 0.60.
2. a smooth grinding method for glass substrate, uses and grinds containing the interarea of ground slurry to glass substrate of cerium dioxide as grinding abrasive particle, wherein,
Described glass substrate consist of following non-alkali glass,
Described smooth grinding method comprises the stage of carrying out under the following conditions grinding: when the amount of grinding of the described glass substrate when the fluctuating of the interarea by described glass substrate is scaled the fluctuating of 20mm spacing and the height of the fluctuating obtained is changed to 0.10 μm from 0.14 μm is set to X (μm), 0.04/X is made to be more than 0.12
The strain point of described non-alkali glass is more than 710 DEG C, and the mean thermal expansion coefficients at 50 ~ 350 DEG C is 30 × 10 -7~ 43 × 10 -7/ DEG C, glass viscosity reaches 10 2temperature T during dPas 2be less than 1710 DEG C, glass viscosity reaches 10 4temperature T during dPas 4be less than 1320 DEG C, in based on oxide compound % by mole, contain
MgO+CaO+SrO+BaO is greater than 18.2 and is less than 21,
MgO/ (MgO+CaO+SrO+BaO) is more than 0.25,
MgO/ (MgO+CaO) is more than 0.3,
MgO/ (MgO+SrO) is more than 0.60,
Al 2o 3× (MgO/ (MgO+CaO+SrO+BaO)) is more than 5.5.
3. the smooth grinding method of glass substrate as claimed in claim 1 or 2, wherein, the fluctuating of the interarea of the glass substrate before smooth grinding is scaled the fluctuating of 20mm spacing and the height of fluctuating that obtains is less than 0.2 μm.
4. the smooth grinding method of the glass substrate according to any one of claims 1 to 3, wherein, carries out smooth grinding to the interarea of the glass substrate obtained by float forming.
5. an alkali-free glass substrate, it uses the smooth grinding method of the glass substrate according to any one of claim 1 ~ 4 to carry out smooth grinding.
6. alkali-free glass substrate as claimed in claim 5, wherein, the fluctuating of the interarea of the glass substrate after smooth grinding is scaled the fluctuating of 20mm spacing and the height of fluctuating that obtains is less than 0.07 μm.
7. the alkali-free glass substrate as described in claim 5 or 6, wherein, the square surfaceness of 5 μm of the interarea of the glass substrate after smooth grinding is below 0.30nm.
8. the alkali-free glass substrate according to any one of claim 5 ~ 7, wherein, length is at least more than 900mm.
CN201380029856.5A 2012-06-05 2013-05-30 Glass substrate finish-polishing method, and alkali-free glass substrate finish-polished according to said method Pending CN104364217A (en)

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