CN105189385A - Glass plate for chemical reinforcement purposes, and method for producing same - Google Patents

Glass plate for chemical reinforcement purposes, and method for producing same Download PDF

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Publication number
CN105189385A
CN105189385A CN201480023702.XA CN201480023702A CN105189385A CN 105189385 A CN105189385 A CN 105189385A CN 201480023702 A CN201480023702 A CN 201480023702A CN 105189385 A CN105189385 A CN 105189385A
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Prior art keywords
glass
sheet glass
temperature
compression
mgo
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Chinese (zh)
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西沢学
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AGC Inc
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Asahi Glass Co Ltd
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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
    • 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
    • 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
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
    • 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

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

The present invention provides a glass plate which has a high glass transition temperature and shows small compaction (C) in a heat treatment at a low temperature (150 to 300 degrees centigrade). The present invention relates to a glass plate for chemical reinforcement purposes, which has a virtual viscosity of 1012.8 d.Pa.s or less and contains, in molar percentage in terms of oxide content, 60 to 79% of SiO2, 2.5 to 18% of Al2O3, 0 to 3% of B2O3, 1 to 15% of MgO, 0 to 1% of CaO, 0 to 1% of SrO, 0 to 1% of BaO, 0 to 1% of ZrO2, 7 to 15.5% of Na2O, 0 to 0.5% of K2O and 0 to 2% of Li2O, wherein Na2O+K2O is 7 to 15.5%, Na2O/(Na2O+K2O) is 0.9 to 1, MgO+CaO+SrO+BaO is 1 to 18%, MgO-0.5Al2O3 is 1 to 8, MgO+0.5Al2O3 is 1 to 20, the glass transition temperature of the glass plate is 580 to 720 degrees centigrade, and the compaction (C) of the glass plate is 20 ppm or less.

Description

Chemical enhanced sheet glass and manufacture method thereof
Technical field
The present invention is the chemical enhanced sheet glass utilized in various contact panel, various display pannels etc., is the sheet glass obtained by the patternings such as conducting film on this sheet glass.
Background technology
Chemical enhanced sheet glass can use soda lime glass, alkali alumino-silicates glass, utilizes the various manufacturing process manufactures such as the flat method of float glass process, roller, fusion method.
Above-mentioned float glass process as the manufacturing process pulled out in the horizontal direction by sheet glass fully can guarantee the length of annealing furnace, and on the other hand, in the method that fusion method etc. is shaped in vertical direction, the limited length system of annealing furnace, therefore annealing time is not enough.
If annealing time is not enough, speed of cooling after the shaping of then sheet glass accelerates, consequently, on a glass by the thermal technology's sequence during patternings such as nesa coating, the contraction (hereinafter referred to as " intensity of compression ") of the glass sheet size that the stabilization phenomenon of glass causes becomes large.Therefore, Problems existing is, becomes precision during film patterning to reduce.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2009-196879 publication
Summary of the invention
Invent problem to be solved
The object of the present invention is to provide a kind of chemical enhanced sheet glass, its manufacture TFT panel, with the TFT panel of touch sensing or touch sensing (following, these are generically and collectively referred to as " display member ") time low temperature (150 ~ 300 DEG C) under thermal treatment in, even the sheet glass that the fusion method that speed of cooling when utilizing forming of glass is fast etc. manufacture, intensity of compression (C) is also little, one-tenth film patterning precision on sheet glass high (being difficult to produce position skew), is suitable for display member.
For the mode of dealing with problems
The present invention finds by imaginary viscosity, composition, second-order transition temperature and intensity of compression (C) are set in specified range, can realize above-mentioned purpose, thus complete the present invention.
That is, the present invention is as described below.
1. a chemical enhanced sheet glass, its imaginary viscosity is 10 12.8below dPas, and represent with the molar percentage of following oxide-base standard, contain:
The SiO of 60 ~ 79% 2,
The Al of 2.5 ~ 18% 2o 3,
The B of 0 ~ 3% 2o 3,
The MgO of 1 ~ 15%,
The CaO of 0 ~ 1%,
The SrO of 0 ~ 1%,
The BaO of 0 ~ 1%,
The ZrO of 0 ~ 1% 2,
The Na of 7 ~ 15.5% 2o,
The K of 0 ~ 0.5% 2o,
The Li of 0 ~ 2% 2o, wherein
Na 2o+K 2o is 7 ~ 15.5%,
Na 2o/ (Na 2o+K 2o) be 0.9 ~ 1,
MgO+CaO+SrO+BaO is 1 ~ 18%,
MgO-0.5Al 2o 3be 1 ~ 8,
MgO+0.5Al 2o 3be 1 ~ 20,
Second-order transition temperature is 580 ~ 720 DEG C,
Intensity of compression (C) is below 20ppm.
2. the chemical enhanced sheet glass according to preceding paragraph 1, wherein, photoelastic constant is 27 ~ 33nm/MPa/cm.
3. the chemical enhanced sheet glass according to preceding paragraph 1 or 2, wherein, viscosity becomes 10 4temperature (T during dPaS 4) and glass surface devitrification temperature (T c) pass be T 4-T c>=-20 DEG C.
4. the chemical enhanced sheet glass according to preceding paragraph 1 or 2, wherein, viscosity becomes 10 4temperature (T during dPaS 4) and inside glass devitrification temperature (T d) pass be T 4-T d>=50 DEG C.
5. the chemical enhanced sheet glass according to preceding paragraph 3, its sheet glass be shaped for using float glass process.
6. the chemical enhanced sheet glass according to preceding paragraph 4, its sheet glass be shaped for using fusion method (fusion).
Invention effect
In thermal treatment under the low temperature of chemical enhanced sheet glass of the present invention in the manufacturing process of display member (150 ~ 300 DEG C), intensity of compression (C) little (below 20ppm), is difficult to position skew when producing the one-tenth film patterning on sheet glass.
Therefore, chemical enhanced sheet glass of the present invention can be suitable as the chemical enhanced sheet glass of the one-piece type protective glass of particularly contact panel sensor of built-inization of IC circuit of high speed, high-weatherability, multifunction, high reliability, driving mechanism etc. of answering the maximization of counter plate, high-precision refinement, display box.
In addition, chemical enhanced sheet glass of the present invention is the sheet glass that the manufacturing process utilizing the speed of cooling such as fusion method fast manufactures, and therefore imaginary viscosity is 10 12.8below dPas.In addition, chemical enhanced sheet glass of the present invention is be suitable for chemical enhanced glass, and the surface compression stress after therefore chemical enhanced is high, and Surface stress layer easily deeply, possesses high strength as display member.
Accompanying drawing explanation
Fig. 1 represents MgO and the Al in sheet glass of the present invention 2o 3the chart of relation.
Fig. 2 is for representing example 19,22 (embodiment) of the present invention and the imaginary viscosity of sheet glass of example 25 (comparative example) and the chart of the relation of intensity of compression.
Fig. 3 (A) ~ (D) is for schematically showing the figure of an example of touch sensing plate, Fig. 3 (A) is vertical view, the b-b line cross section that Fig. 3 (B) is Fig. 3 (A), the c-c line cross section that Fig. 3 (C) is Fig. 3 (A), Fig. 3 (D) is the cross section near end.
Fig. 4 is the schematic diagram of the formation for illustration of the touch sensing plate shown in Fig. 3 (A) ~ (D).
Fig. 5 is for representing the schema of an example of the manufacture method of the touch sensing plate shown in Fig. 3 (A) ~ (D).
Fig. 6 is the sectional view of TFT panel or outer insert-type (oncell) contact panel.
Fig. 7 is the sectional view of interior insert-type (incell) contact panel.
Fig. 8 is the sectional view of the contact panel of outer hung type (outcell).
Embodiment
< chemical enhanced sheet glass > of the present invention
The imaginary viscosity of chemical enhanced sheet glass of the present invention (hereinafter also referred to sheet glass of the present invention) is 10 12.8below dPas, and represent with the molar percentage of following oxide-base standard, contain: the SiO of 60 ~ 79% 2, 2.5 ~ 18% Al 2o 3, 0 ~ 3% B 2o 3, 1 ~ 15% MgO, the CaO of 0 ~ 1%, SrO, the BaO of 0 ~ 1%, the ZrO of 0 ~ 1% of 0 ~ 1% 2, 7 ~ 15.5% Na 2o, 0 ~ 0.5% K 2o, 0 ~ 2% Li 2o, wherein Na 2o+K 2o is 7 ~ 15.5%, Na 2o/ (Na 2o+K 2o) be 0.9 ~ 1, MgO+CaO+SrO+BaO be 1 ~ 18%, MgO-0.5Al 2o 3be 1 ~ 8, MgO+0.5Al 2o 3be 1 ~ 20, second-order transition temperature is 580 ~ 720 DEG C, and intensity of compression (C) is below 20ppm.
(intensity of compression)
The intensity of compression (C) of sheet glass of the present invention is below 20ppm.Intensity of compression (C) is more preferably below 18ppm, more preferably below 16ppm.If be below 20ppm, then in the thermal treatment under the low temperature (150 ~ 300 DEG C) in the manufacturing process of display member, be difficult to position skew when producing the one-tenth film patterning on sheet glass.
(measuring method of intensity of compression)
In the present invention, so-called intensity of compression (C), refers to the value utilizing the following method illustrated to measure.
First, after the glass becoming object is melted at 1600 DEG C, melten glass is flowed out, cools after being configured as tabular.By the sheet glass attrition process obtained, obtain 2 all through the sample of mirror ultrafinish with thickness 2mm, size 100mm × 20mm.
Then, the sheet glass obtained is heated to glass transition temperature Tg+150 DEG C, keeps at such a temperature, after 1 minute, being cooled to room temperature with the cooling rate specified.Then, 2 place's impressions are got with interval A (A=90mm) in the surface of sheet glass on long side direction.
Then, also anneal can be carried out.So-called anneal, refers to after raw materials melt, after being cooled to the temperature of below strain point, is again heated to the operation (removing chemical intensification treatment operation) of the temperature of more than strain point.The time needed in annealing was preferably all process steps within one day.Then, chemical intensification treatment is implemented.
Then, sheet glass is heated to 300 DEG C with heat-up rate 100 DEG C/h (=1.6 DEG C/min), keeps, after 1 hour, being cooled to room temperature with cooling rate 100 DEG C/h at 300 DEG C.Further, again measure indent spacers from, this distance is set as B.Following formula is used to calculate intensity of compression (C) from A, B of obtaining therefrom.It should be noted that, A, B use opticmicroscope to measure.
C[ppm]＝(A-B)/A×10 6
(imaginary viscosity)
The imaginary viscosity of sheet glass of the present invention is 10 12.8below dPas.In order to the imaginary viscosity of sheet glass is set as 10 12.8below dPas, is preferably set as being equivalent to more than 20 DEG C/min by the speed of cooling after the shaping of sheet glass.
The imaginary viscosity of sheet glass is preferably 10 12.6below dPas (speed of cooling is equivalent to more than 30 DEG C/min), is preferably 10 12.4below dPas (speed of cooling is equivalent to more than 50 DEG C/min), is preferably 10 12.2below dPas (speed of cooling is equivalent to more than 70 DEG C/min), is preferably 10 12.1below dPas (speed of cooling is equivalent to more than 100 DEG C/min), more preferably 10 12.0below dPas (speed of cooling is equivalent to more than 120 DEG C/min).
Even if sheet glass of the present invention cools with the speed being equivalent to more than 20 DEG C/min, also can realize above-mentioned low compressibility, and sheet glass produce time productivity high, therefore particularly preferably.
(calculation method of imaginary viscosity)
Glass imaginary viscosity (η) can (G.W.Scherer, RelaxationinGlassandComposites, Wiley, NewYork (1986), p.159) calculate according to following (formula 4).
Log 10η=12.3-log 10| q| (formula 4)
The unit of η is dPas.
Q is speed of cooling, and unit is DEG C/s.
The small pieces of the more glass sheets small pieces, such as 1 centimeter square that the glass sheets from below thickness 1mm are cut are heat-treated with various speed of cooling q, are cooled respectively, measure the physics value of each glass flake.Cooling starting temperature is preferably not by the sufficiently high temperature of cooling rate.Typical case, is preferably Tg+50 DEG C ~ about+150 DEG C.
Implement the not special restriction of physics value of mensuration, be preferably density, preferably specific refractory power etc. and density have the physics value of substantial connection.Speed of cooling (log is represented in x-axis 10), represent that each has implemented the physics value of the glass flake of Overheating Treatment in y-axis, make working curve.The speed of cooling of this glass is represented relative to the value (q) of x-axis of the physics value (y-axis) not implementing heat treated glass flake.
The present inventor is from experiment and found that of trial and error: even if implement chemical intensification treatment or anneal, the intensity of compression (C) of the speed of cooling of 50 DEG C/min is suppressed for less (to below 20ppm), relative to the increase of speed of cooling during forming of glass, also can keep low compressibility, thus complete the present invention.
(Tg)
The second-order transition temperature (Tg) of sheet glass of the present invention is more than 580 DEG C and less than 720 DEG C.Be above-mentioned scope by the second-order transition temperature (Tg) of sheet glass of the present invention, preferred for reduction intensity of compression (C), and in the low-temperature heat treatment (150 DEG C ~ 300 DEG C) in the manufacturing process of display member, the mobility of the alkali ion in glass diminishes, to the movability step-down of the transistor unit (sensor) of the IC circuit of sensor, driving mechanism etc., the performance degradation of sensor can be suppressed.Tg is preferably more than 600 DEG C, is more preferably more than 640 DEG C, more preferably more than 680 DEG C.
In sheet glass of the present invention, the reason being defined in above-mentioned composition is as described below.
(SiO 2)
SiO 2for forming the composition of the skeleton of glass, in order to keep thermotolerance and the chemical durability of glass, reduce density, mean thermal expansion coefficients at 50 ~ 350 DEG C and intensity of compression (C), content is set as more than 60 % by mole (hreinafter referred to as " % ").Be preferably more than 62%, be more preferably more than 63%.
In addition, in order to reduce photoelastic constant, reducing viscosity when glass melts, meltability being remained well, by SiO 2content be set as less than 79%.Be preferably less than 77%, be more preferably less than 75%, more preferably less than 74%.
(Al 2O 3)
With regard to Al 2o 3; in order to improve second-order transition temperature; improve weathering resistance (solarization), thermotolerance and chemical durability; improve Young's modulus; mean thermal expansion coefficients at reducing by 50 ~ 350 DEG C; intensity of compression (C) is suppressed for lower; reduce photoelastic constant; improve chemical enhanced characteristic; the mobility of the alkali ion in glass is diminished; reduce the movability to the transistor unit (sensor) of the IC circuit of sensor or driving mechanism etc., suppress the performance degradation of sensor, content is set as more than 2.5%.Be preferably more than 4%, be more preferably more than 6%, more preferably more than 7%.
In addition, in order to reduce viscosity when glass melts, meltability is suppressed to be deteriorated, by the devitrification temperature [superficial devitrification temperature (T of glass surface c) and the inside devitrification temperature (T of inside glass d)] suppress, for lower, to keep good plasticity, by Al 2o 3content be set as less than 18%.Be preferably less than 16%, be more preferably less than 15%.
(B 2O 3)
B 2o 3there is viscosity when reducing glass melting, promote to melt, reduce the effect of devitrification temperature, in order to improve strength characteristics, also can containing reaching 3%.In order to suppress the excessive reduction of second-order transition temperature, the excessive rising of photoelastic constant, content is set as less than 3%.Be preferably less than 1.5%.Be more preferably less than 0.5%, more preferably do not contain in fact.
It should be noted that, so-called " not containing in fact ", refer to and do not contain except the inevitable impurity except being mixed into from raw material etc., that is, refer to and expressly do not contain.
When using as TFT panel glass or interior insert-type contact panel sheet glass, if B 2o 3containing ratio is low, then when sheet glass manufactures, and the B in the melting operation when glass melts, clarification operation and forming process 2o 3volatile quantity few, uniformity and the flatness of the sheet glass of manufacture are excellent.Consequently, when as when requiring the TFT panel sheet glass of high-flatness, compared with TFT panel sheet glass in the past, display quality is excellent.
In addition, if B when considering glass melting 2o 3the carrying capacity of environment that causes of volatilization, be then preferably B 2o 3containing ratio lower.
But, when the sheet glass in order to waste liquid crystal display recycling object and when using cullet, can use containing B 2o 3cullet.
(MgO)
MgO has and reduces viscosity when glass melts, promotes to melt, reduce the effect of devitrification temperature, and has the effect of the weathering resistance improving sheet glass, therefore content is set as more than 1%.Be preferably more than 3%, be more preferably more than 5%, more preferably more than 7%.
In order to reduce mean thermal expansion coefficients, the intensity of compression (C) at 50 ~ 350 DEG C, by devitrification temperature (T c), photoelastic constant suppresses for lower, is set as less than 15%.Be preferably less than 13%, be more preferably less than 11%, more preferably less than 10%.
(CaO)
CaO has and reduces viscosity when glass melts, promotes to melt, reduce the effect of devitrification temperature, therefore can contain.In order to suppress the increase of intensity of compression (C), content is set as less than 1%.Be preferably less than 0.5%, be more preferably and do not contain in fact.
(SrO)
SrO has and reduces viscosity when glass melts, promotes to melt, reduces devitrification temperature, reduces the effect of photoelastic constant, therefore can contain.In order to suppress the increase of intensity of compression (C), the content of SrO is set as less than 1%.Be preferably less than 0.5%, be more preferably and do not contain in fact.
(BaO)
BaO has and reduces viscosity when glass melts, promotes to melt, reduces devitrification temperature, reduces the effect of photoelastic constant, therefore can contain.In order to suppress the increase of intensity of compression (C), content is set as less than 1%.Be preferably less than 0.5%, be more preferably and do not contain in fact.
(ZrO 2)
ZrO 2there is viscosity when reducing glass melting, promote to melt, reduce the effect of devitrification temperature, therefore can contain.In order to suppress the increase of intensity of compression (C), content is set as less than 1%.Be preferably less than 0.5%, be more preferably and do not contain in fact.
(RO)
MgO, CaO, SrO and BaO have and reduce viscosity when glass melts, promote to melt, reduce the effect of devitrification temperature, in order to improve the weathering resistance of sheet glass, in addition, in order to reduce photoelastic constant, are set as with total amount more than 1%.Be preferably more than 3%, be more preferably more than 5%, more preferably more than 7%.In order to the increase of the mean thermal expansion coefficients at suppress glass 50 ~ 350 DEG C and intensity of compression (C), be set as with total amount less than 18%.Be preferably less than 16%, be more preferably less than 12.5%, more preferably less than 10%.
(Na 2O)
Na 2the effect that O has to be made chemical enhancedly to become easily, reduce viscosity when glass melts, promote to melt, reduce devitrification temperature, is therefore set as more than 7% by content.Be preferably more than 9%, be more preferably more than 11%.More preferably more than 12%.
With by intensity of compression (C) suppress for less be the first object, by Na 2the content of O is set as less than 15.5%.In order to suppress the deterioration of the increase of intensity of compression (C), mean thermal expansion coefficients at 50 ~ 350 DEG C, chemical durability, weathering resistance, being preferably less than 14.5%, being more preferably less than 13.5%.More preferably less than 13%.
(K 2O)
K 2o has and reduces viscosity when glass melts, promotes to melt, reduce the effect of devitrification temperature, therefore can contain.In order to suppress the increase of intensity of compression (C), by K 2the content of O is set as less than 0.5%.Be more preferably less than 0.2%, more preferably do not contain in fact.
(Li 2O)
Li 2o has and reduces viscosity when glass melts, promotes to melt, reduce the effect of devitrification temperature, therefore can contain.In order to suppress the increase of intensity of compression (C), content is set as less than 1%.Be more preferably less than 0.5%, more preferably do not contain in fact.
(R 2O)
Na 2o and K 2the effect that O has to be made chemical enhancedly to become easily, reduce viscosity when glass melts, promote to melt, reduce devitrification temperature, in addition, in order to reduce photoelastic constant, by Na 2o and K 2the content of the total amount of O is set as more than 7%.Be preferably more than 9%, be more preferably more than 11%, more preferably more than 12%.
With by intensity of compression (C) suppress for less be the first object, be the second object to improve weathering resistance, be set as less than 15.5%.Be preferably less than 15%, be more preferably less than 14%, be more preferably less than 13%.
(formula 1)
In addition, in order to reduce intensity of compression (C), Na 2o and K 2the mode that O meets 0.9 ~ 1 with following (formula 1) contains.
Na 2o/ (Na 2o+K 2o) (formula 1)
Above-mentioned (formula 1) becomes the index of the intensity of compression (C) in the thermal treatment reduced under low temperature (150 ~ 300 DEG C).The present inventor is from experiment and the result of trial and error, find: meet scope of the present invention at above-mentioned each composition, and the value obtained by above-mentioned (formula 1) is when becoming 0.9 ~ 1, Tg is 580 ~ 720 DEG C, and the mean thermal expansion coefficients at 50 ~ 350 DEG C meets 65 × 10 -7~ 85 × 10 -7, and intensity of compression (C) meets below 20ppm.Be preferably more than 0.95, more preferably 1.
(formula 2)
MgO and Al 2o 3: MgO and Al 2o 3the mode meeting 1 ~ 8 with following (formula 2) contains.It should be noted that, at " MgO ", " Al of following (formula 2) 2o 3" middle MgO and Al substituted into contained by the composition of sheet glass 2o 3respective " % by mole ".
MgO-0.5Al 2o 3(formula 2)
Above-mentioned (formula 2) becomes and reduces photoelastic constant and the index reducing the intensity of compression (C) in the thermal treatment under low temperature (150 ~ 300 DEG C).The present inventor, from experiment and the result of trial and error, finds: above-mentioned each composition meets scope of the present invention, and the value obtained by above-mentioned (formula 2) is the closer to the centre of 1 ~ 8, namely more close to 4, more can reduce intensity of compression (C).Be preferably more than 2, be more preferably more than 3.Be preferably less than 7.5, more preferably less than 7, be particularly preferably less than 6.In addition, in order to obtain low photoelastic constant, be preferably more than 2.
(diagram of formula 2)
It should be noted that, MgO is being set as the longitudinal axis, by Al 2o 3when being set as transverse axis, be 1 ~ 8 and MgO and Al in above-mentioned formula (2) 2o 3during for above-mentioned compositing range, scope of the present invention is the part of being surrounded by solid line lines in FIG.
The scope that can reduce intensity of compression (C) is in FIG, within the scope of the invention, and MgO-0.5Al 2o 3=1 and MgO-0.5Al 2o 3the part becoming the straight line of 5 close to Y intercept of the central authorities of=8 these two straight lines, that is, in FIG within the scope of the invention and close to MgO-0.5Al 2o 3the part of the straight line of=4.
(formula 3)
In addition, MgO and Al 2o 3the mode meeting 1 ~ 20 with following (formula 3) contains.It should be noted that, at " MgO ", " Al of following (formula 3) 2o 3" middle MgO and Al contained by composition substituting into sheet glass 2o 3respective " % by mole ".
MgO+0.5Al 2o 3(formula 3)
Above-mentioned (formula 3) becomes devitrification characteristic, specifically following T for meeting in glass manufacture operation 4-T cfor-50 ~ 350 DEG C, or T 4-T dfor the index of-50 ~ 350 DEG C.The present inventor, from experiment and the result of trial and error, finds: above-mentioned each composition meets scope of the present invention, and when the value obtained by above-mentioned (formula 3) is 1 ~ 20, Tg is that the mean thermal expansion coefficients at 580 ~ 720 DEG C and 50 ~ 350 DEG C meets 65 × 10 -7~ 85 × 10 -7/ DEG C, and T 4-T cor T 4-T dmeet above-mentioned scope.
(formula 3 and moulding method)
As the manufacturing process of sheet glass of the present invention, applicable float glass process and fusion method (glass tube down-drawing), when for fusion method, above-mentioned (formula 3) is preferably less than 14, is more preferably less than 13, and more preferably less than 12.
In addition, when for float glass process, above-mentioned (formula 3) is preferably less than 18, is more preferably less than 16, and more preferably less than 14.In addition, in order to obtain low photoelastic constant, being preferably more than 3, being more preferably more than 5, more preferably more than 7.
(diagram of formula 3)
It should be noted that, MgO being set as the longitudinal axis, by Al 2o 3when being set as transverse axis, above-mentioned (formula 3) is 1 ~ 20 and MgO and Al 2o 3during for above-mentioned compositing range, scope of the present invention is the part of being surrounded by solid line in FIG.
(average coefficient of linear expansion)
The average coefficient of linear expansion of sheet glass of the present invention at 50 ~ 350 DEG C is preferably 85 × 10 -7/ DEG C below.By being above-mentioned scope, dimensional change in the manufacturing process of display member is few, it is less on the impact of quality (residual stress or photoelastic effect) that stress when bonding with display pannels such as liquid-crystal displays causes, and is therefore especially preferred in display quality.
It should be noted that, be preferably 80 × 10 -7/ DEG C below, be more preferably 78 × 10 -7/ DEG C below, more preferably 76 × 10 -7/ DEG C below.In addition, when using soda-lime glass as display pannel sheet glass, with regard to the viewpoint of both thermal expansion differences, be preferably 65 × 10 -7/ DEG C more than.
(T c)
Glass surface devitrification temperature (the T of sheet glass of the present invention c) be preferably less than 1300 DEG C.Be preferably less than 1275 DEG C, be more preferably less than 1250 DEG C, be particularly preferably less than 1225 DEG C.It should be noted that, if consider the easiness guaranteeing other physical property, then glass surface devitrification temperature (T c) be more than 900 DEG C.
So-called glass surface devitrification temperature (T c), refer to the glass particle put in the dish of platinum through pulverizing, controlling to carry out thermal treatment in 17 hours in the electric furnace for steady temperature, by the observation by light microscope after thermal treatment, at the mean value of the top temperature of the surperficial crystallization of glass with the minimum temperature of non-crystallization.
(T d)
Inside glass devitrification temperature (the T of sheet glass of the present invention d) be preferably less than 1300 DEG C.Be preferably less than 1275 DEG C, be more preferably less than 1250 DEG C, more preferably less than 1225 DEG C, more preferably less than 1200 DEG C.It should be noted that, if consider the easiness guaranteeing other physical property, then inside glass devitrification temperature (T d) be more than 900 DEG C.
So-called inside glass devitrification temperature (T d), refer to the glass particle put in the dish of platinum through pulverizing, controlling to carry out thermal treatment in 17 hours in the electric furnace for steady temperature, by the observation by light microscope after thermal treatment, at the mean value of the top temperature of the inside crystallization of glass with the minimum temperature of non-crystallization.
(T 4)
The viscosity of sheet glass of the present invention becomes 10 4temperature (the T of dPas 4) be preferably less than 1350 DEG C.Be preferably less than 1300 DEG C, be more preferably less than 1275 DEG C, more preferably less than 1250 DEG C.It should be noted that, if consider the easiness guaranteeing other physical property, then viscosity becomes 10 4temperature (the T of dPas 4) be more than 1100 DEG C.
(viscosity under manufacturing process and devitrification temperature)
As the manufacturing process of sheet glass of the present invention, applicable float glass process and fusion method (glass tube down-drawing), when fusion method, T dunder glass viscosity be preferably 10 4.7more than dPas, is more preferably 10 5.0more than dPas, more preferably 10 5.3more than dPas, is particularly preferably 10 5.5more than dPas.It should be noted that, if consider the easiness guaranteeing other physical property, then when for fusion method, T dunder glass viscosity be preferably 10 7.0below dPas.
When manufacturing process is float glass process, T cunder glass viscosity be preferably 10 3.8more than dPas, is more preferably 10 3.9more than dPas, more preferably 10 4.0more than dPas.It should be noted that, if consider the easiness guaranteeing other physical property, then when for float glass process, T cunder glass viscosity be preferably 10 7.0below dPas.
(manufacturing process and devitrification temperature)
Viscosity under devitrification temperature, as shown in earlier paragraphs, is generally used as index by the judgement of shaping possibility.But, according in the method for earlier paragraphs, must from 10 5.5dPas to 10 3.8dPas measures viscosity continuously, therefore evaluates numerous and diverse.Therefore, as easy evaluation method, also desirable and T 4the temperature difference evaluate.
As the manufacturing process of sheet glass of the present invention, applicable float glass process and fusion method (glass tube down-drawing), if devitrification when considering preventing board forming of glass, then as the physical property of sheet glass, when for fusion method, T 4-T dbe preferably 100 ~ 350 DEG C, preferably meet T 4-T d>=50 DEG C, be more preferably and meet T 4-T d>=150 DEG C, more preferably meet T 4-T d>=200 DEG C.
In addition, when for float glass process, T 4-T cbe preferably-50 ~ 350 DEG C, preferably meet T 4-T c>=-20 DEG C, be more preferably and meet T 4-T c>=-10 DEG C, more preferably meet T 4-T c>=0 DEG C.
(T 2)
The viscosity of sheet glass of the present invention becomes 10 2temperature (T during dPas 2) be preferably less than 1850 DEG C, be more preferably less than 1800 DEG C, be more preferably less than 1750 DEG C, be more preferably less than 1700 DEG C, more preferably less than 1650 DEG C.
(density)
In order to the lightweight of display member, the density of sheet glass of the present invention is preferably 2.50g/cm 3below, 2.45g/cm is more preferably 3below, more preferably 2.43g/cm 3below, 2.41g/cm is particularly preferably 3below.It should be noted that, if consider the easiness guaranteeing other physical property, then the density of sheet glass of the present invention is preferably 2.35g/cm 3above.
(photoelastic constant)
The photoelastic constant of sheet glass of the present invention is preferably below 33nm/MPa/cm, is more preferably below 31nm/MPa/cm, more preferably below 30nm/MPa/cm, is particularly preferably below 29nm/MPa/cm.
Sometimes following phenomenon is confirmed: make sheet glass have birefringence because of the stress produced when the use of the manufacturing process of display member or display member, make the display of black become ash thus, the contrast gradient of LCD reduces.By photoelastic constant is set as below 33nm/MPa/cm, this phenomenon can be suppressed for less.
If consider the easiness guaranteeing other physical property, then the photoelastic constant of sheet glass of the present invention is preferably more than 27nm/MPa/cm.It should be noted that, photoelastic constant can be measured by disk compression method.
(Young's modulus)
The Young's modulus of sheet glass of the present invention is preferably more than 66GPa, is more preferably more than 70GPa, more preferably more than 74GPa.The Young's modulus of sheet glass of the present invention is preferably below 80GPa.By being set as this scope, can expecting that the amount of bow of the sheet glass when utilizing finger etc. to be pressed by display member diminishes, suppressing the breakage caused with the contact of peripheral member etc.
In addition, have as inferior advantage: in display member manufacturing process, when transporting sheet glass, keep the amount of bow of central part during two ends little, thus suppress faults such as coming in contact between sheet glass, maybe can reduce the space between sheet glass, therefore processing blades number once increases, and productivity increases.
In addition, generally speaking, if Young's modulus is high, then the raising of the mechanical characteristics of sheet glass, raising to the weather resistance of breaking is contributed to.
(additive)
Sheet glass of the present invention preferably comprises above-mentioned mother's composition in essence, but also can contain other compositions in the scope not damaging object of the present invention.Other compositions can add up to containing less than 2%, are preferably containing less than 1%, are more preferably containing less than 0.5%.
Such as, also can weathering resistance, meltability, increased devitrification resistance, UV-preventing, infrared rays cover, ultraviolet through, infrared rays through etc. be improved as object, or, with the form that the impurity using cullet to cause because using the recycling of rear discarded display pannel is mixed into, and containing ZnO, Li 2o, WO 3, Nb 2o 5, V 2o 5, Bi 2o 3, MoO 3, P 2o 5, Ga 2o 3, I 2o 5, In 2o 5, Ge 2o 5deng.
(finings)
With regard to sheet glass of the present invention, in order to improve the meltability, clarification of glass, also can contain SO in glass 3, F, Cl, SnO 2count the mode of less than 2% with total amount, these raw materials are added into female constitutive material.
In addition, in order to improve the chemical durability of glass, also ZrO can be contained in glass 2, Y 2o 3, La 2o 3, TiO 2, SnO 2count less than 2% with total amount, be preferably containing less than 1%, be more preferably containing less than 0.5%.Among those, Y 2o 3, La 2o 3and TiO 2also the raising of the Young's modulus of glass is contributed to.
(tinting material)
With regard to sheet glass of the present invention, in order to adjust the tone of glass, also Fe can be contained in glass 2o 3, CeO 2deng tinting material.The content of such tinting material is preferably less than 1% with total amount.
With regard to sheet glass of the present invention, if consider carrying capacity of environment, be then preferably in fact not containing As 2o 3, Sb 2o 3.In addition, if consider stably to carry out float forming, be then preferably in fact not containing ZnO.But the manufacture that the application of the fireballing thinner glass of the pull-out of sheet glass of the present invention to glass or utilization are undertaken by the shaping of fusion method is more effective.
The Manufacturing approach and use > of < sheet glass of the present invention
Sheet glass of the present invention can be suitable for the chemical enhanced sheet glass doing to be suitable for display member.Below, be described in detail.
(manufacture method of sheet glass)
When manufacturing sheet glass of the present invention, experiencing in the same manner as in time manufacturing TFT panel sheet glass, protective glass sheet glass in the past and melting, clarify, be shaped and annealing operation.
Just melt with regard to operation, to become the mode raw materials of the composition of obtained sheet glass, above-mentioned raw materials is fed in calciner continuously, is preferably heated to about 1450 ~ 1650 DEG C, obtains melten glass.
Also oxide compound, carbonate, oxyhydroxide can be used in raw material, and halogenide etc. such as the muriate added as required.Raw material granularity also can use aptly and never produce the small particle size raw material that the Large stone raw material of hundreds of microns dissolving residual degree does not extremely produce the several microns of degree of dispersing, not being aggregated into the degree of offspring when raw material transports.Also granulation body can be used.Also can by the oxidation-reduction degree of water content, β-OH, Fe or redox [Fe 2+/ (Fe 2++ Fe 3+)] etc. melting condition suitably adjust, use.
As clarification operation, sheet glass of the present invention is for containing alkalimetal oxide (Na 2o, K 2o) alkali glass plate, therefore can use SO effectively 3as finings.In addition, the froth breaking method of also applicable utilization decompression.As the finings utilized in the froth breaking method of decompression, preferably use the halogens such as Cl or F.
As forming process, applicable float glass process and fusion method (glass tube down-drawing), obtain glass ribbon.
As annealing operation, preferably utilized by glass ribbon the speed of cooling of more than 20 DEG C/min to be cooled to room temperature state and after cut-out, obtain sheet glass.
(thickness of sheet glass)
The thickness of sheet glass of the present invention is preferably less than 2 centimetres.If the thickness of sheet glass is less than 2 centimetres, then to indicating meter or sensor one-piece type protective glass, the slimming of goods can be installed and lightweight is made contributions.Be preferably less than 1.5 centimetres, more preferably less than 1.0 centimetres, more preferably less than 0.5 centimetre, more preferably less than 0.3 centimetre.
(method of chemical strengthening treatment)
As the method for sheet glass of the present invention being carried out to chemical intensification treatment, as long as the K ion in the Na ion of surface layer of glass and melting salt can be made to carry out ion-exchange, just there is no particular limitation, such as, can enumerate glass-impregnated at the saltpetre (KNO through heating 3) method in melting salt.
For forming the chemical intensification treatment condition with the chemical enhanced layer (compressive stress layers) of desired surface compression stress in glass, if be sheet glass, then also different from the difference of its thickness etc., but typically sheet glass is immersed in the KNO of 350 ~ 550 DEG C 3in melting salt 2 ~ 20 hours.From the view point of economy, preferably flood under the condition of 350 ~ 500 DEG C, 2 ~ 16 hours, preferred dipping time is 2 ~ 10 hours.
Also before or after chemical enhanced, etching, grinding or annealing can be implemented.Order, the number of processes of each operation are not particularly limited.
In addition, the cut-out of glass also can any stage before contact panel shown below makes or afterwards, implements once or repeatedly.The cutting-off method of glass does not specify, and can implement known method.
(surface compression stress (CS))
After chemical intensification treatment is carried out to sheet glass of the present invention, or, the surface compression stress (CS) of the sheet glass before chemical intensification treatment or after implementing etching, grinding, annealing is afterwards generally more than 550MPa, is typically more than 650MPa.In addition, in situation that the thickness of glass is such lower than 2mm etc., surface compression stress is preferably below 1400MPa.If more than 1400MPa, then likely inner tensile stress (CT) becomes excessive.Be more preferably below 1300MPa, be typically below 1200MPa.
(thickness (DOL) of surface compression stressor layers)
After chemical intensification treatment is carried out to sheet glass of the present invention, or, before chemical intensification treatment or implement afterwards to etch, grinding, sheet glass after annealing the thickness (DOL) of surface compression stressor layers usually preferably more than 10 μm, more preferably more than 15 μm, be typically more than 20 μm.
In addition, in situation that the thickness of glass is such lower than 2mm etc., the thickness of surface compression stressor layers is preferably less than 90 μm.If more than 90 μm, then likely inner tensile stress (CT) becomes excessive.Be more preferably less than 80 μm, be typically less than 70 μm.
(inner tensile stress (CT))
After carrying out chemical intensification treatment to sheet glass of the present invention, or the inner tensile stress (CT) of the sheet glass before chemical intensification treatment or after implementing etching, grinding, annealing is afterwards preferably below 50MPa.Be preferably below 45MPa, more preferably below 40MPa, most preferably be below 30MPa.The thickness (DOL) of inner tensile stress (CT) by surface compression stress (CS), surface compression stressor layers and the thickness (t) of glass, utilize following formula to calculate.
CT＝CS×DOL/(t-2×DOL)
If inner tensile stress (CT) is large, then form fragment during glassbreak, the tendency grow dispersed Powderedly.
(TFT and interior insert-type)
(forming and effect)
Sheet glass of the present invention can be preferably used for TFT panel or interior insert-type contact panel (hereinafter referred to as " scheme 1 ").The sectional view of scheme 1 is shown in Fig. 6.Top become touch surface, indicating meter depending on recognizing side.Tensile stress is produced respectively at the back side 110b and 130b of filter substrate 110 and array substrate 130 by the power pressed from top.
Therefore, if applied by chemical enhanced produced stress under compression this face, then the intensity raising of counter plate has larger effect.In addition, about respective front (opposing face at the back side), if also apply by chemical enhanced produced stress under compression, then the destruction of the substrate caused for the press-in stress produced by particulate or partition member has larger strength-enhancing effect.
That is, for the surperficial 110a of filter substrate 110, the destruction inhibition for the press-in stress produced by the particulate particles be clipped between Polarizer 100 and filter substrate 110 is had.For the surperficial 130a of array substrate, there is the destruction inhibition of the press-in stress for partition member 140.
(TFT and interior insert-type)
(manufacture method of array substrate etc.)
As array substrate or the array substrate (hereinafter referred to as " array substrate etc. ") being built-in with touch sensing, when using the sheet glass to sheet glass enforcement of the present invention is chemical enhanced, for the surface possessed implementing chemical enhanced sheet glass to sheet glass of the present invention, the manufacture method of the scheme 1 of the film formation process of gate insulating film film forming is described.
Use the manufacture method of the scheme 1 sheet glass of the present invention being implemented to chemical enhanced sheet glass, as long as possess following film formation process, just there is no particular limitation, this film formation process is after the film-forming region on the surface of sheet glass of the present invention being implemented to chemical enhanced sheet glass is warming up to the temperature (hereinafter referred to as film-forming temperature) in the scope of 150 ~ 300 DEG C, keep 5 ~ 60 minutes under above-mentioned film-forming temperature, make above-mentioned array substrate gate insulating film film forming in above-mentioned film-forming region.
Herein, film-forming temperature is preferably 150 ~ 250 DEG C, is more preferably 150 ~ 230 DEG C, more preferably 150 ~ 200 DEG C.In addition, the time remaining on this film-forming temperature is preferably 5 ~ 30 minutes, is more preferably 5 ~ 20 minutes, more preferably 5 ~ 15 minutes.
The film forming of gate insulating film is carried out in film-forming temperature as above and the scope of hold-time, and therefore sheet glass during this period can thermal contraction.The intensity of compression (C) sheet glass of the present invention being implemented to chemical enhanced sheet glass is little, is therefore difficult to the skew producing into film figure.
Film forming in film formation process such as realizes by known CVD.
(TFT and interior insert-type)
(being assembled into the method for panel)
In the manufacture method of the solution of the present invention 1, above-mentioned array substrate etc. and known filter substrate can be used to manufacture.
That is, TFT panel etc. can be manufactured by a series of operation comprising following operation: on above-mentioned array substrate etc., filter substrate, form alignment film respectively, and carry out the orientation treatment process that rubs; Use common spherical partition member, gap between the substrate making tft array substrate etc. and filter substrate keep specifying, carries out the bonding process of fitting with high precision; From substrate, unit is divided into the segmentation process of specified dimension; By Liquid crystal pour extremely through the injection process of the unit of segmentation; And unit is attached to the Polarizer attaching operation of Polarizer.
Also touch sensing array can be made on filter substrate.Filter substrate can use sheet glass of the present invention, also can not use.In order to give high strength, preferably use plate of the present invention.
(outer insert-type)
(forming and effect)
Sheet glass of the present invention can be suitable for outer insert-type contact panel (hereinafter referred to as " scheme 2 ").The sectional view of scheme 2 is shown in Fig. 7.
Use 2 glass sheets in scheme 1, in scheme 2, re-use a slice " touch sensing plate ".In scheme 2, in 3 glass sheets, at least 1 uses sheet glass of the present invention.
In the figure 7, top become touch surface, indicating meter depending on recognizing side.In scheme 2, touch sensing plate 160 is inserted in the inner side of Polarizer 100.Tensile stress is produced respectively at the back side 160b, 110b and 130b that touch sensing plate 160, filter substrate 110 and array substrate 130 are respective by the power pressed from top.Therefore, if applied by chemical enhanced produced stress under compression this face, then the intensity raising of counter plate has larger effect.
In addition, about respective front (opposing face at the back side), if also apply by chemical enhanced produced stress under compression, then the destruction of the substrate caused for the press-in stress produced by particulate or partition member has larger strength-enhancing effect.
That is, at the front 160a of touch sensing plate 160, the destruction inhibition for the press-in stress produced by the particulate particles be clipped between Polarizer 100 and touch sensing plate 160 is had.At the front 110a of filter substrate 110, there is the destruction inhibition for the press-in stress produced by the particulate particles be clipped between touch sensing plate 160.For the front 130a of array substrate, there is the destruction inhibition of the press-in stress for partition member 140.
(outer hung type)
(forming and effect)
Sheet glass of the present invention can be suitable for outer hung type contact panel (hereinafter referred to as " scheme 3 ").The sectional view of scheme 3 is shown in Fig. 8.
Use 2 glass sheets in scheme 1, in scheme 3, re-use a slice " touch sensing plate ".In scheme 3, in 3 glass sheets, at least 1 uses sheet glass of the present invention.
In fig. 8, top become touch surface, indicating meter depending on recognizing side.In scheme 3, touch sensing plate 160 is inserted in the outside of Polarizer 100.Tensile stress is produced respectively at the back side 160b, 110b and 130b that touch sensing plate 160, filter substrate 110 and array substrate 130 are respective by the power pressed from top.Therefore, if applied by chemical enhanced produced stress under compression this face, then the intensity raising of counter plate has larger effect.
In addition, about respective front (opposing face at the back side), if also apply by chemical enhanced produced stress under compression, then the destruction of the substrate caused for the press-in stress produced by particulate or partition member has larger strength-enhancing effect.That is, for the front 160a of touch sensing plate 160, the destruction inhibition of the press-in stress produced for the particulate particles being present in daily living space, the grains of sand, fiber etc. by touch sensing surface is had.
At the front 110a of filter substrate 110, there is the destruction inhibition for the press-in stress produced by the particulate particles be clipped between Polarizer 100.For the front 130a of array substrate, there is the destruction inhibition of the press-in stress for partition member 140.
(formation 1 of touch sensing plate)
In the touch sensing plate 10 of Fig. 3, the first nesa coating 14 in the drawings x direction extends existence, arranges multiple in the y direction orthogonal with this x direction.On the other hand, the second nesa coating 16 in the drawings y direction extends existence, and in x direction, arrangement is multiple.Big area portion 14a and big area portion 16a is separated from each other, arranges in the mode replaced on x direction and y direction, is to arrange to improve input position detection.Therefore, the first nesa coating 14 and the second nesa coating 16 utilize connection section 14b and connection section 16b to be formed in the mode of intersecting.
The typical live width of connection section 14b and connection section 16b is about 10 ~ 50 μm.Therefore, if use sheet glass become about more than 1m, then require the dimensional precision of 10 ~ 50 μm/1m=10 ~ 50ppm.From now on, along with the high-precision refinement of sensor, the narrowing of live width can be contemplated to.
(formation 2 of touch sensing plate)
As shown in Fig. 3 (A) and (B), at the first nesa coating 14 and the cross part of the second nesa coating 16 and the cross part of connection section 14b and connection section 16b, form cross part insulating film 28 in the mode of crossing over the second nesa coating 16 in the x direction.
In addition, at this cross part, the first nesa coating 14 is formed on this cross part insulating film 28 in the mode of crossing over cross part insulating film 28 and the second nesa coating 16 in the x direction.Thus, form the bridge (cross part) that the first nesa coating 14 and the second nesa coating 16 are intersected with state of insulation, the state of insulation of the first nesa coating 14 that maintenance crosses one another and formed and the second nesa coating 16.
(formation 3 of touch sensing plate)
In the touch sensing plate 10 of Fig. 3, the formation material of nesa coating 14 and 16 can utilize the conductive material of various known transparent (having photopermeability) for forming sensor part in the touch sensing of capacitance type.
Specifically, such as, ITO (tin indium oxide) and IZO (indium zinc oxide) etc. can be enumerated.Wherein, preferably ITO can be utilized.The formation material of cross part insulating film 28 can utilize various known transparent insulating material.Specifically, can illustrate: the various photo-resists etc. such as acrylic acid series, polyimide system.
(formation 4 of touch sensing plate)
Fig. 4 is the vertical view schematically showing touch sensing plate 10.In the diagram, photomask 18 is for being formed in the sensor cover peripheral part of sheet glass 12 and having the film of the insulativity of opacifying property.Photomask 18 be in order to cover from the indicating meter combined with touch sensing plate 10 light leak, hide for driving the metal line 20 of touch sensing or IC etc. and arrange.
As shown in Fig. 4 and Fig. 3 (D), photomask 18 (sensor cover 12b) is formed with metal line 20.Metal line 20 forms many according to the number of the first nesa coating 14 and the second nesa coating 16, and one end of each metal line 20 is connected to the first nesa coating 14 or the second nesa coating 16.
In addition, with regard to another side of each metal line 20, when making touch sensing driving IC on the same substrate, be connected with this IC, when not making driving IC on the same substrate, such as, be connected with the flexible circuit board 30 being connected to the indicating meter combined with touch sensing plate 10.By having this metal line 20, the low electric conductivity of the nesa coating comprising ITO etc. can be made up, and easily extract the signal of sensor.
In the touch sensing plate 10 of Fig. 3, metal line 20 can utilize various metallic substance.Specifically, can illustrate: 3 layers of metallic substance etc. of 3 layers of metallic substance (MAM) of Mo/Al/Mo, 3 layers of metallic substance of Mo-Nb alloy/Al/Mo-Nb alloy, Mo-Nb alloy/Al-Nb alloy/Mo-Nb alloy.
(formation 5 of touch sensing plate)
Can easily imagine: along with maximization, the high-precision refinement of contact panel, metal line number increases.The increase of metal line number can cause the increase of the width of photomask 18, causes the increase of the useless area of what is called had nothing to do with sensor.Or need the live width making metal wire to attenuate, dimensional precision becomes strict.
(making method 1 of touch sensing plate)
Below, with reference to the schema of Fig. 5, an example of the manufacture method of touch sensing plate 10 is described.It should be noted that, touch sensing plate 10 of the present invention is not limited to utilize this order to manufacture.The formation method of each film is also not limited to example shown below, according to the formation material etc. of film, can utilize the various methods that known touch sensing plate uses.
(making method 2 photomask of touch sensing plate)
Sheet glass of the present invention can be suitable for the chemical enhanced sheet glass of the sensor board of outer insert-type or outer hung type contact panel.
Sheet glass of the present invention is being implemented to the surface of chemical enhanced sheet glass, first, to surround the mode (with reference to Fig. 4) in the region becoming active region A (activeareaA), sheet glass 12 is printing photomask 18.Thermal treatment (thermal technology's sequence 1) is implemented according to printing process.As long as the printing of photomask 18 utilizes in the manufacture of contact panel the known method utilized.
(the making method 3 cross part nesa coating of touch sensing plate)
Then, the film forming all sidedly such as ITO of cross part nesa coating 16b (becoming a part for the second nesa coating 16 afterwards) will be become.As long as the film forming of ITO etc. utilizes the known methods such as sputtering method to carry out.Now, sheet glass is implemented to the thermal treatment (thermal technology's sequence 2) of 150 ~ 300 DEG C, 5 ~ 60 minutes.Then, patterning is carried out.The known methods such as photolithographic method are utilized to carry out as long as patterning also uses.
(the making method 4 cross part insulating film of touch sensing plate)
Then, insulating film film forming all sidedly on cross part nesa coating 16b is made.Now, thermal treatment (thermal technology's sequence 3) is implemented.Then, carry out patterning in the mode making a part of cross part nesa coating 16b expose, form cross part insulating film 28.Now, if in thermal technology's sequence 1 ~ 3, glass shrinks significantly, then likely a part of cross part nesa coating 16b is not exposed and produces the undesirable condition etc. of broken string.Or, need the exposed mask for patterning preparing to have have modified the shrinkage of glass, consuming cost.As long as film and patterning utilize carry out according to the known method of the formation material of cross part insulating film 28.
(making method 5 nesa coating of touch sensing plate)
Then, the film forming comprehensively such as the ITO of the first nesa coating 14 and the second nesa coating 16 except cross part nesa coating 16b is made to become.Now, sheet glass is implemented to the thermal treatment (thermal technology's sequence 4) of 150 ~ 300 DEG C, 5 ~ 60 minutes.Then, carry out patterning, complete clear sensor wiring portion thus.
Now, if in thermal technology's sequence 1 ~ 4, glass shrinks significantly, then think that cross part nesa coating 16b likely breaks with the nesa coating 16 except cross part nesa coating 16b, or the first nesa coating 14 likely exceedes cross part insulating film 28 and is short-circuited with the second nesa coating 16.
Or, need the exposed mask for patterning preparing to have have modified the shrinkage of glass, consuming cost.As in the past, as long as the film forming of ITO etc. utilizes the known methods such as sputtering method to carry out, as long as patterning also utilizes known method to carry out.And then, photomask 18 is formed metal line 20, carries out patterning.
(making method 6 of touch sensing plate protects insulating film)
Then, protection insulating film 24 film forming is made in the mode of the sensor cover 12ba of comprehensive stacked coated glass sheets 12, so that the mode being used for driving the necessary part such as the metal line 20 of contact panel sensor or IC part to expose is carried out patterning.Carry out according to the known method of the formation material of protection insulating film 24 as long as film and patterning utilize.
Embodiment
Below, in further detail the present invention is described by embodiment and Production Example, but the present invention is not limited to these embodiments and Production Example.
The embodiment (example 1 ~ 13,18 ~ 22) of sheet glass of the present invention and comparative example (example 14 ~ 17,23 ~ 25) are illustrated.It should be noted that, the bracket in table is calculated value.
To become the mode of the composition shown in table 1 ~ 4, the raw material of each composition of allotment sheet glass, by raw material 100 mass parts relative to this sheet glass composition with SO 3the vitriol counting 0.1 mass parts that converts is added into raw material, uses platinum crucible heat 3 hours at 1600 DEG C of temperature and melt.When melting, inserting platinum agitator and stirring 1 hour, carrying out homogenizing of glass.Then, melten glass is flowed out and after cooling, grinding becomes tabular, and carries out attrition process.
Measure the mean thermal expansion coefficients (unit: × 10 at 50 ~ 350 DEG C of the glass obtained therefrom -7/ DEG C), second-order transition temperature (Tg) (unit: DEG C), density, T 4, intensity of compression (C), photoelastic constant, Young's modulus, devitrification temperature (glass surface devitrification temperature (T c), inside glass devitrification temperature (T d)), T 4, T dunder glass viscosity (unit: dPas), in addition, calculate T 4-T cand T c-T d, be shown in table 1 ~ 3.The measuring method of each physical property is below shown.
(1) Tg:Tg is the value using TMA to measure, and is obtained by Japanese JISR3103-3 (calendar year 2001).
(2) density: measured not containing the sheet glass of the about 20g of bubble by Archimedes method.
(3) T 4: use rotary viscosity design determining viscosity, measure and become 10 4temperature T during dPas 4(DEG C).
In addition, according to the measurement result of the glass viscosity under the high temperature (1000 ~ 1600 DEG C) of melten glass, obtaining the coefficient of Fulcher (Off Le チ ャ ー) formula, by using the Fulcher formula of this coefficient, obtaining inside glass devitrification temperature (T d) under glass viscosity.
(4) intensity of compression (C): measured by the measuring method of above-mentioned intensity of compression (C).
Mean thermal expansion coefficients at (5) 50 ~ 350 DEG C: use differential dilatometer (TMA) to measure, obtained by Japanese JISR3102 (nineteen ninety-five).
(6) devitrification temperature [glass surface devitrification temperature (T c) and inside glass devitrification temperature (T d)]: in platinum dish, drop into the glass particle through pulverizing, controlling to carry out thermal treatment in 17 hours in the electric furnace for steady temperature, by the observation by light microscope after thermal treatment, the top temperature of the surperficial crystallization at glass and the mean value of the minimum temperature of non-crystallization are set as glass surface devitrification temperature T c(DEG C), in addition, is set as inside glass devitrification temperature T by the top temperature of the inside crystallization at glass and the mean value of the minimum temperature of non-crystallization d(DEG C).
(7) photoelastic constant: use the light of 546nm as light source, measured by disk compression method.
(8) Young's modulus: the glass of thickness 7 ~ 10mm is measured by ultrasonic pulse method.
SO in glass 3residual quantity is 100 ~ 500ppm.
Table 1
[table 2]
[table 3]
[table 4]
From table 1 ~ table 4, the glass transition temperature Tg of the glass of embodiment (example 1 ~ 13,18 ~ 22) is high.In addition, the mean thermal expansion coefficients of the glass of embodiment at 50 ~ 350 DEG C is 65 × 10 -7~ 85 × 10 -7/ DEG C, the dimensional change therefore in display member manufacturing process is few, and colour filter and array board are aimed at punctual pattern and become easy.And then, due to thermal stresses when panel uses cause few on the impact of quality, so be especially preferred in display quality.
In addition, because intensity of compression (C) is below 20ppm, so position skew when not easily producing the one-tenth film patterning on sheet glass.Therefore, can be suitable as reply in recent years heat treated low temperature, the sheet glass of especially giant display component manufacture, such as female glass be the sheet glass of more than 2m.
In addition, the T of example 1 ~ 13 4-T cmeet-50 ~ 350 DEG C, or T 4-T dmeet-50 ~ 350 DEG C, devitrification when sheet glass is shaped is suppressed.
In addition, the T of example 6,7,11,12,13 4-T dbe 100 ~ 350 DEG C, T dunder glass viscosity be 10 4.7more than dPas, is suitable for the shaping utilizing fusion method.
It should be noted that, each physics value (T of example 18 c, T d, T 4, T 4-T c, T 4-T d, photoelastic constant, Young's modulus) also meet scope of the present invention.
The intensity of compression (C) of example 14 is greater than 20ppm, and the dimensional change in display member manufacturing process is large, and colour filter and array board are aimed at punctual pattern and become difficulty, the position skew easily when producing the one-tenth film patterning on sheet glass.
The second-order transition temperature of example 16,17 is less than 580 DEG C, has the possibility that the ambulant increase of alkali or thermotolerance have problems.
The intensity of compression (C) of the glass shown in table 1 ~ 3 all represents the compression angle value of carrying out the sheet glass cooling gained with 50 DEG C/min.The compression angle value of carrying out the sheet glass cooled with each speed of cooling of 50 DEG C/min, 70 DEG C/min, 150 DEG C/min, 300 DEG C/min is represented in table 4.In addition, then, illustrate and implement with anneal (keep 1h at 630 ~ 650 DEG C, then cool with 30 DEG C/h) or the presence or absence of chemical intensification treatment (435 DEG C, 4h) the compression angle value distinguished.
In example 19, illustrate and the sheet glass of the composition shown in example 19 is heated to glass transition temperature Tg+50 DEG C, keep at such a temperature after 1 minute, after being cooled to room temperature with each speed of cooling of 50 DEG C/min, 70 DEG C/min, 150 DEG C/min, 300 DEG C/min, through the respective intensity of compression (C) of the sheet glass of chemical intensification treatment.
In example 20, illustrate and the sheet glass of the composition shown in example 20 is heated to glass transition temperature Tg+50 DEG C, keep at such a temperature, after 1 minute, being cooled to the intensity of compression after room temperature (C) with the speed of cooling of 50 DEG C/min.
In example 21, illustrate and the sheet glass of the composition shown in example 21 is heated to glass transition temperature Tg+50 DEG C, keep at such a temperature after 1 minute, after being cooled to room temperature with the speed of cooling of 50 DEG C/min, implement anneal, then, through the respective intensity of compression (C) of the sheet glass of chemical intensification treatment.
In example 22, illustrate and the sheet glass of the composition shown in example 22 is heated to glass transition temperature Tg+50 DEG C, keep at such a temperature after 1 minute, after being cooled to room temperature with each speed of cooling of 50 DEG C/min, 70 DEG C/min, 150 DEG C/min, 300 DEG C/min, through the respective intensity of compression (C) of the sheet glass of chemical intensification treatment.
In example 23, illustrate and the sheet glass of the composition shown in example 23 is heated to glass transition temperature Tg+50 DEG C, keep at such a temperature, after 1 minute, being cooled to the intensity of compression after room temperature (C) with the speed of cooling of 50 DEG C/min.
In example 24, illustrate and the sheet glass of the composition shown in example 24 is heated to glass transition temperature Tg+50 DEG C, keep at such a temperature after 1 minute, after being cooled to room temperature with the speed of cooling of 50 DEG C/min, implement anneal, then, through the respective intensity of compression (C) of the sheet glass of chemical intensification treatment.
In example 25, illustrate and the sheet glass of the composition shown in example 25 is heated to glass transition temperature Tg+50 DEG C, keep at such a temperature after 1 minute, after being cooled to room temperature with each speed of cooling of 50 DEG C/min, 70 DEG C/min, 150 DEG C/min, 300 DEG C/min, through the respective intensity of compression (C) of the sheet glass of chemical intensification treatment.
In example 21 ~ 23 and example 24 ~ 25, illustrate that the anneal that two kinds of glass form and chemical intensification treatment are on the impact of intensity of compression (C).Anneal and chemical intensification treatment without improving effect to intensity of compression (C), show as on the contrary and increase tendency.
In example 19,22,25 and Fig. 2, illustrate that the chemical intensification treatment of three kinds of glass compositions is on the impact of the intensity of compression (C) relative to imaginary viscosity.
Known: to be 10 in imaginary viscosity 12.4in the glass (example 19,22) that intensity of compression (C) under dPas (speed of cooling 50 DEG C/min) is below 20ppm, even if imaginary viscosity (even if speed of cooling accelerates), also can maintain low degree of compression, on the other hand, be 10 in imaginary viscosity 12.4intensity of compression (C) under dPas (speed of cooling 50 DEG C/min) is more than in the glass (example 25) of 20ppm, and the increase of (situation that speed of cooling accelerates) intensity of compression of the situation of imaginary viscosity is remarkable.
For the present invention in detail and be illustrated with reference to specific embodiment, but those skilled in the art knows, and can carry out various change or correction when without departing from the spirit or scope of the invention.
Use specific mode to understand the present invention in detail, but those skilled in the art know, and can carry out various change and distortion when not departing from the intent of the present invention and scope.It should be noted that, the Japanese patent application (Japanese publication 2013-092045) that the application filed an application based on April 25th, 2013, its entirety is incorporated to herein by reference.
Utilizability in industry
Sheet glass of the present invention is suitable as the liquid-crystal display component sheet glass with contact panel sensor, may be used for other indicating meter plates with contact panel sensor, such as, plasm display panel (PDP), inorganic EL display etc.
Nomenclature
10 touch sensing plates
12 sheet glass
14 first nesa coatings
16 second nesa coatings
18 photomasks
20 metal lines
24 protection insulating films
28 cross part insulating films
30 flexible circuit boards
100 Polarizers
110 filter substrates
120 liquid crystal
130 array substrates
140 partition members
150 sealing agents
160 touch sensing plates
The front of 110a filter substrate
The back side of 110b filter substrate
The front of 130a array substrate
The back side of 130b array substrate
The front of 160a touch sensing plate
The back side of 160b touch sensing plate

Claims (6)

1. a chemical enhanced sheet glass, its imaginary viscosity is 10 12.8below dPas, and represent with the molar percentage of following oxide-base standard, contain:
The SiO of 60 ~ 79% 2,
The Al of 2.5 ~ 18% 2o 3,
The B of 0 ~ 3% 2o 3,
The MgO of 1 ~ 15%,
The CaO of 0 ~ 1%,
The SrO of 0 ~ 1%,
The BaO of 0 ~ 1%,
The ZrO of 0 ~ 1% 2,
The Na of 7 ~ 15.5% 2o,
The K of 0 ~ 0.5% 2o,
The Li of 0 ~ 2% 2o, wherein
Na 2o+K 2o is 7 ~ 15.5%,
Na 2o/ (Na 2o+K 2o) be 0.9 ~ 1,
MgO+CaO+SrO+BaO is 1 ~ 18%,
MgO-0.5Al 2o 3be 1 ~ 8,
MgO+0.5Al 2o 3be 1 ~ 20,
Second-order transition temperature is 580 ~ 720 DEG C,
Intensity of compression (C) is below 20ppm.
2. chemical enhanced sheet glass according to claim 1, wherein, photoelastic constant is 27 ~ 33nm/MPa/cm.
3. chemical enhanced sheet glass according to claim 1 and 2, wherein, viscosity becomes 10 4temperature (T during dPaS 4) and glass surface devitrification temperature (T c) pass be T 4-T c>=-20 DEG C.
4. chemical enhanced sheet glass according to claim 1 and 2, wherein, viscosity becomes 10 4temperature (T during dPaS 4) and inside glass devitrification temperature (T d) pass be T 4-T d>=50 DEG C.
5. chemical enhanced sheet glass according to claim 3, its sheet glass be shaped for using float glass process.
6. chemical enhanced sheet glass according to claim 4, its sheet glass be shaped for using fusion method.
CN201480023702.XA 2013-04-25 2014-04-16 Glass plate for chemical reinforcement purposes, and method for producing same Pending CN105189385A (en)

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JP2013-092045 2013-04-25
PCT/JP2014/060869 WO2014175144A1 (en) 2013-04-25 2014-04-16 Glass plate for chemical reinforcement purposes, and method for producing same

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