CN105217942B - The manufacturing method and glass substrate of glass substrate - Google Patents

The manufacturing method and glass substrate of glass substrate Download PDF

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Publication number
CN105217942B
CN105217942B CN201510387342.8A CN201510387342A CN105217942B CN 105217942 B CN105217942 B CN 105217942B CN 201510387342 A CN201510387342 A CN 201510387342A CN 105217942 B CN105217942 B CN 105217942B
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glass substrate
temperature
heat treatment
heating
heat
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CN105217942A (en
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滨上耕
小山昭浩
冈本美里
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Avanstrate Inc
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Avanstrate Inc
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Priority claimed from JP2015125385A external-priority patent/JP6082434B2/en
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Abstract

The present invention is a kind of raising production efficiency and reduces the dimensional stability to heating in house of glass substrate and the manufacturing method and glass substrate of the uneven glass substrate of the dimensional stability to heating in house that reduces glass substrate.The heat treatment of glass substrate is carried out when manufacturing glass substrate.In the heat treatment, after being heat-treated with 60 DEG C~260 DEG C of temperature, that is, heat treatment temperature lower than strain point to glass substrate entirety, until from heat treatment temperature to low 50 DEG C~300 DEG C of the medium temperature than heat treatment temperature, it is all with the cooling glass substrate of the 1st speed, then all with the cooling glass substrate of the 2nd speed more fireballing than the 1st until from medium temperature to room temperature.

Description

The manufacturing method and glass substrate of glass substrate
Technical field
The present invention relates to the manufacturing methods and glass substrate of a kind of glass substrate of heat treatment step comprising glass substrate.
Background technique
In recent years, in display panel field, the High precision of pixel is constantly promoted in order to promote image quality.As this is high-precision The progress of refinement, glass substrate for display panel also more demanding dimensional accuracy.For example, in the manufacturing step of display panel In, it is desirable that a kind of glass substrate that pyrocondensation is small, even if being heat-treated at high temperature, the size of glass substrate is also not susceptible to become Change.
In general, the dimensional stability to heating in house of glass substrate can get higher with the strain point of glass and be become smaller.Therefore, in order to inhibit heat Shrinkage, it is known to a kind of to change glass composition to improve the method (patent document 1) of strain point.However, if change glass composition Strain point is improved, then has the tendency that devitrification temperature is got higher, there are problems that glass substrate is difficult to manufacture.
[background technology document]
[patent document]
[patent document 1] Japanese patent special table 2014-503465
Summary of the invention
[problem to be solved by the invention]
As the difficulty for not incurring glass substrate manufacture, and reduce the method for the pyrocondensation of glass substrate, it is known to as follows Method: the resulting glass substrate of sheet material severing of glass of the formings such as fusion method will be utilized, is heat-treated and (is annealed under line) under line. However, making the face direction of glass substrate when glass substrate heating, cooling that can generate temperature difference, there are glass bases in annealing under line The problem of dimensional stability to heating in house unevenness on the face direction of plate.In addition, when making the temperature heating, cooling of glass substrate, existing in annealing under line If increasing heating rate, cooling rate, the dimensional stability to heating in house of glass substrate will not reduce, if reducing heating rate, cooling rate, The problem of production efficiency decline of glass substrate.
Therefore, the purpose of the present invention is to provide a kind of manufacturing method of glass substrate and glass substrate, glass can be improved The production efficiency of substrate, while reducing the dimensional stability to heating in house of glass substrate, in addition, the dimensional stability to heating in house on the face direction of glass substrate can be reduced Unevenness.
[technical means to solve problem]
The manufacturing method and glass substrate of glass substrate of the invention include the following embodiments and the accompanying drawings.
(embodiment 1)
A kind of manufacturing method of glass substrate, which is characterized in that the heat treatment step comprising glass substrate,
The heat treatment step comprises the steps of:
With temperature 60 DEG C~260 DEG C of heat treatment temperature lower than strain point, the glass substrate entirety is heat-treated；
From the heat treatment temperature, until 50 DEG C~300 DEG C of medium temperature lower than the heat treatment temperature, with 1 speed cools down the glass substrate entirety；And
After the heat treatment step, until the medium temperature to room temperature, than the described 1st the fireballing 2nd Speed cools down the glass substrate entirety.
(embodiment 2)
A kind of manufacturing method of glass substrate, which is characterized in that the heat treatment step comprising glass substrate,
The heat treatment step comprises the steps of:
From room temperature, when temperature is heat-treated until low 60 DEG C~260 DEG C of heat treatment temperature than strain point, be from The room temperature rises, until 50 DEG C~300 DEG C of medium temperature lower than the heat treatment temperature, with the 3rd speed to the glass Substrate entirety is heated；
Until from the medium temperature to the heat treatment temperature, with than the 3rd slow-footed 4th speed to the glass Glass substrate entirety is heated；And
The glass substrate entirety is heat-treated with the heat treatment temperature.
(embodiment 3)
According to the manufacturing method for the glass substrate that embodiment 1 or 2 is recorded, wherein the 1st speed and the 2nd speed Average speed, the average speed than the 3rd speed and the 4th speed is slow.
(embodiment 4)
According to the manufacturing method for the glass substrate that any one of embodiment 1 to 3 is recorded, wherein the glass substrate is answered Height is 655 DEG C or more.
(embodiment 5)
According to the manufacturing method for the glass substrate that any one of embodiment 1 to 4 is recorded, in the heat treatment step, It is the laminated body to the glass substrate that muti-piece is laminated in the state of sandwiching the glass substrate between bodies in thickness direction It is heat-treated.
(embodiment 6)
A kind of manufacturing method of glass substrate, which is characterized in that at the heat comprising flat-panel monitor single-glass substrate Step is managed,
The heat treatment step has:
Heating maintains step, and heating the glass substrate to the heat treatment temperature being within the scope of 400 DEG C~600 DEG C is Only, and the heat treatment temperature is maintained；And
Cooling step, with 0.5 DEG C/min of the 1st cooling rate less than 10 DEG C/min, from the heat treatment temperature Spend until 50 DEG C~150 DEG C of medium temperature lower than the heat treatment temperature, after the cooling glass substrate, with 10 DEG C/ Minute is less than the cooling glass substrate of 25 DEG C/min of the 2nd cooling rate.
(embodiment 7)
According to the manufacturing method for the glass substrate that embodiment 6 is recorded, wherein being formed on the glass substrate and including The semiconductor layer of IGZO.
(embodiment 8)
According to the manufacturing method for the glass substrate that embodiment 6 or 7 is recorded, in the cooling step, with the 2nd drop After warm speed cools down the glass substrate, until further cooling down the glass substrate to room temperature with the 1st cooling rate.
(embodiment 9)
According to the manufacturing method for the glass substrate that any one of embodiment 6 to 9 is recorded, in the heat treatment step, The glass substrate is horizontally placed in furnace, before carrying out the heating stepses, by the ambient air temperature in the furnace Until being heated to the heat treatment temperature.
In the heat treatment step, it is also possible to block-by-block to be heat-treated at the single chip mode heat of multiple glass substrates Reason.
(embodiment 10)
A kind of glass substrate, which is characterized in that be to maintain 5 points with the heat treatment temperature within the scope of 400 DEG C~600 DEG C The liquid crystal display glass substrate of clock~30 minute heat treatment,
By 500 DEG C be set as the 1st evaluation temperature, 450 DEG C be set as the 2nd evaluation temperature, 500 DEG C be set as the 3rd evaluation temperature, with Dimensional stability to heating in house when each evaluation temperature is again heat-treated the glass substrate after maintaining 30 minutes, is set to the 1st pyrocondensation In the case where rate C1, the 2nd dimensional stability to heating in house C2, the 3rd dimensional stability to heating in house C3, meet | C1-C2 |/| C3-C1 | < 0.28
Relational expression.
[The effect of invention]
According to the manufacturing method and glass substrate of the glass substrate, the production efficiency of glass substrate can be improved, subtract simultaneously The dimensional stability to heating in house of small glass substrate, and the unevenness of the dimensional stability to heating in house of glass substrate can be reduced.
Detailed description of the invention
Fig. 1 is the flow chart for indicating an example of the process of the manufacturing method of glass plate of present embodiment.
Fig. 2 is an example that the supporting plate of laminated body of glass substrate is placed in the heat treatment for indicate present embodiment progress Side view.
Fig. 3 (a) is the figure for indicating the position on glass substrate, is (b) thermal history for indicating each position on glass substrate An example figure.
Fig. 4 is the curve graph for showing an example of relationship of the area and strain that indicate thermal history difference.
Fig. 5 is the figure of an example of Temperature Distribution when indicating to be heat-treated glass substrate.
Fig. 6 (a) is an example of the carrying state of the glass substrate in the heat treatment for indicate present embodiment progress in furnace Side view, (b) be the glass substrate of (a) from bottom surface side figure.
Fig. 7 is the figure for indicating an example of temperature history of glass substrate.
Fig. 8 is indicated to evaluate heat treatment method to the glass substrate in present embodiment after heat treatment and be heat-treated When glass substrate dimensional stability to heating in house result an example figure.
Specific embodiment
Hereinafter, the manufacturing method for the glass substrate that the present invention will be described in detail.
Fig. 1 is the flow chart for indicating an example of the process of the manufacturing method of glass plate of present embodiment.The glass to be manufactured There is no particular restriction for glass substrate, such as linear foot cun and crossfoot cun are respectively preferably 500mm~3500mm.The thickness of glass substrate is excellent It is selected as 0.1~1.1 (mm), the plate of more preferably 0.75mm very thin rectangular shape below.
Firstly, the glass after melting for example, by fusion method or float method isoperimetric perception method, is shaped the band of specific thicknesses Shape glass, that is, sheet material glass (step S1).
It then, is plain plate, that is, glass substrate (step S2) of specific length by the sheet material glass severing of forming.By severing institute The glass substrate obtained makes the laminated body (step S3) of glass substrate with protecting the bodies of glass substrate alternately laminated.It connects , (step S4) is heat-treated to the laminated body of the glass substrate.The processing of step S3 and the processing of step S4 are this realities Apply the heat treatment i.e. annealing steps of mode.It will be described in detail hereinafter about annealing steps.
Glass substrate after heat treatment is transported to cutting step, product size is cut into, obtains glass substrate (step S5).After carrying out the end face processing comprising end face grinding, grinding and chamfering cutting to resulting glass substrate, glass base is cleaned Plate (step S6).Clean glass substrate is optically inspected, checks whether there is and is lacked comprising scratch, dust, spot or optics Sunken damage (step S7).The glass substrate of quality qualification obtains layer with protecting the paper of glass substrate alternately laminated after inspection Laminated body is piled up on supporting plate and is packed (step S8) by stack.By the glass substrate after bale packing to supplier's shipment.
As such glass substrate, the glass substrate of following glass composition is illustrated.That is, to manufacture the glass that following glass forms The mode of glass substrate modulates the raw material of melten glass.
SiO255~80 mole %,
Al2O38~20 mole %,
B2O30~12 mole %,
0~17 mole % of RO (total content of RO MgO, CaO, SrO and BaO).
From from the perspective of reducing dimensional stability to heating in house, SiO2Preferably 60~75 mole %, more preferably 63~72 mole %.
In RO, it be preferably 0~10 mole %, SrO is preferably 0~10%, BaO excellent that MgO, which is preferably 0~10 mole %, CaO, It is selected as 0~10%.
In addition it is also possible to for including at least SiO2、Al2O3、B2O3And RO, and mole ratio ((2 × SiO2)+Al2O3)/((2 ×B2O3)+RO) and be 4.5 or more glass.Furthermore it is preferred that at least any one comprising MgO, CaO, SrO and BaO, and mole It is 0.1 or more than (BaO+SrO)/RO.
In addition, the B indicated with mole %2O32 times of containing ratio it is total with the containing ratio of the RO indicated with mole %, Preferably 30 mole % are hereinafter, more preferably 10~30 mole %.
In addition, the containing ratio of the alkali metal oxide in the glass substrate of the glass composition can also be 0 mole % or more And 0.4 below mole %.
In addition, the oxide (tin oxide, iron oxide) for the metal that valence mumber changes in glass adds up to 0.05~1.5 not Ear %, is substantially free of As2O3、Sb2O3And PbO, but it is not necessarily but any.
The glass substrate manufactured in present embodiment is suitable for glass substrate for display, such as flat-panel monitor glass Glass substrate, liquid crystal display glass substrate or organic el display glass substrate.
Moreover, the glass substrate manufactured in present embodiment is particularly suited for the LTPS (Low- for fine display Temperature poly silicon), TFT display glass substrate or IGZO (Indium-Gallium-Zinc- Oxide) oxide semiconductors, TFT display glass substrate such as.
In present embodiment using melten glass forming sheet material glass method, be using float method or fusion method etc., but The glass substrate of present embodiment includes in the manufacturing method of glass substrate of heat treatment, from fusion method (overflow down draw down online Method) in be difficult to extend annealing device in manufacturing line in terms of set out, be suitable for fusion method.Subtracted by the heat treatment of present embodiment The dimensional stability to heating in house of glass substrate before small dimensional stability to heating in house is 80ppm hereinafter, more preferably 40ppm~60ppm.
Hereinafter, successively illustrating the annealing steps of present embodiment according to embodiment 1,2.So-called line in present embodiment Lower annealing anneals to the glass substrate of manufacture after referring to that the manufacturing line from manufacture glass substrate is removed.
(annealing steps of the 1st embodiment)
Then, the annealing steps of the 1st embodiment are described in detail.
Firstly, multiple glass substrates 11 of severing in step S2 to be replaced to block-by-block stacking with multiple bodies 12, glass is made The laminated body 10 (step S3) of glass substrate.In the present embodiment, it describes to glass made of the multiple glass substrates 11 of stacking The monolithic that the case where laminated body 10 of substrate is heat-treated transports glass substrate 11 but it is also possible to be block-by-block and be heat-treated The heat treatment of mode.In addition it is also possible to be following method: not laminated glass substrate 11 is separated from each other multiple glass substrates 11 Specific range, and each glass substrate 11 is heat-treated.
Fig. 2 is the side view for indicating to be loaded with an example of the supporting plate 20 of laminated body 10 (hereinafter referred to as laminated body 10) of glass substrate Figure.In this, it is set as the front side of supporting plate 20, the rear side of supporting plate 20 being set as on the right side of the drawing of Fig. 2 on the left of the drawing of Fig. 2.The drawing of Fig. 2 Upside is set as direction, being set as lower direction on the downside of drawing.On supporting plate 20, laminated body 10 is with stacking direction for substantially front-rear direction And it loads.The supporting plate 20 for loading laminated body 10 is transported in furnace 40, is heat-treated in furnace 40 to laminated body 10.Furnace 40 The interior heat generating device 41 for being equipped with the environmental gas (air) for heating furnace 40, heat generating device 41 is heat source, so that the ring of furnace 40 Border gas heating.It is confined space in furnace 40 when being heat-treated, the heat transfer of environmental gas is laminated to laminated body 10 The heat treatment of body 10 (glass substrate 11).In this, the stacking direction of laminated body 10 is not necessarily completely the same with front-rear direction.Example Such as, as shown in Fig. 2, in the case that glass substrate 11 is tiltedly put, angle formed by stacking direction and front-rear direction corresponds to glass substrate 11 inclination angle relative to up and down direction.In addition it is also possible to which the stacking direction of laminated body 10 is the mode of up and down direction, will be laminated Body 10 lays flat and is placed in supporting plate 20.
Supporting plate 20 has abutment portion 21, mounting portion 22, backplate 23 etc..
Abutment portion 21, mounting portion 22 and backplate 23 are formed by metals such as such as steels, pass through the integrated landform such as welding At.
Base station 21 is the plate of general rectangular, and the opening 21a for being used to be inserted into fork truck pawl is equipped in end face.
Mounting portion 22 is fixed on the top of base station 21, in the laminated body 10 of the top of mounting portion 22 mounting glass substrate.In This, the upper surface of mounting portion 22 is not necessarily to fully horizontally.For example, as shown in Fig. 2, in the case where glass substrate 11 is tiltedly put, The upper surface of mounting portion 22 can also be made to tilt according to the angle of placing vertically of glass substrate 11.
Backplate 23 is that the plate of general rectangular is generally vertically fixed on the top of base station 21 with mounting portion 22 The rear end of mounting portion 22.Backplate 23 supports the rear end for being loaded in the stacking direction of the laminated body 10 on top of mounting portion 22.In This, backplate 23 is It is not necessary to completely vertical.For example, as shown in Fig. 2, in the case where glass substrate 11 is tiltedly put, it can also basis The angle of placing vertically of glass substrate 11 tilts backplate 23.
Then, illustrate laminated body 10.Laminated body 10 has multiple glass substrates 11, multiple bodies 12.
Bodies 12 is sandwiched between glass substrate 11.Bodies 12 plays the glass substrate 11 for preventing from being laminated each other The effect of contiguity.Therefore, muti-piece is laminated in thickness direction in the state that glass substrate 11 is clipped between bodies and forms glass The laminated body 10 of glass substrate.The material of the heat resistance with the resistance to temperature when heat treatment of laminated body 10 can be used in bodies 12 Material.Bodies 12 preferably has the thermal conductivity higher than glass substrate 11.
As the material of such bodies 12, such as may be selected from carbon graphite, alumina fibre, silicon oxide fibre and more One kind or their combination that hole matter ceramics are selected.
The thermal conductivity in direction, the thickness of bodies 12 are preferably thicker in face in order to improve glass substrate 11.On the other hand, In order to reduce the volume of laminated body 10, the thickness of bodies 12 is preferably relatively thin.Therefore, the thickness of bodies 12 is preferably 0.02mm ~2mm or so.From performance prevent glass substrate 11 from touching each other effect, the area of bodies 12 preferably with glass substrate 11 area degree is identical or area greater than glass substrate 11.
Alternatively, it is also possible to instead of bodies 12, or together with bodies 12, insert between any number of glass substrates 11 Enter the heating plate for heating layer stack 10.The electrode plate to generate heat by circulating current for example can be used in heating plate.In this feelings Under condition, the resistance value of electrode plate can change according to the temperature of electrode plate, therefore according to the temperature of electrode plate and in electrode plate stream The logical magnitude of current changes.Therefore, the temperature of heating plate can be controlled based on the magnitude of current to circulate in electrode plate.As a result, may be used Equably to adjust the heat distribution between multiple glass substrates 11.
In addition, recycled paper, pulp based paper also can be used in bodies 12.
It in the present embodiment, is in the state of clamping laminated body 10 with a pair of of thermal insulation board 15a, 15b, to stacking Body 10 is heat-treated.
The both ends of stacking direction of a pair of of thermal insulation board 15a, 15b configuration in laminated body 10.In Fig. 2, thermal insulation board 15a matches It sets in rear end, thermal insulation board 15b is configured in front end.Heat-insulated material 15a, 15b are formed by the low material of thermal conductivity ratio glass substrate. The material low as thermal conductivity ratio glass substrate, such as optional one kind selected from ceramics, aluminium oxide, silica, Ji Yanrong, Or their combination.
In order to maintain heat-proof quality, the thermal resistance of thermal insulation board 15a, 15b are preferably 0.1 DEG C/W or more.On the other hand, in order not to Interfere configuration in the heating and cooling of the glass substrate 11 of the end of laminated body 10, the thermal resistance of thermal insulation board 15a, 15b are preferably 10 DEG C/W or less.In order to maintain heat-proof quality, the thickness of thermal insulation board 15a, 15b are preferably thicker.On the other hand, in order to reduce laminated body The thickness of 10 volume, thermal insulation board 15a, 15b is preferably relatively thin.Therefore, the thickness of thermal insulation board 15a, 15b is preferably the left side 10~50mm It is right.The effect touched each other that the glass substrate 11 of the lateral end outside the stacking direction of laminated body is prevented from performance, every The area of hot plate 15a, 15b are preferably area identical as the area of glass substrate 11 or greater than glass substrate 11.
If clamping the both ends of the stacking direction of laminated body 10 with thermal insulation board 15a, 15b, it is located at 10 front of laminated body The glass substrate 11 for holding (front end), the heat of glass substrate 11 is flowed to from environmental gas via the main surface of the glass substrate 11 It is suppressed, can become and outside the face direction of the main surface of the glass substrate 11 in the stacking direction center for being located at glass substrate 11 The form of the thermally conductive homomorphosis of side flowing.That is, in all glass substrates 11 of stacking, packet of the heat from glass substrate 11 End regions containing edge enter, and heat is conducted towards the middle section surrounded by end regions.As a result, the multiple of stacking can be made Heat distribution is impartial in a thickness direction for glass substrate 11.
Then, illustrate the heat treatment of step S4.
To the laminated body 10 made in the processing of step S3, it is heat-treated under the line for leaving production line.Herein at heat In reason, specific time is placed under the environmental gas for the specific temperature that exists while rotating the laminated body of glass substrate, makes glass The heat distribution that the end regions of substrate spread the middle section surrounded by end regions is the same, thus by end regions throughout center The Strain Distribution in region is adjusted so as to the same.
Specifically, the supporting plate 20 for being loaded with the laminated body 10, control fever dress are moved in into the furnace 40 being heat-treated It sets 41 movement and the air (environmental gas) in heating furnace 40, thus glass substrate 11 is heat-treated.
From the aspect for reducing dimensional stability to heating in house and keeping the Strain Distribution of glass substrate the same, the temperature of heat treatment is preferably glass The temperature range of the temperature of -60 DEG C of strain point of temperature to -260 DEG C of strain point of glass substrate 11.In this, so-called strain point, Refer to general strain point of glass, is comparable to 1014.5The temperature of the viscosity of pool.Heat treatment time is such as 0.5~120 small When.There is no particular restriction for the time history of temperature when heat treatment in environmental gas, and the temperature of environmental gas is in strain point- Time within the temperature range of 560 DEG C of temperature to strain point is at least 0.5 hour, preferably 1 hour or more.If less than 0.5 Hour or 1 hour, then dimensional stability to heating in house will not be reduced sufficiently, if being longer than 120 hours, though dimensional stability to heating in house sufficiently reduces, glass substrate 11 production efficiency reduces.
In addition, strain point is different because of glass types difference, but in order to reduce pyrocondensation, glass substrate 11 preferably has strain The high glass composition of point, the strain point of the glass of glass substrate 11 is preferably 600 DEG C or more, and more preferably 655 DEG C or more, such as It is 661 DEG C.In the case, heat treatment temperature is strain point (661 DEG C)-(60 DEG C~260 DEG C)=601 DEG C~401 DEG C.For Reduce the pyrocondensation of glass substrate 11 as fine glass substrate for display, is not limited to the temperature range, for example, Maximum temperature, heat treatment temperature when heat treatment can be 250 DEG C~700 DEG C, and can be 300 DEG C~600 DEG C, can also be 350 DEG C~600 DEG C, it can also be 400 DEG C~550 DEG C.
There is no particular restriction for hot environment gas locating for the laminated body of glass substrate, can be the ring of rate of oxygen 5~50% Border gas may be, for example, aeriferous atmospheric ambient gas.
Fig. 3 (a), (b) are the figures for indicating an example of thermal history of each position on glass substrate 11.In this, so-called heat is gone through Journey refers to the course of the temperature of the glass substrate 11 changed by heat treatment.The stacking of glass substrate 11 is clamped in stacking direction In the state of body 10, laminated body 10 is moved in the furnace 40 being heat-treated, increase the temperature of the environmental gas in furnace 40, then The heat of environmental gas can conduct side outside the stacking direction of laminated body 10 to glass substrate 11.The edge comprising edge of glass substrate 11 Heat transfer of the region 11a by hot environment gas, the middle section 11b phase surrounded by edge region 11a with glass substrate 11 Than quickly heating up.Environmental gas is set to cool down and be in addition, the edge region 11a of the glass substrate 11 of the condition of high temperature is exposed on It radiates in the environmental gas of low temperature, the middle section 11b than glass substrate 11 quickly cools down.Therefore, such as Fig. 3 (a), (b) Shown, on glass substrate 11, the periphery point A is than the quickly heating, cooling of the periphery point B.If thermal history generates poor, the area Ze Yuan in this way Domain 11a is throughout middle section 11b (periphery point A spreads the periphery point B), and dimensional stability to heating in house is different, and generation is drawn high and compression stress, and occurs Strain.In order to make the dimensional stability to heating in house in 11 face of glass substrate uniformly inhibit the generation strained, it is necessary to eliminate the edge of glass substrate 11 Difference of the region 11a throughout the temperature change of middle section 11b, that is, the difference of thermal history must be reduced.
In this, the temperature when being formed on glass substrate 11 includes the semiconductor layer of LTPS, IGZO is 400 DEG C~600 DEG C (in the case that strain point is 661 DEG C, 60 DEG C~260 DEG C of temperature lower than strain point), as long as therefore reducing in the temperature range Glass substrate 11 dimensional stability to heating in house.So in present embodiment, with the point A of glass substrate 11 and the highest temperature on the periphery point B Degree is heat-treated in the mode of 400 DEG C~600 DEG C of temperature range.Dimensional stability to heating in house not only because of heat-treated glass substrate 11 when Maximum temperature and change, can also change because of thermal history.Especially, the maximum temperature as shown in Fig. 3 (b), when heat treatment I.e. heat treatment temperature (such as 500 DEG C) rises, until 50 DEG C~300 DEG C of temperature lower than heat treatment temperature (such as 450 DEG C~200 DEG C) Until influence of the thermal history to dimensional stability to heating in house it is big.Dimensional stability to heating in house be by for evaluating dimensional stability to heating in house temperature, in this be in glass It is heat-treated at such as 400 DEG C~500 DEG C of temperature when forming the semiconductor layer comprising LTPS, IGZO on substrate 11, thus Reduce dimensional stability to heating in house in the temperature region.In addition, in 400 DEG C~500 DEG C temperature regions below of the temperature region, pyrocondensation also subtracts It is small.That is, the evaluation temperature close to dimensional stability to heating in house at a temperature of, dimensional stability to heating in house is influenced it is big, temperature difference it is bigger, to the shadow of dimensional stability to heating in house Sound is smaller.Therefore, in present embodiment, with maximum temperature, that is, heat treatment temperature in heat treatment to low 50 DEG C~300 DEG C In temperature region until temperature, the repressed mode of difference of the thermal history on the face direction of glass substrate 11 is heat-treated. In Fig. 3 (b), the difference of the thermal history within the temperature range of 300 DEG C~500 DEG C is illustrated.By the edge for reducing glass substrate 11 The difference (the area D in Fig. 3 (b)) of region 11a (periphery point A) and the thermal history on middle section 11b (periphery point B), and can inhibit The unevenness of dimensional stability to heating in house on 11 face of glass substrate, and strain is inhibited to generate.
The area D formed by the difference of the thermal history of point A and the thermal history of point B is smaller, then strain value is smaller.Fig. 4 is aobvious Show the curve graph of an example of the area for the difference for indicating thermal history and the relationship of strain.As shown in figure 4, being set as 2kgf/ that will strain cm2It is to be heat-treated in a manner of D1 is below to glass substrate 11 by area in situation below.In addition, being set as that will strain 4kgf/cm2It is to be heat-treated to glass substrate 11, be set as that will strain in a manner of D2 is below by area in situation below 9kgf/cm2It is to be heat-treated in a manner of D3 is below to glass substrate 11 by area in situation below.Area D1~D3's Value corresponds to time × temperature unit.The value of area D1~D3 can according to the size of glass substrate 11, thickness, composition etc. and Arbitrarily change.The feasible value of required strain when as a result, can also be according to the panel of manufacture fine display, and it is appropriate Temperature, time in the heat treatment of ground change glass substrate 11.
In addition, being reached and edge region 11a (periphery point A) with the temperature of the middle section 11b (periphery point B) of glass substrate 11 The mode of the same maximum temperature of temperature be heat-treated.By the middle section 11b (periphery point B) for making glass substrate 11 Temperature reaches maximum temperature, and the difference of the dimensional stability to heating in house of edge region 11a (periphery point A) and middle section 11b (periphery point B) becomes smaller, and Strain can be reduced to generate.The constant temperature (holding) of middle section 11b (periphery point B) be any, example the time of maximum temperature For example 0.5 hour~4 hours, more preferably 1 hour~2 hours.In order to reach specific dimensional stability to heating in house, with from edge region 11a (point The periphery A) reach the mode of maximum temperature throughout the temperature of the glass substrate 11 on middle section 11b (periphery point B) and be heat-treated, In order to inhibit strain to generate, it is heat-treated in a manner of the difference of the thermal history on the face direction for reducing glass substrate 11.
Fig. 5 is the figure of an example of Temperature Distribution when indicating to be heat-treated glass substrate.As described above, from heat treatment When maximum temperature, that is, heat treatment temperature (such as 60 DEG C~260 DEG C temperature lower than strain point), until than the heat treatment temperature Thermal history until low 50 DEG C~300 DEG C of medium temperature influences dimensional stability to heating in house big.In the glass substrate 11 of stacking, in order to press down Make the difference of the thermal history in the temperature range, it is necessary to make the speed (temperature gradient) from medium temperature to maximum temperature, compare room temperature The speed (temperature gradient) of~medium temperature is slow (slow).In Fig. 5, the liter in small temperature region Tm1~Tm2 is influenced on pyrocondensation Warm speed S1 is (Tm2-Tm1)/(t1-t0), and the heating rate S2 influenced in big temperature region Tm2~Tm3 on pyrocondensation is (Tm3-Tm2) the speed S3 in/(t2-t1), highest temperature region Tm3 is (Tm3-Tm3)/(t3-t2)=0, to pyrocondensation The cooling rate S4 influenced in big temperature region Tm3~Tm2 is (Tm2-Tm3)/(t4-t3), and small temperature is influenced on pyrocondensation The cooling rate S5 spent in the Tm2~Tm1 of region is (Tm1-Tm2)/(t5-t4).In this, temperature is Tm1 < Tm2 < Tm3, Tm1=room temperature (such as 25 DEG C), Tm2=medium temperature (such as 300 DEG C), Tm3=maximum temperature (such as 500 DEG C).In this, room Temperature is not limited to 25 DEG C, for example, 1 DEG C~30 DEG C.In addition, maximum temperature is not limited to 500 DEG C, it is (60 DEG C of strain point- ~260 DEG C) arbitrary temp, medium temperature is not limited to 300 DEG C, is any temperature of maximum temperature-(50 DEG C~300 DEG C) Degree.Medium temperature changes according to maximum temperature, but maximum temperature can also be set as to the model of strain point-(60 DEG C~260 DEG C) Temperature is enclosed, and medium temperature is fixed as 300 DEG C.In the case, from maximum temperature to 300 DEG C of heating, cooling velocity ratio Heating, cooling velocity from 300 DEG C to 25 DEG C is slow.In addition, heating rate, cooling rate are risen to 11 entirety of glass substrate Temperature, the average speed to cool down.
In heating-up time t0~t2, risen with influencing the heating rate S2 in big temperature region Tm2~Tm3 on pyrocondensation The mode of warm speed S1 > heating rate S2, heats laminated body 10.Pyrocondensation is influenced in small temperature region Heating rate S1 be such as 60 DEG C/h~300 DEG C/h, more preferably 80 DEG C/h~250 DEG C/h, to pyrocondensation shadow Ringing the heating rate S2 in big temperature region is such as 20 DEG C/h~60 DEG C/h, more preferably 20 DEG C/h~40 DEG C/h.Maintaining the time t3-t2 of maximum temperature Tm3 is such as 0.5 hour~4 hours, preferably 1~4 hour, more preferably It is 1 hour~2 hours.In addition, in temperature fall time t3~t5, to influence the drop in big temperature region Tm2~Tm3 on pyrocondensation Warm speed S4 carries out laminated body 10 cold in a manner of the absolute value timing cooling rate S5 > cooling rate S4 by cooling rate But (heat dissipation) is handled.Pyrocondensation is influenced cooling rate S4 in big temperature region be such as -20 DEG C/h~-60 DEG C/it is small When, more preferably -20 DEG C/h~-40 DEG C/h, for influencing the cooling rate S5 in small temperature region on pyrocondensation Such as -60 DEG C/h~-300 DEG C/h, more preferably -80 DEG C/h~-250 DEG C/h.In addition, pyrocondensation is in cooling When influence of influence when being greater than heating, therefore the absolute value of speed can also be set as to S2 > S4, make cooling rate S4 ratio liter Warm speed S2 is slow.In addition it is also possible to which the average speed AS1 of heating rate S1 and heating rate S2 is than cooling rate S3 and cooling speed The fast mode of the average speed AS2 of S4, the i.e. mode of average speed AS1 > average speed AS2 are spent, keeps cooling rate slack-off.By It is small in being influenced on pyrocondensation, in the temperature region for the Tm2 to Tm1 (room temperature) for being not likely to produce strain, accelerate heating rate, cooling speed Degree, shorten heating-up time, temperature fall time, thus shorten laminated body 10 is heat-treated, the time of cooling treatment.Exist as a result, It is influenced in small temperature region Tm1~Tm2 to what dimensional stability to heating in house reduced, heat treatment time can be shortened, raising glass substrate 11 Production efficiency.On the other hand, big due to being influenced on pyrocondensation, in the medium temperature for being easy to produce strain to highest temperature when being heat-treated Degree is to slow down heating rate, cooling rate in temperature region Tm2~Tm3 of heat treatment temperature, when extending heating-up time, cooling Between, thus strain is inhibited to generate.The unevenness of the dimensional stability to heating in house of glass substrate 11 can be reduced as a result, and strain is inhibited to generate, and improved The production efficiency of glass substrate 11.
For from be set to furnace 40 in heat source to the edge region 11a (periphery point A) of glass substrate 11 transmitting heat time, and For from heat source to the time of middle section 11b (periphery point B) transmitting heat, as shown in Fig. 3 (b), from heat source via edge region 11a (periphery point A) and to middle section 11b (periphery point B) transmitting heat time be longer time.Therefore, to edge region 11a (point The periphery A) after the transmitting hot time, i.e. after edge region 11a (periphery point A) becomes 300 DEG C of medium temperature, compare edge region The heating rate that 11a (periphery point A) becomes 300 DEG C of medium temperature from room temperature, slows down heating rate (keeping temperature gradient gentle).It is logical It crosses and slows down heating rate, the speed for inhibiting edge region 11a (periphery point A) to be heated by heat source, it is ensured that hot from edge region 11a (point A weeks Side) to the time of middle section 11b (periphery point B) transmitting, thus the thermal history of point A and the difference of the thermal history of point B become smaller.This Outside, it for heat dissipation, and compared to the time radiated from region 11a (periphery point A), is passed through from middle section 11b (periphery point B) The heat dissipation time radiated by edge region 11a (periphery point A) is longer.Therefore, edge region 11a (periphery point A) cools down (heat dissipation) extremely It is fast compared to the cooling that edge region 11a (periphery point A) becomes 300 DEG C of medium temperature from maximum temperature after 300 DEG C of medium temperature Degree, and slow down cooling rate.Pass through and carry out such heat treatment, cooling treatment, it is ensured that heat from edge region 11a (periphery point A) to The time of middle section 11b (periphery point B) transmitting, furthermore, it is possible to ensure the time on cooling middle section 11b (periphery point B), from And it can inhibit the thermal history influenced in big medium temperature to the temperature region of maximum temperature (300 DEG C~500 DEG C) on pyrocondensation Difference.
By such heat treatment, the dimensional stability to heating in house of glass substrate 11 can be set as 0~15ppm.The dimensional stability to heating in house of glass substrate 11 Preferably 0~12ppm, more preferably 0~6ppm.Such dimensional stability to heating in house can form by adjusting the glass of glass substrate and heat The temperature of processing is reached with heat treatment time.
In the present embodiment, in a pair of of thermal insulation board 15a, the 15b for utilizing thermal conductivity ratio glass substrate 11 low in stacking side To in the state of the laminated body 10 for clamping glass substrate 11, laminated body 10 is moved in the furnace 40 being heat-treated, and make in furnace 40 Environmental gas temperature rise.About the temperature gradient of the environmental gas in furnace 40, make 300 DEG C~500 DEG C of temperature gradient It is gentler than the temperature gradient of room temperature~300 DEG C, the heat distribution between multiple glass substrates 11 thus can be made the same.Therefore, can reduce The unevenness of the dimensional stability to heating in house of each glass substrate 11 after heat treatment.
In this, heating plate can also be configured in any position of the stacking direction of laminated body 10, with multiple glass substrates 11 Between heat distribution become the same mode, laminated body 10 is heated using heating plate.
Moreover, being thus to promote glass using the material with the thermal conductivity higher than glass substrate 11 as bodies 12 Direction is thermally conductive in the face of substrate 11, can make the end regions of glass substrate 11 as the heat distribution of middle section.Therefore, may be used Inhibiting the unevenness of the dimensional stability to heating in house in the face direction of glass substrate 11, the strain for also inhibiting the difference because of dimensional stability to heating in house to generate generates, so as to Keep the Strain Distribution of glass substrate the same.
In addition, comparing heat treatment for glass substrate 11 in the case where the single chip mode of block-by-block heat-treated glass substrate 11 The case where laminated body 10 being laminated, heating rate, cooling rate can be accelerated.When can shorten heat treatment in single chip mode Between, therefore for example can be set to S1=120 DEG C/h of heating rate~400 DEG C/h, S2=40 DEG C/h of heating rate~ 120 DEG C/h, maintain time t3-t2=0.5 hour~2 hour of maximum temperature Tm3, S4=-40 DEG C of cooling rate/small When~-120 DEG C/h, S5=-120 DEG C/h~-400 DEG C/h of cooling rate.
Further, it is also possible to according to the thickness of the stacking direction of laminated body 10, Lai Biangeng heating rate, cooling rate.For example, Laminated body 10 stacking direction with a thickness of in 50cm situation below, in order to transmit heat, Ke Yishe as early as possible in stacking direction It is S1=90 DEG C/h~300 DEG C/h of heating rate, S2=30 DEG C/h of heating rate~90 DEG C/h maintain highest Time t3-t2=0.5 hour~3 hour of temperature Tm3, S4=-30 DEG C/h~-90 DEG C/h of cooling rate, cooling S5=-90 DEG C/h~-300 DEG C/h of speed.The more thin then heating rate of the thickness of the stacking direction of laminated body 10, cooling Speed is faster, can also the heating speed in the case where the glass substrate 11 of stacking direction stacking is 1 piece, i.e. single chip mode Degree, cooling rate are heat-treated.Even if the thickness of the stacking direction of laminated body 10 is thinning, heating rate, drop can not also be changed The size relation of warm speed it is heat-treated.
(annealing steps of the 2nd embodiment)
Then, the annealing steps of the 2nd embodiment are described in detail.2nd embodiment is to carry out heat to glass substrate block-by-block The embodiment of the heat treatment of the single chip mode of processing.The manufacturing method of the glass substrate of 2nd embodiment is also shown in Fig. 1 Process carry out.It in the case, is to support glass shown in aftermentioned Fig. 6 (a) in the loading of the glass substrate of step S3 The mode of the support member support of glass substrate loads glass substrate 11.
Fig. 6 (a) is the side view for indicating an example of carrying state of the glass substrate 11 in furnace, and Fig. 6 (b) is from bottom surface side Observe the figure of the glass substrate 11 of Fig. 6 (a).Glass substrate 11 be horizontally placed in the supporting member 112 in furnace 140 it On, it is heat-treated in furnace 140.Firstly, by the glass substrate 11 of severing in step S2 shown in Fig. 1 to be supported component The mode of 112 supports, is placed on supporting member 112 (step S3), is placed on supporting member 112 in glass substrate 11 In the state of, made annealing treatment (step S4).In the present embodiment, it is not laminated multiple glass substrates 11, but by one Block (single layer) glass substrate 11 is heat-treated in the state of being placed on supporting member 112.Alternatively, it is also possible to being monolithic side The heat treatment of formula will be placed in the conveying of 11 block-by-block of the glass substrate on supporting member 112 on one side, is heat-treated on one side.In addition, The glass substrate 11 being placed on supporting member 112 can be arranged multiple in furnace, each glass substrate 11 is heat-treated, Further, it is also possible to glass substrate 11 and supporting member 112 is alternately laminated, make glass substrate 11 each other using supporting member 112 Specific range is separated, and each glass substrate 11 is heat-treated.
Supporting member 112 including, for example, with heat resistance fibrous structures, carbon fiber, alumina fibre, silicon oxide fibre, Porous ceramic, carbon graphite, carbon felt, metal component, brick component, and equipped with multiple in furnace 140.Supporting member 112 is with glass The mode of 11 general horizontal of substrate supports the lower surface (bottom surface) of glass substrate 11.
In addition, the interval of the quantity of the supporting member 112 of support glass substrate 11, each supporting member 112, support glass base The position of plate 11 is any.In addition, glass substrate 11 can be expanded and be deformed, therefore if being heat-treated to glass substrate 11 Supporting member 112 preferably has flexibility.
The heat generating device 141 of the environmental gas (air) for heating furnace 140 is equipped in furnace 140, heat generating device 141 is Heat source, the environmental gas of heating furnace 140.Heat generating device 141 adds including, for example, ceramic heater, far infra-red heater, halogen Hot device, in such a way that the temperature of glass substrate 11 becomes aftermentioned thermal history, the environmental gas of glass substrate 11 and furnace 140. The heat of environmental gas is transmitted to glass substrate 11, is heated also with far infrared, infrared ray to glass substrate 11, with glass The mode that the temperature of glass substrate 11 becomes the temperature in the range of 400 DEG C~600 DEG C is heat-treated.When being heat-treated, furnace It is confined space, the influence being not easily susceptible to outside furnace 140 in 140.Heat generating device 141 with the Temperature Distribution in furnace 140 substantially Mode, control calorific value, fever time.Temperature Distribution in furnace 140 is substantially the same, and heat generating device 141 is set to furnace 140 Interior position, quantity are any.Glass substrate 11 is supported the support of component 112, and is equipped with spy in the lower surface of glass substrate 11 Fixed space.Substantially due to the Temperature Distribution in furnace 140, the upper surface of glass substrate 11, be supported component 112 The lower surface of the glass substrate 11 of support, thermal history are equal.If generating heat between the upper surface and lower surface of glass substrate 11 to go through Path difference, then upper surface is different from the dimensional stability to heating in house of lower surface, generates stretching and compression stress, and generates warpage.Therefore, glass is eliminated The difference of the temperature change of the upper surface and lower surface of glass substrate 11, the difference for reducing thermal history.
Then, the heat treatment of step S4 is illustrated.
Firstly, control heat generating device 141, carries out in such a way that the ambient air temperature in furnace 140 becomes heat treatment temperature Processing.In this, so-called heat treatment temperature refers to and forms the semiconductor layer comprising LTPS, IGZO for being used for fine display Formation temperature on glass substrate 11 is specifically the temperature of 400 DEG C~600 DEG C of range.Manufacture fine display When the working process temperature of glass substrate 11 be (to be equivalent to 10 than the strain point of glass14.5The temperature of the viscosity of pool, such as 661 DEG C) low temperature.In the temperature region lower than working process temperature, if the dimensional stability to heating in house of glass substrate is larger, glass Glass substrate is not appropriate for as the glass substrate for being used to manufacture fine display.Therefore, with manufacture fine display Under the heat treatment temperature of the range of equal temperature region i.e. 400 DEG C~600 DEG C of the working process temperature of glass substrate, to glass Substrate 11 is heat-treated, and in heat treatment temperature temperature region below, makes 0~15ppm of dimensional stability to heating in house, preferably 0~ 10ppm, more preferably 0~6ppm, further preferably 0~3ppm.
Then, after the ambient air temperature in furnace 140 becomes heat treatment temperature, generally horizontally by glass substrate 11 It is placed on the supporting member 112 in furnace 140, the input port of the glass substrate 11 of sealed furnace 140, makes to become closed in furnace 140 Space.In the state that the ambient air temperature in furnace 140 is set as heat treatment temperature, glass substrate 11 is put into furnace 140, It is possible thereby to glass substrate 11 in a short time.
In addition, the ambient air temperature presence in the temperature of glass substrate 11 and furnace 140 is poor, glass substrate 11 is loaded Glass substrate 11 can also preheat glass substrate 11 sharply in the case where thermal deformation (thermal expansion) when in furnace 140 Later, it is placed in furnace 140.By preheating to glass substrate 11, the sharply thermal deformation of glass substrate 11 can be inhibited, from And strain, warpage, the recess etc. of the generation of glass substrate 11 can be reduced.In addition it is also possible to inhibit because of glass substrate 11 and support structure Part 112 slides, and damages to caused by glass substrate 11.
Then, heat generating device 141 is controlled, with 20 DEG C/min or more~heating rate less than 120 DEG C/min, heating glass Glass substrate 11, until 400 DEG C~600 DEG C within the scope of heat treatment when maximum temperature, that is, heat treatment temperature.By glass substrate 11 Temperature the step of being heated to until heat treatment temperature be heating stepses.After by heating stepses, by glass substrate 11 Temperature was with heat treatment temperature maintenance 5 minutes~120 minutes.The constant temperature of glass substrate 11 is maintained to the step of heat treatment temperature Rapid is to maintain step.In maintaining step, the temperature of glass substrate 11 can change in the range of 400 DEG C~600 DEG C, glass The temperature of substrate 11 can also fix.For example, can the slow speed of heating rate than 20 DEG C/min~120 DEG C/min or The slow speed of the 1st cooling rate than 0.5 DEG C/min~10 DEG C/min, by the temperature of glass substrate 11 maintain 400 DEG C~ In the range of 600 DEG C.After maintaining step, with 0.5 DEG C/min or more~the 1st cooling rate less than 10 DEG C/min, Until from heat treatment temperature to low 50 DEG C~150 DEG C of the 1st medium temperature than heat treatment temperature, cooling glass substrate 11.With the 1st After the cooling glass substrate 11 of cooling rate, with 10 DEG C/min or more~the 2nd cooling rate less than 25 DEG C/min, from the 1st Until medium temperature to the 2nd medium temperature, cooling glass substrate 11.After with the cooling glass substrate 11 of the 2nd cooling rate, with 1st cooling rate further cools down glass substrate 11 until the 2nd medium temperature to room temperature.By the temperature of glass substrate 11 from The step of heat treatment temperature is cooled to room temperature is cooling step, is cooled to the 1st cooling from heat treatment temperature to the 1st medium temperature Step, from the 2nd cooling step that is cooled to of the 1st medium temperature to the 2nd medium temperature, from the 2nd medium temperature to the cooling of room temperature For the 3rd cooling step.
Fig. 7 is the figure for indicating the thermal history of glass substrate 11.In this, so-called thermal history refers to because of the heat treatment in furnace 140 And the course of the temperature of the glass substrate 11 changed.Temperature shown in figure is Tm1 < Tm2 < Tm3 < Tm4, Tm1=room temperature (such as 25 DEG C), the 2nd medium temperature of Tm2=(such as 200 DEG C), the 1st medium temperature of Tm3=(such as 400 DEG C), at Tm4=heat It manages temperature (such as 500 DEG C).
Heating stepses, maintenance step, the speed in each cooling step, the range of time are as shown below.
(1) heating stepses: t1-t0=5 minutes~20 minutes, Tm4-Tm1=400 DEG C~600 DEG C, heating rate S1= (Tm4-Tm1)/(t1-t0)=20 DEG C/min~120 DEG C/min；
(2) maintain step: t2-t1=5 minutes~120 minutes, Tm4-Tm4=0, speed S2=(Tm4-Tm4)/ DEG C/min (t2-t1)=0；
(3) the 1st cooling steps: t3-t2=15 minutes~100 minutes, Tm4-Tm3=50 DEG C~150 DEG C, cooling rate S3 (the 1st cooling rate)=(Tm4-Tm3)/(t3-t2)=0.5 DEG C/min~10 DEG C/min；
(4) the 2nd cooling steps: t4-t3=10 minutes~15 minutes, Tm3-Tm2=150 DEG C~250 DEG C, cooling rate S4 (the 2nd cooling rate), (Tm3-Tm2)/(t4-t3)=10 DEG C/min~25 DEG C/min；
(5) the 3rd cooling steps: t5-t4=15 minutes~100 minutes, Tm2-Tm1=50 DEG C~150 DEG C, cooling rate S5 (the 1st cooling rate)=(Tm2-Tm1)/(t5-t4)=0.5 DEG C/min~10 DEG C/min.
In this, room temperature is not limited to 25 DEG C, for example, 0 DEG C~30 DEG C.In addition, heat treatment temperature is not limited to 500 DEG C, be 400 DEG C~600 DEG C of arbitrary temp, the 1st medium temperature is not limited to 400 DEG C, be heat treatment temperature-(50 DEG C~ 150 DEG C) arbitrary temp.The temperature for the range that 2nd medium temperature is 150 DEG C~250 DEG C, can also be fixed as 200 DEG C.This Outside, heating rate, cooling rate are to all average speed for carrying out heating, cooling of glass substrate 11.
Compared with maintaining step, cooling step, heating stepses are small on the pyrocondensation of glass substrate 11 influence, are not likely to produce because of heat Strain caused by the unevenness of shrinkage, therefore processing time (=Tm4-Tm1) can be shortened, it may also speed up heating rate.Adding In hot step, the time is handled by shortening, accelerates heating rate, the production efficiency of glass substrate 11 can be improved.
In the same manner as cooling step, step is maintained to influence the pyrocondensation of glass substrate 11 big, by the place for making cooling step Time (=t5-t2) is managed than maintaining the processing time (=t2-t1) of step long, can reduce dimensional stability to heating in house.Therefore, cold by making But short processing time of the processing time of step than maintaining step, can be improved the production efficiency of glass substrate 11.Pass through extension The processing time for maintaining step, the low hot shrinkage rate of glass substrate 11 may be implemented, therefore according to the heat required glass substrate 11 Shrinkage, any change maintain the processing time of step, it is possible thereby to improve the production efficiency of glass substrate 11, reduce dimensional stability to heating in house. In addition, the plate thickness of glass substrate 11 the thin, heat is transferred to the inside of glass substrate 11 fastlyer, therefore can be according to glass substrate The thin and thick of 11 plate thickness, and shorten the processing time for maintaining step.In addition, temperature, that is, the heat treatment temperature for maintaining step is to be based on The semiconductor layer comprising LTPS, IGZO for being used for fine display is formed in the formation temperature of glass substrate 11 and is set Temperature, therefore, as long as the temperature range same with formation temperature, can be the temperature lower than strain point of glass.It does not need Until the strain point that temperature in furnace 40 is risen to glass, therefore heating cost is low, can reduce glass substrate 11 with low cost Dimensional stability to heating in house.
In addition, strain point is different and different according to glass types, in order to reduce pyrocondensation, glass substrate 11 preferably has strain The higher glass composition of point, the strain point of the glass of glass substrate 11 is preferably 600 DEG C or more, and more preferably 655 DEG C or more, example Such as 661 DEG C.
1st cooling step influences greatly the pyrocondensation of glass substrate 11, and therefore, processing time (=t3-t2) is more cooling than the 2nd The processing time (=t4-t3) of step is long, and cooling rate S3 is slower than the cooling rate S4 of the 2nd cooling step.To glass substrate 11 pyrocondensation influences big slave heat treatment temperature into the heat treatment of the 1st medium temperature (such as 400 DEG C), handles the time than other Step is long, slows down cooling rate, it is possible thereby to reduce the unevenness of the dimensional stability to heating in house of glass substrate 11, strain is inhibited to generate.
2nd cooling step is small on the pyrocondensation of glass substrate 11 influence, therefore handles time (=t4-t3) step more cooling than the 1st The rapid processing time (=t3-t2) is short, and cooling rate S4 is faster than the cooling rate S3 of the 1st cooling step.Extremely with heat treatment temperature The temperature region of 1st medium temperature is compared, and the 1st medium temperature to the region of the 2nd medium temperature is to the pyrocondensation shadow of glass substrate 11 Sound is small, is not likely to produce strain caused by the unevenness because of dimensional stability to heating in house.Therefore, in the 2nd cooling step, keep the processing time colder than the 1st But step is short, and accelerates cooling rate, and the production efficiency of glass substrate 11 thus can be improved.
3rd cooling step is small on the pyrocondensation of glass substrate 11 influence, therefore can the arbitrary cooling glass base of cooling rate Plate 11.By keeping the cooling rate S5 of the 3rd cooling step slower than the cooling rate S4 of the 2nd cooling step, glass base can be inhibited The thermal deformation of plate 11, and can inhibit because glass substrate 11 and supporting member 12 slide, it is damaged to caused by glass substrate 11.
In addition, the 3rd cooling step is small on the pyrocondensation of glass substrate 11 influence, therefore can also be with the cooling of the 2nd cooling step Speed S4 cools down glass substrate 11.In the 3rd cooling step, is cooled down with cooling rate S4, glass substrate thus can be improved 11 production efficiency.
By such heat treatment, the dimensional stability to heating in house of glass substrate 11 can be set as 0~15ppm.The pyrocondensation of glass substrate 11 Rate is preferably 0~10ppm, more preferably 0~6ppm.Such dimensional stability to heating in house can by adjusting the glass of glass substrate form, with And heat treatment temperature and heat treatment time and reach.In addition, being influenced in the pyrocondensation on glass substrate in small temperature region, lead to The shortening processing time is spent, heating rate, cooling rate are accelerated, and the production efficiency of glass substrate 11 can be improved.In addition, in monolithic Glass substrate 11 in the case where, equably transmitting heat is easy on the face direction of glass substrate 11, therefore by with this embodiment party The annealing steps of formula handle glass substrate 11, and the production efficiency of glass substrate 11 can be improved, and reduce dimensional stability to heating in house.
Then, illustrate the glass substrate after the heat treatment (annealing under line) of the 1st embodiment or the 2nd embodiment 11 evaluation and evaluation result.Glass substrate 11 maintains 5 minutes~30 points with the heat treatment temperature within the scope of 400 DEG C~600 DEG C The liquid crystal display glass substrate of Zhong Erwei after heat treatment.
It is that investment heat-treatment furnace is heat-treated in the evaluation of glass substrate 11 after the completion of heat treatment.Evaluation temperature is (1) 500 DEG C of the 1st evaluation temperature, (2) 50 DEG C the 2nd evaluation temperature (450 DEG C) lower than the 1st evaluation temperature, (3) are than the 1st evaluation High 50 DEG C of temperature of the 3rd evaluation temperature (550 DEG C).Dimensional stability to heating in house after annealing under line, which optionally has, is not suitable for that fine will be used for Display includes the case where semiconductor layer of LTPS, IGZO is formed in glass substrate 11.It is of particular importance that inhibiting and manufacturing Temperature (temperature is known as working process temperature) when the semiconductor layer formation of the glass substrate 11 of fine display is substantially The dimensional stability to heating in house of glass substrate 11 near the range of equal temperature region i.e. 400 DEG C~600 DEG C.Therefore, high-precision with manufacture In the equal temperature region of temperature when the semiconductor layer formation of the glass substrate 11 of thin display, the heat of glass substrate 11 is evaluated Shrinkage.
It is that the temperature in heat-treatment furnace is set as the 1st evaluation for evaluating the evaluation heat treatment method of glass substrate 11 Glass substrate 11 is put into the heat-treatment furnace for being set as each evaluation temperature by temperature, the 2nd evaluation temperature, the 3rd evaluation temperature respectively, In the heat treatment furnace after heat treatment in 30 minutes, simultaneously natural cooling is taken out from heat-treatment furnace.It will be evaluated using this method The dimensional stability to heating in house of glass substrate 11 when heat treatment is set to the 1st dimensional stability to heating in house C1, the 2nd dimensional stability to heating in house C2, the 3rd dimensional stability to heating in house C3.At this point, Glass substrate 11 suitable for manufacturing fine display is the glass substrate for meeting following relationship.
Relational expression: | C1-C2 |/| C3-C1 | < 0.28
Wherein, the 1st dimensional stability to heating in house when C1=was with the maintenance of the 1st evaluation temperature 30 minutes, C2=maintain 30 with the 2nd evaluation temperature The 2nd dimensional stability to heating in house when minute, the 3rd dimensional stability to heating in house when C3=was with the maintenance of the 3rd evaluation temperature 30 minutes.
Fig. 8 is indicated to evaluate heat treatment method to the glass substrate 11 after the heat treatment of the 1st embodiment and carry out hot place The figure of an example of the result of the dimensional stability to heating in house of the glass substrate 11 when reason.In glass substrate suitable for manufacturing fine display, Dimensional stability to heating in house is smaller when below the working process temperature of fine display.Therefore, by making the 1st evaluation temperature to the 2nd evaluation temperature Dimensional stability to heating in house (C1~C2) in the temperature region of degree, less than the pyrocondensation in the temperature region of the 1st evaluation temperature to the 3rd evaluation temperature Rate (C1~C3), and can realize the glass substrate for being suitable for manufacturing fine display.Heat of the glass substrate 11 in the 1st embodiment It is to be handled with heat treatment temperature Tm3 (400 DEG C~600 DEG C), therefore as shown in figure 8, than the 1st heat treatment temperature in processing The dimensional stability to heating in house in temperature region until the 1st low evaluation temperature to the 2nd evaluation temperature is reduced to 15ppm or less.However, than Dimensional stability to heating in house reduction amplitude in temperature region until the 1st high evaluation temperature to the 3rd evaluation temperature of 1 heat treatment temperature is little, For the dimensional stability to heating in house close with the dimensional stability to heating in house (such as 80ppm) before heat treatment.Glass substrate 11 is in the manufacture to fine display Dimensional stability to heating in house in influential temperature region becomes extremely low compared with not influencing the temperature region of manufacture of fine display, It is consequently adapted to the manufacture of fine display.In addition, in the temperature region for being more than heat treatment temperature, by inhibiting glass substrate 11 dimensional stability to heating in house reduces, and can inhibit the unevenness of pyrocondensation, the strain in glass substrate 11.
(experimental example of the 1st embodiment)
In order to confirm the effect of the 1st embodiment, made using the overflow downdraw of one of fusion method multiple with following The glass substrate of glass composition.The strain point of glass substrate is 660 DEG C.
Glass composition
SiO267.0 mole %,
Al2O310.6 mole %,
B2O311.0 mole %,
11.4 mole % of RO (total content of RO MgO, CaO, SrO and BaO).
Annealing
For this glass substrate, anneal in the method for the 1st embodiment.In embodiment, laminated glass substrate, with Temperature region phase in the temperature region until 500 DEG C of maximum temperature of 300 DEG C to heat treatment temperature, with 300 DEG C to room temperature Than slowing down heating rate, cooling rate, extending the heating-up time, the mode of temperature fall time is heat-treated.In a comparative example, shape At the laminated body of glass substrate, heating rate is not changed according to temperature region, is heat-treated to cooling rate (previous example).
The measurement of dimensional stability to heating in house
Glass substrate is cut into the rectangle of specific dimensions before heat treatment, is formed and is crossed at long side both ends, in short side Central portion obtains two glass samples to half cut-off.It is heat-treated that (heating rate is 10 DEG C/minute to a wherein glass sample Clock is placed 1 hour at 450 DEG C).Length of the measurement without another glass sample of heat treatment.Moreover, utilizing laser microscope Deng the departure that the glass sample after heat treatment is measured to scribing line together with untreated glass sample, the length of glass sample is found out Residual quantity is spent, the pyrocondensation amount of sample is thus found out.Residual quantity used as the pyrocondensation amount, the length with the glass sample before heat treatment Degree, finds out dimensional stability to heating in house according to the following formula.The dimensional stability to heating in house of the glass sample is set as to the dimensional stability to heating in house of glass substrate.
Dimensional stability to heating in house (ppm)=(residual quantity)/(length of the glass sample before heat treatment) × 106
Dimensional stability to heating in house is detected to the glass substrate before annealing, is 50ppm.
When detecting dimensional stability to heating in house to the glass substrate after annealing, in embodiment, the heat of the glass substrate of the end of stacking direction Shrinkage is 2ppm, and the dimensional stability to heating in house of the glass substrate of the central portion of stacking direction is 3ppm.On the other hand, in previous example, stacking The dimensional stability to heating in house of the glass substrate of the end in direction is 10ppm, and the dimensional stability to heating in house of the glass substrate of the central portion of stacking direction is 18ppm。
In addition, the difference of the thermal history in the edge region and middle section of glass substrate reduces, the dimensional stability to heating in house in edge region is 2ppm, The dimensional stability to heating in house of middle section is 3ppm.On the other hand, in previous example, the dimensional stability to heating in house in edge region is 11ppm, the heat of middle section Shrinkage is 18ppm.
In this way, changing heating rate, cooling rate and according to temperature region, in the heat treatment step by multiple glass Heat distribution between substrate is adjusted to impartial, the unevenness of the dimensional stability to heating in house of the glass substrate after thus can reducing heat treatment.
(experimental example of the 2nd embodiment)
In order to confirm the effect of the 2nd embodiment, multiple realities having with the 1st embodiment are made using overflow downdraw Test a glass substrate for same glass composition.The plate thickness of glass substrate is 0.5mm, and the strain point of glass substrate is 660 DEG C.
Annealing
For the glass substrate, anneal in the method for the 2nd embodiment.In embodiment, by one piece of glass base It is onboard to be placed on supporting member, with compared with the temperature region of the 1st medium temperature to the 2nd medium temperature, 500 DEG C of heat treatment temperature The mode slack-off to the cooling rate of the temperature region of the 1st medium temperature is heat-treated.In a comparative example, same as embodiment One piece of glass substrate is placed on supporting member by ground, is not heat-treated with changing cooling rate according to temperature region.
The measurement of dimensional stability to heating in house is with method identical with the measurement of dimensional stability to heating in house of the 1st embodiment progress.Before heat treatment The dimensional stability to heating in house of glass sample is 40~50ppm.
If heat treatment temperature=500 DEG C, the 1st medium temperature=400 DEG C, the 2nd medium temperature=200 DEG C, hold time= 10 minutes, change heating rate, the 1st cooling rate, the 2nd cooling rate, and compare the dimensional stability to heating in house of glass sample.Its result is shown In table 1.
[table 1]
As shown in the embodiment 1,2 of table 1, as long as the 1st cooling rate, the 2nd cooling rate are in the speed model of present embodiment In enclosing, then heating rate be 20 DEG C/min or more~less than 120 DEG C/min in the range of, can reduce the heat of glass substrate The unevenness of shrinkage, dimensional stability to heating in house is also smaller.In addition, as shown in embodiment 3~7, the 1st cooling rate be 0.5 DEG C/min or more~ Less than 10 DEG C/min, the 2nd cooling rate be 10 DEG C/min or more~less than 25 DEG C/min in the range of, can be by glass base The dimensional stability to heating in house of plate is reduced to 15ppm hereinafter, the unevenness of dimensional stability to heating in house is also smaller.Moreover, by making to influence dimensional stability to heating in house the 1st big drop Warm speed is slower, can further decrease dimensional stability to heating in house.In addition, as shown in comparative example 1~3, not in the speed model of present embodiment In enclosing, in the case where the 1st cooling rate 2 cooling rate of >, although the dimensional stability to heating in house of glass substrate reduces, still above 15ppm, therefore judge not effective heat treatment.
Then, compare to hold time and be set as 0 minute, 1 minute, 5 minutes, 30 minutes, 60 minutes, 120 minutes, 150 The dimensional stability to heating in house of glass sample when minute.In addition, setting heat treatment temperature=500 DEG C, the 1st medium temperature=400 DEG C, among the 2nd Temperature=200 DEG C, heating rate=50 DEG C, the 1st cooling rate=3 DEG C/min, the 2nd cooling rate=13 DEG C/min.By its As a result it is shown in table 2.
[table 2]
It holds time (minute) Dimensional stability to heating in house (ppm)
Comparative example 1 0 18±3
Comparative example 2 1 16±2
Embodiment 1 5 8±1
Embodiment 2 30 7±1
Embodiment 3 60 6±1
Embodiment 4 120 6±1
Comparative example 3 150 8±1
As shown in the Examples 1 to 4 of table 2,5 minutes or more and 120 minutes are set as hereinafter, can make by that will hold time The dimensional stability to heating in house of glass substrate becomes 10ppm hereinafter, the unevenness of dimensional stability to heating in house is also smaller.On the other hand, as shown in Comparative Examples 1 and 2, if It holds time less than 5 minutes, then the dimensional stability to heating in house of glass substrate is more than 15ppm, therefore is not appropriate for as maintenance heat treatment temperature Time.In addition, as shown in comparative example 3, it is known that it is longer than 120 minutes by making to hold time, it can be by the pyrocondensation of glass substrate Rate is set as 10ppm or less.However, if extend hold time if annealing time is elongated and production efficiency reduces, and can not be by pyrocondensation Rate is set as 6ppm hereinafter, therefore, it is considered that the processing held time more than 120 minutes is not appropriate for.
Then, compare by treatment temperature set be 350 DEG C, 400 DEG C, 500 DEG C, 600 DEG C, 650 DEG C when glass sample Dimensional stability to heating in house.In addition, setting hold time=10 minutes, the 1st medium temperature=400 DEG C, the 2nd medium temperature=200 DEG C, heating speed Spend=50 DEG C, the 1st cooling rate=3 DEG C/min, the 2nd cooling rate=13 DEG C/min.It the results are shown in table 3.
[table 3]
Heat treatment temperature (DEG C) Dimensional stability to heating in house (ppm)
Comparative example 1 350 16±4
Embodiment 1 400 9±2
Embodiment 2 500 6±1
Embodiment 3 600 8±1
Comparative example 2 650 12±2
As shown in the Examples 1 to 3 of table 3, by the way that heat treatment temperature is set as 400 DEG C or more and 600 DEG C hereinafter, can be by glass The dimensional stability to heating in house of glass substrate be set as 10ppm hereinafter, and dimensional stability to heating in house unevenness it is also smaller.On the other hand, as shown in comparative example 1, work as heat When treatment temperature is 350 DEG C, the dimensional stability to heating in house of glass substrate is more than 15ppm, therefore judges not effective heat treatment.In addition, such as Shown in comparative example 2, when heat treatment temperature be 650 DEG C when, although the dimensional stability to heating in house of glass substrate can be set as 15ppm hereinafter, Not effective heat treatment is thought from thermal efficiency viewpoint.
As shown above, change cooling rate and according to temperature region, the glass substrate after can reduce heat treatment Dimensional stability to heating in house.
More than, it is described in detail by the manufacturing method of glass substrate of the invention, but the present invention is not limited to the realities Mode and embodiment etc. are applied, without departing from the spirit and scope of the invention, naturally it is also possible to carry out various modifications or changes.
[explanation of symbol]
10 laminated bodies
11 glass substrates
12 bodies
15a, 15b thermal insulation board
20 supporting plates
21 abutment portions
22 mounting portions
23 backplates
40,140 furnace
41,141 heat generating device
112 supporting members

Claims (5)

1. a kind of manufacturing method of glass substrate, which is characterized in that the heat treatment step comprising glass substrate,
The heat treatment step comprises the steps of:
The glass substrate entirety is heat-treated with 60 DEG C~260 DEG C of temperature, that is, heat treatment temperature lower than strain point；
It is cold with the 1st speed until from the heat treatment temperature to 50 DEG C~300 DEG C of medium temperature lower than the heat treatment temperature The glass substrate is all；And
After the heat treatment step, until the medium temperature to room temperature, with the 2nd speed more fireballing than the described 1st The cooling glass substrate is all.
2. a kind of manufacturing method of glass substrate, which is characterized in that the heat treatment step comprising glass substrate,
The heat treatment step comprises the steps of:
When being heat-treated until from room temperature to low 60 DEG C~260 DEG C of temperature, that is, heat treatment temperature than strain point, from the room Temperature is complete with the 3rd speed heating glass substrate until 50 DEG C~300 DEG C of medium temperature lower than the heat treatment temperature Body；
Until from the medium temperature to the heat treatment temperature, to heat the glass than the described 3rd slow-footed 4th speed Substrate is all；And
The glass substrate entirety is heat-treated with the heat treatment temperature.
3. the manufacturing method of glass substrate according to claim 1, wherein the heat treatment step comprises the steps of:
When being heat-treated until from room temperature to low 60 DEG C~260 DEG C of temperature, that is, heat treatment temperature than strain point, from the room Temperature is complete with the 3rd speed heating glass substrate until 50 DEG C~300 DEG C of medium temperature lower than the heat treatment temperature Body；And
Until from the medium temperature to the heat treatment temperature, to heat the glass than the described 3rd slow-footed 4th speed Substrate is all；
The average speed of 1st speed and the 2nd speed is slower than the average speed of the 3rd speed and the 4th speed.
4. the manufacturing method of glass substrate according to any one of claim 1 to 3, wherein the strain of the glass substrate Point is 655 DEG C or more.
5. the manufacturing method of glass substrate according to claim 1 or 2, wherein in the heat treatment step, be to The laminated body of glass substrate made of muti-piece is laminated in the state that the glass substrate is clipped between bodies in thickness direction It is heat-treated.
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