WO2018228070A1 - Coating composition, tin oxide electrode coating, and tin oxide electrode protection method - Google Patents

Coating composition, tin oxide electrode coating, and tin oxide electrode protection method Download PDF

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WO2018228070A1
WO2018228070A1 PCT/CN2018/084999 CN2018084999W WO2018228070A1 WO 2018228070 A1 WO2018228070 A1 WO 2018228070A1 CN 2018084999 W CN2018084999 W CN 2018084999W WO 2018228070 A1 WO2018228070 A1 WO 2018228070A1
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coating
weight
coating composition
tin oxide
oxide electrode
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PCT/CN2018/084999
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French (fr)
Chinese (zh)
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王兴龙
严永海
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东旭科技集团有限公司
东旭集团有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints

Definitions

  • the invention relates to the field of coatings, in particular to a coating composition, a tin oxide electrode coating and a method for protecting a tin oxide electrode.
  • the existing TFT glass substrate includes a heating season of the electric flux melting furnace in the manufacturing process, and the hot air roasting kiln is generally adopted in the natural gas and air combustion mode.
  • the temperature rising process of heating the temperature in the kiln from room temperature to 1600 ° C is generally divided into three stages, and the slope of the temperature rising curve of each stage is different, and the heating rate is also different.
  • the tin oxide electrode in the electric melting furnace is sintered by SnO 2 powder and various additives, and its disadvantage is that it is easy to volatilize and reduce; second, the thermal shock resistance is poor.
  • the reducing atmosphere is easy to form due to poor fuel control; when the fire is switched over, the temperature in the kiln will fluctuate sharply; after the fire, the rapid change of the heating rate will result.
  • the temperature difference between the upper and lower kiln is too large, which will cause the tin oxide in the electrode brick to be reduced and volatilized, or the electrode may be brittle, causing fatal damage to the tin oxide electrode, resulting in the electric melting furnace being unable to be used or causing a production accident.
  • Another object of the present invention is to provide a tin oxide electrode coating which is formed by coating a coating composition and a method for protecting a tin oxide electrode by the tin oxide electrode coating, using the coating composition in tin oxide
  • the protective coating formed on the electrode has the advantages of wide temperature resistance range and strong adhesion. The tin oxide electrode is protected by the coating and the temperature is slowly increased, thereby effectively ensuring that the tin oxide electrode is not in the kiln.
  • the protective coating eventually falls off after the temperature rise is completed, and does not Other harmful elements are introduced into the work system.
  • a first aspect of the present invention provides a coating composition comprising a mineral powder, a glass frit and a binder, wherein the mineral powder contains SiO 2 , Al 2 O 3 And R 2 O and Fe 2 O 3 , and the content of the SiO 2 is 60-75 wt%, and the content of the Al 2 O 3 is 25-40 wt%, based on the total weight of the mineral powder.
  • the content of R 2 O is 0.5 to 2.5% by weight
  • the content of the Fe 2 O 3 is 0.5 to 3.5% by weight
  • R is an alkali metal.
  • the content of the SiO 2 is 62.5-66 wt%
  • the content of the Al 2 O 3 is 32-34 wt%
  • the content of the R 2 O is based on the total weight of the mineral powder. 1-1.5% by weight
  • the content of the Fe 2 O 3 is 1-2% by weight.
  • R is sodium or potassium.
  • the content of the glass frit is 40-65 parts by weight with respect to 100 parts by weight of the mineral powder; more preferably, the content of the glass frit is 50 with respect to 100 parts by weight of the mineral powder. - 60 parts by weight.
  • the binder is used in an amount such that the viscosity of the uniformly mixed coating composition is from 8,000 to 12,000 poise; more preferably, the binder is used in an amount such that the viscosity of the uniformly mixed coating composition is 10000-11000 poise.
  • the glass frit has a particle size of 0.3 mm or less; more preferably, the glass frit has a particle size of 0.2 to 0.3 mm.
  • the binder is a silicate and/or a metasilicate; more preferably, the binder is a metasilicate; further preferably, the metasilicate is sodium metasilicate .
  • the coating composition further contains an additive, further preferably, the additive is boron oxide and/or tin oxide; still more preferably, the additive is used in an amount of 100 parts by weight relative to 100 parts by weight of the mineral powder. 1-2 parts by weight.
  • the additive is boron oxide and/or tin oxide; still more preferably, the additive is used in an amount of 100 parts by weight relative to 100 parts by weight of the mineral powder. 1-2 parts by weight.
  • the pH of the composition is from 5 to 8; more preferably, the pH of the composition is from 6 to 7.
  • a second aspect of the present invention provides a tin oxide electrode coating which is formed by coating a coating composition provided by the present invention.
  • a third aspect of the invention provides a method for protecting a tin oxide electrode, wherein the method comprises:
  • the coating composition provided by the invention By applying the coating composition provided by the invention to the tin oxide electrode to obtain a protective coating, not only the effect of slowly increasing the temperature of the tin oxide electrode during the kiln can be achieved, but also the protection of the tin oxide electrode to protect the electric fluxing device At the same time, because the composition of the glass powder in the coating is the same or similar to the composition of the glass liquid, this ensures that the coating dissolves into the glass liquid in the late stage of the kiln, and the process of discharging the furnace material is not introduced into the kiln. Other harmful elements.
  • FIG. 1 is a schematic view showing a state in which an electrode coating layer is formed by using the coating composition provided by the present invention before the start of temperature rise;
  • FIG. 2 is a schematic view showing a state in which an electrode is pushed into a furnace after the temperature rise is completed;
  • Fig. 3 is a schematic view showing the peeling state of the electrode coating provided by the present invention after the temperature rise is completed.
  • a coating composition comprising a mineral powder, a glass frit and a binder, wherein the mineral powder contains SiO 2 , Al 2 O 3 And R 2 O and Fe 2 O 3 , and the content of the SiO 2 is 60-75 wt%, and the content of the Al 2 O 3 is 25-40 wt%, based on the total weight of the mineral powder.
  • the content of R 2 O is 0.5 to 2.5% by weight
  • the content of the Fe 2 O 3 is 0.5 to 3.5% by weight
  • R is an alkali metal.
  • the content of the SiO 2 is from 62.5 to 66% by weight based on the total weight of the mineral powder, the Al 2 O
  • the content of 3 is 32 to 34% by weight
  • the content of the R 2 O is 1 to 1.5% by weight
  • the content of the Fe 2 O 3 is 1 to 2% by weight.
  • R is an alkali metal and is represented by one or more of lithium, sodium, potassium, rubidium, cesium and cesium.
  • R is sodium or potassium.
  • the mineral powder When the mineral powder has the above-described component composition, the mineral powder can have the advantages of high refractoriness and good plasticity, and specifically, the refractoriness can reach 1400-1700 °C.
  • SiO 2 and Al 2 O 3 in the mineral powder are the main components of the liquid crystal substrate, which simultaneously ensures that no other harmful elements are introduced into the glass liquid when the subsequent coating is detached.
  • the sand mass fraction of the mineral powder is preferably less than 50%, more preferably 40 to 45%, in view of softness and plasticity.
  • the particle size of the mineral powder is not particularly limited, but is usually not less than 100 mesh.
  • the mineral powder has a particle size of 100 to 350 mesh.
  • the whiteness value of the mineral powder is preferably more than 90% in terms of purity.
  • the mineral powder has a degree of refractoriness of from 1400 to 1700 ° C, more preferably from 1400 to 1550 ° C.
  • the mineral powder has a plasticity index of more than 153.6 Kg.cm, more preferably 155 to 165 Kg.cm.
  • the type and composition of the glass frit are not particularly limited, and may be various commonly used glass frits in the art, for example, the composition may be: SiO 2 71-73 wt%, CaO 6.0-6.5 wt% , MgO 1-4.5% by weight, Al 2 O 3 1.5-2.0% by weight, R 2 O 14-17% by weight, R is an alkali metal; according to a preferred embodiment of the present invention, the present invention employs TFT glass powder, The composition may be SiO 2 60-63 wt%, Al 2 O 3 17-20 wt%, B 2 O 3 1-4 wt%, MgO 1-4 wt%, CaO 3-6 wt%, SrO 1-4 wt.
  • R is an alkali metal.
  • R is also an alkali metal, and is represented by one or more of lithium, sodium, potassium, rubidium, cesium, and cesium.
  • R is sodium or potassium.
  • the content of the glass frit is not particularly limited, in order to further satisfy the temperature resistance range of the coating composition at 500-1600 ° C and the detachment time of the coating in the kiln stage, in the present invention, 100 parts by weight of the mineral powder, the glass powder is contained in an amount of 40 to 65 parts by weight; preferably, the glass powder is contained in an amount of 50 to 60 parts by weight relative to 100 parts by weight of the mineral powder.
  • the particle size of the glass frit is not particularly limited and may be conventionally selected by those skilled in the art, but from the viewpoint of coating peeling time and accelerated coating decomposition, in the present invention, the glass frit is The particle size is 0.3 mm or less; preferably, the glass frit has a particle size of 0.2 to 0.3 mm.
  • the glass powder of the above particle size is used, and when it is first melted and detached, the coating layer in the vicinity can be driven off by a large area to accelerate the decomposition of the coating.
  • the binder is preferably a silicate and/or a metasilicate. From the standpoint of avoiding the introduction of other harmful elements into the working system, it is preferred that the binder be a metasilicate.
  • the metasilicate may be, for example, sodium metasilicate or potassium metasilicate. Since sodium metasilicate is a kind of bonding material with strong weather resistance and strong adhesion, and its hardening speed is fast, when the coating composition is applied to an electrode, the formation of the surface coating of the electrode can be accelerated. Conducive to shorten working hours. Therefore, in the present invention, the metasilicate is preferably sodium metasilicate.
  • the sodium metasilicate can be obtained commercially, and for example, it can be sodium metasilicate pentahydrate (Na 2 SiO 3 ⁇ 5H 2 O) of Qingdao Darun Chemical Co., Ltd.
  • the amount of the binder to be used is not particularly limited, and the amount of the binder used in the present invention is considered from the viewpoints of operability at the time of coating and peeling property after coating.
  • the viscosity of the uniformly mixed coating composition is from 8,000 to 12,000 poise; preferably, the binder is used in an amount such that the viscosity of the uniformly mixed coating composition is from 10,000 to 11,000 poise.
  • the method for measuring the viscosity is measured by the GB2794-81 adhesive viscosity measuring method (rotary viscometer method).
  • composition of the present invention may further contain various additives known in the art without affecting the technical effects of the present invention.
  • an additive for example, boron oxide and/or tin oxide can be used.
  • the amount of the above additive to be used is not particularly limited and may be a conventional amount in the art.
  • the additive is used in an amount of from 1 to 2 parts by weight based on 100 parts by weight of the mineral powder.
  • the pH of the coating composition may be from 5 to 8, and the pH of the composition is preferably from 6 to 7 from the viewpoint of further reducing the damage of the pH to the tin oxide electrode.
  • the present invention also provides a tin oxide electrode coating formed by coating and coating the coating composition.
  • the invention also provides a method for protecting a tin oxide electrode, the method comprising:
  • the coating method in the present invention is not particularly limited and may be carried out in various manners well known to those skilled in the art, and for example, coating methods such as brushing, spraying, dip coating, spin coating, and cast coating may be used.
  • coating methods such as brushing, spraying, dip coating, spin coating, and cast coating may be used.
  • the number of times of application is not particularly limited, and may be one time or may be applied multiple times layer by layer.
  • the thickness of the protective coating formed is preferably from 0.5 to 3 mm, more preferably from 1 to 2 mm.
  • the glass powder in the coating composition is not particularly limited and can be conventionally selected by those skilled in the art.
  • the glass powder having the same or similar composition as the glass liquid in the reaction system is used, so that when the kiln is finished and the space temperature in the kiln reaches the working temperature, the glass powder is first melted and dissolved, and the electrode coating is decomposed and detached, and enters. In the kiln, no other harmful components are introduced into the glass.
  • FIG. 1 is a schematic view showing a state in which an electrode coating layer is formed by using the coating composition provided by the present invention before starting the temperature rise;
  • FIG. 2 is a schematic view showing a state in which an electrode is pushed into the furnace after the temperature rise is completed; and
  • FIG. 3 is a view of the present invention provided after the temperature rise is completed. Schematic diagram of the electrode coating peeling state. Next, a method of protecting a tin oxide electrode of the present invention will be described with reference to Figs.
  • the protection method provided by the present invention comprises:
  • Step 1) Formulating a coating composition
  • the mineral powder and the glass powder are dry-mixed into a group and homogenized in the container, and then the sodium metasilicate solution is added to the container, and the pH is adjusted after mixing;
  • Step 2) Coating a tin oxide electrode coating
  • the side electrode 1 is opposite to the inner side of the pool wall, the concave depth is ⁇ x, and the bottom electrode 2 and the upper surface of the bottom of the pool The depth of the depression is ⁇ x, and the solution composition solution prepared in the step 1) is coated on the side electrode 1 and the bottom electrode 2 in the figure to form a tin oxide electrode having a thickness ⁇ x as shown in FIG. Coating 3.
  • the kiln flame is ignited and the tin oxide electrode coating is in direct contact with the flame. It was raised to 1450-1550 °C with 3-4 heating stages.
  • the electrode is pushed into the kiln to a depth of ⁇ x as shown in FIG. 2, so that the coating still unmelted on the electrode surface sufficiently contacts the glass liquid in the glass cell furnace 4.
  • the coating is completely detached, dissolved in the pool, and discharged with the glass liquid in the washing stage to complete the heating process of the electric melting furnace.
  • the coating thickness of the electrode is ⁇ x, and ⁇ x can be determined according to actual operation requirements.
  • the thickness of the ⁇ x may be from 0.5 to 3 mm, preferably from 1 to 2 mm, from the combination of the rate of temperature rise in the final rapid temperature rise phase and the time required for temperature rise.
  • the viscosity was measured by GB2794-81 adhesive viscosity measurement method (rotary viscometer method).
  • the mineral powder and the glass frit of Preparation Example 1 were placed in a container at a ratio shown in Table 3 below for dry mixing and stirred uniformly, and then a sodium metasilicate aqueous solution was slowly added to the container and uniformly mixed to achieve the viscosity shown in Table 3. And adjust the pH to 7.
  • a coating composition C1 was obtained.
  • the composition of the glass frit used is the same as the composition of the glass in the kiln, and the particle size is 0.2 mm.
  • the composition of the glass powder is specifically SiO 2 62% by weight, Al 2 O 3 18% by weight, B 2 O 3 3 % by weight, MgO 2 % by weight. CaO 4% by weight, SrO 2% by weight, BaO 7% by weight, and ZnO 2% by weight.
  • the mineral powder and the glass frit of Preparation Example 2 were placed in a container at a ratio shown in Table 3 below for dry mixing and stirred uniformly, and then a sodium metasilicate aqueous solution was slowly added to the container and uniformly mixed to achieve the viscosity shown in Table 3. And adjust the pH to 7.
  • a coating composition C2 was obtained.
  • the composition of the glass frit used was the same as that of the molten glass in the kiln, and the particle size was 0.2 mm, and the composition of the glass frit was the same as that of the glass frit of Example 1.
  • the mineral powder and the glass frit of Preparation Example 3 were placed in a container at a ratio shown in Table 3 below, and dry-mixed and stirred uniformly. Then, a sodium metasilicate aqueous solution was slowly added to the container and uniformly mixed to achieve the viscosity shown in Table 3. And adjust the pH to 7. A coating composition C3 was obtained.
  • the composition of the glass frit used was the same as that of the molten glass in the kiln, and the particle size was 0.2 mm, and the composition of the glass frit was the same as that of the glass frit of Example 1.
  • the mineral powder and the glass frit of Preparation Example 4 were placed in a container at a ratio shown in Table 3 below, and dry-mixed and stirred uniformly. Then, a sodium metasilicate aqueous solution was slowly added to the container and uniformly mixed to achieve the viscosity shown in Table 3. And adjust the pH to 5. A coating composition C4 was obtained.
  • the composition of the glass frit used was the same as that of the molten glass in the kiln, and the particle size was 0.3 mm, and the composition of the glass frit was the same as that of the glass frit of Example 1.
  • the mineral powder and the glass frit of Preparation Example 5 were placed in a container at a ratio shown in Table 3 below for dry mixing and stirred uniformly, and then a sodium metasilicate aqueous solution was slowly added to the container and uniformly mixed to achieve the viscosity shown in Table 3. And adjust the pH to 8.
  • a coating composition C5 was obtained.
  • the composition of the glass frit used was the same as that of the molten glass in the kiln, and the particle size was 0.3 mm, and the composition of the glass frit was the same as that of the glass frit of Example 1.
  • Example 1 The procedure of Example 1 was carried out except that the composition of the glass frit was: SiO 2 73% by weight, CaO 6.0% by weight, MgO 4.0% by weight, Al 2 O 3 2.0% by weight, K 2 O 15% by weight; glass powder The particle size was 0.3 mm; potassium metasilicate was used as a binder to obtain a coating composition C6.
  • Example 1 The procedure of Example 1 was carried out except that the composition of the glass frit was: SiO 2 71% by weight, CaO 6.5% by weight, MgO 4.5% by weight, Al 2 O 3 1.5% by weight, K 2 O 16.5% by weight, and particle size was 0.3 mm; potassium metasilicate was used as a binder to obtain a coating composition C7.
  • Example 1 The procedure of Example 1 was carried out except that the mineral powder was replaced with the mineral powder of Comparative Example 1, to obtain a coating composition D1.
  • Example 1 The procedure of Example 1 was carried out except that the mineral powder was replaced with the mineral powder of Comparative Example 2 to obtain a coating composition D2.
  • Coating composition Mineral powder (parts by weight) Glass powder (parts by weight) Adhesive (parts by weight) Viscosity C1 (Preparation Example 1) 100 50 20 10000 C2 (Preparation Example 2) 100 55 18 10100 C3 (Preparation Example 3) 100 60 16 10500 C4 (Preparation Example 4) 100 62 20 9000 C5 (Preparation Example 5) 100 65 18 11500 C6 (Preparation Example 1) 100 50 20 10000 C7 (Preparation Example 1) 100 55 18 10200 D1 (Comparative Example 1) 100 50 19 10000 D2 (Comparative Example 2) 100 50 18 10000
  • a tin oxide electrode is inserted into the electrode hole reserved in the wall body of the kiln body or the bottom of the pool, and the side electrode 1 is opposite to the inner side of the pool wall, and the concave depth is ⁇ x, and the bottom electrode 2
  • the depth of the depression from the upper surface of the bottom of the tank is ⁇ x
  • the coating compositions C1-C7 and D1-D2 prepared in the examples and the comparative examples are applied to the side-insertion electrode 1 and the bottom-insertion electrode, respectively, in each test example. 2
  • a tin oxide electrode coating 3 having a thickness of ⁇ x was formed (tin oxide electrode coatings S1-S7 and DS1-DS2 were respectively obtained), and ⁇ x is shown in Table 4.
  • the kiln flame is ignited and the tin oxide electrode coating 3 is in direct contact with the flame.
  • the first stage is heated at a heating rate of 5 ° C / 2 d
  • the second stage is heated by a heating rate of 8 ° C / h for 5 d
  • the third stage is raised to 1400 ° C with a heating rate of 12 ° C / h, as shown in Figure 2.
  • the electrode pushes ⁇ x into the kiln, so that the coating which is still unmelted on the surface of the tin oxide electrode is in full contact with the glass liquid in the glass cell furnace, so that the electrode coating is completely detached (as shown in FIG. 3), and the electrode coating is completely recorded.
  • the time of detachment i.e., the time from when the temperature rise temperature is reached to when the electrode coating is completely detached
  • Table 4 The time of detachment (i.e., the time from when the temperature rise temperature is reached to when the electrode coating is completely detached) is shown in Table
  • the tin oxide electrode coating with the S1-S7 coating provided by the present invention can be quickly detached, and no transverse or longitudinal cracks are found on the tin oxide electrode after the coating is detached, and there is no deformation phenomenon.
  • the tin oxide electrodes can work normally.
  • the coatings of DS1 and DS2 were raised to 1000 °C in the second stage of the kiln, due to the poor bonding performance of the coating, the melting and shedding phenomenon occurred first.
  • the temperature in the kiln reached 1300 °C.
  • the layers have all fallen off and lost their protection. Cracks and even cracks, electrode deformation, etc. appear on the electrode after the coating is detached, resulting in the electrode not working properly.
  • the coating composition provided by the invention not only ensures that the electrode is slowly warmed up without damage during the rapid temperature rising phase, but also achieves rapid shedding of the coating after the temperature rise is completed.

Abstract

A coating composition, a tin oxide electrode coating, and a tin oxide electrode protection method. The coating composition contains mineral powder, glass powder and an adhesive. The mineral powder contains in percentage by weight: 60-75% of SiO2, 25-40% of Al2O3, 0.5-2.5% of R2O, and Fe2O3, and R is an alkali metal.

Description

涂层组合物、氧化锡电极涂层以及氧化锡电极的保护方法Coating composition, tin oxide electrode coating and tin oxide electrode protection method 技术领域Technical field
本发明涉及涂层领域，具体涉及一种涂层组合物、氧化锡电极涂层以及氧化锡电极的保护方法。The invention relates to the field of coatings, in particular to a coating composition, a tin oxide electrode coating and a method for protecting a tin oxide electrode.
背景技术Background technique
现有TFT玻璃基板在制造过程中包括电助熔窑炉升温阶段，该阶段一般采用天燃气和空气助燃方式进行热风烤窑。将窑内的温度从室温加热到1600℃的升温过程一般分为三个阶段，且每个阶段的升温曲线斜率不同，升温速率也不相同。而电助熔窑炉中的氧化锡电极是由SnO 2粉末与多种添加物烧结而成，它的缺点一是容易挥发和还原；二是耐热冲击性差。在烤窑升温过程中，特别是过大火之前由于燃料控制不好而易形成还原性气氛；过大火切换时，窑内温度又会产生剧烈波动；过大火之后，又因升温速率的快速变化导致窑内上下温差过大，这些都会使电极砖中氧化锡还原挥发，或者发生电极脆裂，对氧化锡电极造成致命损害，导致电助熔窑炉无法使用甚至引发生产事故。 The existing TFT glass substrate includes a heating season of the electric flux melting furnace in the manufacturing process, and the hot air roasting kiln is generally adopted in the natural gas and air combustion mode. The temperature rising process of heating the temperature in the kiln from room temperature to 1600 ° C is generally divided into three stages, and the slope of the temperature rising curve of each stage is different, and the heating rate is also different. The tin oxide electrode in the electric melting furnace is sintered by SnO 2 powder and various additives, and its disadvantage is that it is easy to volatilize and reduce; second, the thermal shock resistance is poor. During the heating process of the kiln, especially before the fire, the reducing atmosphere is easy to form due to poor fuel control; when the fire is switched over, the temperature in the kiln will fluctuate sharply; after the fire, the rapid change of the heating rate will result. The temperature difference between the upper and lower kiln is too large, which will cause the tin oxide in the electrode brick to be reduced and volatilized, or the electrode may be brittle, causing fatal damage to the tin oxide electrode, resulting in the electric melting furnace being unable to be used or causing a production accident.
因此，需要提供一种在热风烤窑期间，能够有效地保护氧化锡电极，从而保护电助熔设备的涂层。Therefore, there is a need to provide a coating that can effectively protect a tin oxide electrode during a hot air kiln to protect an electric fluxing device.
发明内容Summary of the invention
本发明的一个目的在于提供一种涂层组合物，该涂层组合物具有耐火度高、塑性好的优点。本发明的另一目的在于提供一种由涂层组合物涂覆成型而成的氧化锡电极涂层以及通过该氧化锡电极涂层保护氧化锡电极的方法，利用该涂层组合物在氧化锡电极上形成的保护涂层具有耐温范围广、 粘结力强的优点，通过该涂层将氧化锡电极保护起来，并使之缓慢升温，有效地保证了氧化锡电极在烤窑期间，不被窑内气氛还原，且不受窑内升温曲线不同阶段斜率急变以及升温速率切换的影响而引起的电极脆裂或性能损坏，此外，在完成升温后该保护涂层最终脱落，而不会向工作体系中引入其他有害元素。It is an object of the present invention to provide a coating composition which has the advantages of high refractoriness and good plasticity. Another object of the present invention is to provide a tin oxide electrode coating which is formed by coating a coating composition and a method for protecting a tin oxide electrode by the tin oxide electrode coating, using the coating composition in tin oxide The protective coating formed on the electrode has the advantages of wide temperature resistance range and strong adhesion. The tin oxide electrode is protected by the coating and the temperature is slowly increased, thereby effectively ensuring that the tin oxide electrode is not in the kiln. It is reduced by the atmosphere in the kiln, and is not subject to brittle cracking or performance damage caused by the rapid change of the slope in different stages of the heating curve in the kiln and the switching of the heating rate. In addition, the protective coating eventually falls off after the temperature rise is completed, and does not Other harmful elements are introduced into the work system.
为了实现上述目的，本发明第一方面提供了一种涂层组合物，所述涂层组合物含有矿物粉、玻璃粉和粘接剂，其中，所述矿物粉含有SiO 2、Al 2O 3、R 2O和Fe 2O 3，且以所述矿物粉的总重量为基准，所述SiO 2的含量为60-75重量％，所述Al 2O 3的含量为25-40重量％，所述R 2O的含量为0.5-2.5重量％，所述Fe 2O 3的含量为0.5-3.5重量％，R为碱金属。 In order to achieve the above object, a first aspect of the present invention provides a coating composition comprising a mineral powder, a glass frit and a binder, wherein the mineral powder contains SiO 2 , Al 2 O 3 And R 2 O and Fe 2 O 3 , and the content of the SiO 2 is 60-75 wt%, and the content of the Al 2 O 3 is 25-40 wt%, based on the total weight of the mineral powder. The content of R 2 O is 0.5 to 2.5% by weight, the content of the Fe 2 O 3 is 0.5 to 3.5% by weight, and R is an alkali metal.
优选地，以所述矿物粉的总重量为基准，所述SiO 2的含量为62.5-66重量％，所述Al 2O 3的含量为32-34重量％，所述R 2O的含量为1-1.5重量％，所述Fe 2O 3的含量为1-2重量％。 Preferably, the content of the SiO 2 is 62.5-66 wt%, the content of the Al 2 O 3 is 32-34 wt%, and the content of the R 2 O is based on the total weight of the mineral powder. 1-1.5% by weight, the content of the Fe 2 O 3 is 1-2% by weight.
优选地，R为钠或钾。Preferably, R is sodium or potassium.
优选地，相对于100重量份的所述矿物粉，所述玻璃粉的含量为40-65重量份；更优选地，相对于100重量份的所述矿物粉，所述玻璃粉的含量为50-60重量份。Preferably, the content of the glass frit is 40-65 parts by weight with respect to 100 parts by weight of the mineral powder; more preferably, the content of the glass frit is 50 with respect to 100 parts by weight of the mineral powder. - 60 parts by weight.
优选地，所述粘接剂的用量使得均匀混合后的涂层组合物的粘度为8000-12000泊；更优选地，所述粘接剂的用量使得均匀混合后的涂层组合物的粘度为10000-11000泊。Preferably, the binder is used in an amount such that the viscosity of the uniformly mixed coating composition is from 8,000 to 12,000 poise; more preferably, the binder is used in an amount such that the viscosity of the uniformly mixed coating composition is 10000-11000 poise.
优选地，所述玻璃粉的粒度为0.3mm以下；更优选地，所述玻璃粉的粒度为0.2-0.3mm。Preferably, the glass frit has a particle size of 0.3 mm or less; more preferably, the glass frit has a particle size of 0.2 to 0.3 mm.
优选地，所述粘接剂为硅酸盐和/或偏硅酸盐；更优选地，所述粘接剂为偏硅酸盐；进一步优选地，所述偏硅酸盐为偏硅酸钠。Preferably, the binder is a silicate and/or a metasilicate; more preferably, the binder is a metasilicate; further preferably, the metasilicate is sodium metasilicate .
优选地，该涂层组合物还含有添加剂，进一步优选地，所述添加剂为氧化硼和/或氧化锡；更进一步优选地，相对于100重量份的所述矿物粉， 所述添加剂的用量为1-2重量份。Preferably, the coating composition further contains an additive, further preferably, the additive is boron oxide and/or tin oxide; still more preferably, the additive is used in an amount of 100 parts by weight relative to 100 parts by weight of the mineral powder. 1-2 parts by weight.
优选地，所述组合物的pH为5-8；更优选地，所述组合物的pH为6-7。Preferably, the pH of the composition is from 5 to 8; more preferably, the pH of the composition is from 6 to 7.
本发明第二方面提供了一种氧化锡电极涂层，该氧化锡电极涂层由本发明提供的涂层组合物涂覆成型而成。A second aspect of the present invention provides a tin oxide electrode coating which is formed by coating a coating composition provided by the present invention.
本发明第三方面提供了一种氧化锡电极的保护方法，其中，该方法包括：A third aspect of the invention provides a method for protecting a tin oxide electrode, wherein the method comprises:
1)将本发明提供的涂层组合物涂覆于氧化锡电极表面，形成保护涂层的步骤；1) a step of applying a coating composition provided by the present invention to a surface of a tin oxide electrode to form a protective coating layer;
2)当所述氧化锡电极升至工作温度后，使所述保护涂层熔解的步骤。2) a step of melting the protective coating after the tin oxide electrode is raised to the operating temperature.
通过将本发明提供的涂层组合物涂覆于氧化锡电极上得到保护涂层，不仅可以在烤窑期间实现氧化锡电极缓慢升温的效果，达到了保护氧化锡电极从而保护了电助熔设备的目的同时，又因涂层中玻璃粉的组成与玻璃液的组分相同或近似，这就保证了涂层在烤窑后期溶解到玻璃液中，随洗炉料排出的过程不向窑内引入其他有害元素。By applying the coating composition provided by the invention to the tin oxide electrode to obtain a protective coating, not only the effect of slowly increasing the temperature of the tin oxide electrode during the kiln can be achieved, but also the protection of the tin oxide electrode to protect the electric fluxing device At the same time, because the composition of the glass powder in the coating is the same or similar to the composition of the glass liquid, this ensures that the coating dissolves into the glass liquid in the late stage of the kiln, and the process of discharging the furnace material is not introduced into the kiln. Other harmful elements.
本发明的其他特征和优点将在随后的具体实施方式部分予以详细说明。Other features and advantages of the invention will be described in detail in the detailed description which follows.
附图说明DRAWINGS
图1是升温开始前，利用本发明提供的涂层组合物形成电极涂层的状态示意图；1 is a schematic view showing a state in which an electrode coating layer is formed by using the coating composition provided by the present invention before the start of temperature rise;
图2是升温完成后向炉内推入电极的状态示意图；2 is a schematic view showing a state in which an electrode is pushed into a furnace after the temperature rise is completed;
图3是升温完成后本发明提供的电极涂层脱落状态的示意图。Fig. 3 is a schematic view showing the peeling state of the electrode coating provided by the present invention after the temperature rise is completed.
附图标记说明Description of the reference numerals
1、侧插电极             2、底插电极1, side insert electrode 2, bottom insert electrode
3、电极保护涂层         4、玻璃池炉3, electrode protection coating 4, glass pool furnace
具体实施方式detailed description
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。Specific embodiments of the present invention will be described in detail below. It is to be understood that the specific embodiments described herein are merely illustrative and not restrictive.
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应该被视为在本文中具体公开。The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to include values that are close to the ranges or values. For numerical ranges, the endpoint values of the various ranges, the endpoint values of the various ranges and the individual point values, and the individual point values can be combined with one another to yield one or more new ranges of values. The scope should be considered as specifically disclosed herein.
根据本发明的第一方面，本发明提供了一种涂层组合物，所述涂层组合物含有矿物粉、玻璃粉和粘接剂，其中，所述矿物粉含有SiO 2、Al 2O 3、R 2O和Fe 2O 3，且以所述矿物粉的总重量为基准，所述SiO 2的含量为60-75重量％，所述Al 2O 3的含量为25-40重量％，所述R 2O的含量为0.5-2.5重量％，所述Fe 2O 3的含量为0.5-3.5重量％，R为碱金属。 According to a first aspect of the present invention, there is provided a coating composition comprising a mineral powder, a glass frit and a binder, wherein the mineral powder contains SiO 2 , Al 2 O 3 And R 2 O and Fe 2 O 3 , and the content of the SiO 2 is 60-75 wt%, and the content of the Al 2 O 3 is 25-40 wt%, based on the total weight of the mineral powder. The content of R 2 O is 0.5 to 2.5% by weight, the content of the Fe 2 O 3 is 0.5 to 3.5% by weight, and R is an alkali metal.
在本发明中，为了进一步提高涂层组合物的耐火度和塑性，优选地，以所述矿物粉的总重量为基准，所述SiO 2的含量为62.5-66重量％，所述Al 2O 3的含量为32-34重量％，所述R 2O的含量为1-1.5重量％，所述Fe 2O 3的含量为1-2重量％。 In the present invention, in order to further improve the refractoriness and plasticity of the coating composition, preferably, the content of the SiO 2 is from 62.5 to 66% by weight based on the total weight of the mineral powder, the Al 2 O The content of 3 is 32 to 34% by weight, the content of the R 2 O is 1 to 1.5% by weight, and the content of the Fe 2 O 3 is 1 to 2% by weight.
上述R为碱金属，表示为锂、钠、钾、铷、铯和钫中的一种或多种。优选地，R为钠或钾。The above R is an alkali metal and is represented by one or more of lithium, sodium, potassium, rubidium, cesium and cesium. Preferably, R is sodium or potassium.
通过所述矿物粉具有上述成分组成，能够使所述矿物粉具有耐火度高、塑性好的优点，具体而言，其耐火度能够达到1400-1700℃。另外，矿物粉中的SiO 2和Al 2O 3又是液晶基板的主要组成成分，这样同时保证了后续涂层脱落时不向玻璃液中引入其他有害元素。 When the mineral powder has the above-described component composition, the mineral powder can have the advantages of high refractoriness and good plasticity, and specifically, the refractoriness can reach 1400-1700 °C. In addition, SiO 2 and Al 2 O 3 in the mineral powder are the main components of the liquid crystal substrate, which simultaneously ensures that no other harmful elements are introduced into the glass liquid when the subsequent coating is detached.
在本发明中，出于对软质和塑性方面的考虑，所述矿物粉的砂质质量分数优选小于50％，更优选为40-45％。In the present invention, the sand mass fraction of the mineral powder is preferably less than 50%, more preferably 40 to 45%, in view of softness and plasticity.
对于所述矿物粉的粒度没有特别的限定，但通常不低于100目，优选地，所述矿物粉的粒度为100-350目。通过选用上述粒径的矿物粉，更利于 涂抹成型、进一步地利于熔化后的溶解排出。The particle size of the mineral powder is not particularly limited, but is usually not less than 100 mesh. Preferably, the mineral powder has a particle size of 100 to 350 mesh. By selecting the mineral powder of the above particle size, it is more advantageous for smear forming, and further facilitates dissolution and discharge after melting.
在本发明中，出于对纯度方面的考虑，所述矿物粉的白度值优选大于90％。In the present invention, the whiteness value of the mineral powder is preferably more than 90% in terms of purity.
在本发明中，出于调整厚度系数的方面去考虑，所述矿物粉的密度为2.4-2.6g/cm 3，更优选为2.5-2.6g/cm 3。 In the present invention, the coefficient for adjustments to consider the thickness of the mineral powder density of 2.4-2.6g / cm 3, more preferably 2.5-2.6g / cm 3.
在本发明中，优选所述矿物粉的耐火度为1400-1700℃，更优选为1400-1550℃。In the present invention, it is preferred that the mineral powder has a degree of refractoriness of from 1400 to 1700 ° C, more preferably from 1400 to 1550 ° C.
在本发明中，优选所述矿物粉的塑性指数大于153.6Kg·cm，更优选为155-165Kg·cm。In the present invention, it is preferred that the mineral powder has a plasticity index of more than 153.6 Kg.cm, more preferably 155 to 165 Kg.cm.
在本发明中，对所述玻璃粉的种类和成分没有特别限定，可以为本领域各种常用的玻璃粉，例如，其组成可以为：SiO 2 71-73重量％，CaO 6.0-6.5重量％，MgO 1-4.5重量％，Al 2O 3 1.5-2.0重量％，R 2O 14-17重量％，R为碱金属；根据本发明的一种优选实施方式，本发明采用TFT玻璃粉，其组成可以为SiO 2 60-63重量％，Al 2O 3 17-20重量％，B 2O 3 1-4重量％，MgO 1-4重量％，CaO 3-6重量％，SrO 1-4重量％，BaO 6-9重量％，ZnO 0-2.5重量％，R为碱金属。在此，同样上述R为碱金属，表示为锂、钠、钾、铷、铯和钫中的一种或多种。优选地，R为钠或钾。 In the present invention, the type and composition of the glass frit are not particularly limited, and may be various commonly used glass frits in the art, for example, the composition may be: SiO 2 71-73 wt%, CaO 6.0-6.5 wt% , MgO 1-4.5% by weight, Al 2 O 3 1.5-2.0% by weight, R 2 O 14-17% by weight, R is an alkali metal; according to a preferred embodiment of the present invention, the present invention employs TFT glass powder, The composition may be SiO 2 60-63 wt%, Al 2 O 3 17-20 wt%, B 2 O 3 1-4 wt%, MgO 1-4 wt%, CaO 3-6 wt%, SrO 1-4 wt. %, BaO 6-9 wt%, ZnO 0-2.5 wt%, and R is an alkali metal. Here, R is also an alkali metal, and is represented by one or more of lithium, sodium, potassium, rubidium, cesium, and cesium. Preferably, R is sodium or potassium.
在本发明中，对所述玻璃粉的含量没有特别的限定，为了进一步满足涂层组合物的耐温范围在500-1600℃和烤窑阶段涂层的脱落时间，在本发明中，相对于100重量份的所述矿物粉，所述玻璃粉的含量为40-65重量份；优选地，相对于100重量份的所述矿物粉，所述玻璃粉的含量为50-60重量份。In the present invention, the content of the glass frit is not particularly limited, in order to further satisfy the temperature resistance range of the coating composition at 500-1600 ° C and the detachment time of the coating in the kiln stage, in the present invention, 100 parts by weight of the mineral powder, the glass powder is contained in an amount of 40 to 65 parts by weight; preferably, the glass powder is contained in an amount of 50 to 60 parts by weight relative to 100 parts by weight of the mineral powder.
在本发明中，对玻璃粉的粒度没有特别的限定，可以为本领域技术人员常规选择，但从涂层脱落时间和加速涂层分解的角度来考虑，在本发明中，所述玻璃粉的粒度为0.3mm以下；优选地，所述玻璃粉的粒度为0.2-0.3mm。本发明中采用上述粒度的玻璃粉，当它率先熔化脱离时，可以 大面积的带动附近的涂层脱落，加速涂层分解。In the present invention, the particle size of the glass frit is not particularly limited and may be conventionally selected by those skilled in the art, but from the viewpoint of coating peeling time and accelerated coating decomposition, in the present invention, the glass frit is The particle size is 0.3 mm or less; preferably, the glass frit has a particle size of 0.2 to 0.3 mm. In the present invention, the glass powder of the above particle size is used, and when it is first melted and detached, the coating layer in the vicinity can be driven off by a large area to accelerate the decomposition of the coating.
在本发明中，所述粘接剂优选为硅酸盐和/或偏硅酸盐。从避免向工作体系中引入其他有害元素的方面来考虑，优选所述粘接剂为偏硅酸盐。In the present invention, the binder is preferably a silicate and/or a metasilicate. From the standpoint of avoiding the introduction of other harmful elements into the working system, it is preferred that the binder be a metasilicate.
作为所述偏硅酸盐例如可以为偏硅酸钠、偏硅酸钾。由于偏硅酸钠是一种耐候性、粘结力很强的粘结材料，并且其硬化速度快，在将涂层组合物涂覆于电极上时，能够加速电极表面涂层的形成，有利于缩短工时。因此，在本发明中，所述偏硅酸盐优选为偏硅酸钠。The metasilicate may be, for example, sodium metasilicate or potassium metasilicate. Since sodium metasilicate is a kind of bonding material with strong weather resistance and strong adhesion, and its hardening speed is fast, when the coating composition is applied to an electrode, the formation of the surface coating of the electrode can be accelerated. Conducive to shorten working hours. Therefore, in the present invention, the metasilicate is preferably sodium metasilicate.
在本发明中，对所述偏硅酸钠没有特别的限定，为了进一步增加涂层组合物的粘度和粘结强度，优选使用可溶固体成分为90％以上，20℃下密度为1.43-1.47g/cm 3，波美度°Bé＝38-48的偏硅酸钠。作为所述偏硅酸钠可以通过商购获得，例如可以为青岛大润化工公司的五水偏硅酸钠(Na 2SiO 3·5H 2O)。 In the present invention, the sodium metasilicate is not particularly limited, and in order to further increase the viscosity and bond strength of the coating composition, it is preferred to use a soluble solid content of 90% or more and a density of 1.43-1.47 at 20 ° C. g/cm 3 , Baume degree ° Bé = 38-48 sodium metasilicate. The sodium metasilicate can be obtained commercially, and for example, it can be sodium metasilicate pentahydrate (Na 2 SiO 3 ·5H 2 O) of Qingdao Darun Chemical Co., Ltd.
在本发明的涂层组合物中，对所述粘接剂的用量没有特殊的限定，从涂覆时的操作性以及涂覆后的脱落性综合考虑，本发明中所述粘接剂的用量使得均匀混合后的涂层组合物的粘度为8000-12000泊；优选地，所述粘接剂的用量使得均匀混合后的涂层组合物的粘度为10000-11000泊。通过使用上述用量的粘接剂，不仅能够保证在快速升温阶段下电极缓慢升温不受损伤，同时又保证了升温完成后涂层的快速脱落。另外，在本发明中，粘度的测定方法采用GB2794-81胶粘剂黏度测定方法(旋转粘度计法)进行测出。In the coating composition of the present invention, the amount of the binder to be used is not particularly limited, and the amount of the binder used in the present invention is considered from the viewpoints of operability at the time of coating and peeling property after coating. The viscosity of the uniformly mixed coating composition is from 8,000 to 12,000 poise; preferably, the binder is used in an amount such that the viscosity of the uniformly mixed coating composition is from 10,000 to 11,000 poise. By using the above-mentioned amount of the adhesive, it is possible not only to ensure that the electrode is slowly heated and not damaged during the rapid temperature rise, and at the same time, the coating is quickly peeled off after the temperature rise is completed. Further, in the present invention, the method for measuring the viscosity is measured by the GB2794-81 adhesive viscosity measuring method (rotary viscometer method).
在不影响本发明的技术效果的前提下，本发明的组合物还可以含有本领域所公知的各种添加剂。作为这样的添加剂，例如可以为氧化硼和/或氧化锡。The composition of the present invention may further contain various additives known in the art without affecting the technical effects of the present invention. As such an additive, for example, boron oxide and/or tin oxide can be used.
作为上述添加剂的用量没有特别的限定，可以为本领域的常规用量。例如，相对于100重量份的所述矿物粉，所述添加剂的用量为1-2重量份。The amount of the above additive to be used is not particularly limited and may be a conventional amount in the art. For example, the additive is used in an amount of from 1 to 2 parts by weight based on 100 parts by weight of the mineral powder.
在本发明中，所述涂层组合物的pH可以为5-8，从进一步减少pH对 氧化锡电极的损害来考虑，所述组合物的pH优选为6-7。In the present invention, the pH of the coating composition may be from 5 to 8, and the pH of the composition is preferably from 6 to 7 from the viewpoint of further reducing the damage of the pH to the tin oxide electrode.
本发明还提供了一种氧化锡电极涂层，由所述涂层组合物涂覆成型而成。The present invention also provides a tin oxide electrode coating formed by coating and coating the coating composition.
本发明还提供了一种氧化锡电极的保护方法，该方法包括：The invention also provides a method for protecting a tin oxide electrode, the method comprising:
1)将本发明的涂层组合物涂覆于氧化锡电极表面，形成保护涂层的步骤；1) a step of applying the coating composition of the present invention to the surface of a tin oxide electrode to form a protective coating;
2)当所述氧化锡电极的工作环境升至工作温度后，使所述保护涂层熔解的步骤。2) a step of melting the protective coating after the working environment of the tin oxide electrode is raised to the working temperature.
本发明中对涂覆的方法没有特别的限定，可以采用本领域技术人员所熟知的各种方式进行，例如可以使用涂刷、喷涂、浸涂、旋涂和浇涂等涂覆方法。作为涂覆的次数也没有特别的限定，可以为一次，也可以逐层多次涂抹。The coating method in the present invention is not particularly limited and may be carried out in various manners well known to those skilled in the art, and for example, coating methods such as brushing, spraying, dip coating, spin coating, and cast coating may be used. The number of times of application is not particularly limited, and may be one time or may be applied multiple times layer by layer.
作为形成的保护涂层的厚度优选为0.5-3mm，更优选为1-2mm。通过使保护涂层的厚度在上述范围内，不仅保证在快速升温阶段下电极缓慢升温不受损伤，同时又保证了升温完成后涂层的快速脱落。The thickness of the protective coating formed is preferably from 0.5 to 3 mm, more preferably from 1 to 2 mm. By making the thickness of the protective coating within the above range, it is not only ensured that the electrode is slowly heated and not damaged during the rapid temperature rising period, and at the same time, the coating is quickly peeled off after the temperature rise is completed.
本发明的涂层保护法中，对涂层组合物中玻璃粉没有特殊限定，可以为本领域技术人员常规选择。优选采用与反应体系中玻璃液的相同或相近成分的玻璃粉，这样，当烤窑结束，窑内空间温度达到工作温度时，玻璃粉率先熔化、溶解，带动电极涂层的分解、脱落，进入窑池内，而不向玻璃液中引入其他有害成分。In the coating protection method of the present invention, the glass powder in the coating composition is not particularly limited and can be conventionally selected by those skilled in the art. Preferably, the glass powder having the same or similar composition as the glass liquid in the reaction system is used, so that when the kiln is finished and the space temperature in the kiln reaches the working temperature, the glass powder is first melted and dissolved, and the electrode coating is decomposed and detached, and enters. In the kiln, no other harmful components are introduced into the glass.
图1是升温开始前，利用本发明提供的涂层组合物形成电极涂层的状态示意图；图2是升温完成后向炉内推入电极的状态示意图；图3是升温完成后本发明提供的电极涂层脱落状态的示意图。下面结合图1-图3对本发明的氧化锡电极的保护方法进行说明。1 is a schematic view showing a state in which an electrode coating layer is formed by using the coating composition provided by the present invention before starting the temperature rise; FIG. 2 is a schematic view showing a state in which an electrode is pushed into the furnace after the temperature rise is completed; and FIG. 3 is a view of the present invention provided after the temperature rise is completed. Schematic diagram of the electrode coating peeling state. Next, a method of protecting a tin oxide electrode of the present invention will be described with reference to Figs.
具体地，在制造TFT玻璃基板中电助熔窑炉的热风烤窑阶段，本发明提供的保护方法包括：Specifically, in the hot air roasting stage of the electric flux melting furnace in the manufacture of the TFT glass substrate, the protection method provided by the present invention comprises:
步骤1)配制涂层组合物Step 1) Formulating a coating composition
将矿物粉料、玻璃粉干混为一组放入容器内均化，然后向容器内加入偏硅酸钠溶液，混均后调节pH；The mineral powder and the glass powder are dry-mixed into a group and homogenized in the container, and then the sodium metasilicate solution is added to the container, and the pH is adjusted after mixing;
步骤2)涂覆氧化锡电极涂层Step 2) Coating a tin oxide electrode coating
在窑炉本体池壁墙体或池底砌体预留的电极孔洞中插入氧化锡电极，侧插电极1与池壁内侧相对，凹入深度为Δx，底插电极2与池底上表面之间的凹陷深度为Δx，将步骤1)中配制好的涂层组合物溶液涂覆在图中侧插电极1和底插电极2上，形成如图1所示的厚度为Δx的氧化锡电极涂层3。Inserting a tin oxide electrode into the electrode hole reserved in the wall body of the kiln body or the bottom of the pool, the side electrode 1 is opposite to the inner side of the pool wall, the concave depth is Δx, and the bottom electrode 2 and the upper surface of the bottom of the pool The depth of the depression is Δx, and the solution composition solution prepared in the step 1) is coated on the side electrode 1 and the bottom electrode 2 in the figure to form a tin oxide electrode having a thickness Δx as shown in FIG. Coating 3.
步骤3)氧化锡电极涂层脱落Step 3) The tin oxide electrode coating peels off
点燃烤窑火焰，氧化锡电极涂层直接接触火焰。采用3-4个升温阶段升至1450-1550℃。投料试生产时，氧化锡电极达到正常使用的工作温度后，如图2所示将电极向窑内推进Δx深度，使电极表面仍然未熔化的涂层充分接触玻璃池炉4内的玻璃液，如图3所示使涂层完全脱落、溶入池中，随洗炉阶段的玻璃液一起排出体外，完成电助熔窑炉升温过程。The kiln flame is ignited and the tin oxide electrode coating is in direct contact with the flame. It was raised to 1450-1550 °C with 3-4 heating stages. During the trial production, after the tin oxide electrode reaches the normal working temperature, the electrode is pushed into the kiln to a depth of Δx as shown in FIG. 2, so that the coating still unmelted on the electrode surface sufficiently contacts the glass liquid in the glass cell furnace 4. As shown in Fig. 3, the coating is completely detached, dissolved in the pool, and discharged with the glass liquid in the washing stage to complete the heating process of the electric melting furnace.
本发明提供的保护方法用于上述TFT玻璃基板中烤窑阶段时，对所述电极的涂层厚度为Δx没有特别的限定，可根据实际操作需要确定Δx。从最终快速升温阶段的升温速率以及升温所需时间综合考虑，所述Δx的厚度可以为0.5-3mm，优选为1-2mm。通过涂覆上述Δx厚度的涂层，不仅保证在快速升温阶段下电极缓慢升温不受损伤，同时又保证了升温完成后涂层的快速脱落。When the protection method provided by the present invention is used in the kiln stage of the above TFT glass substrate, the coating thickness of the electrode is Δx, and Δx can be determined according to actual operation requirements. The thickness of the Δx may be from 0.5 to 3 mm, preferably from 1 to 2 mm, from the combination of the rate of temperature rise in the final rapid temperature rise phase and the time required for temperature rise. By coating the above-mentioned Δx thickness coating, it is not only ensured that the electrode is slowly heated and not damaged during the rapid temperature rising period, and at the same time, the coating is quickly peeled off after the temperature rise is completed.
下面通过实施例对本发明进行进一步的说明，但本发明并不仅限于下述实施例。The invention is further illustrated by the following examples, but the invention is not limited to the following examples.
以下的例子中，粘度的测定方法采用GB2794-81胶粘剂黏度测定方法(旋转粘度计法)进行测出。In the following examples, the viscosity was measured by GB2794-81 adhesive viscosity measurement method (rotary viscometer method).
制备例1-5以及制备对比例1-2Preparation Examples 1-5 and Preparation of Comparative Examples 1-2
按照表1所示成分及含量将100目的石英粉(SiO 2≥99.2重量％)与300目的高岭土粉(白度≥90％)和300目的地开石粉(白度≥90％)混合搅拌均匀，得到矿物粉K1-K5和DK1-DK2。得到的矿物粉的砂质质量分数、矿物粉的耐火度以及矿物粉的塑性指数如表2所示。 According to the composition and content shown in Table 1, 100 mesh quartz powder (SiO 2 ≥ 99.2% by weight) and 300 mesh kaolin powder (whiteness ≥ 90%) and 300 destination kaishi powder (whiteness ≥ 90%) are mixed and stirred uniformly. Mineral powders K1-K5 and DK1-DK2 were obtained. The sand mass fraction of the obtained mineral powder, the refractoriness of the mineral powder, and the plasticity index of the mineral powder are shown in Table 2.
表1Table 1
Figure PCTCN2018084999-appb-000001
Figure PCTCN2018084999-appb-000001
表2Table 2
  砂质质量分数(％)Sand quality score (%) 耐火度(℃)Refractoriness (°C) 塑性指数(Kg·cm)Plasticity index (Kg·cm)
K1K1 4040 15501550 165165
K2K2 4343 15201520 162162
K3K3 4545 14901490 160160
K4K4 4848 14801480 158158
K5K5 5050 14401440 160160
DK1DK1 5555 13001300 150150
DK2DK2 5858 13501350 140140
实施例1Example 1
将制备例1的矿物粉和玻璃粉按照下述表3所示比例放入容器中进行干混并搅拌均匀，然后缓慢向容器中加入偏硅酸钠水溶液并混合均匀，达到表3所示粘度，并调节pH为7。得到涂层组合物C1。采用的玻璃粉的成分与窑内玻璃液成分相同，粒度为0.2mm，其成分组成具体为SiO 2 62重量％，Al 2O 3 18重量％，B 2O 3 3重量％，MgO 2重量％，CaO 4重量％，SrO 2重量％，BaO 7重量％，ZnO 2重量％。 The mineral powder and the glass frit of Preparation Example 1 were placed in a container at a ratio shown in Table 3 below for dry mixing and stirred uniformly, and then a sodium metasilicate aqueous solution was slowly added to the container and uniformly mixed to achieve the viscosity shown in Table 3. And adjust the pH to 7. A coating composition C1 was obtained. The composition of the glass frit used is the same as the composition of the glass in the kiln, and the particle size is 0.2 mm. The composition of the glass powder is specifically SiO 2 62% by weight, Al 2 O 3 18% by weight, B 2 O 3 3 % by weight, MgO 2 % by weight. CaO 4% by weight, SrO 2% by weight, BaO 7% by weight, and ZnO 2% by weight.
实施例2Example 2
将制备例2的矿物粉和玻璃粉按照下述表3所示比例放入容器中进行干混并搅拌均匀，然后缓慢向容器中加入偏硅酸钠水溶液并混合均匀，达到表3所示粘度，并调节pH为7。得到涂层组合物C2。采用的玻璃粉的成分与窑内玻璃液成分相同，粒度为0.2mm，其成分组成与实施例1的玻璃粉相同。The mineral powder and the glass frit of Preparation Example 2 were placed in a container at a ratio shown in Table 3 below for dry mixing and stirred uniformly, and then a sodium metasilicate aqueous solution was slowly added to the container and uniformly mixed to achieve the viscosity shown in Table 3. And adjust the pH to 7. A coating composition C2 was obtained. The composition of the glass frit used was the same as that of the molten glass in the kiln, and the particle size was 0.2 mm, and the composition of the glass frit was the same as that of the glass frit of Example 1.
实施例3Example 3
将制备例3的矿物粉和玻璃粉按照下述表3所示比例放入容器中进行干混并搅拌均匀，然后缓慢向容器中加入偏硅酸钠水溶液并混合均匀，达到表3所示粘度，并调节pH为7。得到涂层组合物C3。采用的玻璃粉的成分与窑内玻璃液成分相同，粒度为0.2mm，其成分组成与实施例1的玻璃粉相同。The mineral powder and the glass frit of Preparation Example 3 were placed in a container at a ratio shown in Table 3 below, and dry-mixed and stirred uniformly. Then, a sodium metasilicate aqueous solution was slowly added to the container and uniformly mixed to achieve the viscosity shown in Table 3. And adjust the pH to 7. A coating composition C3 was obtained. The composition of the glass frit used was the same as that of the molten glass in the kiln, and the particle size was 0.2 mm, and the composition of the glass frit was the same as that of the glass frit of Example 1.
实施例4Example 4
将制备例4的矿物粉和玻璃粉按照下述表3所示比例放入容器中进行干混并搅拌均匀，然后缓慢向容器中加入偏硅酸钠水溶液并混合均匀，达到表3所示粘度，并调节pH为5。得到涂层组合物C4。采用的玻璃粉的成分与窑内玻璃液成分相同，粒度为0.3mm，其成分组成与实施例1的玻璃粉相同。The mineral powder and the glass frit of Preparation Example 4 were placed in a container at a ratio shown in Table 3 below, and dry-mixed and stirred uniformly. Then, a sodium metasilicate aqueous solution was slowly added to the container and uniformly mixed to achieve the viscosity shown in Table 3. And adjust the pH to 5. A coating composition C4 was obtained. The composition of the glass frit used was the same as that of the molten glass in the kiln, and the particle size was 0.3 mm, and the composition of the glass frit was the same as that of the glass frit of Example 1.
实施例5Example 5
将制备例5的矿物粉和玻璃粉按照下述表3所示比例放入容器中进行干混并搅拌均匀，然后缓慢向容器中加入偏硅酸钠水溶液并混合均匀，达到表3所示粘度，并调节pH为8。得到涂层组合物C5。采用的玻璃粉的成分与窑内玻璃液成分相同，粒度为0.3mm，其成分组成与实施例1的玻璃 粉相同。The mineral powder and the glass frit of Preparation Example 5 were placed in a container at a ratio shown in Table 3 below for dry mixing and stirred uniformly, and then a sodium metasilicate aqueous solution was slowly added to the container and uniformly mixed to achieve the viscosity shown in Table 3. And adjust the pH to 8. A coating composition C5 was obtained. The composition of the glass frit used was the same as that of the molten glass in the kiln, and the particle size was 0.3 mm, and the composition of the glass frit was the same as that of the glass frit of Example 1.
实施例6Example 6
按照实施例1的方法进行，不同的是玻璃粉的成分为：SiO 2 73重量％，CaO 6.0重量％，MgO 4.0重量％，Al 2O 3 2.0重量％，K 2O 15重量％；玻璃粉的粒度为0.3mm；选用偏硅酸钾作为粘接剂，得到涂层组合物C6。 The procedure of Example 1 was carried out except that the composition of the glass frit was: SiO 2 73% by weight, CaO 6.0% by weight, MgO 4.0% by weight, Al 2 O 3 2.0% by weight, K 2 O 15% by weight; glass powder The particle size was 0.3 mm; potassium metasilicate was used as a binder to obtain a coating composition C6.
实施例7Example 7
按照实施例1的方法进行，不同的是玻璃粉的成分为：SiO 2 71重量％，CaO 6.5重量％，MgO 4.5重量％，Al 2O 3 1.5重量％，K 2O 16.5重量％，粒度为0.3mm；选用偏硅酸钾作为粘接剂，得到涂层组合物C7。 The procedure of Example 1 was carried out except that the composition of the glass frit was: SiO 2 71% by weight, CaO 6.5% by weight, MgO 4.5% by weight, Al 2 O 3 1.5% by weight, K 2 O 16.5% by weight, and particle size was 0.3 mm; potassium metasilicate was used as a binder to obtain a coating composition C7.
对比例1Comparative example 1
按照实施例1的方法进行，不同的是将矿物粉替换为制备对比例1的矿物粉，得到涂层组合物D1。The procedure of Example 1 was carried out except that the mineral powder was replaced with the mineral powder of Comparative Example 1, to obtain a coating composition D1.
对比例2Comparative example 2
按照实施例1的方法进行，不同的是将矿物粉替换为制备对比例2的矿物粉，得到涂层组合物D2。The procedure of Example 1 was carried out except that the mineral powder was replaced with the mineral powder of Comparative Example 2 to obtain a coating composition D2.
表3table 3
涂层组合物Coating composition 矿物粉(重量份)Mineral powder (parts by weight) 玻璃粉(重量份)Glass powder (parts by weight) 粘接剂(重量份)Adhesive (parts by weight) 粘度(泊)Viscosity
C1C1 (制备例1)100(Preparation Example 1) 100 5050 2020 1000010000
C2C2 (制备例2)100(Preparation Example 2) 100 5555 1818 1010010100
C3C3 (制备例3)100(Preparation Example 3) 100 6060 1616 1050010500
C4C4 (制备例4)100(Preparation Example 4) 100 6262 2020 90009000
C5C5 (制备例5)100(Preparation Example 5) 100 6565 1818 1150011500
C6C6 (制备例1)100(Preparation Example 1) 100 5050 2020 1000010000
C7C7 (制备例1)100(Preparation Example 1) 100 5555 1818 1020010200
D1D1 (对比例1)100(Comparative Example 1) 100 5050 1919 1000010000
D2D2 (对比例2)100(Comparative Example 2) 100 5050 1818 1000010000
测试例1-9Test Example 1-9
如图1所示，在窑炉本体池壁墙体或池底砌体预留的电极孔洞中插入氧化锡电极，侧插电极1与池壁内侧相对，凹入深度为Δx，底插电极2与池底上表面之间的凹陷深度为Δx，各测试例中分别将实施例及对比例中配制好的涂层组合物C1-C7和D1-D2涂覆于侧插电极1和底插电极2上，形成厚度为Δx的氧化锡电极涂层3(分别得到氧化锡电极涂层S1-S7和DS1-DS2)，Δx如表4所示。As shown in Fig. 1, a tin oxide electrode is inserted into the electrode hole reserved in the wall body of the kiln body or the bottom of the pool, and the side electrode 1 is opposite to the inner side of the pool wall, and the concave depth is Δx, and the bottom electrode 2 The depth of the depression from the upper surface of the bottom of the tank is Δx, and the coating compositions C1-C7 and D1-D2 prepared in the examples and the comparative examples are applied to the side-insertion electrode 1 and the bottom-insertion electrode, respectively, in each test example. 2, a tin oxide electrode coating 3 having a thickness of Δx was formed (tin oxide electrode coatings S1-S7 and DS1-DS2 were respectively obtained), and Δx is shown in Table 4.
点燃烤窑火焰，氧化锡电极涂层3直接接触火焰。第一阶段采用5℃/的升温速率升温2d，第二阶段采用8℃/h的升温速率升温5d，第三阶段采用12℃/h的升温速率升至1400℃后，如图2所示将电极向窑内推入Δx，使氧化锡电极表面仍然未熔化的涂层与玻璃池炉内的玻璃液充分接触，使电极涂层完全脱落(如图3所示)，并记录电极涂层完全脱落的时间(即从达到升温温度后至电极涂层完全脱落的时间)，并表示在表4中。The kiln flame is ignited and the tin oxide electrode coating 3 is in direct contact with the flame. The first stage is heated at a heating rate of 5 ° C / 2 d, the second stage is heated by a heating rate of 8 ° C / h for 5 d, and the third stage is raised to 1400 ° C with a heating rate of 12 ° C / h, as shown in Figure 2. The electrode pushes Δx into the kiln, so that the coating which is still unmelted on the surface of the tin oxide electrode is in full contact with the glass liquid in the glass cell furnace, so that the electrode coating is completely detached (as shown in FIG. 3), and the electrode coating is completely recorded. The time of detachment (i.e., the time from when the temperature rise temperature is reached to when the electrode coating is completely detached) is shown in Table 4.
表4Table 4
  涂层coating 涂层组合物Coating composition Δx厚度(mm)Δx thickness (mm) 完全脱落的时间(h)Time of complete shedding (h)
测试例1Test example 1 S1 S1 C1C1 22 1010
测试例2Test example 2 S2 S2 C2C2 22 99
测试例3Test Example 3 S3 S3 C3C3 22 88
测试例4Test Example 4 S4 S4 C4C4 22 77
测试例5Test Example 5 S5 S5 C5C5 22 66
测试例6Test Example 6 S6 S6 C6C6 22 1010
测试例7Test Example 7 S7 S7 C7C7 22 99
测试例8Test Example 8 DS1DS1 D1D1 22 --
测试例9Test Example 9 DS2DS2 D2D2 22 --
从表4可知，本发明提供的具有S1-S7涂层的氧化锡电极涂层能够快速脱落，在涂层脱落后的氧化锡电极上均未发现任何横向或纵向的裂纹，且无任何变形现象，氧化锡电极均能正常工作。对比例DS1和DS2涂层在烤窑第二阶段升至1000℃时，由于涂层结合性能较差，率先出现熔解脱落 现象；在第三阶段快速升温期，窑内温度达到1300℃时，涂层已全部脱落，失去保护作用。涂层脱落后的电极上出现裂纹甚至炸裂、电极变形等现象，导致电极无法工作正常。本发明提供的涂层组合物不仅保证了在快速升温阶段下电极缓慢升温不受损伤，同时又实现了升温完成后涂层的快速脱落。It can be seen from Table 4 that the tin oxide electrode coating with the S1-S7 coating provided by the present invention can be quickly detached, and no transverse or longitudinal cracks are found on the tin oxide electrode after the coating is detached, and there is no deformation phenomenon. The tin oxide electrodes can work normally. When the coatings of DS1 and DS2 were raised to 1000 °C in the second stage of the kiln, due to the poor bonding performance of the coating, the melting and shedding phenomenon occurred first. In the third stage of rapid heating, the temperature in the kiln reached 1300 °C. The layers have all fallen off and lost their protection. Cracks and even cracks, electrode deformation, etc. appear on the electrode after the coating is detached, resulting in the electrode not working properly. The coating composition provided by the invention not only ensures that the electrode is slowly warmed up without damage during the rapid temperature rising phase, but also achieves rapid shedding of the coating after the temperature rise is completed.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solutions of the present invention within the scope of the technical idea of the present invention. These simple variants All fall within the scope of protection of the present invention.
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。It should be further noted that the specific technical features described in the above specific embodiments may be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention has various possibilities. The combination method will not be described separately.
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。In addition, any combination of various embodiments of the invention may be made as long as it does not deviate from the idea of the invention, and it should be regarded as the disclosure of the invention.

Claims (10)

  1. 一种涂层组合物，其特征在于，所述涂层组合物含有矿物粉、玻璃粉和粘接剂，其中，所述矿物粉含有SiO 2、Al 2O 3、R 2O和Fe 2O 3，且以所述矿物粉的总重量为基准，所述SiO 2的含量为60-75重量％，所述Al 2O 3的含量为25-40重量％，所述R 2O的含量为0.5-2.5重量％，所述Fe 2O 3的含量为0.5-3.5重量％，R为碱金属。 A coating composition, characterized in that the coating composition contains mineral powder, glass powder and a binder, wherein the mineral powder contains SiO 2 , Al 2 O 3 , R 2 O and Fe 2 O 3 , and based on the total weight of the mineral powder, the content of the SiO 2 is 60-75 wt%, the content of the Al 2 O 3 is 25-40 wt%, and the content of the R 2 O is 0.5 to 2.5% by weight, the content of the Fe 2 O 3 is 0.5 to 3.5% by weight, and R is an alkali metal.
  2. 根据权利要求1所述的涂层组合物，其特征在于，以所述矿物粉的总重量为基准，所述SiO 2的含量为62.5-66重量％，所述Al 2O 3的含量为32-34重量％，所述R 2O的含量为1-1.5重量％，所述Fe 2O 3的含量为1-2重量％； The coating composition according to claim 1, wherein the content of the SiO 2 is from 62.5 to 66% by weight based on the total weight of the mineral powder, and the content of the Al 2 O 3 is 32. -34% by weight, the content of R 2 O is 1-1.5% by weight, and the content of Fe 2 O 3 is 1-2% by weight;
    优选地，R为钠或钾。Preferably, R is sodium or potassium.
  3. 根据权利要求1所述的涂层组合物，其特征在于，相对于100重量份的所述矿物粉，所述玻璃粉的含量为40-65重量份；The coating composition according to claim 1, wherein the glass frit is contained in an amount of 40 to 65 parts by weight with respect to 100 parts by weight of the mineral powder;
    优选地，相对于100重量份的所述矿物粉，所述玻璃粉的含量为50-60重量份。Preferably, the glass frit is contained in an amount of 50 to 60 parts by weight with respect to 100 parts by weight of the mineral powder.
  4. 根据权利要求1-3中的任意一项所述的涂层组合物，其特征在于，所述粘接剂的用量使得均匀混合后的涂层组合物的粘度为8000-12000泊；The coating composition according to any one of claims 1 to 3, wherein the binder is used in an amount such that the viscosity of the uniformly mixed coating composition is from 8,000 to 12,000 poise;
    优选地，所述粘接剂的用量使得均匀混合后的涂层组合物的粘度为10000-11000泊。Preferably, the binder is used in an amount such that the viscosity of the uniformly mixed coating composition is from 10,000 to 11,000 poise.
  5. 根据权利要求1-3中的任意一项所述的涂层组合物，其特征在于，所述玻璃粉的粒度为0.3mm以下；The coating composition according to any one of claims 1 to 3, wherein the glass frit has a particle size of 0.3 mm or less;
    优选地，所述玻璃粉的粒度为0.2-0.3mm。Preferably, the glass frit has a particle size of 0.2 to 0.3 mm.
  6. 根据权利要求1-3中的任意一项所述的涂层组合物，其特征在于，所述粘接剂为硅酸盐和/或偏硅酸盐；The coating composition according to any one of claims 1 to 3, wherein the binder is a silicate and/or a metasilicate;
    优选地，所述粘接剂为偏硅酸盐；Preferably, the binder is a metasilicate;
    优选地，所述偏硅酸盐为偏硅酸钠。Preferably, the metasilicate is sodium metasilicate.
  7. 根据权利要求1-3中的任意一项所述的涂层组合物，其特征在于，该涂层组合物还含有添加剂；The coating composition according to any one of claims 1 to 3, wherein the coating composition further contains an additive;
    优选地，所述添加剂为氧化硼和/或氧化锡；Preferably, the additive is boron oxide and/or tin oxide;
    优选地，相对于100重量份的所述矿物粉，所述添加剂的用量为1-2重量份。Preferably, the additive is used in an amount of from 1 to 2 parts by weight relative to 100 parts by weight of the mineral powder.
  8. 根据权利要求1-3中的任意一项所述的涂层组合物，其特征在于，所述组合物的pH为5-8；The coating composition according to any one of claims 1 to 3, wherein the composition has a pH of 5-8;
    优选地，所述组合物的pH为6-7。Preferably, the composition has a pH of from 6 to 7.
  9. 一种氧化锡电极涂层，其特征在于，其由权利要求1-8所述的涂层组合物涂覆成型而成。A tin oxide electrode coating characterized by being coated and formed from the coating composition of claims 1-8.
  10. 一种氧化锡电极的保护方法，其特征在于，该方法包括：A method for protecting a tin oxide electrode, the method comprising:
    1)将权利要求1-8中的任意一项所述的涂层组合物涂覆于氧化锡电极表面，形成保护涂层的步骤；1) a step of applying the coating composition according to any one of claims 1 to 8 to a surface of a tin oxide electrode to form a protective coating layer;
    2)当所述氧化锡电极升至工作温度后，使所述保护涂层熔解的步骤。2) a step of melting the protective coating after the tin oxide electrode is raised to the operating temperature.
PCT/CN2018/084999 2017-06-12 2018-04-28 Coating composition, tin oxide electrode coating, and tin oxide electrode protection method WO2018228070A1 (en)

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CN107189502B (en) * 2017-06-12 2019-04-30 东旭科技集团有限公司 The guard method of coating composition, tin oxide electrode coating and tin oxide electrode
CN110963671A (en) * 2019-12-06 2020-04-07 彩虹集团有限公司 Method for protecting electrodes of advanced glass kiln in thermal state
CN114751625A (en) * 2022-04-27 2022-07-15 陕西彩虹工业智能科技有限公司 Preparation of high-temperature-resistant electrode heating brick and glass processing method in glass kiln

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