• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
      PRINTED FLEXIBLE TRANSPARENT CONDUCTIVE PLATE AND METHOD OF MANUFACTURING THE SAME.The present invention relates to a stamped flexible transparent conductor and a method of manufacturing it. The transparent conductive plate comprises a transparent transparent base, a transparent printing glue and a conductive film incorporated in the transparent printing glue. The surface of the printing glue is provided with the stamped and interconnected groove core. The total area outside the groove web is greater than 80 percent of the total surface of the transparent conductive plate. The groove depth is less than the thickness of the transparent printing glue. The conductive film is formed by the sintered conductive paint. The conductive paint is uniformly filled at the base of the interconnected grooves. The thickness of the conductive film is less than the depth of the groove. The transparent conductive plate is provided with the conductive core formed by the conductive film and a transmission area outside the groove core.
    公开号:BR112013020827A2
    申请号:R112013020827-9
    申请日:2011-11-15
    公开日:2020-09-01
    发明作者:Zheng Cui；Yulong Gao；Linsen Chen；Xiaohong Zhou
    申请人:Nanchang O-Film Tech. Co., Ltd.；
    IPC主号:
    专利说明:

    Patent Specification Report for "CHAPA b
    "PRINTED FLEXIBLE TRANSPARENT DRIVER AND METHOD OF MANUFACTURING THE SAME". 8 ~
    Field of the invention 5 The present invention relates to a manufacturing method for a transparent conductive plate, and more particularly it relates to a transparent conductive plate based on the printing technology or conducting with conductive ink and a manufacturing method this.
    Background of the invention 10 The transparent conductive sheet is a sheet having good electrical conductivity and high transmittance in visible light.
    Currently, r c: transparent conductive plates have been widely used in the fields
    - such as flat panel screens, photovoltaic devices, touch panels, and electromagnetic shielding, thus having a very large market space.
    With the rapid development of the device towards light and the thin transparent transparent conductive plate it became the focus of the study, due to these thin and light characteristics, etc.
    The flexible transparent conductive sheet can generally be divided into two types, that is, printed and unprinted type.
    In most practical applications, such as touch screens, the former generally requires exposure, imaging, stripping and cleaning processes to stamp the conductive transparent film before use.
    While the latter will undoubtedly be the main direction of the development of the transparent conductive sheet, because of the higher production efficiency and the omission of the stamping process which is complex and easily causes pollution to the environment.
    ITO dominated the market for transparent conductive sheet.
    The method for making an ITO stamped film mainly includes screen printing, inkjet printing method, and start-up processes in the semiconductor manufacturing process.
    However, due to the unlimited Indian mineral resources and low resistance in ITO bending, the transparent conductive plate stamped based on nanometal materials has become the ideal solution in the above history. «The manufacturing method for the transparent conductive sheet%
    u stamping based on nanometal materials is usually a method ». printing process including the following steps: the conductive ink is first prepared by the nanoparticle size metallic material, then an improved printing process is loaded to print the conductive ink on the flexible surface of the transparent substrate, finally, the conductive ink - log is sintered to form the desired conductive networks.
    The width of a network cable exceeds the resolution of the human eye, areas on the flexible surface outside the network cable are regions of light transmission.
    The square resistance of the surface and the transmittance of light are controllable within a given range by changing the width and geometry of the cable.
    bo.
    The printed transparent conductive flexible sheet with excellent performance was acquired using the printing method by the 15 Japanese companies Dai Nippon Printing, Fujifilm and Gunze, as well as the German company PolylC.
    Among them, the plate obtained by PoIylC has a resolution of 15µm, a square surface resistance of 0.4-1Q / sq, and a light transmittance that exceeds 80%. Regardless, the conductive net of the transparent conductive plate 20 manufactured by the printing method is a projecting structure exposed on a transparent substrate surface, thus it has insufficient resistance to cracking and anti-cracking capacity.
    In addition, the resolution of the graphics of this structure is limited by the printing technique and can be hardly high.
    In order to comply with the high definition order requirement, the resolution of the network graphics must be reduced.
    Finally, due to the limitation of the printing technique, the amount of conductive ink of the width of the fixed line is also difficult to increase, in other words, on the premise of the determined line width and conductive ink, it is difficult to increase the quantity conductive materials, and improve the conductivity of the sheet.
    Summary of the invention}
    To overcome the deficiencies of the prior art, the present
    WK Vention supplies a stamped flexible transparent conductive plate and a N
    And method to manufacture the flexible transparent conductive sheet, so that
    A to a conductive network is incorporated into the networks of a polymer layer.
    Y ro transparent, and anti-cracking resistance of the conductive plate is improved, and the volume of the conductive plate in the width of the fixed line is high, thus improving the conductivity of the conductive plate. In an objective of the present invention, a technical solution is provided as: A stamped flexible transparent conductive sheet, from bottom to top, includes: a flexible transparent substrate; a transparent printing glue integrally attached to the substrate; and a conductive material located on a transparent printing glue surface; wherein the surface of the transparent printing glue defines an inter-pit network. connected and for printing, a total area outside the pit network is more than 15 Õ ° / o of a plate area, a pit depth is less than a thickness of the transparent printing glue; the conductive material is a conductive paint before sintering and is a conductive film after sintering, the conductive film is also filled on a base of the pit network and interconnected, a thickness of the conductive film is less than the depth of the pit network; the plate comprises a conductive network formed by the conductive film and a light transmitting region located outside the pit network. Preferably, the interconnected pit network for printing is a combination of pit using a polygon pit as a basic unit, in which a shape of the basic unit is selected from the group consisting of square, rectangular, round, regular hexagonal, regular triangle, and a combination of these, and two adjacent basic units are communicated through a shared side, or two adjacent basic units are communicated through a single pit to form a discrete pit matrix. Preferably, a radial cross-section of any pit in the pit network is rectangular having the pit depth greater than
    L pit width, and pit width ranges from 50Onm to 10Oµm. and . . Preferably, the transparent printing glue is a structure of the peel selected from the group consisting of a thermo-polymer. : y "
    plastic, a thermosetting polymer, and a UV-curable polymer, and the light transmittance in visible light of this exceeds 90%. Preferably, a conductive film is at least selected from the group consisting of metal, carbon nanotubes, graphite paint, and conductive polymer material, which has a solid flexible shell structure in a normal state after sintering. - 10 In addition, in another objective of the present invention, a technical solution is provided as: 'A method for manufacturing the printed flexible transparent conductive sheet' includes the following steps: 1, designing and determining a structure. 'Three-dimensional conductive network according to demand, the conductive network 15 being prepared according to a pit network in a transparent printing glue of the plate, where a total area outside the pit network is greater than 80 % of an area of the plate, a depth of the pit is greater than a width of the pit; ll, manufacture a matrix having a microstructure complementary to the pit network using a
    20 chromatography combining lithography techniques with microelectroforming or diamond cutting; lll, form the pit network in the transparent printing glue using the matrix using a printing technology; and lV, fill a conductive paint in the pit network and sinter the conductive paint
    frog. Preferably, in step I, the design of the three-dimensional structure of the conductive network comprises: Cí) selecting raw materials to manufacture the transparent conductive plate, the raw materials comprising a flexible transparent substrate, a transparent printing glue, and a conductive material; ® coat the transparent print string with a
    30 fixed thickness on a surface of the substrate to form a transparent composite material, and determine a transmittance of light to that of the transparent composite material in the visible light; ® determine a geo-
    Metric R e 5/11 e Line width of the pit network on the premise of axb> t, where t
    G represents the transmittance of light from the desired conductive transparent plate to that of da, and b represents an index of light transmission area outside the pit network in the total area of the plate; and Ci) determine a pit depth h 5 according to a resistance and a solid content of the conductive paint combined with the depth of the pit obtained and a result of testing a square resistance of the transparent conductive plate surface. Preferably, the method of filling the conductive ink in step lV comprises cracking or aerosol printing. The present invention has the following characteristics and advantages: It is proposed that the conductive paint be filled in the pit and synthesized to form the conductive network of the transparent conductive plate. The basic idea is to fill a sufficient amount of conductive ink in the transparent printing glue pit, the conductive ink is then dried and sintered to form the transparent conductive plate. Because the specific volumetric index of the electrically conductive material is generally small, the thickness of the conductive material sheet is consequently less than the depth of the pit. Thus, the conductive mesh obtained by the method is incorporated in the transparent printing glue pit and is well protected, and the crack resistance and anti-cracking capacity is greatly improved. It is proposed to use the pit having a rectangular cross-section and a depth / width index being greater than 1: 1 to restrict the flow of conductive paint. Before sintering, a cross section of the conductive sheet obtained by the printing technique is formed as essentially hemispherical, as shown in FIG. la and FIG. 1b. At the same width as the line, its area is definitely smaller than that of a rectangular shape with "depth greater than width". Thus, this method can increase the volume of the conductive plate having a fixed line width, and thus the conductivity of the transparent conductive plate is improved to the maximum extent. This is the second innovation different from the conventional transparent conductive plate. Brief Description of Drawings @ d The FlG. la is a schematic cross-sectional view of a conductive paint prior to sintering; 5 to FlG. lb is a schematic cross-sectional view of a conductive paint filled in a pit before sintering; the FlG. 2 is a schematic plan view of a transparent conduit plate sintered by a pit network embodiment of the present invention; 10 FlG-3 is an isometric perspective view of a sintered transparent conductor plate shown in FlG. 2: FlG. 4 is a flow chart of a method for designing the network
    P of the pit; m to FlG. 5 is a schematic top view of a transparent conductive plate 15 sintered by another embodiment of the pit network of the present invention; Detailed Description Reference will now be made to the drawings to describe, in detail, modalities of the present invention - Mode One, a transparent conductive plate is manufactured by combining the pit using a regular hexagonal pit as a basic unit. In the illustrated modality, with reference to the FlG. 2 and FIG. 3, a stamped transparent conductive plate includes a transparent transparent substrate 11, a layer of transparent printing string 12 integrally attached to substrate 11, and a conductive tablet 13 equally filled in a base of the transparent printing glue pit. 12. The flexible transparent substrate 11 is a PET with a thickness of 1OOµm. Transparent printing glue 12 is solvent-free UV treatment acrylic resin with a thickness of 5 µm. The pit network defined on a transparent printing glue surface 12 forms a hexagonal matrix. The radius r of a hexagon circle
    , 7/11 hexagonal matrix equals 5µm, pit width d varies from 50Onm to 1Oµm,
    B 4 preferably 1µm, depth h is 2µm, an angle of the sidewall is "approximately 82". The sintered conductive film 13 is silver, which is also filled in the base of the transparent printing glue 12 and is interconnected. The silver foil is approximately 30Onm.The pit network filled with silver foil forms a conductive net, and the area outside the pit is the non-conductive light transmitting region, an index c of the total area outside the pit in the area The total of the transparent conductive plate is 82.6% The light transmittance of the transparent conductive plate in visible light is 72%, and the square resistance of the surface is 2Q / sq. With reference to FlG. 4, a The process for manufacturing the stamped flexible transparent conductive plate especially includes the following steps: I, a two-dimensional pattern of a conductive network, that is, the pit network is designed according to demand, and a desired pit depth is determined. As most at FlG. 3, the design process specifically includes: CD a PET with a light transmittance greater than 9Õ ° / o is selected, in this modality, the PET has the transmittance of light in visible light at = 90% and a thickness of 1OOµm; the transparent printable glue 12 is UV-free acrylic resin with a viscosity of 100cps; conductive ink is nano-silver conductive ink having a particle size ranging from 2 to 10 nm and with a solid content of approximately 41%, a viscosity of 53cps, a surface tension of 30dyn / cm; ® UV 12 printing glue with 25 µm thickness is coated on a PET 11 surface, and the transmittance of the light of the transparent composite substrate in visible light is determined to be a = 90%; @ according to the specifications of a design of a transmittance of the transparent conductive plate> 72 ° 6 (t represents an absolute transmittance) and axb> t, b> 80% is then obtained; a hexagonal pit network of the pit with good isotropic strength is selected, and on the premise of b, the pit width d = 1µm is determined in combination with the processing capacity of the die; © the solid content of the silver paint is approximately 32%, the sintering temperature is 140 ° C, the sintering time is 5 minutes, and the measured resistivity is': 2.5µC) "cm.
    The square resistance of the transparent conductive plate surface is required to be less than 10Q / sq.
    In the above conditions, when 5 the depth of the test pit h equals 2µm, the resulting square resistance of the surface is 8 Q / sq, which complies with the design requirement.
    II, use plate fixer with direct laser writing based on DMD, the pit network is defined in a photosensitive layer coated on a flat glass surface; a Ni film matrix is then manufactured having a complementary microstructure to the pit network using microelectroforming technology; the matrix is coated on a cylinder surface to form a cylinder matrix. lll, using roll-to-roll UV printing technique, the drawn pit network is formed on transparent printing glue 12 on a surface of PET 11. The treatment wavelength of transparent printing glue 12 is 365nm, when the cumulative irradiation energy reaches 360-50Omj / cm ', the glue is treated. lV, the conductive silver paint is filled in the pit network using the cracking process.
    Specifically, the process includes the following 20 steps: (1) the silver ink with a thickness of 5 µm is coated on the surface of the transparent printing glue 12; (2) the silver paint positioned outside the pit is cracked by a steel scraper; (3) the silver paint is sintered using an infrared-assisted hot air oven, and the conductive silver mesh is formed, where the sintering temperature is 140 "C, the sintering time is 5 minutes.
    Mode Two: transparent conductive sheets are manufactured by combining the pit with a square pit as a basic unit.
    In this modality, with reference to the FlG. 5, a stamped transparent conductor plate 30 includes a flexible transparent substrate 11, a layer of transparent printing glue 12 disposed on the substrate 11, and a conductive film 13 also filled in a base of the
    ~ 'P -.
    9/11 transparent printing glue 12. ¶ The transparent transparent substrate 11 is PC with a thickness of 50 µm. The transparent printing glue 12 is PMMA with a thickness of 6 µm. The pit network defined on a transparent glue surface 5 forms a square matrix. A lateral length of the square is 400 µm, the width of the pit d is 1Oµm, depth h is 11µm, an angle of the side wall is approximately 88 °. The sintered conductive film 13 is made of copper, which is also filled at the base of the transparent printing coil pit network and is interconnected. The thickness of the copper foil is approximately 1µm- The pit network filled with copper foil forms a conductive net, and areas outside the pit are non-conductive light-transmitting regions. An index c of a total area outside the pit in the total area of the transparent conductive plate is 95.5%. The light transmittance of the transparent conductive plate in visible light is 89%, 15 and the square resistance of the surface is 7Q / sq. With reference to FlG. 4, a process for making the stamped flexible transparent conductive plate specifically includes the following steps: I, a two-dimensional pattern of a conductive network, that is, the depth of the pit is designed according to demand, and a depth of the pit is determined. As shown in FIG. 3, the design process specifically includes: lj) a PC with a high light transmittance is selected and has a light transmittance at = 91% visible light and a thickness of 50 µm; the transparent printing band 12 is PMMA with a viscosity of 400Ocps; conductive ink is conductive nanocopper ink having a particle size ranging from 2 to 10 nm and with a solid content of approximately 40 ° 6, a viscosity of 8-18cps, a surface tension of 17-21mN / m; ® PMMA with a thickness of 15µm is coated on the surface of PET 11, and a light transmittance of the transparent composite substrate 30 in visible light is determined to be a = 91%; C3 according to specifications of a drawing of a transparent conductivity of the conductive plate> 85% (t represents absolute transmittance) and axb> t,
    b> 93% is thus obtained; a network of the square resistance matrix pit is selected, and on the premise of b, the pit width d = 10µm is determined in combination with aerosol printing capabilities; (Á) o 3
    The solid content of the copper paint is approximately 40%, the resistivity is 5- 5 7 ° C) ° cm. The square resistance of the transparent conductive plate surface is required to be less than 10Q / sq. In the above conditions, when the depth of the test pit h equals 11 µm, the square resistance of the resulting surface is 7 Q / sq, meeting the requirements of the drawing. ll, the drawn pit network is engraved on a 10 copper surface using a diamond cutting process, a Ni film matrix is then manufactured having a microstructure complementary to the pit network using microelectroforming technology; the matrix is coated on a cylinder surface to form a cylinder matrix. lll, using the roll-to-roll UV printing technique, the mesh network designed is formed on the PMMA 12 of a PET 11 surface. The PMMA printing temperature is 160 ° C. lV, the copper ink is filled into the pit network using aerosol printing technology. The copper paint is sintered using a pulse UV treatment system to form the conductive copper network. The pulse energy is 207 J / pulse, the frequency is 25 pulses / s, the time is 1 second. The detailed description above of the two modalities is intended to facilitate the understanding of the technical solution of the present invention, but not to limit the scope of the modality of the present invention. In the described conditions, the transmittance of the (uz of the transparent conductive plate can be freely controlled by changing the index of the width of the pit d in a radius r of the hexagon circumscribed circle; by changing the depth of the pit and the solid content of the silver paint. Conductive paint 30 may include another metallic paint, carbon nanotube paint, graphene paint, or paint of conductive polymer material, which has a film structure solid flexible in normal state after sintering.
    In addition, the said interconnected pit network and for printing
    W is a combination of the pit using a polygon pit as a base unit, in which a shape of the base unit is selected from the group consisting of square (Mode Two), rectangular, round, hexa- 5 regular gonal (Mode Three), regular triangle, and a combination of these, and two adjacent basic units are communicated through a shared side, or two adjacent basic units are communicated through a single pit to form a discrete pit matrix ( not shown).
    权利要求:
    Claims (8)
    [1]
    CLAIMS,, + "1. .Transparent flexible conductive sheet stamped, from bottom to top, the sheet comprising: * Y, 'a flexible transparent substrate; 5 an integral transparent printing glue attached to the substrate; et a conductive material located on a surface of the transparent printing glue; d where the surface of the transparent printing glue defines 10 an interconnected and stamped pit network, a total area outside the pit network is more than 80 ° / ô of an area of the plate, the depth of the pit 7 is less than the thickness of the transparent printing thread, the conductive material is a conductive ink before sintering and is a conductive film after sintering, the conductive film is also filled in 15 a base of the pit network and interconnected, a thickness of the conductive film is less than the depth of the pit network; the plate comprises a conductive network formed by the conductive film and a transmitting region of light located outside the pit network.
    [2]
    2. Stamped flexible transparent conductive sheet according to claim 1, wherein the interconnected and stamped pit network is a pit combination using a polygon pit as a basic unit, where a shape of the basic unit is selected from the group consisting of square, rectangular, round, regular hexagonal, regular triangle, and a combination of these, and two adjacent basic units are communicated through a shared side, or two adjacent basic units are communicated through a single pit to form a discrete pit matrix.
    [3]
    3. Printed transparent conductive flexible sheet, in accordance
    L with claim 1 ,. wherein a radial cross-section of any pit 30 of the pit network is rectangular having a pit depth greater than the pit width, and the pit width ranges from 50Onm to 10µm.
    [4]
    4. Transparent transparent conductive plate stamped in accordance
    "" 2/3 of claim 1, wherein the transparent printing glue is a structure of the peel selected from the group consisting of a thermoplastic polymer, a thermosetting polymer, and a UV-curable polymer. , and the transmittance of Iuz in its visible light exceeds 90%. 5
    [5]
    5. Stamped transparent flexible conductive sheet according to claim 1, wherein the conductive film is at least selected from the group consisting of metal, carbon nanotubes, graphene paint, and conductive polymer material, which has a structure of the solid flexible pellule in the normal state after sintering. 10
    [6]
    6. Method for manufacturing the stamped flexible transparent conductive plate, as defined in claim 1, comprising the following steps: I, designing and determining a three-dimensional structure of a conductive network according to demand, the conductive network being prepared according to a pit network in a transparent printing glue of the sheet, where the total area outside the pit network is greater than 8 ° / o of the sheet area, the pit depth is greater than the Fossa width; ll, manufacture a matrix having a microstructure complementary to the pit network using a micromachining process that combines techniques of Iitography with microelectroformation or diamond cutting; lll, form the pit network in the transparent printing coIy using printing technology; and lV, fill a conductive ink in the pit network and sinter the conductive ink.
    [7]
    7. Method according to claim 6, in which in step I, the design of the three-dimensional structure of the conductive network comprises: Ci) selecting raw materials to manufacture the transparent conductive plate, the raw materials comprising a transparent flexible substrate !, a transparent printing glue and a conductive material; ® coat the transparent printing glue with a thickness fixed on a substrate surface to form a transparent composite material, and determine a transmittance of light to that of the composite material. m transparent deposit in visible light; : - ® determine a geometric structure and | width of line d of. ~ pit network on the premise of axb> t, where t represents the transmittance of the light of the desired transparent conductive plate, and b represents an index of. light transmission area outside the pit network to the total plate area; and © determine a pit depth h according to a resistance and a solid content of the conductive paint combined with the depth of the pit obtained and a result of testing a square resistance 10 of the surface of the transparent conductive plate.
    [8]
    8. Method according to claim 6, wherein the method of filling the conductive ink in step lV comprises cracking or aerosol printing.
    L lt,. í! g.
    0 hl: 7
    EZ .—
    I 1/4 ¥ W 'a. !
    '> "> fi'" I L "'À" "d FI FIG la 12 13 t d <h'T ·' k & * ÍÈ S '- si"': 'h'! 8 "'': r * ^ y í. € /" d 'i,, r-f r "" 11, 0 FIG lb
    II
    I f
    .Z «èg g.
    ,;
    I '"7 i" @ 4 & N' "'' F" - lZjW '"
    I q FIG 2
    WÚ r "." Y. ¶% 7 "'¢ G, {IW' C" '· "' * i L ,, <-" rm: Xµ, 'e ,, "" r' ': "ú ,, K" Jm »mrmr' w .. F 'Mj w ·% - f' W i "" 3 W i -. ""% "·>".,. ..., "" 1 "ft 'i · - · ~ ·,." "·."% Rf "-.' B4%" "1 ¥ ',. - .- h .. = µ · m. '· J ·'; ¶ "" 'm2 "'% 7", .-, ar ·. 'T' * k R ': "V'." X. C f "'"' g 4 "'" 5 'KE + e · µ.. · Qw, J' + "m._ | i" = ';' · ±% ± Y "i y t" "". Íà "" '' "" G, {"'·. 1 1, "Fj L;> i'íÍ ~ -.4 ~ ~ 5 _---- <i, r '" ~~ j; fj ". ·'" '¶Tm ""' "~ ·:;" '"'" Tji: 7 "" "" -. - _ ~ _,, ~ 4. [: "W ') 4 C." · ¥ .._: u ~ _ i FIG 3
    R ^ "
    W 'a Select a flexible transparent substrate, a transparent printing coil and a conductive material Determine the light transmittance a of the material Draw the transparent composite t-value in the visible light of the transmittance. ~ wF ±> f "" "" Determine the task cycle b of the light transmission area outside the pit Determine the pattern e Solid content and resistance line width d of the conductive paint pit Pre-test of the different depth of the groove h No '"" Does the resistance value of the "' surface meet the requirements" ~ _ of the design k "'Yes L Determine the depth of the pit h FIG 4
    X k. . - - -.
    N rí 4/4
    Z
    W
    Z £
    1.0Lm t, à I 4®lim [iÊ - · fµ FlG "". S.a ^
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    法律状态:
    2020-09-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-10-20| B08F| Application dismissed because of non-payment of annual fees [chapter 8.6 patent gazette]|Free format text: REFERENTE A 8A ANUIDADE. |
    2021-01-05| B11B| Dismissal acc. art. 36, par 1 of ipl - no reply within 90 days to fullfil the necessary requirements|
    2021-11-23| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    优先权:
    申请号 | 申请日 | 专利标题
    CN201110058431XA|CN102222538B|2011-03-11|2011-03-11|Graphical flexible transparent conductive film and preparation method thereof|
    CN201110058431.X|2011-03-11|
    PCT/CN2011/001910|WO2012122690A1|2011-03-11|2011-11-15|Patterned flexible transparent conductive sheet and manufacturing method thereof|
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