WO2015146260A1 - 均一膜厚かつ矩形断面を有するパターン膜形成方法、形成装置 - Google Patents

均一膜厚かつ矩形断面を有するパターン膜形成方法、形成装置 Download PDF

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Publication number
WO2015146260A1
WO2015146260A1 PCT/JP2015/051780 JP2015051780W WO2015146260A1 WO 2015146260 A1 WO2015146260 A1 WO 2015146260A1 JP 2015051780 W JP2015051780 W JP 2015051780W WO 2015146260 A1 WO2015146260 A1 WO 2015146260A1
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Prior art keywords
ink
film
pattern
blanket
ink film
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PCT/JP2015/051780
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English (en)
French (fr)
Japanese (ja)
Inventor
靖之 日下
洋史 牛島
真理子 藤田
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独立行政法人産業技術総合研究所
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Priority to JP2016510084A priority Critical patent/JP6655844B2/ja
Publication of WO2015146260A1 publication Critical patent/WO2015146260A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00—Inking and printing with a printer's forme
    • B41M1/02—Letterpress printing, e.g. book printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41F—PRINTING MACHINES OR PRESSES
    • B41F17/00—Printing apparatus or machines of special types or for particular purposes, not otherwise provided for
    • B41F17/001—Pad printing apparatus or machines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41F—PRINTING MACHINES OR PRESSES
    • B41F17/00—Printing apparatus or machines of special types or for particular purposes, not otherwise provided for
    • B41F17/24—Printing apparatus or machines of special types or for particular purposes, not otherwise provided for for printing on flat surfaces of polyhedral articles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • H05K3/1275—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by other printing techniques, e.g. letterpress printing, intaglio printing, lithographic printing, offset printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00—Inking and printing with a printer's forme
    • B41M1/02—Letterpress printing, e.g. book printing
    • B41M1/04—Flexographic printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N10/00—Blankets or like coverings; Coverings for wipers for intaglio printing
    • B41N10/02—Blanket structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
    • B41N7/00—Shells for rollers of printing machines
    • B41N7/06—Shells for rollers of printing machines for inking rollers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/01—Tools for processing; Objects used during processing
    • H05K2203/0104—Tools for processing; Objects used during processing for patterning or coating
    • H05K2203/0134—Drum, e.g. rotary drum or dispenser with a plurality of openings

Definitions

  • the present invention relates to a method for producing a pattern film by printing, and in particular, a method for forming a pattern film having a substantially uniform film thickness regardless of the dimension of the pattern width, a smooth surface, and a rectangular cross-sectional shape. Relates to the device.
  • Typical examples of functional inks include fine particle dispersion ink made of conductive metal, organic semiconductor ink, oxide semiconductor sol-gel ink, insulating polymer ink, and the like. Form the device.
  • Examples of bottom-gate / bottom-contact thin film transistors include (a) gate electrode formation by patterning of conductive ink, (b) gate insulating film formation by coating or patterning, and (c) source and drain by patterning of conductive ink. It can be formed by printing in the order of electrode formation and (d) patterning of the organic semiconductor layer.
  • the surface and the cross-sectional shape of the ink layer pattern film are important. Further, when using a conductive pattern film, it is known that the high-frequency characteristics are affected by the cross-sectional shape, and the cross-section of the conductive film is preferably rectangular.
  • the ink solvent contained in the subsequent layer is in contact with the lower layer, so that the components constituting the lower layer are affected or dissolved, and the desired characteristics cannot be obtained.
  • the ink solvent contained in the subsequent layer is in contact with the lower layer, so that the components constituting the lower layer are affected or dissolved, and the desired characteristics cannot be obtained.
  • Typical printing methods known so far include screen printing, screen offset printing, inkjet printing, letterpress printing, gravure printing, gravure offset printing, flexographic offset printing, reverse transfer printing (or reverse offset printing), microcontact Printing.
  • These printing technologies include a method for completing printing by transferring ink in a highly fluid state to a transfer target (printed target), and after the ink film has become semi-dry by increasing the elasticity and viscosity of the ink film. It can be roughly divided into a method of performing printing and completing printing.
  • the former method for transferring fluid ink includes screen printing, ink jet printing, letterpress printing, and gravure printing.
  • the latter method of transferring an ink film in a semi-dry state includes gravure offset printing, flexographic offset printing, reverse transfer printing, and microcontact printing.
  • screen printing and gravure printing can obtain an almost constant film thickness pattern regardless of the pattern size, but screen printing gives an impression of undesirable surface shapes such as mesh marks and spikes.
  • a pattern having a kamaboko-like or bowl-shaped cross-sectional shape is formed.
  • the film thickness can be adjusted depending on the discharge amount, but the pattern size also changes at the same time, and the cross-sectional shape of the pattern becomes a semi-cylindrical or bowl shape due to the action of surface tension.
  • letterpress printing an ink having fluidity is usually inked into the letterpress using an anilox roll, so that the film thickness also changes depending on the pattern size, and the cross-sectional shape becomes a kamaboko or bowl shape.
  • none of the methods can obtain a pattern having a constant film thickness and a rectangular cross section regardless of the pattern size. In both cases, the viscoelasticity of the ink is adjusted by using a blanket.
  • in gravure offset printing and flexographic offset printing first, ink is applied to an intaglio or letterpress, and only a necessary pattern portion is transferred to a blanket.
  • the ink at the time of transfer to the blanket has fluidity
  • the ink film pattern to be printed becomes kamaboko-like or bowl-like due to surface tension.
  • the film thickness of the pattern to be formed becomes non-uniform depending on the pattern size.
  • the microcontact printing method is characterized in that the relief printing plate itself is made of a silicone resin having a solvent absorbability. Therefore, the transfer film is transferred after being in a semi-dry state.
  • the resulting ink film surface has a curved surface, and the film thickness changes depending on the pattern size.
  • the reverse transfer printing method is a method in which ink is first applied to a blanket, an unnecessary portion is removed by bringing the relief plate and the blanket into contact after being in a semi-dry state, and then a pattern remaining on the blanket is printed.
  • the reverse transfer printing method is a method in which the ink film has a uniform film thickness and is removed after the semi-dried state, so that a rectangular cross-sectional pattern can be obtained with a uniform film thickness regardless of the pattern size. Is the only way.
  • letterpress printing a method of inking in a semi-dry state by pressing the letterpress on an endless belt made of stainless steel or the like coated with an ink film has also been proposed (see Patent Document 2).
  • a rectangular cross-sectional pattern can be obtained with a uniform film thickness regardless of the pattern size, but it is necessary to clean both a blanket and a relief plate called a printing plate. Further, since the blanket and the substrate to be printed are in direct contact with each other during printing, the blanket is deformed by the printing pressure, and the transferred pattern is also deformed, so that a desired pattern dimension may not be obtained. Furthermore, in the process of removing the unnecessary part of the ink film from the blanket by the punching plate, if the transfer of the ink film to the punching plate is incomplete, the unnecessary part will be transferred to the printing medium, causing the defect It becomes. In particular, when conductive ink is used, such a defective transfer portion can cause migration.
  • the reverse transfer printing method is a method in which unnecessary portions are transferred to a printing plate, the amount of ink necessary for uniform application over the entire blanket for each printing, regardless of the area of the pattern area. Consume. In particular, when the area of the required pattern region is small with respect to the surface area of the blanket, the ink use efficiency is deteriorated.
  • letterpress printing in the method of inking in a semi-dry state by pressing the letterpress to an endless belt having an engraving on the surface made of stainless steel or the like coated with an ink film, the same surface as a normal anilox roll Since the ink is held and inked using an endless belt having a sculpture on the surface, it is impossible to avoid the occurrence of unevenness on the surface of the print pattern.
  • the present invention has been made in view of the above problems, and can obtain a rectangular cross-sectional shape equivalent to reverse transfer printing, can achieve higher ink use efficiency than the reverse transfer printing method, and can be used for pattern-unnecessary portions. It is an object of the present invention to provide a pattern film forming technique that can simultaneously achieve that ink transfer that is not performed can be avoided and that a pattern film having a substantially constant film thickness can be formed regardless of the pattern size.
  • Topographic printing has not received much attention in the printing electronics technology because it is difficult to form a uniform and smooth ink film, but the present inventor is able to increase the efficiency of ink use and provide a pattern.
  • Paying attention to letterpress printing that hardly causes unintended ink transfer to unnecessary parts we have conducted tests and research on the formation of uniform and smooth ink films.
  • the present inventor does not use an anix roll having a surface engraving or an endless belt having an engraving on the surface in intaglio printing.
  • a blanket made of solvent-absorbing silicone rubber and having a smooth surface for inking into the convex part of the relief plate it is possible to form a pattern film having a substantially constant film thickness and a rectangular cross section regardless of the pattern size.
  • ⁇ 1> (a) A step of forming an ink film by applying ink to a blanket made of a solvent-absorbing silicone rubber and having a smooth surface; (A) a step of transferring the ink film to the convex portions of the relief plate by pressing the relief plate against the ink film formed on the smooth surface of the blanket; (C) a step of transferring the ink film onto the surface of the transfer object by pressing the ink film transferred onto the surface of the convex portion of the relief plate against the transfer object; A pattern film forming method comprising: ⁇ 2>
  • the ink solvent comprises a quick-drying solvent and a slow-drying solvent, and in the step (a), all or most of the quick-drying solvent contained in the ink film applied to the blanket is evaporated to the blanket.
  • the pattern film forming method according to ⁇ 1> wherein the ink film having a uniform film thickness in a semi-dried state is formed by being absorbed by absorption of water.
  • the method according to ⁇ 1> or ⁇ 2> including a step of causing a relief printing plate having an ink film to exist in a vapor atmosphere of a quick-drying solvent between the steps (a) and (c).
  • a blanket made of a solvent-absorbing silicone rubber and having a smooth surface at least partially; an ink film forming means for forming an ink film on the smooth surface of the blanket; and a relief plate having convex portions of a predetermined pattern
  • the convex film surface of the relief printing plate is pressed against the semi-dried ink film so that the ink film is transferred and the ink film transferred to the convex film surface.
  • a pattern film forming apparatus configured such that the ink film is transferred onto the surface of the transfer object by being pressed against the transfer object.
  • the present invention can include the following aspects.
  • ⁇ 6> The method for forming a patterned film according to any one of ⁇ 1> to ⁇ 4>, wherein the smooth surface of the blanket has a surface roughness Ra of 50 nm or less.
  • ⁇ 7> The patterned film according to any one of ⁇ 1> to ⁇ 4>, ⁇ 6>, wherein the silicone rubber is made of polydimethylsiloxane and has a hardness of 0.5 to 50 MPa. Forming method.
  • the quick-drying solvent is one or more selected from ethanol, methanol, 1-propanol, pentane, hexane, cyclohexane, toluene, xylene, and the slow-drying solvent is water, dimethyl sulfoxide, N— ⁇ 1>- ⁇ 4>, ⁇ 6>, ⁇ 7>
  • the pattern film forming apparatus further comprising a chamber that is a vapor atmosphere of a quick-drying solvent and that has a relief plate having a transferred ink film.
  • the patterned film forming apparatus according to ⁇ 5> or ⁇ 9>, wherein the smooth surface of the blanket has a surface roughness Ra of 50 nm or less.
  • the silicone rubber is made of polydimethylsiloxane and has a hardness of 0.5 to 50 MPa.
  • the ink film forming means is any one selected from a slit type coater (including a cap coater, a gap coater, a curtain coater, etc.), a spray type coater, and an ink jet coater.
  • a slit type coater including a cap coater, a gap coater, a curtain coater, etc.
  • spray type coater including a spray type coater, and an ink jet coater.
  • the yield can be increased because the transfer of the ink film to an unnecessary portion can be avoided. Since the inking from the blanket can be performed a plurality of times, the use efficiency of the ink is high, and the ink film formation cost and the manufacturing cost of the ink film-equipped device can be reduced. Since printing is performed with a letterpress plate that is harder than the blanket, deformation of the pattern can be suppressed. For example, a resist mask with high dimensional accuracy can be obtained by using the resist ink for patterning. Regardless of the pattern size, the cross-section of the pattern film can be made a rectangular shape having a cross-sectional rectangularity s of 0.90 or more, which will be described later. For example, the high-frequency characteristics can be improved by using it for patterning of conductive ink. .
  • the ink film other than the part in contact with the relief printing plate remains on the blanket, by pressing the relief printing plate so as to contact only the ink film remaining on the blanket, inking is performed once. Multiple inking is possible. For this reason, the use efficiency of ink can be appropriately raised according to the pattern shape.
  • the pattern since only the necessary part on the blanket is transferred to the convex part of the relief plate, the pattern is not required due to a process defect when removing the unnecessary part on the blanket by contact with the relief plate, as in the reverse transfer printing method. Unintended ink transfer to the part cannot occur.
  • the ink film that is semi-dried and suppressed in fluidity is printed by being inked on the convex portions of the relief printing plate, so that the adverse effect of the solvent contained in the printed ink film on the lower layer is minimized. Can be suppressed.
  • FIG. 1 The conceptual diagram which shows each process of the pattern film formation method by the Example of this invention.
  • A is a step of forming an ink film (3) on the surface of the blanket (2)
  • (b) is a step of transferring the ink film (3) on the surface of the blanket (2) to the surface of the convex portion of the relief printing plate (4).
  • C shows the step of transferring the ink film (3) on the surface of the relief plate (4) to the transferred object (5)
  • (d) shows the transferred object to which the ink film (3) has been transferred.
  • the product (5) and the letterpress (4) after the transfer are shown.
  • FIG. 1 The figure which shows the film thickness profile of the pattern film formed by Example 1 of this invention, and the comparative example 1.
  • the left figure shows Example 1 of the present invention, and the right figure shows Comparative Example 1.
  • (20) and (30) show a film thickness profile of a pattern with a width of 0.5 mm
  • (21) and (31) show a film thickness profile of a pattern with a width of 1.0 mm.
  • the figure which shows the film thickness profile (The pattern width is 1, 2, 4, 8 micrometers respectively) of the pattern film formed by Example 2 of this invention.
  • the figure which shows the film thickness profile (The pattern width is 1, 2, 4, 8 micrometers respectively) of the pattern film formed by Example 3 of this invention.
  • the figure which shows the film thickness profile (The pattern width is 1, 2, 4, 8 micrometers respectively) of the pattern film formed by the comparative example 2.
  • the present invention will be described in detail below.
  • the present invention is carried out using a letterpress, a blanket, an ink, and a transferred material (hereinafter also referred to as “printed material”).
  • the relief plate As the relief plate, a known one can be used regardless of whether it is made of resin or metal, and one having excellent acceptance from a blanket and transferability to a printing medium is preferred.
  • the relief printing material has a higher elastic modulus than that of the blanket, and it is desirable to form a pattern with high resolution and high accuracy when the ink film is received from the blanket so that it is not easily deformed. Further, as a material for the relief printing plate, it is desirable not to swell due to the residual solvent contained in the ink film transferred from the blanket in order to form a pattern with high resolution and high accuracy. In the step of bringing the blanket and the relief plate into contact with each other, a level difference of the uneven portion is necessary so that the concave portion of the relief plate does not contact the blanket due to deformation of the blanket or the relief plate itself.
  • the printed material is a material having a relatively high surface free energy and high surface smoothness.
  • Examples thereof include glass, silicon compounds such as silicon, solid metal, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, and polyimide. . These printing materials can be used more preferably than low surface free energy materials such as polytetrafluoroethylene.
  • a composition for reverse transfer printing is suitably used (see, for example, Patent Document 3). That is, it contains a surfactant as a surface energy adjusting agent, contains a fast-drying solvent and a slow-drying solvent, and further contains a solid content that expresses the functionality of the ink film.
  • the solid content expressing the functionality of the ink film is not particularly limited, and fine particles made of a conductive metal, an organic semiconductor, an oxide semiconductor, an insulating polymer, and the like can be used. More preferably, the ink is for forming a conductive pattern film.
  • the solvent loss rate v on the silicone rubber blanket is represented by the sum of the vapor pressure of the solvent and the evaporation rate ve defined by the surrounding environment and the absorption rate vu into the blanket.
  • the evaporation rate ve of the solvent used in the ink can be calculated from the change in weight ⁇ m over a predetermined time ⁇ t under a predetermined ambient environment, for example, by introducing the solvent having a density ⁇ into a petri dish having a surface area Aa.
  • the loss rate v of the quick-drying solvent per unit area of the blanket is It is h / t or more and that of the slow-drying solvent is less than h / t, and the solvent may be appropriately selected for the desired h and t.
  • the quick-drying solvent and the slow-drying solvent The loss rate v is 1 ⁇ m / min or more and less than that, respectively.
  • the loss rate of the slow drying solvent is preferably less than 0.1 ⁇ m / min.
  • Examples of the fast-drying organic solvent in this example include ethanol, methanol, 1-propanol, pentane, hexane, cyclohexane, toluene, xylene and the like, and examples of the slow-drying solvent include water, dimethyl sulfoxide, N-methylpyrrolidone, propylene oxide. Etc.
  • solvents such as propylene glycol monomethyl ether acetate, propylene glycol normal propyl ether, propylene glycol normal butyl ether, and 3-methoxy-3-methyl-butyl acetate have a high boiling point and a small ve, but have a high absorption rate vu to the blanket.
  • the method according to the present invention generally has the following advantages.
  • the surface free energy of stainless steel varies greatly depending on the degree of surface contamination, it is generally relatively high at 50 mJ / m 2 , so that the ink film is sufficiently dried and then transferred from the stainless belt to the ink film on the relief printing plate. This is often difficult and causes pattern defects.
  • the method according to the present invention does not require a special drying device such as wind, heat, and vacuum exhaust, and realizes a semi-dry state of the ink by utilizing the solvent absorption ability of silicone rubber.
  • the semi-dried state can be precisely controlled, and the time margin capable of transferring the ink film to the relief printing plate can be set in a wide range by selecting an appropriate solvent.
  • the offset material having no engraving on the surface is used in the method according to the present invention, printing of an ink film having good surface flatness can be realized as described below.
  • the present inventor has found that the silicone rubber surface that has absorbed the organic solvent has a lower adhesiveness or peeling force than the surface before the solvent absorption. It uses a transfer mechanism that is fundamentally different from such printing technology. Therefore, in selecting a material, the surface free energy of the relief printing plate need not necessarily be high with respect to the blanket.
  • the adhesiveness between the relief printing plate and the ink film interface is What is necessary is just to be larger than the adhesiveness between interfaces.
  • the adhesiveness between the relief plate and the ink film interface and the adhesion between the blanket and the ink film interface can also be adjusted by surface treatment (for example, VUV (vacuum ultraviolet) treatment) on the relief plate and / or the blanket. it can.
  • the ink film thickness in the method according to the present invention is required to be approximately 1 ⁇ m or less, although it is affected by the ink viscoelastic modulus in the semi-dry state. This is because the ink film needs to be broken in the process of receiving the necessary portion of the ink film by the relief printing plate. This is because the greater the strain at the break point of the ink film in the semi-dry state (that is, the higher the film-forming property), the more difficult it is to accept the ink only on the convex portion. It is necessary to reduce the ink film thickness or increase the pressure on the relief printing plate.
  • the strain at the time when the fracture occurs is desirably 30% or less. If the loss elastic modulus is larger than the storage elastic modulus of the ink film (for example, the loss tangent tan ⁇ is 0.5 or more), it may be difficult to maintain the shape of the pattern. is there.
  • the blanket material a solvent-absorbing silicone rubber is used, and a crosslinked product of polydimethylsiloxane is mainly used.
  • the methyl group of the crosslinked product of polydimethylsiloxane may be modified.
  • the hardness of the silicone rubber is preferably about 0.5 MPa to 50 MPa.
  • the surface of the blanket is formed flat in the case of a sheet-like blanket so as to form an ink film having a uniform thickness, and is formed on a cylindrical peripheral surface in the case of a roll-like blanket, and the surface roughness Ra is It is formed on a smooth surface of 50 nm or less (preferably 10 nm or less).
  • ink is applied onto the blanket using a known coating means such as a slit coater (including a cap coater, a gap coater, a curtain coater, etc.), a spray coater, and an ink jet coater.
  • a known coating means such as a slit coater (including a cap coater, a gap coater, a curtain coater, etc.), a spray coater, and an ink jet coater.
  • the ink film is transferred to the convex portions of the relief plate by pressing the relief plate against the ink film formed on the smooth surface of the blanket.
  • the relief plate is pressed against the ink film that is in a semi-dried state on the blanket, and the ink is received on the projections.
  • the relief plate and the blanket need only be in close contact with each other, and it is not necessary to make contact over a long time.
  • this method is a transfer method using the difference in surface free energy and adhesiveness, a particularly high printing pressure is not required, but in order to ensure that the blanket and the convex part are in close contact with each other, several kPa or more are required.
  • patterning is completed by transferring the ink film to the surface of the printing medium by pressing the relief plate receiving the ink film against the printing body. If the transferability is poor at this time, the transferability can be improved by hydrophilizing the substrate.
  • a fast-drying solvent or a slow-drying solvent contained in the ink for example, the one with a higher content in the ink
  • the adhesive force between the ink film and the relief printing plate can be reduced by allowing the solvent to exist in a vapor atmosphere of a solvent having a close chemical composition or by applying a stream of the vapor.
  • a process of transferring the ink film to the convex part of the relief plate by pressing the relief plate against the ink film formed on the smooth surface of the blanket, and the ink film transferred to the convex part surface of the relief plate against the transferred object a step (vapor annealing process) of causing the relief printing plate having the ink film to exist in the vapor atmosphere of the quick-drying solvent can be included between the step of transferring the ink film to the surface of the transfer object.
  • the annealing time is the vapor partial pressure of the solvent (for example, 0.2 atm or more, preferably 0.5 to 1.0 atm, more preferably 0.7 to 1.0 atm) and temperature (for example, room temperature or more, 100 ° C.
  • This vapor annealing process utilizes the principle based on the control of the semi-dry state of the ink as described above.
  • the blanket and letterpress may be in the form of a sheet or roll, so the patterning method may be a sheet format, a roll-to-sheet method, a roll-to-roll method, Also good.
  • a pigment ink (a nano silver ink manufactured by DIC Company) in which silver nanoparticles are dispersed in ethanol as a main solvent was used.
  • Silicone rubber (Shin-Etsu Chemical KE106 cured at room temperature) was used as a blanket material.
  • a resin letterpress (JemFlex DGX170) manufactured by JEOL Ltd. was used as the letterpress. The letterpress has 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1 mm wide line patterns.
  • the absorption rate vu of ethanol with respect to the silicone rubber used in this example was about 0.9 ⁇ m / min. Further, the evaporation rate ve of ethanol was about 10 ⁇ m / min.
  • Comparative Example 1 instead of a silicone rubber blanket, a smooth stainless steel blanket without surface engraving was used. After uniform application of nano silver ink on the blanket, a normal temperature dryer was used for 3 seconds instead of waiting for a certain period of time. The ink film on the glass surface was cured in the same manner as in Example 1 except that it was dried.
  • Example 1 of the present invention is shown in the left figure of FIG. 2, and Comparative Example 1 is shown in the right figure of FIG.
  • the left diagram of FIG. 2 shows that the present invention enables patterning of an ink film having a substantially constant film thickness regardless of the pattern size and a rectangular cross-sectional shape.
  • the film thickness varied greatly depending on the pattern size, and a good rectangular cross-sectional shape could not be obtained.
  • the width of the pattern is w
  • the maximum film thickness of the pattern is hmax
  • the cross-sectional area is a
  • the cross section rectangularity s takes a maximum value of 1 when it is completely square, and the rectangularity of the cross section decreases as the value of s decreases. For example, when the cross section is semicircular, s is ⁇ / 4 ⁇ 0. 785.
  • Table 1 shows the maximum film thickness hmax and the cross-sectional rectangularity s of the pattern formed for each line pattern width w with respect to Example 1 of the present invention. From Table 1, it can be seen that in the present invention, it is possible to form a pattern with a cross-sectional rectangularity s> 0.9. That is, the film thickness is almost constant regardless of the line pattern width (the difference in cross-sectional rectangularity of each pattern width with respect to the average cross-sectional rectangularity of all pattern widths is 15% or less, preferably 10% or less, more preferably 6% or less. ) Was obtained.
  • Example 1 although the maximum film thickness of the pattern changed by 70 nm at maximum with respect to the pattern width, this is within the coating film thickness accuracy applied by the coater used in Example 1, and the present invention. It is not deteriorated by the method. It can be improved as appropriate by using an appropriate coater system according to the accuracy required at the time of manufacture.
  • a pigment ink (a nano silver ink manufactured by DIC Company) in which silver nanoparticles are dispersed in ethanol as a main solvent was used.
  • Silicone rubbers A, B, and C which were prepared from three types of Shin-Etsu Chemical KE106, and silicone rubber B treated with VUV (vacuum ultraviolet) were used as the blanket material and letterpress material.
  • the surface free energies estimated by the Owens-Wendt method were 16.4, 12.7, 8.6, and 49.9 mJ / m 2 , respectively.
  • the absorption rate vu of ethanol with respect to the silicone rubber used in this example was about 0.9 ⁇ m / min.
  • the evaporation rate ve of ethanol was about 10 ⁇ m / min.
  • the relief plate used had a line pattern with a width of 1, 2, 4, and 8 ⁇ m.
  • irradiation was performed for 20 seconds under the condition of oxygen concentration of 0.1% or less using a VUV treatment apparatus (Oak Seisakusho VUS-3150).
  • the surface free energy estimated here is a value calculated using water, diiodomethane, or ethylene glycol as a probe liquid, and is shown as an index for relative evaluation of surface adhesion. The validity of the value is not considered here.
  • Example 2 when the silicone rubber B was used as the blanket material and the VUV-treated silicone rubber B was used as the relief printing material among the above materials, whether or not the ink film was accepted by the relief printing, and was accepted by the relief printing.
  • the relief printing plate was brought into contact with the glass plate to transfer the ink film to the glass of the printing medium, and printing was completed.
  • the glass substrate to which the ink pattern was transferred was heated and baked in an oven to cure the ink film.
  • the materials and printing conditions not described in Example 2 were formed in the same manner as in Example 1 to form an ink film on the glass surface.
  • Example 2 Except for using silicone rubber B and C as a blanket material and using silicone rubber A as a relief printing material, whether or not an ink film can be accepted by the relief printing plate, and the glass of the ink film accepted by the relief printing plate, as in Example 2. The possibility of accepting the substrate was examined. The results of Examples 2 and 3 are shown in Table 2. From Table 2, in all combinations of Examples 2 and 3, line patterns of 1, 2, 4, and 8 ⁇ m width could be printed.
  • the pattern film formation according to the present invention can be satisfactorily performed by performing the VUV treatment (Example 2), and the blanket and the letterpress have different compositions (different surface energies). ) It was found that the pattern film formation according to the present invention can be satisfactorily performed using the material (Example 3).
  • Comparative Example 2 a cross-sectional profile of the pattern when directly inked with a bar coater on a relief printing plate made of silicone rubber B and transferred to glass is shown in FIG. From FIG. 5, the film thickness greatly changed depending on the pattern size, and a good rectangular cross-sectional shape could not be obtained. In particular, it was found that the film thickness decreased as the pattern width became smaller, and good conduction performance was not ensured.
  • Example 3 for the ink film transferred from the blanket made of silicone rubber B to the relief printing plate made of silicone rubber A, the peel force at the interface between the silicone rubber A and the transfer ink film was peeled off at a rate of 100 mm / min, peel angle It was 6.9 N / m when measured at 45 degrees.
  • the relief printing plate having the ink film transferred by the above method was allowed to stand still for 20 seconds in a chamber saturated with ethanol vapor at 50 ° C. with respect to the atmosphere, the peeling force was measured by the same method as described above. 3.2 N / m. Moreover, it was confirmed that the transferability from the relief printing plate to the printing medium is improved by using this process.
  • a pattern film having a substantially uniform film thickness and a rectangular cross section can be obtained regardless of the pattern width. Therefore, it can be used for forming various pattern films such as electrode films, wiring films, insulating films, etc., and by forming such various films in order, it can also be used for manufacturing various devices. Can be used. By using a hydrophilic treatment such as ultraviolet irradiation, the same silicone rubber can be used for both blanket and letterpress materials, which facilitates material procurement and management.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Printing Methods (AREA)
  • Manufacturing Of Printed Wiring (AREA)
PCT/JP2015/051780 2014-03-28 2015-01-23 均一膜厚かつ矩形断面を有するパターン膜形成方法、形成装置 WO2015146260A1 (ja)

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JP2019188339A (ja) * 2018-04-25 2019-10-31 国立研究開発法人産業技術総合研究所 機能性パターン薄膜の形成方法

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JP2006351358A (ja) * 2005-06-16 2006-12-28 Toppan Printing Co Ltd ブランケット及び有機ｅｌ素子
JP2011074121A (ja) * 2009-09-29 2011-04-14 Dic Corp 微細パターン形成用インキ組成物
JP2012051305A (ja) * 2010-09-03 2012-03-15 Hitachi High-Technologies Corp 画像形成装置および画像形成方法
JP2013194123A (ja) * 2012-03-19 2013-09-30 Sony Corp オフセット印刷ブランケット用洗浄液およびオフセット印刷ブランケットの洗浄方法ならびに表示装置の製造方法および印刷物の製造方法。

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JP5168029B2 (ja) * 2008-08-25 2013-03-21 凸版印刷株式会社 印刷装置及び印刷物の製造方法
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JP2006351358A (ja) * 2005-06-16 2006-12-28 Toppan Printing Co Ltd ブランケット及び有機ｅｌ素子
JP2011074121A (ja) * 2009-09-29 2011-04-14 Dic Corp 微細パターン形成用インキ組成物
JP2012051305A (ja) * 2010-09-03 2012-03-15 Hitachi High-Technologies Corp 画像形成装置および画像形成方法
JP2013194123A (ja) * 2012-03-19 2013-09-30 Sony Corp オフセット印刷ブランケット用洗浄液およびオフセット印刷ブランケットの洗浄方法ならびに表示装置の製造方法および印刷物の製造方法。

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019188339A (ja) * 2018-04-25 2019-10-31 国立研究開発法人産業技術総合研究所 機能性パターン薄膜の形成方法
JP7028443B2 (ja) 2018-04-25 2022-03-02 国立研究開発法人産業技術総合研究所 機能性パターン薄膜の形成方法及びこれに用いる機能性インク

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