WO2015199204A1 - パターン形成方法、透明導電膜付き基材、デバイス及び電子機器 - Google Patents
パターン形成方法、透明導電膜付き基材、デバイス及び電子機器 Download PDFInfo
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- WO2015199204A1 WO2015199204A1 PCT/JP2015/068429 JP2015068429W WO2015199204A1 WO 2015199204 A1 WO2015199204 A1 WO 2015199204A1 JP 2015068429 W JP2015068429 W JP 2015068429W WO 2015199204 A1 WO2015199204 A1 WO 2015199204A1
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- pattern
- line
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
Definitions
- the present invention relates to a pattern forming method, a substrate with a transparent conductive film, a device, and an electronic apparatus, and more specifically, a pattern forming method including a step of performing patterning by selectively depositing a functional material on the edge of a liquid by drying.
- the present invention relates to a substrate with a transparent conductive film, a device, and an electronic apparatus obtained by the method.
- a liquid repellent is applied to the entire surface of the substrate in advance, and a part of the liquid repellent is made hydrophilic by irradiating a laser to form a pattern composed of a liquid repellent part and a hydrophilic part.
- a method of forming fine lines by applying droplets to the hydrophilic portion by inkjet has a problem that the process becomes complicated because a liquid repellent is applied or patterning is performed with a laser.
- a method in which a functional material, which is a solid content in a droplet, is deposited on the periphery of the droplet using convection inside the droplet to form a pattern having a finer width than the droplet.
- Patent Document 1 a method in which a functional material, which is a solid content in a droplet, is deposited on the periphery of the droplet using convection inside the droplet to form a pattern having a finer width than the droplet.
- Patent Document 2 describes that a transparent conductive film is formed by forming a ring having a fine width of conductive fine particles and connecting a plurality of these rings using this method.
- the present applicant separates the conductive material in the liquid applied in a line shape into edges by the movement of the liquid to form a parallel line pattern consisting of a pair of fine lines, and further It has been proposed to form a transparent conductive film having a parallel line pattern (Patent Document 3).
- a transparent conductive film having a parallel line pattern is used as, for example, a transparent electrode for an image display device, even if the pattern itself is hardly visible and has excellent transparency, it is incorporated into the image display device. It was found that sometimes moire (interference fringes) may be visually recognized.
- moire can be prevented by preventing the parallel line pattern formation direction from being the same as the pattern formation direction (for example, pixel array pattern) of the image display device. .
- an object of the present invention is to provide a pattern forming method capable of improving the degree of freedom of the pattern forming direction with respect to the substrate without impairing productivity, and a substrate with a transparent conductive film obtained by the method, a device, and an electronic apparatus. It is in.
- a droplet made of a liquid containing a functional material is ejected from a plurality of nozzles of the droplet ejection device while moving the droplet ejection device relative to the substrate, the droplet ejection device is combined on the substrate.
- At least one set of droplets adjacent to each other as a target is arranged at an interval in both the relative movement direction and the direction orthogonal to the relative movement direction, so that these droplets are united, Adjusting one or both of the droplet volume and the spacing of the droplets;
- a pattern forming method of forming a pattern including the functional material by depositing the functional material on an edge of the linear liquid by drying the linear liquid formed by combining the droplets.
- a plurality of droplet groups applied from a plurality of nozzles to a pixel group arranged in parallel to the nozzle column of the droplet discharge device are set in a direction intersecting the nozzle column.
- the product V ⁇ R [pL ⁇ npi] is adjusted to a range of 4.32 ⁇ 10 4 [pL ⁇ npi] to 5.18 ⁇ 10 5 [pL ⁇ npi].
- the adjustment of the application intervals of the line-like liquids is performed by adjusting the time intervals for discharging the droplets from the nozzles, and 9.
- the maximum discharge time difference ⁇ t max of the liquid containing the functional material discharged from the nozzles adjacent to each other to form one linear liquid is set to 200 [ ms]
- the functional material is selectively deposited on the edge in the process of applying the first linear liquid on the substrate and drying the first linear liquid, and includes the functional material 2 Forming a first parallel line pattern constituted by a line segment;
- the second linear liquid is applied on the base material so as to intersect the first parallel line pattern formation region, and the functional material is applied in the process of drying the second linear liquid.
- the pattern forming method according to any one of 1 to 11, wherein a pattern is formed in which the first parallel line pattern and the second parallel line pattern intersect at at least one intersection.
- the difference between the surface energy in the formation region of the first parallel line pattern and the surface energy outside the formation region of the first parallel line pattern is 5 mN / m. 14.
- the contact angle of the second linear liquid in the first parallel line pattern formation region and the first parallel line pattern formation region outside the first parallel line pattern formation region 14.
- the contact angle of the solvent having the highest boiling point among the solvents in the second linear liquid outside the formation region of the first parallel line pattern is set to 6 ° or less. 14.
- the inside of the first parallel line pattern forming region is included. 14. The pattern forming method as described in 13 above, wherein the region is washed.
- 21 The pattern forming method as described in 20 above, wherein as the cleaning, cleaning using heating, cleaning with electromagnetic waves, cleaning with a solvent, cleaning with gas, and cleaning with plasma is performed.
- a substrate with a transparent conductive film comprising a transparent conductive film containing a pattern formed by the pattern forming method according to any one of 1 to 24 on a substrate surface.
- the device which has a base material with a transparent conductive film of said 25.
- a perspective cross-sectional view conceptually illustrating how a parallel line pattern is formed from a line-shaped liquid The top view explaining notionally an example (comparative example) of the method of forming a line-shaped liquid
- the top view which explains conceptually an example (comparative example) of the method of forming a mesh-shaped pattern
- the top view explaining notionally other examples (comparative example) of the method of forming a mesh-like pattern The top view explaining notionally the chamfering from the base material in which the pattern was formed by the method shown in FIG.
- the top view explaining notionally an example of the pattern formation method of this invention Plan view for conceptually explaining an example of a droplet discharge condition from a droplet discharge device
- Plan view for conceptually explaining still another example of the condition for ejecting droplets from the droplet ejection apparatus The enlarged view of the part shown by (xi) in FIG.
- FIG. 17 is a plan view conceptually illustrating the line-shaped liquid formed according to the embodiment of FIG.
- FIG. 1 is a perspective cross-sectional view conceptually illustrating how a parallel line pattern is formed from a line-shaped liquid, and the cross-section corresponds to a vertical section cut in a direction perpendicular to the line-shaped liquid formation direction. To do.
- 1 is a substrate
- 2 is a line-shaped liquid containing a functional material
- 3 is formed by selectively depositing a functional material on the edge of the line-shaped liquid 2.
- It is a coating film (hereinafter also referred to as a parallel line pattern).
- a linear liquid 2 containing a functional material is applied on a substrate 1.
- the functional material is selectively applied to the edge of the line-shaped liquid 2 by utilizing the coffee stain phenomenon. Deposit.
- the coffee stain phenomenon can be caused by setting conditions for drying the line-shaped liquid 2.
- the drying of the line-shaped liquid 2 arranged on the substrate 1 is faster at the edge compared to the central portion, and the solid content reaches a saturated concentration as the drying proceeds, and the solid content locally reaches the edge of the line-shaped liquid 2. Precipitation occurs.
- the edge of the line-shaped liquid 2 is fixed by the deposited solid content, and shrinkage in the width direction of the line-shaped liquid 2 due to subsequent drying is suppressed.
- the liquid of the line-like liquid 2 forms a convection from the central portion toward the edge so as to supplement the liquid lost by evaporation at the edge.
- a parallel line pattern 3 made of fine lines containing a functional material is formed on the substrate 1.
- the parallel line pattern 3 formed from one line-shaped liquid 2 is composed of a set of two line segments 31 and 32.
- the application of the line liquid on the substrate can be performed using a droplet discharge device. Specifically, a liquid containing a functional material is discharged from a nozzle of the droplet discharge device while moving the droplet discharge device relative to the substrate, and the discharged droplets are united on the substrate. Thus, a line-like liquid containing a functional material can be formed.
- the droplet discharge device can be constituted by, for example, an inkjet head provided in the inkjet recording device.
- FIG. 2 is a plan view conceptually illustrating an example (comparative example) of a method for forming a line-shaped liquid.
- reference numeral 7 denotes a droplet discharge device, which includes an inkjet head 71.
- Reference numerals 72a to 72f denote nozzles provided in the inkjet head 71.
- a liquid containing a functional material is continuously discharged from one nozzle 72 a of the inkjet head 71 while the droplet discharge device 7 is moved relative to the base material 1.
- the discharged liquid droplets coalesce on the substrate 1, whereby one line-shaped liquid 2 along the relative movement direction of the liquid droplet discharge device 7 can be formed.
- a plurality of line-shaped liquids 2 can be formed by operating the other nozzles 72b to 72f in the same manner.
- the parallel liquid pattern 3 can be formed from the line-shaped liquid 2 by drying the line-shaped liquid 2 thus formed as shown in FIG.
- the parallel line pattern 3 is formed along the relative movement direction of the droplet discharge device 7. That is, the line segments 31 and 32 constituting the parallel line pattern are formed along the relative movement direction of the droplet discharge device 7.
- a mesh pattern can be formed by intersecting parallel line patterns.
- FIG. 3 is a plan view conceptually illustrating an example (comparative example) of a method for forming a mesh pattern.
- the droplet discharge device (not shown in FIG. 3) is moved along the relative movement direction D with respect to the base material 1, and a plurality of first lines are formed in the direction D.
- a liquid 2 is formed.
- the relative movement direction D is along the direction along the one side of the rectangular substrate 1 (left and right direction in the drawing).
- the first parallel line pattern 3 can be formed from each first line-shaped liquid 2 as shown in FIG. 3 (b).
- the first parallel line pattern 3 is composed of line segments 31 and 32.
- the droplet discharge device is rotated by 90 ° with respect to the base material, and the relative movement direction D with respect to the base material 1 is rotated by 90 ° with respect to the direction in which the first linear liquid 2 is formed. In this way, the relative movement direction D is changed.
- the droplet discharge device is moved along the changed relative movement direction D to form a plurality of second line-shaped liquids 4 in the direction D.
- the relative movement direction D is along a direction along the other side orthogonal to the one side of the rectangular substrate 1 (up and down direction in the drawing).
- the second parallel line patterns 5 can be formed from the respective second line-shaped liquids 4 as shown in FIG. 3 (d).
- the second parallel line pattern 5 is composed of line segments 51 and 52.
- a mesh-like pattern 6 formed by intersecting the first parallel line pattern 3 and the second parallel line pattern 5 can be formed.
- the first parallel line pattern 3 is formed in a direction along one side of the rectangular base material 1
- the second parallel line pattern 5 is formed in a direction along another side orthogonal to the one side. ing.
- FIG. 4 is a plan view conceptually illustrating chamfering from a base material on which a pattern is formed by the method shown in FIG.
- the base material 1 on which the pattern 6 is formed is used by chamfering to a predetermined size suitable for a device in which the pattern 6 is incorporated.
- a cut line at the time of chamfering is indicated by a broken line C.
- the base material 1 is cut out and used along the side of the base material 1. In this case, it can be seen that four pieces of chamfering are possible.
- base material piece Even if the pattern 6 itself of the base material 1 cut out along the cut line C (hereinafter sometimes referred to as “base material piece”) cannot be visually recognized, the base material piece is used.
- base material piece When incorporated in the device, it was found that the formation direction of the pattern 6 of the base material piece and the formation direction of the pattern included in the device were easily overlapped, and moire was easily recognized.
- the “formation direction of the pattern 6” is a formation direction of line segments (for example, the above-described line segments 31, 32, 51, and 52) constituting the pattern, and may include a plurality of directions.
- the formation direction of the pattern 6 corresponds to the direction along the side of the base material piece.
- a lattice-like pattern such as a pixel array in an image display device can be preferably exemplified.
- the base material 1 is cut out along the direction inclined with respect to the side of the base material 1. That is, the cut line C is set along a direction that is inclined with respect to the side of the substrate 1.
- the inclination angle is set to 45 °.
- the pattern 6 is formed in a direction inclined from the direction along the side of the base material piece. Thereby, it is possible to prevent moiré when the base piece is incorporated in the device.
- the pattern forming method shown in FIG. 3 has a problem in terms of achieving both moire prevention and chamfering efficiency.
- the relative movement direction D of the droplet discharge device with respect to the substrate is changed between when the first line-shaped liquid is applied and when the second line-shaped liquid is applied. Need to change. For example, a process for changing the arrangement direction of the base material or the arrangement direction of the droplet discharge device is required, and a problem is found from the viewpoint of productivity.
- FIG. 5 is a plan view conceptually illustrating another example (comparative example) of a method of forming a mesh pattern.
- the relative movement direction D of the droplet discharge device (not shown in FIG. 5) is set to a direction inclined with respect to the side of the substrate 1 from the viewpoint of preventing moire.
- the droplet discharge device is moved along a relative movement direction D inclined at 45 ° with respect to the side of the substrate 1, and a plurality of first devices are moved in the direction D.
- a line-like liquid 2 is formed.
- the first parallel line pattern 3 can be formed from each first line-shaped liquid 2 as shown in FIG.
- the first parallel line pattern 3 is composed of line segments 31 and 32.
- the droplet discharge device is rotated by 90 ° with respect to the base material, and the relative movement direction D with respect to the base material 1 is rotated by 90 ° with respect to the direction in which the first linear liquid 2 is formed. In this way, the relative movement direction D is changed.
- the droplet discharge device is moved along the changed relative movement direction D that is inclined with respect to the side of the base material 1, and a plurality of second portions are moved in the direction D.
- a line-like liquid 4 is formed.
- the second parallel line patterns 5 can be formed from the respective second line-shaped liquids 4 as shown in FIG. 5 (d).
- the second parallel line pattern 5 is composed of line segments 51 and 52.
- a mesh-like pattern 6 formed by intersecting the first parallel line pattern 3 and the second parallel line pattern 5 can be formed.
- the first parallel line pattern 3 and the second parallel line pattern 5 are formed in a direction inclined with respect to the side of the rectangular substrate 1.
- FIG. 6 is a plan view conceptually illustrating chamfering from a base material on which a pattern is formed by the method shown in FIG. Similarly to FIG. 4, the cut-out line at the time of chamfering is indicated by a broken line C in the figure.
- the pattern 6 is formed in a direction inclined with respect to the side of the base material 1. Therefore, moire can be prevented.
- FIG. 7 is a plan view conceptually illustrating an example of the pattern forming method of the present invention.
- reference numeral 7 denotes a droplet discharge device, which includes an inkjet head 71.
- Reference numerals 72a to 72f denote nozzles provided in the inkjet head 71.
- droplets made of a liquid containing a functional material are discharged onto the substrate 1 from the plurality of nozzles 72a to 72f of the droplet discharge device 7.
- the liquid droplets discharged from different nozzles are united on the substrate 1 to form the line-shaped liquid 2 in a direction inclined with respect to the relative movement direction D.
- the case where one line-shaped liquid 2 is formed by one pass by relative movement is shown, but it is also preferable to form a plurality of line-shaped liquids 2 by one pass by relative movement. It is.
- the angle (inclination angle) ⁇ in the formation direction of the line-shaped liquid 2 with respect to the relative movement direction D refers to an angle that is clockwise (clockwise) from the relative movement direction D.
- the angle when the angle takes a negative value, it can be converted into an angle of a positive value counterclockwise (counterclockwise).
- the inclination angle ⁇ is 45 °.
- FIG. 8 is a plan view conceptually illustrating an example of a droplet discharge condition from the droplet discharge device.
- reference numerals 2a to 2f denote the landing positions of the droplets ejected from the nozzles 72a to 72f of the inkjet head 71 provided in the droplet ejection device 7, respectively.
- the landing positions 2a to 2f are arranged at intervals in both the relative movement direction D and the direction perpendicular to the relative movement direction D. That is, by ejecting droplets from the nozzles 72a to 72f of the inkjet head 71 provided in the droplet ejecting apparatus 7, the droplets adjacent to each other on the base material 1 are moved in the relative movement direction D and the relative direction. They are arranged at intervals in any direction orthogonal to the moving direction D. Here, the interval is the distance between the centers of the droplets.
- the droplets adjacent to each other may be such that at least one set of the droplets adjacent to each other has an interval in both the relative movement direction D and the direction perpendicular to the relative movement direction D. Further, “arranged with an interval in both the relative movement direction and the direction orthogonal to the relative movement direction” means that the film is arranged in a direction inclined with respect to the relative movement direction.
- a time difference is provided from the nozzles 72a, 72b, 72c, 72d, 72e, 72f in the order of arrangement from the nozzle 72a on one end side to the nozzle 72f on the other end side during the movement process of the droplet discharge device 7.
- the above-described arrangement state is formed by discharging droplets.
- One or both of the droplet volume of the droplets and the interval between the droplets are arranged so that the droplets that have landed on these landing positions 2a to 2f are then united by the adjacent droplets on the substrate 1. Adjust.
- the line-like liquid 2 can be formed along the direction inclined with respect to the relative movement direction D of the droplet discharge device 7 with respect to the substrate 1.
- a functional material can be deposited on the edge of the line-shaped liquid 2 to form a pattern including the functional material, for example, the parallel line pattern described above.
- the pattern formation direction can be a direction inclined with respect to the relative movement direction D.
- the present invention for example, when setting the formation direction of the line-shaped liquid, a process such as changing the arrangement angle of the droplet discharge device is not required, so the pattern formation direction with respect to the base material is not impaired. The effect which can improve the freedom degree of is acquired.
- the product V ⁇ R [pL ⁇ npi] of the total droplet volume V [pL] applied from one nozzle to form one line-like liquid 2 and the nozzle row resolution R [npi]. ] is preferably adjusted to a range of 4.32 ⁇ 10 4 [pL ⁇ npi] or more and 5.18 ⁇ 10 5 [pL ⁇ npi] or less.
- the total droplet volume V [pL] applied from one nozzle to form one line-shaped liquid 2 is different from each nozzle 72 a to 72 f for forming one line-shaped liquid 2.
- a method for adjusting the appropriate amount of the total liquid a method for adjusting the volume per droplet, a method for adjusting the number of droplets to be landed on one landing position, and the like can be preferably exemplified. It is also preferable to use one or more of these methods in combination.
- a droplet discharge device provided with a gradation number changing unit can be suitably used. That is, the droplet volume can be adjusted by adjusting the number of gradations.
- the number of gradations is the number of droplets to be landed per dot (the unit is “dpd” (drops per dot)), and the number of droplets to land at one landing position described above. It can be used as a numerical value corresponding to a number.
- V Vd ⁇ N
- N the number of gradations
- the nozzle row resolution R [npi] is the number of nozzles per inch in the direction orthogonal to the relative movement direction. If the nozzle interval (distance between nozzle centers (also referred to as pitch)) in the direction orthogonal to the relative movement direction is constant, the reciprocal of the nozzle interval [inch] is a numerical value corresponding to the nozzle row resolution R [npi]. Can be used.
- V ⁇ R [pL ⁇ npi] is in the range of 4.32 ⁇ 10 4 [pL ⁇ npi] to 5.18 ⁇ 10 5 [pL ⁇ npi]
- the linear liquid is more linearly formed. This makes it easier to prevent bulges.
- line segments constituting the formed parallel line pattern are more easily formed linearly, and occurrence of disconnection can be suitably prevented. Therefore, when a conductive material is used as the functional material, the effect of further improving sheet resistance and terminal resistance of the pattern obtained can be obtained.
- the droplet containing the functional material discharged from the droplet discharge device preferably has a contact angle on the substrate in the range of 10 [°] to 30 [°].
- the contact angle is a static contact angle.
- a droplet (about 5 ⁇ l) to be measured in a syringe under a 25 ° C., 50% RH environment. It can obtain
- the contact angle can be adjusted as appropriate depending on, for example, the composition of the droplet containing the functional material and the setting of the surface energy of the substrate.
- the contact angle is in the range of 10 [°] to 30 [°], the effect of further improving the transparency of the parallel line pattern to be formed can be obtained.
- the contact angle is in the range of 10 [°] or more and 30 [°] or less, the line-shaped liquid is more easily formed linearly, and bulges can be suitably prevented.
- line segments constituting the formed parallel line pattern are more easily formed linearly, and occurrence of disconnection can be suitably prevented. Therefore, when a conductive material is used as the functional material, the effect of further improving sheet resistance and terminal resistance of the pattern obtained can be obtained.
- each of the nozzles 72a to 72f performs discharge for forming the line-shaped liquid 2, and then discharges for forming a further line-shaped liquid 2 ′ adjacent to the nozzle 72a to 72f at a predetermined interval. It can be performed.
- reference numerals 2a 'to 2f' denote landing positions of droplets ejected from the nozzles 72a to 72f in order to form a further line-shaped liquid 2 '.
- the droplet discharge device 7 can form a plurality of line-like liquids at a predetermined interval in one pass by relative movement.
- the line-shaped liquid is formed obliquely with respect to the relative movement direction D of the droplet discharge device and the base material, so that the line-shaped liquid parallel to each other is applied by one pass.
- the line-shaped liquid is formed along the relative movement direction D of the droplet discharge device and the substrate, the line provided by one pass is used.
- the liquid-like liquid application interval M p can be adjusted only in units of the nozzle interval of the droplet discharge device.
- the selectable application interval Mp is a stepwise (discontinuous) value in the unit of the nozzle interval.
- the linear liquid by forming obliquely to the relative movement direction D of the droplet discharge device and the substrate, is released when the adjustment of imparting interval M p constraints of the nozzle spacing.
- the grant interval M p it becomes possible to freely select from a continuous range.
- the application interval M p of the line-shaped liquid applied by one pass is a distance (also referred to as a pitch) in a direction orthogonal to the formation direction of the line-shaped liquids 2 and 2 ′. This corresponds to the distance between the centers of the line-shaped liquids 2 and 2 'in the width direction.
- the application interval M p is equal to the time interval at which droplets are discharged from the nozzles 72a to 72f, and By adjusting one or both of the relative moving speeds of the droplet discharge device 7 with respect to the base material 1, it can be adjusted as appropriate.
- the granted interval M p readily be able to adjust to a desired value.
- the degree of freedom of patterning can be improved, and compatibility with various devices and various electronic devices can be improved.
- the applying interval M p By adjusting the applying interval M p, it is also preferable to suppress the mutual interference when drying the mutually linearly liquid 2,2 'to next.
- the mutual interference include interference due to steam and interference due to a decrease in temperature of the base material from which the heat of vaporization has been removed.
- the value of the grant interval M p is not particularly limited, preferably set to 400 [[mu] m] or more. Thereby, the mutual interference at the time of drying adjacent line-shaped liquid 2, 2 'can be suppressed suitably.
- the droplet discharge device 7 is composed of one inkjet head 71.
- the nozzles 72 a to 72 f are arranged in a straight line in a direction orthogonal to the relative movement direction of the droplet discharge device 7.
- the droplet discharge device discharges the liquid from the nozzle 72a toward the landing position 2a while moving in the relative movement direction D. Next, the droplet discharge device further moves in the relative movement direction D, and discharges liquid from the nozzle 72b adjacent to the nozzle 72a toward the landing position 2b. Therefore, the nozzle 72a and the nozzle 72b adjacent to each other have a time difference (discharge time difference) in the timing of discharging the liquid.
- the nozzles 72a to 72f are arranged in a straight line in a direction orthogonal to the relative movement direction of the droplet discharge device 7, and the discharge time difference between adjacent nozzles is any two sets of adjacent nozzles. It is the same even if extracted. Under such conditions, the discharge time difference can be set to the maximum discharge time difference ⁇ t max .
- FIG. 9 is a plan view for conceptually explaining another example of the condition for ejecting droplets from the droplet ejection apparatus.
- the droplet discharge device 7 is composed of two inkjet heads 71 (hereinafter sometimes referred to as a two-row head).
- These two inkjet heads 7 are arranged so as to be shifted by a distance corresponding to half of the nozzle interval in the direction perpendicular to the relative movement direction D of each inkjet head 7. In this way, the nozzle resolution R of the entire droplet discharge device 7 is increased by using a two-row head.
- the nozzle resolution R can be further increased by arranging the heads in three or more rows.
- the nozzles 72a, 72c, 72e are not arranged in a straight line in a direction orthogonal to the relative movement direction D. The same applies to the nozzles 72b, 72d, 72f of the left inkjet head 71 in the drawing.
- the discharge time difference between the adjacent nozzles differs depending on how the two sets of adjacent nozzles are extracted.
- the discharge time difference when two sets of adjacent nozzles are extracted so as to maximize the discharge time difference can be set to the maximum discharge time difference ⁇ t max .
- FIG. 10 and 11 are plan views conceptually illustrating still another example of the droplet discharge condition from the droplet discharge device.
- FIG. 11 is an enlarged view of a portion indicated by (xi) in FIG.
- the plurality of inkjet heads 71 are moved in the relative movement direction D. They can be used in a zigzag pattern in a direction orthogonal to the direction. In the example shown in the figure, two-row heads composed of two inkjet heads 71 are arranged in a staggered manner in a direction orthogonal to the relative movement direction D.
- the difference in ejection time between adjacent nozzles differs depending on how the two sets of adjacent nozzles are extracted.
- the influence due to the presence of nozzles adjacent to each other in different two-row heads is significant.
- the discharge time difference when two sets of adjacent nozzles are extracted so as to maximize the discharge time difference can be set to the maximum discharge time difference ⁇ t max .
- the discharge time difference becomes the largest. This can be set as the maximum discharge time difference ⁇ t max .
- FIG. 12 is a plan view conceptually illustrating an example of forming a plurality of line-shaped liquids by a plurality of passes.
- a plurality of line-shaped liquids 2A and 2B are formed by two passes.
- the line-shaped liquid 2A is formed in the first pass, and the line-shaped liquid 2B in the same direction as the line-shaped liquid 2A is formed in the second pass.
- a drying step is provided between each pass to dry the line liquid formed in the previous pass to form a parallel line pattern.
- a drying step is provided between the first pass and the second pass, and in this drying step, the line-shaped liquid 2A formed in the first pass is dried to form the parallel line pattern 3. ing.
- Grant interval M p of the linear liquid imparted by one pass is preferably greater than the grant interval M of the linear liquid that is ultimately granted.
- the line liquid that is finally applied refers to the line liquid in the same direction that is applied by all passes (two passes in the illustrated example) for forming the line liquid in the same direction.
- a part or all of the line-shaped liquid may already be in a dried state, that is, in a parallel line pattern. .
- the thing of the state which dried the line-shaped liquid can also be included in the measuring object of the provision space
- a line-like liquid in the same forming direction by a plurality of passes.
- the second and subsequent passes between two adjacent line-shaped liquids (which may have been already dried) applied in the previous pass. It is preferable to apply a new linear liquid to the gap.
- the application interval M p of the line-shaped liquid given by one pass is finally given. It is preferably n times the application interval M of the linear liquid.
- the line-shaped liquid is formed obliquely with respect to the relative movement direction D of the droplet discharge device and the substrate, so that the elongation rate of the line-shaped liquid is set to the relative movement speed with respect to the substrate of the droplet discharge device.
- the extension speed of the line liquid is a length per unit time in which the line liquid extends in the formation direction of the line liquid.
- the linear liquid extension speed V L [ ⁇ m / s] is defined as V H [ ⁇ m / s] relative movement speed of the droplet discharge device with respect to the base material, and ⁇ [°] as an inclination angle of the linear liquid with respect to the base material.
- V L V H /
- the absolute value of cos ⁇ can be made 1 or less by forming the line-shaped liquid in a direction inclined with respect to the relative movement direction with respect to the base material of the droplet discharge device.
- the extension speed V L of the line-shaped liquid can be made larger than the relative movement speed V H with respect to the base material of the droplet discharge device, that is, V L > V H can be satisfied.
- FIG. 13 is a plan view conceptually illustrating an example of forming a mesh pattern using the pattern forming method of the present invention.
- a droplet discharge device for the substrate 1 in FIG. 13, in FIG. 13
- a relative movement direction D (not shown) is set.
- the droplet discharge device is moved along the relative movement direction D, and a plurality of first line-shaped liquids 2 are formed at predetermined intervals in a direction inclined with respect to the direction D.
- the inclination angle ⁇ is set to 45 °.
- the first parallel line pattern 3 can be formed from each first line-shaped liquid 2 as shown in FIG.
- the first parallel line pattern 3 is composed of line segments 31 and 32.
- the droplet discharge device is moved along the relative movement direction D as shown in FIG.
- a plurality of second line-shaped liquids 4 are formed at predetermined intervals in a direction inclined with respect to the direction D.
- the inclination angle ⁇ is set to ⁇ 45 °.
- the second parallel line patterns 5 can be formed from the respective second line-shaped liquids 4 as shown in FIG. 13 (d).
- the second parallel line pattern 5 is composed of line segments 51 and 52.
- the first parallel line pattern 3 and the second parallel line pattern 5 are formed in a direction inclined with respect to the side of the rectangular substrate 1.
- the pattern 6 is formed in a direction inclined with respect to the side of the base material 1, thereby preventing moire. Can be planned. Therefore, both moire prevention and chamfering efficiency can be achieved.
- the second Since it is not necessary to change the relative movement direction D of the liquid droplet ejection device with respect to the base material when the line-shaped liquid 4 is applied, productivity can be improved. Since it is not necessary to change the orientation of the head with respect to the base material, it is possible to prevent complicated equipment and complicated control.
- FIG. 14 is a plan view conceptually illustrating another example of forming a mesh pattern using the pattern forming method of the present invention.
- the description of FIG. 13 can be used for the configuration indicated by the same reference numerals as in FIG. 13.
- the first linear liquid 2 is formed in a direction inclined with respect to the relative movement direction D (FIG. 14A).
- the inclination angle ⁇ is set to 45 °.
- the first parallel line pattern 3 is formed by drying the first line-shaped liquid 2 (FIG. 14B).
- the relative movement direction D is set in a direction opposite to the relative movement direction D when the first linear liquid 2 is formed.
- the second linear liquid 4 is formed in a direction inclined with respect to the relative movement direction D (FIG. 14C).
- the inclination angle ⁇ is set to ⁇ 45 °.
- the second parallel line pattern 5 is formed by drying the second linear liquid 4 (FIG. 14D).
- the relative movement direction D of the droplet discharge device with respect to the substrate can be set in the reverse direction.
- the droplet discharge device when the droplet discharge device is reciprocated once on the substrate 1, the first line-shaped liquid and the second line-shaped liquid can be formed respectively in the forward path and the return path.
- the droplet discharge device it is relatively easy to discharge the droplet by setting the relative movement direction D in the reverse direction as described above, such as resetting the arrangement angle of the droplet discharge device with respect to the substrate. It can be easily carried out without requiring a process.
- processes such as heating, blowing, and irradiation with energy rays can be exemplified, and one or more of these may be used in combination.
- a drying device also referred to as a dryer
- the drying device only needs to be configured so as to be able to perform the above-described drying process.
- a heater, a blower, an energy beam irradiation device, and the like can be exemplified, and one or more of these may be combined. .
- FIG. 15 is a plan view conceptually illustrating a configuration example of the drying apparatus.
- the drying device 8 is preferably installed so as to move relative to the substrate together with the droplet discharge device 7. As shown in the figure, it is also preferable to mount a drying device 8 together with the droplet discharge device 7 on a carriage 9 used for moving the droplet discharge device 7.
- the drying device may be provided on the base material side.
- a drying device such as a heater on the stage on which the substrate is placed.
- a drying device on each of the droplet discharge device side and the substrate side.
- the present invention is not limited to this example, and the substrate may be moved to fix the droplet discharge device.
- the substrate can be moved and the droplet discharge device can be moved, but the control may be complicated. From the viewpoint of facilitating control, it is preferable to fix one of the substrate and the droplet discharge device and move the other.
- FIG. 16 is a plan view conceptually illustrating another example of the pattern forming method of the present invention.
- a line head in which a plurality of inkjet heads are arranged side by side in the width direction is used as the droplet discharge device 7.
- nozzles are formed over a width equal to or larger than the width of the pattern formation region in the substrate.
- droplet discharge devices 7 are fixed, and the long substrate 1 is conveyed so as to be supplied to the droplet discharge devices 7 in order.
- the substrate 1 is transported in a predetermined direction by a transport means (not shown).
- a conveyance means is not specifically limited, For example, it can comprise with a belt conveyor etc.
- the conveyance direction of the substrate 1 is indicated by an arrow E in the figure.
- the relative movement direction D of the droplet discharge device 7 with respect to the base material 1 is opposite to the transport direction E of the base material 1.
- Each droplet discharge device 7 includes a drying device 8 on the downstream side in the transport direction E of the substrate 1.
- the substrate 1 is conveyed in the order of the upstream droplet discharge device 7, the upstream drying device 8, the downstream droplet discharge device 7, and the downstream drying device 8.
- the substrate 1 to be conveyed is supplied to the upstream droplet discharge device 7.
- the first linear liquid 2 is formed in a direction inclined with respect to the relative movement direction D of the droplet discharge device 7.
- the first linear liquid 2 tilt angle ⁇ is set to 45 °.
- the region where the first line-shaped liquid 2 is formed is provided to the drying device 8 on the upstream side.
- the first parallel line pattern 3 is formed by drying the first line-shaped liquid 2.
- the region where the parallel line pattern 3 is formed is provided to the downstream droplet discharge device 7.
- the second linear liquid 4 is formed in a direction inclined with respect to the relative movement direction D of the droplet discharge device 7.
- the inclination angle ⁇ of the second line-shaped liquid 2 is set to ⁇ 45 °.
- the region where the second line-shaped liquid 4 is formed is provided to the drying device 8 on the downstream side.
- the second parallel line pattern 5 is formed by drying the second linear liquid 4.
- the pattern is moved under the condition that the substrate is moved and the droplet discharge device is fixed.
- a method of forming the film for example, a pattern forming method using a line head as described above) can be suitably applied.
- a droplet set applied from a plurality of nozzles to a pixel set arranged in parallel to a nozzle row of the droplet discharge device
- the line-shaped liquid 2 is also formed obliquely with respect to the relative movement direction D of the droplet discharge device 7 here.
- the droplet 20 containing the functional material is discharged from the droplet discharge device 7 onto the substrate 1 while moving the droplet discharge device 7 relative to the substrate 1.
- the relative movement direction D is set in a direction orthogonal to the direction N of the nozzle row 73 including the nozzles 72a to 72j.
- a pixel set composed of a plurality of pixels (a1, b1, c1) arranged in parallel to the direction N of the nozzle row 73 is used to generate a pixel set from each of the plurality of nozzles 72a, 72b, 72c.
- a droplet 20, i.e. a droplet set, is applied.
- the droplet discharge device 7 when the droplet discharge device 7 is relatively moved in the relative movement direction ⁇ by one pixel, it is composed of a plurality of pixels (b2, c2, d2) arranged in parallel with the direction N of the nozzle row 73.
- the next droplet 20 that is, the next droplet set is applied from each of the plurality of nozzles 72b, 72c, 72d.
- a plurality of droplet groups are provided in an oblique direction with respect to the direction N of the nozzle row 73.
- the next pixel set is selected from the pixels constituting the next row so as to be shifted by one pixel).
- an oblique direction with respect to the direction N of the nozzle row 73 that is, the relative movement direction of the droplet discharge device 7.
- a line-shaped liquid 2 extending in an oblique direction with respect to D can be formed.
- the parallel line pattern 3 formed from one line-shaped liquid 2 is composed of a set of two line segments (thin lines) 31 and 32.
- the parallel line pattern 3 is formed obliquely with respect to the relative movement direction D of the droplet discharge device 7.
- the formation width of the line-shaped liquid 2 can be freely increased by applying droplet sets from a plurality of nozzles. Furthermore, even when the arrangement interval I between the thin wires 31 and 32 generated from the line-shaped liquid 2 is increased, it is possible to suitably prevent the occurrence of bulges. That is, the degree of freedom in setting the arrangement interval I of the thin wires 31 and 32 can be improved without destabilizing the formation of the thin wires 31 and 32 containing the functional material.
- the present invention is not limited to this, and is appropriately set so that the thin lines 31 and 32 have a desired arrangement interval I. be able to. Therefore, an effect with a high degree of freedom in setting the arrangement interval I can be obtained.
- the number of pixels constituting the pixel group is preferably set in a range of 2 to 20 pixels, and more preferably in a range of 2 to 10 pixels.
- the droplet discharge device 7 may have a plurality of nozzles arranged in a plurality of rows.
- the direction of the nozzle row 73 corresponds to the overall arrangement direction N of the plurality of nozzles.
- the mesh-shaped functional pattern is advantageous in realizing the distribution of the functional material on the base material while maintaining low visibility.
- the line segment constituting the parallel line pattern formed as described above can realize a line width of several ⁇ m
- the mesh-like functional pattern is formed by the functional material itself due to its fine line width. Even if it is not transparent, it is not recognized by the human eye and looks as if it is transparent.
- the shape of the thin line pattern of the functional material can be set by the device that uses the functional material.
- a touch sensor used for a touch panel uses a transparent surface electrode to detect a position by a finger or the like.
- a conductive material is used as a functional material in a mesh-like functional pattern, it can be preferably applied to a transparent surface electrode for a touch panel or the like. From the viewpoint of configuring a surface electrode or the like, it is very effective to increase the number of conductive paths to be meshed with a plurality of parallel line patterns having different formation directions.
- 21 is a method for forming such a mesh-like functional pattern.
- a line-like liquid 2 is applied in a mesh form on a substrate 1. That is, the line-shaped liquid 2 is applied so as to intersect at the intersection X.
- the line segments 31 and 32 are cut off at the intersection X where the parallel lines having different directions intersect.
- the ink amount at the intersection formed by the line-shaped liquid 2 is set larger than the other portions.
- intersection X becomes a ring shape having a diameter larger than the interval between the line segments 31 and 32 as shown in FIG.
- Such a ring-shaped part is advantageous in terms of preventing disconnection of the line segments 31 and 32 and facilitating, for example, ensuring conductivity, but such a ring-shaped part is periodically visible. It has been found that there is a limit in terms of further improving the low visibility.
- the line-shaped liquid 2 is applied in the first direction (left and right direction in the figure).
- the functional material is selectively deposited on the edge to form the first parallel line pattern 3 as shown in FIG.
- the second direction is different from the first direction (in this example, the direction is perpendicular to the first direction, and is the vertical direction in the figure). 2 of the line-shaped liquid 4 is applied. That is, the second line-shaped liquid 4 is applied so as to intersect the formation region of the first parallel line pattern 3.
- a functional material is selectively deposited on the edge to form a second parallel line pattern 5 as shown in FIG.
- Reference numerals 51 and 52 denote line segments constituting the second parallel line pattern 5.
- a mesh-like functional pattern is formed by the first parallel line pattern 3 and the second parallel line pattern 5 having different formation directions.
- the line segments 31, 32 and the line segments 51, 52 can be prevented from being interrupted at the intersection X where the parallel lines having different directions intersect.
- FIG. 24 is an enlarged view of a main part showing an example of forming the intersection X.
- FIG. 25A shows an optical micrograph of the mesh-like functional pattern in which the swelling has occurred.
- the length of the conductive path extends along the first parallel line pattern 3 (first direction) and the second parallel line. It was found that there was room for further improvement from the viewpoint of preventing variation in resistance due to differences in the direction along the pattern 5 (second direction).
- the interval between the two line segments 51 and 52 constituting the second parallel line pattern 5 is as follows.
- the average interval A within the formation region of the first parallel line pattern 3 and the average interval B outside the formation region of the first parallel line pattern 3 are adjusted so as to satisfy the following formula (1).
- the formation region of the first parallel line pattern 3 can be said to be a region from one line segment 31 to the other line segment 32 constituting the first parallel line pattern. It can also be said to be an application region of the first line-shaped liquid 2 applied to form the line pattern 3.
- the interval B can be an average value of the intervals measured at a plurality of locations.
- a plurality of (n) measurement points set to measure the average interval A may be arranged at equal intervals along the second direction in the formation region of the first parallel line pattern 3. preferable.
- a plurality (m places) of measurement points set to measure the average interval B are arranged at equal intervals along the second direction outside the region where the first parallel line pattern 3 is formed. Is preferred.
- the average interval A and the average interval B are preferably measured as follows.
- FIG. 26 is a diagram illustrating an example of a method for measuring the average interval A and the average interval B.
- the average interval A is along the line segments 31 and 32 constituting the first parallel line pattern with respect to the interval between the line segments 51 and 52 constituting the second parallel line pattern 5. It can be obtained as the average of the distances measured at a total of seven points A1 to A7, two points A1 and A2 and five points A3 to A7 inside the line segments 31 and 32. At this time, these seven measurement points A1 to A7 are positioned at equal intervals along the formation direction (second direction) of the second parallel line pattern.
- the average interval B is a total of seven measurement points A1 to A7 related to the average interval A described above with respect to the interval between the line segments 51 and 52 constituting the second parallel line pattern 5.
- these five measurement points B1 to B5 are a total of seven measurement points A1 to A7 related to the average interval A described above along the second parallel line pattern forming direction (second direction).
- a total of seven measurement points A1 to A7 related to the measurement of the average interval A and a total of five measurement points B1 to B5 related to the measurement of the average interval B may be positioned at equal intervals along the second direction. it can.
- the measurement points B1 to B5 with the average interval B are set adjacent to the lower side in the figure with respect to the measurement points A1 to A7 with the average interval A. It can also be set adjacent to. At this time, the measurement points B1 to B5 of the average interval B are set on either the upper side (one side) or the lower side (the other side) so that the difference between the average interval A and the average interval B becomes larger. Is preferred.
- the measurement points for the average interval A include the two points A1 and A2 along the line segments 31 and 32 constituting the first parallel line pattern. You may make it include one place along any one of these. Further, the portions along the line segments 31 and 32 may not be included.
- the measurement points for the average interval A include the five points A3 to A7 inside the line segments 31 and 32 constituting the first parallel line pattern. It is not necessary that the number is two or more.
- the measurement points for the average interval B include the five points B1 to B5 outside the line segments 31 and 32 constituting the first parallel line pattern. It is not necessary that the number is two or more.
- the interval between the line segments 51 and 52 constituting the second parallel line pattern 5 measured at each measurement point in order to obtain the average interval A and the average interval B can be defined as follows.
- FIG. 27 is a partially enlarged plan view showing an example of parallel line patterns formed on the substrate.
- FIG. 28 is an explanatory diagram for explaining a cross section along line (a)-(a) in FIG. 27.
- a cross section (longitudinal section) obtained by cutting a set of two thin lines included in the pattern in a direction perpendicular to the line segment direction. Surface).
- the interval I between the line segments 51 and 52 constituting the second parallel line pattern 5 can be defined as the distance between the maximum protrusions of the line segments 51 and 52, as shown in FIG. Therefore, the average interval A and the average interval B can be obtained by measuring the interval I at each of the measurement points described above.
- the adjustment to satisfy the above-described formula (1) is to adjust one or more factors that can affect the ratio B / A of the average interval A and the average interval B.
- factors are not particularly limited and can be appropriately selected.
- the surface energy in the formation region of the first parallel line pattern 3 and the surface energy outside the formation region of the first parallel line pattern 3 are The difference is set to 5 mN / m or less.
- the surface energy in the formation region of the first parallel line pattern 3 can be the surface energy measured in the central region between the line segments 31 and 32 constituting the first parallel line pattern.
- the surface energy in the formation region of the first parallel line pattern 3 is prepared by separately preparing a base material similar to the base material 1 and the first linear liquid 2 on the base material. The surface energy measured in the central region of the dried film can be obtained after 20 ⁇ L of the same liquid is dropped and dried under the same conditions as when the first linear liquid 2 is dried.
- the surface energy outside the region where the first parallel line pattern 3 is formed is the surface energy of the substrate 1 in the region where the first linear liquid 2 for forming the first parallel line pattern 3 is not applied. It can be.
- the surface energy can be calculated from the Young-Fowkes equation.
- the means for adjusting the surface energy difference between the inside and outside of the formation region of the first parallel line pattern 3 is not particularly limited, for example, a method of performing a surface treatment on the region including the outside of the formation region of the first parallel line pattern 3; A method of changing the liquid composition of the first line-like liquid 2 is preferable.
- the surface treatment for changing the surface energy with respect to the substrate 1 is performed before forming the first parallel line pattern 3.
- the method of giving can be mentioned.
- the surface treatment may be performed only on a region outside the formation region of the first parallel line pattern 3, or may be performed on a region including the outside of the formation region and the inside of the formation region. It is also preferable to perform a surface treatment on the entire surface of the substrate 1.
- the liquid composition of the first line-shaped liquid 2 it can be performed by selecting a blending component (functional material, additive, solvent, etc.), adjusting a blending amount of each component, or the like.
- a blending component functional material, additive, solvent, etc.
- adjusting a blending amount of each component or the like.
- the surface energy of the solid surface coated with the functional material contained in the first linear liquid 2 and dried, and the first parallel lines is set to 5 mN / m or less.
- the “solid surface” is the surface of a solid film obtained by applying and drying the functional material contained in the first linear liquid 2 on an arbitrary substrate, and the surface energy of the substrate itself and It refers to the surface of the solid film coated with the substrate so that the contact angle does not affect the surface energy and the contact angle on the surface of the solid film.
- coating of a functional material can be performed by apply
- a liquid having the same composition as that of the first line-like liquid 2 may be used as the coating liquid for forming the solid surface.
- the region between the line segments 31 and 32 is in the first line-shaped liquid 2 that has not been transported to the position of the line segments 31 and 32 due to the coffee stain phenomenon. Some components may remain slightly. Such residual components may cause the spacing between the line segments 51 and 52 constituting the second parallel line pattern 5 to be non-uniform.
- the surface energy of the solid surface obtained by applying and drying the functional material contained in the first line-shaped liquid 2 is an index for realizing more reliable adjustment to satisfy the above-described formula (1). obtain. That is, even if a large amount of residual components are present in the region between the line segments 31 and 32, it is unlikely to affect the interval between the line segments 51 and 52 beyond the effect of the solid surface. Therefore, the reliability can be further improved by adjusting based on the difference between the surface energy of the solid surface and the surface energy outside the formation region of the first parallel line pattern 3.
- the means for adjusting the difference between the surface energy of the solid surface and the surface energy difference outside the formation region of the first parallel line pattern 3 is not particularly limited, and the means described for the first aspect can be preferably used.
- the contact angle of the second linear liquid 4 in the formation region of the first parallel line pattern 3 and the first parallel line pattern 3 is set to 10 ° or less.
- the contact angle in the formation region of the first parallel line pattern 3 can be a contact angle measured in the central region between the line segments 31 and 32 constituting the first parallel line pattern.
- the contact angle in the formation region of the first parallel line pattern 3 is prepared by separately preparing a base material similar to the base material 1, and the first linear liquid 2 and the base material 1 on the base material. A contact angle measured in the central region of the dried film may be obtained after 20 ⁇ L of the same liquid is dropped and dried under the same conditions as those for drying the first linear liquid 2.
- the contact angle outside the formation region of the first parallel line pattern 3 is such that the first line-shaped liquid 2 for forming the first parallel line pattern 3 is not applied on the base material 1 in the region. It can be a contact angle.
- the contact angle can be measured using a contact angle measuring device DM-501 manufactured by Kyowa Interface Chemical Co., Ltd.
- the contact angle is set to a value 5 seconds after the liquid having the same composition as the second linear liquid 4 is dropped.
- the change in wettability with respect to the second linear liquid 4 can be reduced inside and outside the formation region of the first parallel line pattern 3.
- the interval between the line segments 51 and 52 can be set to satisfy the above-described expression (1).
- the contact angle in the formation region of the first parallel line pattern is smaller than the contact angle outside the formation region, if the contact angle difference exceeds 10 °, the contact angle in the formation region of the first parallel line pattern 3 In FIG. 5, the interval between the line segments 51 and 52 of the second parallel line pattern 5 becomes smaller than outside the formation region, resulting in a narrow shape.
- the means for adjusting the difference in contact angle is not particularly limited, and the means described as means for adjusting the surface energy difference in the first embodiment can be preferably used. Furthermore, as a means for adjusting the difference in contact angle, the liquid composition of the second linear liquid 4 can be changed. When changing the liquid composition of the 2nd line-shaped liquid 4, it can carry out by selection of a compounding component (functional material, an additive, a solvent, etc.), adjustment of the compounding quantity of each component, etc. It is also preferable to make the liquid of the second line-shaped liquid 4 different from the liquid of the first line-shaped liquid 2.
- the contact of the second linear liquid 4 on the solid surface coated with the functional material contained in the first linear liquid 2 and dried is set to 10 ° or less.
- the description in the second aspect is incorporated.
- the change in wettability with respect to the second linear liquid 4 can be reduced inside and outside the formation region of the first parallel line pattern 3.
- the interval between the line segments 51 and 52 can be set to satisfy the above-described expression (1).
- the reliability can be further improved by adjusting the contact angle on the solid surface as an index.
- the means for adjusting the difference between the contact angle on the solid surface and the contact angle outside the formation region of the first parallel line pattern 3 is not particularly limited, and the means described for the third aspect can be preferably used.
- the contact angle of the solvent having the highest boiling point among the solvents in the second linear liquid 4 outside the formation region of the first parallel line pattern 3. Is 6 ° or less.
- the contact angle outside the formation region of the first parallel line pattern 3 is on the base material 1 in the region where the first linear liquid 2 for forming the first parallel line pattern 3 is not applied.
- the contact angle can be as follows.
- the contact angle can be measured using a contact angle measuring device DM-501 manufactured by Kyowa Interface Chemical Co., Ltd.
- the contact angle is set to a value 5 seconds after the solvent having the highest boiling point among the solvents in the second linear liquid 4 is dropped.
- the contact angle By setting the contact angle to 6 ° or less, the change in wettability with respect to the second linear liquid 4 can be reduced inside and outside the formation region of the first parallel line pattern 3, and the second parallel lines In the pattern 5, the interval between the line segments 51 and 52 can satisfy the above-described expression (1).
- the means for adjusting the contact angle is not particularly limited, and the means described as means for adjusting the surface energy difference in the first aspect can be preferably used.
- the liquid application amount per length of the second linear liquid 4 in the formation region of the first parallel line pattern 3 and the first The liquid application amount per length of the second linear liquid 4 outside the formation area of the parallel line pattern 3 is made different.
- the length per second length of the second linear liquid 4 in the formation region is relatively small with respect to the outside of the formation region.
- the length of the second linear liquid 4 in the formation region is relatively increased with respect to the outside of the formation region.
- the difference in the liquid application amount inside and outside the formation region of the first parallel line pattern 3 can be adjusted as appropriate so as to satisfy the expression (1).
- the inkjet method is used to form the second line-shaped liquid 4
- the number of droplets ejected per unit length of the second line-shaped liquid 4 and the droplet volume per droplet are set to the first
- the difference in the amount of applied liquid can be set by making the difference between the inside and outside of the region where the parallel line pattern 3 is formed.
- the first parallel line pattern 3 is formed after the first parallel line pattern 3 is formed and before the second linear liquid 4 is applied.
- the region including the inside of the formation region is cleaned.
- the region between the line segments 31 and 32 is the first line shape that has not been transported to the position of the line segments 31 and 32 due to the coffee stain phenomenon.
- Some components in the liquid 2 may remain slightly. Such residual components may cause the spacing between the line segments 51 and 52 constituting the second parallel line pattern 5 to be non-uniform.
- cleaning is removal of such residual components.
- how much residual components are removed is affected by the cleaning conditions, for example, the setting of the type and intensity of cleaning.
- the cleaning is performed by removing residual components so that at least the distance between the line segments 51 and 52 constituting the second parallel line pattern 5 can satisfy the above-described formula (1). possible. In this sense, the cleaning can be positioned as an example of adjustment for satisfying the above-described formula (1).
- the cleaning may be performed only on the first parallel line pattern forming region, or may be performed on the region including the first parallel line pattern forming region and the outside of the forming region. It is also preferable to wash the entire surface of the substrate 1.
- cleaning is performed only in the formation region of the first parallel line pattern, for example, irradiation with electromagnetic waves or the like is performed in a state where the outside of the formation region is masked, or the cleaning solvent is selectively selected using an inkjet method. It becomes possible by giving it in the formation region.
- the cleaning method is not particularly limited, and for example, a cleaning method usually used in industrial products can be used.
- a cleaning method usually used in industrial products can be used.
- the cleaning method by heating includes a continuous heating method using an infrared heater, an oven, a hot plate, etc., and an instantaneous heating method using a xenon flash lamp.
- the heating conditions (temperature, time) and the like are appropriately set within a range in which the interval between the line segments 51 and 52 constituting the parallel line pattern 5 satisfies the above-described formula (1).
- the substrate 1 is a film or the like, it is preferable to set within a range where the substrate 1 is not deformed. From this point of view, a method using a xenon flash lamp that heats instantaneously and particularly causes little damage to a substrate such as a film is preferable.
- a method of irradiating an electron beam, a gamma ray, an ultraviolet ray or the like can be used.
- the electromagnetic wave irradiation conditions are appropriately set in a range in which the interval between the line segments 51 and 52 constituting the parallel line pattern 5 satisfies the above-described formula (1).
- the solvent used for cleaning with the solvent is not limited as long as it can satisfy the above-described formula (1), but a solvent that has little influence on the parallel line pattern formed by depositing the functional material may be selected. preferable.
- a solvent suitable for cleaning can be appropriately selected according to the type of functional material. For example, in the case of water-dispersed silver nanoparticles, an alcohol-based solvent is suitable.
- the conditions for cleaning with plasma can be appropriately set so that the interval between the line segments 51 and 52 constituting the parallel line pattern 5 satisfies the above-described formula (1).
- the liquid containing the functional material discharged from the droplet discharge device preferably has a functional material content in the range of 0.01 wt% to 1 wt%.
- the above-mentioned “liquid containing a functional material discharged from a droplet discharge device” can also be referred to as a liquid containing a functional material before being dried immediately after being applied on a substrate.
- the content of the functional material is in the range of 0.01% by weight to 1% by weight, an effect of further stabilizing the formation of the parallel line pattern can be obtained.
- the functional material contained in the liquid is not particularly limited as long as it is a material for imparting a specific function to the base material. Giving a specific function means, for example, that a conductive material is used as a functional material when imparting conductivity to a base material, and when an insulating property is imparted, the insulating material is functional. Use as a material.
- Preferred examples of the functional material include conductive materials such as conductive fine particles and conductive polymers, insulating materials, semiconductor materials, optical filter materials, dielectric materials, and the like.
- the functional material is preferably a conductive material or a conductive material precursor.
- An electroconductive material precursor refers to what can be changed into an electroconductive material by performing an appropriate process.
- the pattern forming method of the present invention is particularly preferably used when forming a pattern composed of fine lines (line segments) containing a conductive material.
- Preferred examples of the conductive material include conductive fine particles and conductive polymers.
- the conductive fine particles are not particularly limited, but Au, Pt, Ag, Cu, Ni, Cr, Rh, Pd, Zn, Co, Mo, Ru, W, Os, Ir, Fe, Mn, Ge, Sn, Ga.
- fine particles such as In can be exemplified, and among them, use of fine metal particles such as Au, Ag, and Cu is more preferable because a circuit pattern having low electrical resistance and strong corrosion can be formed.
- metal fine particles containing Ag are most preferable.
- the average particle diameter of these metal fine particles is preferably in the range of 1 to 100 nm, more preferably in the range of 3 to 50 nm.
- carbon fine particles are used as the conductive fine particles.
- the carbon fine particles include graphite fine particles, carbon nanotubes, fullerenes and the like.
- the conductive polymer is not particularly limited, but a ⁇ -conjugated conductive polymer can be preferably exemplified.
- the ⁇ -conjugated conductive polymer is not particularly limited, and polythiophenes, polypyrroles, polyindoles, polycarbazoles, polyanilines, polyacetylenes, polyfurans, polyparaphenylenes, polyparaphenylene vinylenes, poly Chain conductive polymers such as paraphenylene sulfides, polyazulenes, polyisothianaphthenes, and polythiazyl can be used.
- polythiophenes and polyanilines are preferable in that high conductivity can be obtained. Most preferred is polyethylene dioxythiophene.
- the conductive polymer used in the present invention comprises the above-described ⁇ -conjugated conductive polymer and polyanion.
- a conductive polymer can be easily produced by chemical oxidative polymerization of a precursor monomer that forms a ⁇ -conjugated conductive polymer in the presence of an appropriate oxidizing agent, an oxidation catalyst, and a polyanion.
- the polyanion is a substituted or unsubstituted polyalkylene, a substituted or unsubstituted polyalkenylene, a substituted or unsubstituted polyimide, a substituted or unsubstituted polyamide, a substituted or unsubstituted polyester, and a copolymer thereof. It consists of a structural unit having a group and a structural unit having no anionic group.
- This polyanion is a solubilized polymer that solubilizes a ⁇ -conjugated conductive polymer in a solvent.
- the anion group of the polyanion functions as a dopant for the ⁇ -conjugated conductive polymer, and improves the conductivity and heat resistance of the ⁇ -conjugated conductive polymer.
- the anion group of the polyanion may be a functional group capable of undergoing chemical oxidation doping to the ⁇ -conjugated conductive polymer.
- a monosubstituted sulfate group A monosubstituted phosphate group, a phosphate group, a carboxy group, a sulfo group and the like are preferable.
- a sulfo group, a monosubstituted sulfate group, and a carboxy group are more preferable.
- polyanions include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, polyisoprene sulfone. Acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly-2-acrylamido-2-methylpropane carboxylic acid, polyisoprene carboxylic acid, polyacrylic acid and the like. . These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.
- it may be a polyanion having F (fluorine atom) in the compound.
- F fluorine atom
- Nafion made by Dupont
- Flemion made by Asahi Glass Co., Ltd.
- perfluoro vinyl ether containing a carboxylic acid group and the like can be mentioned.
- a compound having a sulfonic acid is more preferable since the ink ejection stability is particularly good when the ink jet printing method is used and high conductivity is obtained.
- polystyrene sulfonic acid polyisoprene sulfonic acid
- polyacrylic acid ethyl sulfonic acid and polybutyl acrylate sulfonic acid are preferable.
- These polyanions have the effect of being excellent in conductivity.
- the polymerization degree of the polyanion is preferably in the range of 10 to 100,000 monomer units, and more preferably in the range of 50 to 10,000 from the viewpoint of solvent solubility and conductivity.
- a commercially available material can be preferably used as the conductive polymer.
- a conductive polymer (abbreviated as PEDOT / PSS) made of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid is used in H.264. C. It is commercially available from Starck as the CLEVIOS series, from Aldrich as PEDOT-PASS 483095, 560598, and from Nagase Chemtex as the Denatron series. Polyaniline is also commercially available from Nissan Chemical as the ORMECON series.
- liquid containing the functional material water, an organic solvent, or the like can be used alone or in combination.
- the organic solvent is not particularly limited.
- alcohols such as 1,2-hexanediol, 2-methyl-2,4-pentanediol, 1,3-butanediol, 1,4-butanediol, propylene glycol
- ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether.
- liquid containing the functional material may contain various additives such as a surfactant as long as the effects of the present invention are not impaired.
- a surfactant for example, when the line-like liquid 2 is formed using a droplet discharge device, it becomes possible to stabilize discharge by adjusting the surface tension or the like.
- the surfactant is not particularly limited, but a silicon surfactant or the like can be used. Silicon-based surfactants are those in which the side chain or terminal of dimethylpolysiloxy acid is modified with polyether. For example, KF-351A and KF-642 manufactured by Shin-Etsu Chemical, BYK347 and BYK348 manufactured by Big Chemie are commercially available. ing.
- the addition amount of the surfactant is preferably 1% by weight or less with respect to the total amount of the liquid that forms the line-like liquid 2.
- the base material is not particularly limited.
- glass plastic (polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, acrylic, polyester, polyamide, etc.), metal (copper, nickel, aluminum, iron, etc. or an alloy), A ceramic etc. can be mentioned, These may be used independently and may be used in the bonded state.
- plastic is preferable, and polyethylene terephthalate, polyolefin such as polyethylene and polypropylene, and the like are preferable.
- FIG. 29 is a partially cutaway perspective view showing an example of a parallel line pattern formed on a substrate, and the cross section corresponds to a vertical cross section cut in a direction orthogonal to the direction in which the parallel line pattern is formed. .
- the pair of two thin lines (line segments) 31 and 32 of the parallel line pattern 3 generated from one line-shaped liquid do not necessarily need to be islands completely independent from each other.
- the two line segments 31 and 32 are connected by the thin film portion 30 formed between the line segments 31 and 32 at a height lower than the height of the line segments 31 and 32. It is also preferable that it is formed as a continuous body.
- the line widths W1 and W2 of the line segments 31 and 32 of the parallel line pattern 3 are each preferably 10 ⁇ m or less. If it is 10 micrometers or less, since it will be a level which cannot be visually recognized normally, it is more preferable from a viewpoint of improving transparency. Considering the stability of the line segments 31 and 32, the line widths W1 and W2 of the line segments 31 and 32 are preferably in the range of 2 ⁇ m or more and 10 ⁇ m or less, respectively.
- the widths W1 and W2 of the line segments 31 and 32 are Z, which is the height of the thinnest part where the thickness of the functional material is the thinnest between the line segments 31 and 32.
- the protruding heights 31 and 32 are defined as Y1 and Y2, they are defined as the widths of the line segments 31 and 32 at half the height of Y1 and Y2.
- the height of the thinnest portion in the thin film portion 30 can be set to Z.
- the line widths W1 and W2 of the line segments 31 and 32 are the line segments 31 and 32 from the surface of the substrate 1. Are defined as the widths of the line segments 31 and 32 at half the heights H1 and H2.
- the line widths W1 and W2 of the line segments 31 and 32 constituting the parallel line pattern 3 are extremely thin as described above, from the viewpoint of securing the cross-sectional area and reducing the resistance, Higher heights H1 and H2 of the line segments 31 and 32 are desirable.
- the heights H1 and H2 of the line segments 31 and 32 are preferably in the range of 50 nm to 5 ⁇ m.
- the H1 / W1 ratio and the H2 / W2 ratio are preferably in the range of 0.01 or more and 1 or less, respectively.
- the height Z of the thin part is preferably in the range of 10 nm or less.
- the thin film portion 30 is provided in the range of 0 ⁇ Z ⁇ 10 nm in order to achieve a balance between transparency and stability.
- the H1 / Z ratio and the H2 / Z ratio are each preferably 5 or more, more preferably 10 or more, and 20 or more. Is particularly preferred.
- the range of the arrangement interval I of the line segments 31 and 32 is not particularly limited. As described with reference to FIGS. 17 to 19, when forming a line-shaped liquid, it is applied from a plurality of nozzles to a pixel group arranged in parallel to the nozzle row of the droplet discharge device. A plurality of droplet sets are provided in a direction intersecting the nozzle row, and a plurality of sets of the droplet sets are combined to form a line-shaped liquid extending in the direction intersecting the nozzle row, thereby disposing the arrangement interval I. Can be appropriately set with a high degree of freedom, and bulges can be suitably prevented even when the arrangement interval I is increased.
- the arrangement interval I is, for example, preferably in the range of 10 ⁇ m to 1000 ⁇ m, and more preferably in the range of 10 ⁇ m to 500 ⁇ m. Furthermore, it is also preferable that the arrangement interval I is adjusted to a range of 10 ⁇ m to 300 ⁇ m.
- the arrangement interval I between the line segments 31 and 32 is the distance between the maximum protrusions of the line segments 31 and 32.
- the line segment 31 and the line segment 32 it is preferable to give the same shape (similar cross-sectional area) to the line segment 31 and the line segment 32.
- the heights H1 and H2 of the line segment 31 and the line segment 32 are substantially equal.
- the line widths W1 and W2 of the line segment 31 and the line segment 32 are substantially equal values.
- the line segments 31 and 32 do not necessarily have to be parallel, and it is sufficient that the line segments 31 and 32 are not connected over at least a certain length L in the line segment direction. Preferably, the line segments 31 and 32 are substantially parallel over at least a certain length L in the line segment direction.
- the length L of the line segments 31 and 32 in the line segment direction is preferably 5 times or more the arrangement interval I of the line segments 31 and 32, and more preferably 10 times or more.
- the length L and the arrangement interval I can be set corresponding to the formation length and formation width of the pattern (line-shaped liquid) 2.
- the line segments 31 and 32 may be connected to form a continuous body at the start point and the end point (start point and end point over a certain length L in the line segment direction) of the line-shaped liquid.
- the line segments 31 and 32 have substantially the same line widths W1 and W2, and the line widths W1 and W2 are sufficiently narrower than the distance between the two lines (arrangement interval I). .
- the line segment 31 and the line segment 32 constituting the pattern 3 generated from one line-shaped liquid are formed at the same time.
- the line segments 31 and 32 satisfy all the following conditions (a) to (c). Thereby, it becomes difficult to visually recognize the pattern, the transparency can be improved, the line segment is stabilized, and particularly when the functional material is a conductive material, the effect of reducing the resistance value of the pattern is excellent.
- each line segment 31 and 32 is H1 and H2, and the height of the thinnest part in each line segment is Z, 5 ⁇ H1 / Z and 5 ⁇ H2 / Z.
- the description regarding the parallel line pattern 3 can be applied to the parallel line pattern 5.
- the inclination angle ⁇ of the formation direction of the line-shaped liquid with respect to the relative movement direction D of the droplet discharge device with respect to the base material has been shown mainly for 45 ° and ⁇ 45 °. It is not limited. If the formation direction of the line-shaped liquid is not a direction parallel to the relative movement direction D and is not a direction orthogonal to the relative movement direction D, an arbitrary inclination angle can be set.
- the present invention is not limited to this.
- the present invention by forming a line-shaped liquid along a direction inclined with respect to the relative movement direction D of the droplet discharge device with respect to the substrate, patterning when forming various patterns including parallel line patterns is performed.
- the degree of freedom increases. Accordingly, when various patterns are formed, flexible patterning is possible, and moire prevention and chamfering efficiency can be improved. Furthermore, the burden of resetting the arrangement angle between the inkjet head and the substrate can be reduced, and productivity can be improved.
- the substrate with a transparent conductive film has a transparent conductive film including a pattern formed by the pattern forming method described above on the surface of the substrate. Even if the functional material (conductive material) contained in the transparent conductive film is not transparent, the pattern is difficult to visually recognize by changing the line-shaped liquid into a parallel line pattern and making it thin. You can also.
- the use of the substrate with a transparent conductive film is not particularly limited, and can be used for various devices included in various electronic devices.
- a preferred application of the substrate with a transparent conductive film according to the present invention is a transparent electrode for various types of displays such as liquid crystal, plasma, organic electroluminescence, field emission, etc. It can be suitably used as a transparent electrode for use in touch panels, mobile phones, electronic paper, various solar cells, various electroluminescent light control devices, and the like.
- the substrate with a transparent conductive film according to the present invention is suitably used as a transparent electrode of a device.
- a device For example, a touch panel sensor etc. can be illustrated preferably.
- an electronic device provided with these devices For example, a smart phone, a tablet terminal, etc. can be illustrated preferably.
- Pattern formation method (Example 1) ⁇ Base material> As a base material, a PET base material that was surface-treated so that the contact angle of a liquid containing a functional material was 20.3 ° was prepared. As the surface treatment, corona discharge treatment was performed using “PS-1M” manufactured by Shinko Electric Instrumentation Co., Ltd.
- ⁇ Droplet ejection device As a droplet discharge device, an inkjet head of “KM1024iLHE-30” (standard droplet volume 30 pL) manufactured by Konica Minolta Co., Ltd. was prepared.
- Silver nanoparticles (average particle size: 20 nm): 0.16 wt% Surfactant (manufactured by Big Chemie “BYK348”): 0.05 wt% Diethylene glycol monobutyl ether (abbreviation: DEGBE) (dispersion medium): 20 wt% ⁇ Water (dispersion medium): remaining amount
- DEGBE Diethylene glycol monobutyl ether
- Ink is ejected from a plurality of nozzles of the droplet discharge device while moving the droplet discharge device relative to the base material, and a linear liquid is formed along the X-axis direction inclined by 45 ° with respect to the relative movement direction D. Formed. At this time, the relative movement direction D is a direction along the width direction of the base material.
- the linear liquid along the X-axis direction was evaporated and dried to selectively deposit the functional material on the edge of the linear liquid to form a parallel line pattern along the X-axis direction.
- drying of the line-shaped liquid is promoted by forming a pattern on a base material placed on a stage heated to 70 ° C.
- the Y-axis direction is a direction orthogonal to the above-described X-axis direction.
- the linear liquid along the Y-axis direction was evaporated and dried to selectively deposit the functional material on the edge of the linear liquid to form a parallel line pattern along the Y-axis direction.
- drying of the line-shaped liquid is promoted by forming a pattern on a base material placed on a stage heated to 70 ° C.
- the relative arrangement angle of the droplet discharge device with respect to the base material is not changed between the application of the line liquid along the X-axis direction and the application of the line liquid along the Y-axis direction. . That is, the relative movement direction D of the droplet discharge device with respect to the substrate is the same when the linear liquid along the X-axis direction is applied and when the linear liquid along the Y-axis direction is applied. The direction along the direction.
- the ink ejection by the droplet ejection device when forming the line-shaped liquid along the X-axis direction and the line-shaped liquid along the Y-axis direction was controlled as follows.
- Example 2 In Example 1, the same procedure as in Example 1 was used, except that a PET substrate surface-treated so that the contact angle of the liquid containing the functional material was 8.7 ° was used as the substrate. A pattern was formed.
- the surface treatment was a corona discharge treatment using “PS-1M” manufactured by Shinko Electric Instruments Co., Ltd. as in Example 1, but the treatment strength was adjusted so as to achieve the contact angle.
- Example 3 In Example 1, the same procedure as in Example 1 was used, except that a PET base material that was surface-treated so that the contact angle of the liquid containing the functional material was 10.4 ° was used as the base material. A pattern was formed.
- the surface treatment was a corona discharge treatment using “PS-1M” manufactured by Shinko Electric Instruments Co., Ltd. as in Example 1, but the treatment strength was adjusted so as to achieve the contact angle.
- Example 4 In Example 1, the same procedure as in Example 1 was used, except that a PET base material that was surface-treated so that the contact angle of the liquid containing the functional material was 29.7 ° was used as the base material. A pattern was formed.
- the surface treatment was a corona discharge treatment using “PS-1M” manufactured by Shinko Electric Instruments Co., Ltd. as in Example 1, but the treatment strength was adjusted so as to achieve the contact angle.
- Example 5 In Example 1, the same procedure as in Example 1 was used, except that a PET base material that was surface-treated so that the contact angle of the liquid containing the functional material was 32.3 ° was used as the base material. A pattern was formed.
- the surface treatment was a corona discharge treatment using “PS-1M” manufactured by Shinko Electric Instruments Co., Ltd. as in Example 1, but the treatment strength was adjusted so as to achieve the contact angle.
- Example 6 In Example 1, the number of gradations N was changed to 3 [dpd], and the product V ⁇ R was set to 3.24 ⁇ 10 4 [pL ⁇ npi].
- the concentration of silver nanoparticles in the ink was adjusted to 0.42 wt%.
- the application amount of silver nanoparticles applied per unit length of the line-shaped liquid was set to a value close to that of Example 1.
- Example 1 Except for the above points, a pattern was formed in the same manner as in Example 1.
- Example 7 In Example 1, the number of gradations N was changed to 4 [dpd], and the product V ⁇ R was set to 4.32 ⁇ 10 4 [pL ⁇ npi].
- the concentration of silver nanoparticles in the ink was adjusted to 0.32 wt%.
- the application amount of silver nanoparticles applied per unit length of the line-shaped liquid was set to a value close to that of Example 1.
- Example 1 Except for the above points, a pattern was formed in the same manner as in Example 1.
- Example 8 In Example 1, the number of gradations N was changed to 12 [dpd], and the product V ⁇ R was set to 1.30 ⁇ 10 5 [pL ⁇ npi].
- the concentration of silver nanoparticles in the ink was adjusted to 0.11 wt%.
- the application amount of silver nanoparticles applied per unit length of the line-shaped liquid was set to a value close to that of Example 1.
- Example 1 Except for the above points, a pattern was formed in the same manner as in Example 1.
- Example 9 In Example 1, the number of gradations N was changed to 16 [dpd], and the product V ⁇ R was 1.73 ⁇ 10 5 [pL ⁇ npi].
- the concentration of silver nanoparticles in the ink was adjusted to 0.08 wt%.
- the application amount of silver nanoparticles applied per unit length of the line-shaped liquid was set to a value close to that of Example 1.
- Example 1 Except for the above points, a pattern was formed in the same manner as in Example 1.
- Example 10 In Example 1, the pattern was formed in the same manner as in Example 1 except that the moving speed of the inkjet head was changed to set the maximum ejection time difference ⁇ t max to 101.3 [ms].
- Example 11 In Example 1, a pattern was formed in the same manner as in Example 1 except that the moving speed of the inkjet head was changed so that the maximum ejection time difference ⁇ t max was 192.4 [ms].
- Example 12 In Example 1, a pattern was formed in the same manner as in Example 1 except that the moving speed of the inkjet head was changed to set the maximum ejection time difference ⁇ t max to 222.8 [ms].
- Example 13 In Example 1, once the grant interval M p of the linear liquid applied and 398.8 [ms] by the path, except that the total number of passes was 2 times, in the same manner as in Example 1 pattern Formed.
- the number of passes when forming the line-shaped liquid along the X-axis direction is set to one, and the number of passes when forming the line-shaped liquid along the Y-axis direction is also set to one, so that the total number of passes is Twice.
- Example 14 In Example 1, one and 1196.4 [ms] grant interval M p of the linear liquid applied by the path, a except that the six total number of paths, in the same manner as in Example 1 pattern Formed.
- the number of passes when forming the line-shaped liquid along the X-axis direction is three times, and the number of passes when forming the line-shaped liquid along the Y-axis direction is also three, so that the total number of passes is 6 times.
- Example 15 In Example 1, the gradation number N was changed to 32 [dpd], and the product V ⁇ R was set to 3.45 ⁇ 10 5 [pL ⁇ npi]. Further, with the expansion of the two lines wide, a grant interval M p of the linear liquid imparted by one pass to 1,595.2 [[mu] m], a grant interval M of the linear liquid to be finally granted It was changed to 797.6 [ ⁇ m], respectively.
- the concentration of silver nanoparticles in the ink was adjusted to 0.04 wt%.
- the application amount of silver nanoparticles applied per unit length of the line-shaped liquid was set to a value close to that of Example 1.
- Example 16 In Example 1, the gradation number N was changed to 48 [dpd], and the product V ⁇ R was set to 5.18 ⁇ 10 5 [pL ⁇ npi]. Further, with the expansion of the two lines wide, a grant interval M p of the linear liquid imparted by one pass to 1,595.2 [[mu] m], a grant interval M of the linear liquid to be finally granted It was changed to 797.6 [ ⁇ m], respectively.
- the concentration of silver nanoparticles in the ink was adjusted to 0.027 wt%.
- the application amount of silver nanoparticles applied per unit length of the line-shaped liquid was set to a value close to that of Example 1.
- Example 17 In Example 1, the number of gradations N was changed to 54 [dpd], and the product V ⁇ R was 5.83 ⁇ 10 5 [pL ⁇ npi]. Further, with the expansion of the two lines wide, a grant interval M p of the linear liquid imparted by one pass to 1,595.2 [[mu] m], a grant interval M of the linear liquid to be finally granted It was changed to 797.6 [ ⁇ m], respectively.
- the concentration of silver nanoparticles in the ink was adjusted to 0.024 wt%.
- the application amount of silver nanoparticles applied per unit length of the line-shaped liquid was set to a value close to that of Example 1.
- Example 18 In the first embodiment, when forming the line-shaped liquid, as described with reference to FIGS. 17 to 19, a plurality of pixel sets arranged in parallel to the nozzle row of the droplet discharge device are used. A plurality of droplet sets applied from nozzles are applied in a direction crossing the nozzle row, and a plurality of sets of the droplet sets are combined to form a line-shaped liquid extending in the direction crossing the nozzle row. I made it. Specifically, the number of pixels constituting the pixel group in the nozzle row direction (the number of adjacent pixels) was set to 2. The gradation number N is set to 4 [dpd]. The product V ⁇ R was 8.64 ⁇ 10 4 [pL ⁇ npi].
- Example 19 In Example 18, the number of pixels constituting the pixel group in the nozzle row direction was eight.
- the gradation number N is set to 6 [dpd].
- the product V ⁇ R was 5.18 ⁇ 10 5 [pL ⁇ npi]. Further, with the expansion of the two lines wide, a grant interval M p of the linear liquid imparted by one pass to 1,595.2 [[mu] m], a grant interval M of the linear liquid to be finally granted It was changed to 797.6 [ ⁇ m], respectively.
- the concentration of silver nanoparticles in the ink was adjusted to 0.027 wt%.
- the application amount of the silver nanoparticles applied per unit length of the line-shaped liquid was set to a value close to that of Example 18.
- Comparative Example 1 The composition of the base material, the droplet discharge device and the ink used in Comparative Example 1 is the same as in Example 1.
- ⁇ Pattern formation> While moving the droplet discharge device relative to the substrate, ink is continuously discharged from the nozzle of the droplet discharge device, and the linear liquid is discharged along the X-axis direction, which is the same direction as the relative movement direction D. Formed. At this time, the relative movement direction D is a direction along the width direction of the base material.
- the linear liquid along the X-axis direction was evaporated and dried to selectively deposit the functional material on the edge of the linear liquid to form a parallel line pattern along the X-axis direction.
- drying of the line-shaped liquid is promoted by forming a pattern on a base material placed on a stage heated to 70 ° C.
- the substrate was rotated 90 ° with respect to the droplet discharge device to change the relative arrangement angle of the droplet discharge device with respect to the substrate. That is, the relative movement direction of the droplet discharge device with respect to the substrate was changed. Accordingly, the changed relative movement direction D of the droplet discharge device corresponds to the direction of formation of the previously formed parallel line pattern, that is, the direction orthogonal to the X-axis direction, that is, the Y-axis direction.
- the relative movement direction D after changing the arrangement is a direction along the longitudinal direction of the substrate.
- ink is discharged from the nozzles of the droplet discharge device while moving the droplet discharge device relative to the substrate, and the Y-axis direction is the same direction as the relative movement direction D.
- a line-like liquid was formed.
- the linear liquid along the Y-axis direction was evaporated and dried to selectively deposit the functional material on the edge of the linear liquid to form a parallel line pattern along the Y-axis direction.
- drying of the line-shaped liquid is promoted by forming a pattern on a base material placed on a stage heated to 70 ° C.
- the ink ejection by the droplet ejection device when forming the line-shaped liquid along the X-axis direction and the line-shaped liquid along the Y-axis direction was controlled as follows.
- Pattern properties As the pattern properties, the following items (bulge prevention, double line width and thin line width) were evaluated.
- the double line width ( ⁇ m) is obtained by measuring the distance between a set of two thin lines by observation with an optical microscope. The measured value corresponds to the interval I described above.
- the fine line width ( ⁇ m) is obtained by measuring the width of a set of two fine lines by observation with an optical microscope. The measured values correspond to the above-described widths W1 and W2. In addition, since the width
- the transmittance (total light transmittance) (% T) is the total light transmittance measured using AUTOMATIC ZEMETER (MODEL TC-HIIIDP) manufactured by Tokyo Denshoku. In addition, it corrected using the base material without a pattern, and measured it as the total light transmittance of the produced pattern.
- Sheet resistance The sheet resistance ( ⁇ / ⁇ ) was measured using a Loresta EP (MODEL MCP-T360 type) series 4-probe probe (ESP) manufactured by Dia Instruments. Prior to the above measurement, the substrate is heated on a hot plate at 120 ° C. for 1 hour to heat and sinter the pattern.
- Loresta EP MODEL MCP-T360 type
- ESP 4-probe probe
- Terminal resistance is a value obtained by measuring a resistance value between terminals (that is, between both ends in the longitudinal direction of the strip-shaped region) by forming a pattern in a strip-shaped region of 100 mm ⁇ 5 mm. Prior to the above measurement, the substrate is heated on a hot plate at 120 ° C. for 1 hour to heat and sinter the pattern.
- Example 1 when forming a line-shaped liquid, a plurality of droplets applied from one nozzle to one pixel are applied in a direction intersecting the nozzle row, and the plurality of droplets are combined. Thus, a line-shaped liquid extending in the direction intersecting with the nozzle row was formed.
- Examples 18 and 19 when forming a line-shaped liquid, droplets applied from a plurality of nozzles to a pixel group arranged in parallel to the nozzle row of the droplet discharge device A plurality of sets were provided in a direction intersecting the nozzle row, and a plurality of the droplet sets were combined to form a line-shaped liquid extending in the direction intersecting the nozzle row.
- the number of pixels constituting the pixel group in the nozzle row direction (the number of adjacent pixels) is 1 in Example 1, 2 in Example 18, and 8 in Example 19.
- Example 1 in which the line-shaped liquid is formed obliquely with respect to the relative movement direction of the droplet discharge device and the substrate, the basis for X-axis and Y-axis pattern formation as in Comparative Example 1 It can be seen that there is no need to change the material arrangement and productivity can be improved.
- Comparative Example 1 since the relative movement direction D of the droplet discharge device is set in a direction along the side of the base material, it was impossible to achieve both prevention of moire and improvement of chamfering efficiency. .
- Example 1 is excellent in bulge prevention as compared with Comparative Example 1. Furthermore, it can be seen that if the functional material is a conductive material, the effect of improving the sheet resistance and terminal resistance of the resulting pattern can be obtained.
- Example 20 Preparation of ink Ink 1 having the following composition was prepared.
- -Silver nanoparticle aqueous dispersion 1 (silver nanoparticles: 40 wt%): 1.75 wt% ⁇
- Silicon-based surfactant (“BYK-348" manufactured by Big Chemie): 0.01% by weight ⁇ Pure water: balance
- the base material 1 which consists of a PET base material which made the surface energy E of the base material 52 mN / m by easy-adhesion processing (surface treatment) was used as a base material.
- Pattern formation As a droplet discharge device, an inkjet head of “KM1024iLHE-30” (standard droplet volume 30 pL) manufactured by Konica Minolta Co., Ltd. was prepared. ⁇ Pattern formation> Ink is ejected from a plurality of nozzles of the droplet discharge device while moving the droplet discharge device relative to the base material, and a linear liquid is formed along the X-axis direction inclined by 45 ° with respect to the relative movement direction D. Formed. At this time, the relative movement direction D is a direction along the width direction of the base material.
- a functional material was selectively deposited on the edge of the line-shaped liquid to form a parallel line pattern along the X-axis direction.
- drying of the line-shaped liquid is promoted by forming a pattern on a base material placed on a stage heated to 70 ° C.
- ink is discharged from a plurality of nozzles of the droplet discharge device, and along the Y-axis direction inclined by ⁇ 45 ° with respect to the relative movement direction D, A line-like liquid was formed.
- the Y-axis direction is a direction orthogonal to the above-described X-axis direction.
- a functional material was selectively deposited on the edge of the line-shaped liquid to form a parallel line pattern along the Y-axis direction.
- drying of the line-shaped liquid is promoted by forming a pattern on a base material placed on a stage heated to 70 ° C.
- the relative arrangement angle of the droplet discharge device with respect to the base material is not changed between the application of the line liquid along the X-axis direction and the application of the line liquid along the Y-axis direction. .
- the relative movement direction D of the droplet discharge device with respect to the substrate is the same when the linear liquid along the X-axis direction is applied and when the linear liquid along the Y-axis direction is applied.
- the direction along the direction As described above, a mesh-like pattern in which the parallel line pattern along the X-axis direction intersects with the parallel line pattern along the Y-axis direction was obtained.
- the ink ejection by the droplet ejection device when forming the line liquid along the X-axis direction and the line liquid along the Y-axis direction was controlled as follows.
- the overall size of the mesh-like functional pattern is 50 mm ⁇ 50 mm.
- Example 21 Preparation of ink Ink 2 having the following composition was prepared. -Silver nanoparticle aqueous dispersion 2 (silver nanoparticles: 40 wt%): 1.75 wt% ⁇ Silicon-based surfactant ("BYK-348" manufactured by Big Chemie): 0.01% by weight ⁇ Pure water: balance
- the silver nanoparticle aqueous dispersion 2 is different in the dispersant from the silver nanoparticle aqueous dispersion 1 used in Example 20.
- Example 22 Ink preparation Ink 1 was used as the ink.
- the base material 2 made of a PET base material having a surface energy of 48 mN / m by easy adhesion processing (surface treatment) was used.
- Example 20 Measurement of surface energy and contact angle
- the substrate 1 of Example 20 was replaced with the substrate 2 and measured in the same manner as in Example 20.
- the surface energy C in the formation region of the first parallel line pattern was 56 mN / m.
- the contact angle F of the second linear liquid in the first parallel line pattern formation region is 17 °, and the contact angle of the second linear liquid outside the first parallel line pattern formation region. G was 28 °.
- Example 20 Formation of Pattern In Example 20, the substrate on which the first parallel line pattern was formed was placed on a hot plate at 120 ° C. and washed by heating for 1 hour.
- the second line liquid was applied and dried in the same manner as in Example 20 to form a second parallel line pattern.
- the overall size of the mesh-like functional pattern is 50 mm ⁇ 50 mm.
- Example 23 In Example 22, a mesh pattern was formed in the same manner as in Example 22 except that the cleaning by heating was changed to the cleaning by the following electromagnetic wave.
- Example 24 In Example 22, a mesh-like pattern was formed in the same manner as in Example 22 except that the cleaning by heating was changed to the cleaning with the following solvent.
- Example 25 Ink preparation Ink 1 was used as the ink.
- Example 20 Measurement of surface energy and contact angle
- the substrate 1 of Example 20 was replaced with the substrate 2 and measured in the same manner as in Example 20.
- the surface energy C in the formation region of the first parallel line pattern was 56 mN / m.
- the contact angle F of the second linear liquid in the first parallel line pattern formation region is 17 °, and the contact angle of the second linear liquid outside the first parallel line pattern formation region. G was 28 °.
- Example 20 when applying ink, the amount of applied liquid per length of the second line-shaped liquid in the first parallel line pattern formation region is set to be outside the first parallel line pattern formation region. The same procedure as in Example 20 was conducted, except that the coating was adjusted to 70% of the liquid application amount.
- the overall size of the mesh-like functional pattern is 50 mm ⁇ 50 mm.
- Example 26 Ink preparation Ink 1 was used as the ink.
- the base material 3 made of a PET base material having a surface energy E of 56 mN / m by easy adhesion processing (surface treatment) was used.
- aqueous dispersion 1 of silver nanoparticles (silver nanoparticles: 40% by weight) is applied to the substrate 3 with a wire bar # 7 and dried to obtain a functional material (silver).
- a solid surface of (nanoparticles) was prepared. The surface energy of this solid surface was measured and found to be 61 mN / m. This value was defined as the surface energy D of the solid surface obtained by applying and drying a liquid having the same composition as the first linear liquid.
- Example 20 was replaced with the base material 3, and as a result of measuring in the same manner as in Example 20, the surface energy C in the formation region of the first parallel line pattern was 56 mN / m.
- the contact angle F of the second linear liquid in the parallel line pattern formation region is 15 °
- the contact angle G of the second linear liquid outside the formation region of the first parallel line pattern is 19 °. Met.
- Example 27 Preparation of ink Ink 4 having the following composition was prepared. -Silver nanoparticle aqueous dispersion 1 (silver nanoparticles: 40 wt%): 1.75 wt% ⁇ Diethylene glycol monobutyl ether: 20% by weight ⁇ Pure water: balance
- Formation of Pattern A mesh-like functional pattern was formed in the same manner as in Example 20 except that the ink 1 was replaced with the ink 4 in Example 20.
- Example 28 Ink preparation Ink 1 was used as the ink.
- Example 20 Measurement of surface energy and contact angle
- the substrate 1 of Example 20 was replaced with the substrate 2 and measured in the same manner as in Example 20.
- the surface energy C in the formation region of the first parallel line pattern was 56 mN / m.
- the contact angle F of the second linear liquid in the first parallel line pattern formation region is 17 °, and the contact angle of the second linear liquid outside the first parallel line pattern formation region. G was 28 °.
- Formation of Pattern A mesh-like functional pattern was formed in the same manner as in Example 20 except that the substrate 1 was replaced with the substrate 2 in Example 20.
- the aqueous dispersion 3 of silver nanoparticles is different from the aqueous dispersions 1 and 2 of silver nanoparticles.
- Formation of Pattern A mesh-like functional pattern was formed in the same manner as in Example 20 except that the ink 1 was replaced with the ink 3 and the substrate 1 was replaced with the substrate 2 in Example 20.
- Example 29 Ink preparation Ink 4 was used as the ink.
- Example 27 Formation of Pattern In Example 27, a mesh-like functional pattern was formed in the same manner as in Example 27 except that the substrate 1 was replaced with the substrate 2.
- the average interval A in the formation region of the first parallel line pattern is set as the interval between the two line segments constituting the second parallel line pattern.
- the average value of intervals measured at a total of seven measurement points A 1 to A 7 described in FIG. 6 was obtained.
- the average interval B outside the first parallel line pattern forming region is set to a total of five measurement points B 1 to B described in FIG. It was calculated as the mean value of the measured intervals in B 5. Further, from the values of the average interval A and the average interval B, the value of B / A in the above formula (1) was obtained.
- the resistance ratio is 10% or less, and when the resistance ratio exceeds 10%, it can be evaluated that it is not practically preferable.
- FIG. 25 (b) and FIG. 25 (a) optical micrographs are shown in FIG. 25 (b) and FIG. 25 (a) for the mesh-like functional pattern of Example 22 and the mesh-like functional pattern of Example 29, respectively.
- the direction from the upper left to the lower right is the first direction (the direction of the first parallel line pattern), and the direction from the lower left to the upper right is the second direction (the direction of the second parallel line pattern).
- the present invention is excellent in low visibility. Further, it can be seen that there is no difference in the length of the conductive path between the first direction and the second direction, and thus it is possible to prevent unevenness of the resistance value.
- Example 22 “After cleaning the first parallel line pattern and before applying the second linear liquid, the region including the first parallel line pattern forming region is cleaned” adjustment
- the average interval A and the average interval B were made to satisfy the formula (1) “0.9 ⁇ B / A ⁇ 1.1”.
- cleaning by heating was used, in Example 23, cleaning by electromagnetic waves, and in Example 24, cleaning by solvent was used.
- Example 25 “the amount of liquid applied per length of the second line-shaped liquid in the first parallel line pattern formation region and the second line shape outside the first parallel line pattern formation region” By adjusting “different the amount of liquid applied per length of the liquid”, the average interval A and the average interval B were made to satisfy the formula (1) “0.9 ⁇ B / A ⁇ 1.1”.
- Example 26 “the difference (
- the average interval A and the average interval B are expressed by the equation (1)“ 0.9 ⁇ B /A ⁇ 1.1 ”.
- Example 27 by adjusting “the contact angle of the solvent having the highest boiling point out of the solvent in the second linear liquid outside the first parallel line pattern formation region is 6 ° or less”, the average interval A The average interval B satisfies the formula (1) “0.9 ⁇ B / A ⁇ 1.1”.
- Substrate 2 First line-shaped liquid 20: Droplet 3: First parallel line pattern 31, 32: Line segment (thin line) 4: Second line-shaped liquid 5: Second parallel line pattern 51, 52: Line segment (thin line) 6: Pattern 7: Droplet discharge device 71: Inkjet head 72: Nozzle 8: Drying device 9: Carriage D: Direction of relative movement of the droplet discharge device with respect to the substrate E: Transport direction of the substrate X: Intersection
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Abstract
Description
液滴吐出装置を基材に対して相対移動させながら該液滴吐出装置の複数のノズルから前記基材上に機能性材料を含む液体からなる液滴を吐出する際に、基材上において合一の対象となる互いに隣接する少なくとも1組の液滴は、相対移動方向及び該相対移動方向に直交する方向の何れにも間隔をおいて配置され、これらの液滴を合一するように、該液滴の液滴容量及び前記間隔の一方又は両方を調整し、
前記液滴を合一して形成されたライン状液体を乾燥させることによって該ライン状液体の縁に前記機能性材料を堆積させて該機能性材料を含むパターンを形成するパターン形成方法。
前記ライン状液体の形成において、前記液滴吐出装置のノズル列に対して平行に配置される画素組に対して複数のノズルから付与される液滴組を、ノズル列と交差する方向に複数組付与し、複数組の前記液滴組を合一させて、ノズル列と交差する方向に伸びる前記ライン状液体を形成する前記1記載のパターン形成方法。
前記液滴を合一して形成される前記ライン状液体の縁の直線性を高めるように、前記液滴容量及び前記間隔の一方又は両方を調整する前記1又は2記載のパターン形成方法。
1つの前記ライン状液体を形成するために1つの前記ノズルから吐出される総液滴容量V[pL]と、前記複数のノズルの前記相対移動方向に直交する方向におけるノズル列解像度R[npi]との積V・R[pL・npi]を、4.32×104[pL・npi]以上5.18×105[pL・npi]以下の範囲に調整する前記1~3の何れかに記載のパターン形成方法。
前記液滴容量を、階調数の調整により調整する前記1~4の何れかに記載のパターン形成方法。
前記液滴吐出装置から吐出される前記液滴の前記基材上における接触角が10[°]以上30[°]以下の範囲である前記1~5の何れかに記載のパターン形成方法。
前記相対移動による1回のパスで1つ又は複数の前記ライン状液体を形成する前記1~6の何れかに記載のパターン形成方法。
前記相対移動による1回のパスで互いに平行な複数の前記ライン状液体を形成する際に、該ライン状液体の付与間隔を調整することにより、隣り合う前記ライン状液体を乾燥させる際の相互干渉を抑制する前記1~7の何れかに記載のパターン形成方法。
前記相対移動による1回のパスで互いに平行な複数の前記ライン状液体を形成する際に、該ライン状液体の付与間隔の調整を、各々の前記ノズルから前記液滴を吐出する時間間隔、及び、前記液滴吐出装置の基材に対する相対移動速度の一方又は両方を調整することによって行う前記1~8の何れかに記載のパターン形成方法。
前記相対移動による1回のパスで互いに平行な複数の前記ライン状液体を形成する際に、該ライン状液体の付与間隔を、400[μm]以上に調整する前記1~9の何れかに記載のパターン形成方法。
前記液滴の合一を促進するように、1つの前記ライン状液体を形成するために互いに隣接する前記ノズルからそれぞれ吐出される前記機能性材料を含む液体の最大吐出時間差Δtmaxを、200[ms]以下に調整する前記1~10の何れかに記載のパターン形成方法。
前記基材上に第1の前記ライン状液体を付与し、該第1のライン状液体を乾燥させる過程で該機能性材料を縁部に選択的に堆積させて、該機能性材料を含む2本の線分により構成された第1の平行線パターンを形成し、
次いで、前記基材上に前記第1の平行線パターンの形成領域と交差させるように第2の前記ライン状液体を付与し、該第2のライン状液体を乾燥させる過程で該機能性材料を縁部に選択的に堆積させて、該機能性材料を含む2本の線分により構成された第2の平行線パターンを形成することによって、
前記第1の平行線パターンと前記第2の平行線パターンとが少なくとも1つの交点で交わるパターンを形成する前記1~11の何れかに記載のパターン形成方法。
前記第2の平行線パターンを構成する前記2本の線分間の間隔について、前記第1の平行線パターンの形成領域内における平均間隔Aと、前記第1の平行線パターンの形成領域外における平均間隔Bとが下記式(1)を満たすように調整する前記12記載のパターン形成方法。
0.9≦B/A≦1.1 ・・・式(1)
前記式(1)を満たすための調整として、前記第1の平行線パターンの形成領域内の表面エネルギーと、前記第1の平行線パターンの形成領域外の表面エネルギーとの差を、5mN/m以下にする前記13記載のパターン形成方法。
前記式(1)を満たすための調整として、前記第1のライン状液体に含まれる機能性材料を塗布して乾燥させたベタ面の表面エネルギーと、前記第1の平行線パターンの形成領域外の表面エネルギーとの差を、5mN/m以下にする前記13記載のパターン形成方法。
前記式(1)を満たすための調整として、前記第1の平行線パターンの形成領域内における前記第2のライン状液体の接触角と、前記第1の平行線パターンの形成領域外における前記第2のライン状液体の接触角との差を、10°以下にする前記13記載のパターン形成方法。
前記式(1)を満たすための調整として、前記第1のライン状液体に含まれる機能性材料を塗布して乾燥させたベタ面における前記第2のライン状液体の接触角と、前記第1の平行線パターンの形成領域外における前記第2のライン状液体の接触角との差を、10°以下にする前記13記載のパターン形成方法。
前記式(1)を満たすための調整として、前記第1の平行線パターンの形成領域外における前記第2のライン状液体中の溶剤のうち最も沸点が高い溶剤の接触角を6°以下にする前記13記載のメッシュ状の機能性パターンの形成方法。
前記式(1)を満たすための調整として、前記第1の平行線パターンの形成領域内における前記第2のライン状液体の長さあたりの液体付与量と、前記第1の平行線パターンの形成領域外における前記第2のライン状液体の長さあたりの液体付与量とを異ならせる前記13記載のパターン形成方法。
前記式(1)を満たすための調整として、前記第1の平行線パターンを形成した後に、前記第2のライン状液体を付与する前に、前記第1の平行線パターンの形成領域内を含む領域を洗浄する前記13に記載のパターン形成方法。
前記洗浄として、加熱による洗浄、電磁波による洗浄、溶剤による洗浄、ガスによる洗浄及びプラズマによる洗浄から選ばれた1種又は2種以上を組み合わせた洗浄を行う前記20記載のパターン形成方法。
前記ライン状液体の乾燥に際して、乾燥を促進させる処理を施す前記1~21の何れかに記載のパターン形成方法。
前記液滴吐出装置から吐出される前記液体の機能性材料含有率が、0.01重量%以上1重量%以下の範囲である前記1~22の何れかに記載のパターン形成方法。
前記機能性材料は、導電性材料または導電性材料前駆体である前記1~23の何れかに記載のパターン形成方法。
前記1~24の何れかに記載のパターン形成方法により形成されたパターンを含む透明導電膜を基材表面に有する透明導電膜付き基材。
前記25記載の透明導電膜付き基材を有するデバイス。
前記26記載のデバイスを備えた電子機器。
(イ)各線分31、32の幅をW1、W2としたときに、W1≦10μm、且つW2≦10μmであること。
(ウ)各線分31、32の高さをH1、H2としたときに、50nm<H1<5μm、且つ50nm<H2<5μmであること。
(実施例1)
<基材>
基材として、機能性材料を含む液体の接触角が20.3°となるように表面処理が施されたPET基材を用意した。表面処理としては、信光電気計装社製「PS-1M」を用いてコロナ放電処理を行った。
液滴吐出装置として、コニカミノルタ社製「KM1024iLHE-30」(標準液滴容量30pL)のインクジェットヘッドを用意した。
インク(機能性材料を含む液体)として、以下の組成のものを調製した。
・界面活性剤(ビッグケミー社製「BYK348」):0.05wt%
・ジエチレングリコールモノブチルエーテル(略称:DEGBE)(分散媒):20wt%
・水(分散媒):残量
液滴吐出装置を基材に対して相対移動させながら該液滴吐出装置の複数のノズルからインクを吐出し、相対移動方向Dに対して45°傾斜するX軸方向に沿って、ライン状液体を形成した。このとき、相対移動方向Dは、基材の幅方向に沿う方向である。
・1液滴あたりの液滴容量Vd=30[pL]
・階調数N=8[dpd]
・1つのライン状液体を形成するために1つのノズルから付与される総液滴容量V(=Vd[pL]×N[dpd])=240[pL]
・ノズル列解像度R=360[npi]
・積V・R=8.64×104[pL・npi]
・1つのライン状液体を形成するために互いに隣接するノズルからそれぞれ吐出される機能性材料を含む液体の最大吐出時間差Δtmax=81.0[ms]
・1回のパスにより付与されるライン状液体の付与間隔Mp=797.6[μm]
・最終的に付与されるライン状液体の付与間隔M=398.8[μm]
・総パス数
X軸方向に沿うライン状液体を形成する際のパス数を2回とし、Y軸方向に沿うライン状液体を形成する際のパス数も2回とした。これらパス数の合計である総パス数は4回である。1回のパスにより付与されるライン状液体の付与間隔Mpと、最終的に付与されるライン状液体の付与間隔Mを考慮して、パス数を設定している。
実施例1において、基材として、機能性材料を含む液体の接触角が8.7°となるように表面処理が施されたPET基材を用いたこと以外は、実施例1と同様にしてパターンを形成した。表面処理は、実施例1と同様に信光電気計装社製「PS-1M」を用いたコロナ放電処理であるが、上記接触角となるように処理強度を調整した。
実施例1において、基材として、機能性材料を含む液体の接触角が10.4°となるように表面処理が施されたPET基材を用いたこと以外は、実施例1と同様にしてパターンを形成した。表面処理は、実施例1と同様に信光電気計装社製「PS-1M」を用いたコロナ放電処理であるが、上記接触角となるように処理強度を調整した。
実施例1において、基材として、機能性材料を含む液体の接触角が29.7°となるように表面処理が施されたPET基材を用いたこと以外は、実施例1と同様にしてパターンを形成した。表面処理は、実施例1と同様に信光電気計装社製「PS-1M」を用いたコロナ放電処理であるが、上記接触角となるように処理強度を調整した。
実施例1において、基材として、機能性材料を含む液体の接触角が32.3°となるように表面処理が施されたPET基材を用いたこと以外は、実施例1と同様にしてパターンを形成した。表面処理は、実施例1と同様に信光電気計装社製「PS-1M」を用いたコロナ放電処理であるが、上記接触角となるように処理強度を調整した。
実施例1において、階調数Nを3[dpd]に変更し、積V・Rを3.24×104[pL・npi]とした。
実施例1において、階調数Nを4[dpd]に変更し、積V・Rを4.32×104[pL・npi]とした。
実施例1において、階調数Nを12[dpd]に変更し、積V・Rを1.30×105[pL・npi]とした。
実施例1において、階調数Nを16[dpd]に変更し、積V・Rを1.73×105[pL・npi]とした。
実施例1において、インクジェットヘッドの移動速度を変更して最大吐出時間差Δtmaxを101.3[ms]としたこと以外は、実施例1と同様にしてパターンを形成した。
実施例1において、インクジェットヘッドの移動速度を変更して最大吐出時間差Δtmaxを192.4[ms]としたこと以外は、実施例1と同様にしてパターンを形成した。
実施例1において、インクジェットヘッドの移動速度を変更して最大吐出時間差Δtmaxを222.8[ms]としたこと以外は、実施例1と同様にしてパターンを形成した。
実施例1において、1回のパスにより付与されるライン状液体の付与間隔Mpを398.8[ms]とし、総パス数を2回としたこと以外は、実施例1と同様にしてパターンを形成した。
実施例1において、1回のパスにより付与されるライン状液体の付与間隔Mpを1196.4[ms]とし、総パス数を6回としたこと以外は、実施例1と同様にしてパターンを形成した。
実施例1において、階調数Nを32[dpd]に変更し、積V・Rを3.45×105[pL・npi]とした。また、2本線幅の拡大に伴って、1回のパスにより付与されるライン状液体の付与間隔Mpを1595.2[μm]に、最終的に付与されるライン状液体の付与間隔Mを797.6[μm]に、それぞれ変更した。
実施例1において、階調数Nを48[dpd]に変更し、積V・Rを5.18×105[pL・npi]とした。また、2本線幅の拡大に伴って、1回のパスにより付与されるライン状液体の付与間隔Mpを1595.2[μm]に、最終的に付与されるライン状液体の付与間隔Mを797.6[μm]に、それぞれ変更した。
実施例1において、階調数Nを54[dpd]に変更し、積V・Rを5.83×105[pL・npi]とした。また、2本線幅の拡大に伴って、1回のパスにより付与されるライン状液体の付与間隔Mpを1595.2[μm]に、最終的に付与されるライン状液体の付与間隔Mを797.6[μm]に、それぞれ変更した。
実施例1において、ライン状液体を形成する際に、図17~図19を参照して説明したように、液滴吐出装置のノズル列に対して平行に配置される画素組に対して複数のノズルから付与される液滴組を、ノズル列と交差する方向に複数組付与し、複数組の前記液滴組を合一させて、ノズル列と交差する方向に伸びるライン状液体を形成するようにした。具体的には、ノズル列方向の画素組を構成する画素数(隣接画素数)を2とした。また、階調数Nは4[dpd]に設定した。積V・Rは8.64×104[pL・npi]とした。
実施例18において、ノズル列方向の画素組を構成する画素数を8とした。また、階調数Nは6[dpd]に設定した。積V・Rは5.18×105[pL・npi]とした。また、2本線幅の拡大に伴って、1回のパスにより付与されるライン状液体の付与間隔Mpを1595.2[μm]に、最終的に付与されるライン状液体の付与間隔Mを797.6[μm]に、それぞれ変更した。
比較例1で用いた基材、液滴吐出装置及びインクの組成は、実施例1と同様である。
液滴吐出装置を基材に対して相対移動させながら該液滴吐出装置のノズルから連続的にインクを吐出し、相対移動方向Dと同方向であるX軸方向に沿って、ライン状液体を形成した。このとき、相対移動方向Dは、基材の幅方向に沿う方向である。
・1液滴あたりの液滴容量Vd=30[pL]
・階調数N=8[dpd]
・1回のパスにより付与されるライン状液体の付与間隔Mp=797.6[μm]
・最終的に付与されるライン状液体の付与間隔M=398.8[μm]
・総パス数
X軸方向に沿うライン状液体を形成する際のパス数を2回とし、Y軸方向に沿うライン状液体を形成する際のパス数も2回とした。これらパス数の合計である総パス数は4回である。
各実施例及び比較例で形成されたパターンについて、パターン性状及び物性値を評価した。
パターン性状として、以下の項目(バルジ防止性、2本線幅及び細線幅)について評価した。
表1~5に示す2本線性状は、光学顕微鏡観察により1組2本の細線を細線形成方向に50mmに渡り観察し、バルジ防止性を下記評価基準で評価した。
A:バルジが生じなかった
B:バルジが生じた(3ヶ所以下)
C:バルジが生じた(4ヶ所以上)
2本線幅(μm)は、光学顕微鏡観察により1組2本の細線間の間隔を測定したものである。測定値は、上述した間隔Iに相当する。
細線幅(μm)は、光学顕微鏡観察により1組2本の細線の幅を測定したものである。測定値は、上述した幅W1、W2に相当する。なお、2本の細線の幅は実質的に同じであったため、一方の細線の測定値をもって細線幅(μm)とした。
物性値として、以下の項目(透過率、シート抵抗及び端子抵抗)について評価した。
透過率(全光線透過率)(%T)は、東京電色社製AUTOMATICHAZEMETER(MODEL TC-HIIIDP)を用いて測定した全光線透過率である。なお、パターンのない基材を用いて補正を行い、作成したパターンの全光線透過率として測定した。
シート抵抗(Ω/□)は、ダイアインスツルメンツ社製ロレスタEP(MODEL MCP―T360型)直列4探針プローブ(ESP)を用いて、シート抵抗値を測定した。
上記測定の前に、120℃で1時間、ホットプレート上で基材を加熱することによって、パターンに加熱焼成処理を施している。
端子抵抗(Ω)は、100mm×5mmの短冊状の領域にパターンを形成し、端子間(即ち、短冊状領域の長手方向の両端間)の抵抗値を測定した値である。
上記測定の前に、120℃で1時間、ホットプレート上で基材を加熱することによって、パターンに加熱焼成処理を施している。
(1)接触角の影響
表1に実施例1~5の結果を示す。実施例1~5は、機能性材料を含む液体の接触角を異ならせたものである。
表2に実施例1、6~9及び15~17の結果を示す。実施例1、6~9及び15~17は、1つのライン状液体を形成するために1つのノズルから付与される総液滴容量Vと、ノズル列解像度Rの積V・Rを異ならせたものである。具体的には、階調数Nの調整によって、積V・Rを変化させている。なお、インク中の銀ナノ粒子濃度の調整により、ライン状液体の単位長さ当たりに付与される銀ナノ粒子の付与量が、実施例1と近い値になるようにしている。
表3に実施例1、10~12の結果を示す。実施例1、10~12は、1つのライン状液体を形成するために互いに隣接するノズルからそれぞれ吐出される機能性材料を含む液体の最大吐出時間差Δtmaxを異ならせたものである。
表4に実施例1、13及び14の結果を示す。実施例1、13及び14は、1回のパスにより付与されるライン状液体の付与間隔Mpを異ならせたものである。1回のパスにより付与されるライン状液体の付与間隔Mpに応じて、最終的に付与されるライン状液体の付与間隔Mを実現できるように、パス数を設定している。
表5に実施例1、18及び19の結果を示す。実施例1では、ライン状液体を形成する際に、1画素に対して1つのノズルから付与される液滴を、ノズル列と交差する方向に複数付与し、複数の前記液滴を合一させて、ノズル列と交差する方向に伸びるライン状液体を形成した。これに対して、実施例18及び19では、ライン状液体を形成する際に、液滴吐出装置のノズル列に対して平行に配置される画素組に対して複数のノズルから付与される液滴組を、ノズル列と交差する方向に複数組付与し、複数組の前記液滴組を合一させて、ノズル列と交差する方向に伸びるライン状液体を形成した。ノズル列方向の画素組を構成する画素数(隣接画素数)は、実施例1では1、実施例18では2、実施例19では8としている。
更に、表6に実施例1及び比較例1の結果を示す。
1.インクの調製
下記組成からなるインク1を調製した。
・銀ナノ粒子の水分散液1(銀ナノ粒子:40重量%):1.75重量%
・シリコン系界面活性剤(ビックケミー製「BYK-348」):0.01重量%
・純水:残部
基材として、易接着加工(表面処理)により基材の表面エネルギーEを52mN/mとしたPET基材からなる基材1を用いた。
メッシュ状の機能性パターンを形成する前に、インク1で形成される第1の平行線パターンの形成領域内の表面エネルギー及び第2のライン状液体の接触角について、代用の方法により測定を行った。
基材1に、インク1を20μL滴下し、乾燥させて、液滴の周囲にコーヒーリング現象によるリング状細線を形成した。その後、このリング状細線の内部の中心領域に対する、水、炭酸プロピレン、ジヨードメタンの接触角を測定し、Young-Fowkes式より、表面エネルギーを算出した。ここで、水、炭酸プロピレン、ジヨードメタンの接触角の測定は、協和界面化学社製接触角測定装置「DM-501」を用いて行った(以下に説明する接触角の測定にも同装置を用いた。)。算出された表面エネルギーの値は56mN/mであった。この値を、第1の平行線パターンの形成領域内の表面エネルギーCとした。
ア.第1の平行線パターンの形成領域内における第2のライン状液体の接触角の測定 インク1に対する接触角が22°となる易接着加工付ポリエチレンテレフタレート(PET)基材に、インク1を20μL滴下し、乾燥させて、液滴の周囲にコーヒーリング現象によるリング状細線を形成した。その後、このリング状細線の内部の中心領域に対する、インク1(第2のライン状液体と同組成)の接触角を測定した。測定された接触角は、17°であった。この値を、第1の平行線パターンの形成領域内における第2のライン状液体の接触角Fとした。
基材表面にインク1を3μL滴下して、基材表面における第2のライン状液体の接触角を測定した。測定された接触角は、20°であった。この値を、第1の平行線パターンの形成領域外における第2のライン状液体の接触角Gとした。
<液滴吐出装置>
液滴吐出装置として、コニカミノルタ社製「KM1024iLHE-30」(標準液滴容量30pL)のインクジェットヘッドを用意した。
<パターンの形成>
液滴吐出装置を基材に対して相対移動させながら該液滴吐出装置の複数のノズルからインクを吐出し、相対移動方向Dに対して45°傾斜するX軸方向に沿って、ライン状液体を形成した。このとき、相対移動方向Dは、基材の幅方向に沿う方向である。
X軸方向に沿うライン状液体を蒸発させ、乾燥させることにより、該ライン状液体の縁に機能性材料を選択的に堆積させて、X軸方向に沿う平行線パターンを形成した。ここでは、70℃に加熱されたステージ上に配置した基材にパターン形成することにより、ライン状液体の乾燥を促進させている。
次いで、液滴吐出装置を基材に対して相対移動させながら該液滴吐出装置の複数のノズルからインクを吐出し、相対移動方向Dに対して-45°傾斜するY軸方向に沿って、ライン状液体を形成した。ここで、Y軸方向は、上述したX軸方向と直交する方向である。
Y軸方向に沿うライン状液体を蒸発させ、乾燥させることにより、該ライン状液体の縁に機能性材料を選択的に堆積させて、Y軸方向に沿う平行線パターンを形成した。ここでは、70℃に加熱されたステージ上に配置した基材にパターン形成することにより、ライン状液体の乾燥を促進させている。
上記パターン形成において、X軸方向に沿うライン状液体の付与時と、Y軸方向に沿うライン状液体の付与時とで、基材に対する液滴吐出装置の相対的な配置角度は変更していない。即ち、X軸方向に沿うライン状液体の付与時と、Y軸方向に沿うライン状液体の付与時とで、基材に対する液滴吐出装置の相対移動方向Dは同一であり、基材の幅方向に沿う方向である。
以上のようにして、X軸方向に沿う平行線パターンと、Y軸方向に沿う平行線パターンとが交差するメッシュ状のパターンを得た。
以上のパターン形成において、X軸方向に沿うライン状液体及びY軸方向に沿うライン状液体をそれぞれ形成する際の液滴吐出装置によるインク吐出は、以下のように制御された。
<インク吐出制御>
・1液滴あたりの液滴容量Vd=30[pL]
・階調数N=3[dpd]
・1つのライン状液体を形成するために1つのノズルから付与される総液滴容量V(=Vd[pL]×N[dpd])=90[pL]
・ノズル列解像度R=360[npi]
・積V・R=3.24×104[pL・npi]
・ライン状液体の塗布間隔=282[μm]
・総パス数
X軸方向に沿うライン状液体を形成する際のパス数を1回とし、Y軸方向に沿うライン状液体を形成する際のパス数も1回とした。
1.インクの調製
下記組成からなるインク2を調製した。
・銀ナノ粒子の水分散液2(銀ナノ粒子:40重量%):1.75重量%
・シリコン系界面活性剤(ビックケミー製「BYK-348」):0.01重量%
・純水:残部
基材として、基材1(表面エネルギーE=52mN/m)を用いた。
実施例20のインク1をインク2に代えて、実施例20と同様に測定した結果、第1の平行線パターンの形成領域内の表面エネルギーCは49mN/mであり、第1の平行線パターンの形成領域内における第2のライン状液体の接触角Fは25°であり、第1の平行線パターンの形成領域外における第2のライン状液体の接触角Gは、21°であった。
インク1をインク2に変えた以外は実施例20と同様にして、メッシュ状の機能性パターンを形成した。
1.インクの調製
インクとして、インク1を用いた。
基材として、易接着加工(表面処理)により基材の表面エネルギーを48mN/mとしたPET基材からなる基材2を用いた。
実施例20の基材1を基材2に代えて、実施例20と同様に測定した結果、第1の平行線パターンの形成領域内の表面エネルギーCは56mN/mであり、第1の平行線パターンの形成領域内における第2のライン状液体の接触角Fは17°であり、第1の平行線パターンの形成領域外における第2のライン状液体の接触角Gは、28°であった。
実施例20において、第1の平行線パターンを形成した基材を120℃のホットプレートの上に置いて、1時間、加熱による洗浄を行った。
実施例22において、加熱による洗浄を、下記電磁波による洗浄に変更した以外は実施例22と同様にして、メッシュ状のパターンを形成した。
電磁波による洗浄として、キセノンフラッシュランプによる洗浄を行った。
Xenon社製キセノンフラッシュランプ装置「SINTERON 2000」を用いて、パルス幅500μ秒、印加電圧3.8kVでキセノンフラッシュを1回照射して、第1の平行線パターンの形成領域内を含む領域を洗浄した。
実施例22において、加熱による洗浄を、下記溶剤による洗浄に変更した以外は実施例22と同様にして、メッシュ状のパターンを形成した。
2プロパノールに10分間浸漬させることにより、第1の平行線パターンの形成領域内を含む領域を洗浄した。
1.インクの調製
インクとして、インク1を用いた。
基材として、基材2(表面エネルギーE=48mN/m)を用いた。
実施例20の基材1を基材2に代えて、実施例20と同様に測定した結果、第1の平行線パターンの形成領域内の表面エネルギーCは56mN/mであり、第1の平行線パターンの形成領域内における第2のライン状液体の接触角Fは17°であり、第1の平行線パターンの形成領域外における第2のライン状液体の接触角Gは、28°であった。
実施例20において、インクの塗布に際して、第1の平行線パターンの形成領域内における第2のライン状液体の長さあたりの液体付与量を、第1の平行線パターンの形成領域外における液体付与量の70%に調整して塗布したこと以外は、実施例20と同様にした。
1.インクの調製
インクとして、インク1を用いた。
基材として、易接着加工(表面処理)により基材の表面エネルギーEを56mN/mとしたPET基材からなる基材3を用いた。
まず、銀ナノ粒子の水分散液1(銀ナノ粒子:40重量%)を、基材3に、ワイヤーバー#7にて塗布し、乾燥させて機能性材料(銀ナノ粒子)のベタ面を作製した。このベタ面の表面エネルギーを測定したところ、61mN/mであった。この値を、第1のライン状液体と同一組成の液体を塗布して乾燥させてなるベタ面の表面エネルギーDとした。
実施例20において、基材1を基材3に代えたこと以外は実施例20と同様にして、メッシュ状の機能性パターンを形成した。
1.インクの調製
下記組成からなるインク4を調製した。
・銀ナノ粒子の水分散液1(銀ナノ粒子:40重量%):1.75重量%
・ジエチレングリコールモノブチルエーテル:20重量%
・純水:残部
基材として、基材1(表面エネルギーE=52mN/m)を用いた。
協和界面化学社製接触角測定装置「DM-501」を用いて、第1の平行線パターンの形成領域外におけるジエチレングリコールモノブチルエーテル(沸点231℃)の接触角を測定したところ、接触角Hは5°であった。なお、ジエチレングリコールモノブチルエーテルを滴下後5秒後の値とした。
実施例20において、インク1をインク4に代えたこと以外は実施例20と同様にして、メッシュ状の機能性パターンを形成した。
1.インクの調製
インクとして、インク1を用いた。
基材として、基材2(表面エネルギーE=48mN/m)を用いた。
実施例20の基材1を基材2に代えて、実施例20と同様に測定した結果、第1の平行線パターンの形成領域内の表面エネルギーCは56mN/mであり、第1の平行線パターンの形成領域内における第2のライン状液体の接触角Fは17°であり、第1の平行線パターンの形成領域外における第2のライン状液体の接触角Gは、28°であった。
実施例20において、基材1を基材2に代えたこと以外は実施例20と同様にして、メッシュ状の機能性パターンを形成した。
1.インクの調製
下記組成からなるインク3を調製した。
・銀ナノ粒子の水分散液3(銀ナノ粒子:40重量%):1.75重量%
・シリコン系界面活性剤(ビックケミー製「BYK-348」):0.01重量%
・純水:残部
基材として、基材2(表面エネルギーE=48mN/m)を用いた。
実施例20のインク1をインク3に代え、更に基材1を基材2に代えて、実施例20と同様に測定した結果、第1の平行線パターンの形成領域内の表面エネルギーCは61mN/mであり、第1の平行線パターンの形成領域内における第2のライン状液体の接触角Fは12°であり、第1の平行線パターンの形成領域外における第2のライン状液体の接触角Gは、29°であった。
実施例20において、インク1をインク3に代え、更に基材1を基材2に代えたこと以外は実施例20と同様にして、メッシュ状の機能性パターンを形成した。
1.インクの調製
インクとして、インク4を用いた。
基材として、基材2(表面エネルギーE=48mN/m)を用いた。
協和界面化学社製接触角測定装置「DM-501」を用いて、第1の平行線パターンの形成領域外におけるジエチレングリコールモノブチルエーテル(沸点231℃)の接触角を測定したところ、接触角Hは8°であった。なお、ジエチレングリコールモノブチルエーテルを滴下後5秒後の値とした。
実施例27において、基材1を基材2に代えたこと以外は実施例27と同様にして、メッシュ状の機能性パターンを形成した。
実施例20~30で得られたメッシュ状の機能性パターンにおいて、第2の平行線パターンを構成する2本の線分間の間隔について、第1の平行線パターンの形成領域内における平均間隔Aを、図6で説明した計7箇所の測定箇所A1~A7において測定した間隔の平均値として求めた。また、第2の平行線パターンを構成する2本の線分間の間隔について、第1の平行線パターンの形成領域外における平均間隔Bを、図6で説明した計5箇所の測定箇所B1~B5において測定した間隔の平均値として求めた。更に、これら平均間隔A及び平均間隔Bの値から、上述した式(1)におけるB/Aの値を求めた。
・低視認性の評価方法
実施例20~30で得られたメッシュ状の機能性パターンを目視し、下記の評価基準で評価した。
A:周期的なパターンのようなものが視認できず、全体に亘って均一に見える
B:周期的なパターンのようなものが視認できる
実施例20~30で得られたメッシュ状の機能性パターンについて、以下の方法で抵抗値の方向むらを評価した。
表7より、平均間隔A及び平均間隔Bが式(1)「0.9≦B/A≦1.1」を満たすように調整を行った実施例20~27では、低視認性に優れ、抵抗値の方向むらを防止できることがわかる。一方、かかる調整を行わなかった実施例28~30では、低視認性に劣り、抵抗値の方向むらを十分に防止できないことがわかる。
2:第1のライン状液体
20:液滴
3:第1の平行線パターン
31、32:線分(細線)
4:第2のライン状液体
5:第2の平行線パターン
51、52:線分(細線)
6:パターン
7:液滴吐出装置
71:インクジェットヘッド
72:ノズル
8:乾燥装置
9:キャリッジ
D:基材に対する液滴吐出装置の相対移動方向
E:基材の搬送方向
X:交差部
Claims (27)
- 液滴吐出装置を基材に対して相対移動させながら該液滴吐出装置の複数のノズルから前記基材上に機能性材料を含む液体からなる液滴を吐出する際に、基材上において合一の対象となる互いに隣接する少なくとも1組の液滴は、相対移動方向及び該相対移動方向に直交する方向の何れにも間隔をおいて配置され、これらの液滴を合一するように、該液滴の液滴容量及び前記間隔の一方又は両方を調整し、
前記液滴を合一して形成されたライン状液体を乾燥させることによって該ライン状液体の縁に前記機能性材料を堆積させて該機能性材料を含むパターンを形成するパターン形成方法。 - 前記ライン状液体の形成において、前記液滴吐出装置のノズル列に対して平行に配置される画素組に対して複数のノズルから付与される液滴組を、ノズル列と交差する方向に複数組付与し、複数組の前記液滴組を合一させて、ノズル列と交差する方向に伸びる前記ライン状液体を形成する請求項1記載のパターン形成方法。
- 前記液滴を合一して形成される前記ライン状液体の縁の直線性を高めるように、前記液滴容量及び前記間隔の一方又は両方を調整する請求項1又は2記載のパターン形成方法。
- 1つの前記ライン状液体を形成するために1つの前記ノズルから吐出される総液滴容量V[pL]と、前記複数のノズルの前記相対移動方向に直交する方向におけるノズル列解像度R[npi]との積V・R[pL・npi]を、4.32×104[pL・npi]以上5.18×105[pL・npi]以下の範囲に調整する請求項1~3の何れかに記載のパターン形成方法。
- 前記液滴容量を、階調数の調整により調整する請求項1~4の何れかに記載のパターン形成方法。
- 前記液滴吐出装置から吐出される前記液滴の前記基材上における接触角が10[°]以上30[°]以下の範囲である請求項1~5の何れかに記載のパターン形成方法。
- 前記相対移動による1回のパスで1つ又は複数の前記ライン状液体を形成する請求項1~6の何れかに記載のパターン形成方法。
- 前記相対移動による1回のパスで互いに平行な複数の前記ライン状液体を形成する際に、該ライン状液体の付与間隔を調整することにより、隣り合う前記ライン状液体を乾燥させる際の相互干渉を抑制する請求項1~7の何れかに記載のパターン形成方法。
- 前記相対移動による1回のパスで互いに平行な複数の前記ライン状液体を形成する際に、該ライン状液体の付与間隔の調整を、各々の前記ノズルから前記液滴を吐出する時間間隔、及び、前記液滴吐出装置の基材に対する相対移動速度の一方又は両方を調整することによって行う請求項1~8の何れかに記載のパターン形成方法。
- 前記相対移動による1回のパスで互いに平行な複数の前記ライン状液体を形成する際に、該ライン状液体の付与間隔を、400[μm]以上に調整する請求項1~9の何れかに記載のパターン形成方法。
- 前記液滴の合一を促進するように、1つの前記ライン状液体を形成するために互いに隣接する前記ノズルからそれぞれ吐出される前記機能性材料を含む液体の最大吐出時間差Δtmaxを、200[ms]以下に調整する請求項1~10の何れかに記載のパターン形成方法。
- 前記基材上に第1の前記ライン状液体を付与し、該第1のライン状液体を乾燥させる過程で該機能性材料を縁部に選択的に堆積させて、該機能性材料を含む2本の線分により構成された第1の平行線パターンを形成し、
次いで、前記基材上に前記第1の平行線パターンの形成領域と交差させるように第2の前記ライン状液体を付与し、該第2のライン状液体を乾燥させる過程で該機能性材料を縁部に選択的に堆積させて、該機能性材料を含む2本の線分により構成された第2の平行線パターンを形成することによって、
前記第1の平行線パターンと前記第2の平行線パターンとが少なくとも1つの交点で交わるパターンを形成する請求項1~11の何れかに記載のパターン形成方法。 - 前記第2の平行線パターンを構成する前記2本の線分間の間隔について、前記第1の平行線パターンの形成領域内における平均間隔Aと、前記第1の平行線パターンの形成領域外における平均間隔Bとが下記式(1)を満たすように調整する請求項12記載のパターン形成方法。
0.9≦B/A≦1.1 ・・・式(1) - 前記式(1)を満たすための調整として、前記第1の平行線パターンの形成領域内の表面エネルギーと、前記第1の平行線パターンの形成領域外の表面エネルギーとの差を、5mN/m以下にする請求項13記載のパターン形成方法。
- 前記式(1)を満たすための調整として、前記第1のライン状液体に含まれる機能性材料を塗布して乾燥させたベタ面の表面エネルギーと、前記第1の平行線パターンの形成領域外の表面エネルギーとの差を、5mN/m以下にする請求項13記載のパターン形成方法。
- 前記式(1)を満たすための調整として、前記第1の平行線パターンの形成領域内における前記第2のライン状液体の接触角と、前記第1の平行線パターンの形成領域外における前記第2のライン状液体の接触角との差を、10°以下にする請求項13記載のパターン形成方法。
- 前記式(1)を満たすための調整として、前記第1のライン状液体に含まれる機能性材料を塗布して乾燥させたベタ面における前記第2のライン状液体の接触角と、前記第1の平行線パターンの形成領域外における前記第2のライン状液体の接触角との差を、10°以下にする請求項13記載のパターン形成方法。
- 前記式(1)を満たすための調整として、前記第1の平行線パターンの形成領域外における前記第2のライン状液体中の溶剤のうち最も沸点が高い溶剤の接触角を6°以下にする請求項13記載のメッシュ状の機能性パターンの形成方法。
- 前記式(1)を満たすための調整として、前記第1の平行線パターンの形成領域内における前記第2のライン状液体の長さあたりの液体付与量と、前記第1の平行線パターンの形成領域外における前記第2のライン状液体の長さあたりの液体付与量とを異ならせる請求項13記載のパターン形成方法。
- 前記式(1)を満たすための調整として、前記第1の平行線パターンを形成した後に、前記第2のライン状液体を付与する前に、前記第1の平行線パターンの形成領域内を含む領域を洗浄する請求項13に記載のパターン形成方法。
- 前記洗浄として、加熱による洗浄、電磁波による洗浄、溶剤による洗浄、ガスによる洗浄及びプラズマによる洗浄から選ばれた1種又は2種以上を組み合わせた洗浄を行う請求項20記載のパターン形成方法。
- 前記ライン状液体の乾燥に際して、乾燥を促進させる処理を施す請求項1~21の何れかに記載のパターン形成方法。
- 前記液滴吐出装置から吐出される前記液体の機能性材料含有率が、0.01重量%以上1重量%以下の範囲である請求項1~22の何れかに記載のパターン形成方法。
- 前記機能性材料は、導電性材料または導電性材料前駆体である請求項1~23の何れかに記載のパターン形成方法。
- 請求項1~24の何れかに記載のパターン形成方法により形成されたパターンを含む透明導電膜を基材表面に有する透明導電膜付き基材。
- 請求項25記載の透明導電膜付き基材を有するデバイス。
- 請求項26記載のデバイスを備えた電子機器。
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