CN105377449B - Coating film-forming methods, the base material with transparent conductive film, device and electronic equipment - Google Patents
Coating film-forming methods, the base material with transparent conductive film, device and electronic equipment Download PDFInfo
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- CN105377449B CN105377449B CN201480039215.2A CN201480039215A CN105377449B CN 105377449 B CN105377449 B CN 105377449B CN 201480039215 A CN201480039215 A CN 201480039215A CN 105377449 B CN105377449 B CN 105377449B
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- functional material
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- compatibility
- forming methods
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Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/227—Drying of printed circuits
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1241—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing
- H05K3/125—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing by ink-jet printing
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/0108—Transparent
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/09—Shape and layout
- H05K2201/09209—Shape and layout details of conductors
- H05K2201/09654—Shape and layout details of conductors covering at least two types of conductors provided for in H05K2201/09218 - H05K2201/095
- H05K2201/09736—Varying thickness of a single conductor; Conductors in the same plane having different thicknesses
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/09—Shape and layout
- H05K2201/09209—Shape and layout details of conductors
- H05K2201/09654—Shape and layout details of conductors covering at least two types of conductors provided for in H05K2201/09218 - H05K2201/095
- H05K2201/098—Special shape of the cross-section of conductors, e.g. very thick plated conductors
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/05—Patterning and lithography; Masks; Details of resist
- H05K2203/0502—Patterning and lithography
- H05K2203/0545—Pattern for applying drops or paste; Applying a pattern made of drops or paste
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
- H05K2203/0783—Using solvent, e.g. for cleaning; Regulating solvent content of pastes or coatings for adjusting the viscosity
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
- H05K2203/1105—Heating or thermal processing not related to soldering, firing, curing or laminating, e.g. for shaping the substrate or during finish plating
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
- H05K2203/1173—Differences in wettability, e.g. hydrophilic or hydrophobic areas
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/15—Position of the PCB during processing
- H05K2203/1581—Treating the backside of the PCB, e.g. for heating during soldering or providing a liquid coating on the backside
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- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Electromagnetism (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
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Abstract
The purpose of the present invention is to provide a kind of coating film-forming methods, it can be stably formed the pattern for including the filament with thin line width, the solid constituent residual outside the pattern formation specified position of thin thread part can be reduced, the coating film-forming methods are that pattern (2) drying that is upper on a substrate (1) and being formed will be coated with containing the liquid of functional material, when the film for being selectively piled up in edge part to form above-mentioned functional material, by making the solvent and the solvent low with the compatibility of above-mentioned functional material that aforesaid liquid contains with the compatibility of above-mentioned functional material is high, above-mentioned functional material is set to be piled up in the above-mentioned edge part of above-mentioned film.
Description
Technical field
The present invention relates to be used to form the coating film-forming methods for the film for making functional material be piled up in edge part, be utilized
By the base material with transparent conductive film, device and the electronic equipment of the film that the coating film-forming methods are formed.
Background technology
In recent years, the multifunction, densification of device are developed, and are seeking to be formed containing functional material
The technology of small pattern, while also requiring cost effective, manufacturing process simplification.
As above-mentioned method for forming pattern, proposition has forms pattern using print process.But use various print processes, pole
Limit also only forms the pattern of 20 μm or so of line width, it is difficult to meet required miniaturization.
Patent document 1 describes the convection current by using liquid internal, and the solid constituent contained in liquid is gathered in painting
The peripheral portion of film, so as to form more small electrical wiring pattern compared with film size.
On the other hand, in recent years, with the raising of the demand of slim TV etc., exploitation has liquid crystal, plasma, organic electroluminescence
The display technology of the various modes such as luminous or Flied emission.
In the different all displays of these display modes, transparent electrode is required inscape.In addition, except TV with
Outside, transparent even if in touch panel, mobile phone, Electronic Paper, various solar cells, various electroluminescent Light modulating devices
Electrode is also indispensable technology essential factor.
In the past, transparent electrode was mainly using transparent in glass, transparent plastic foil etc. by vacuum vapour deposition or sputtering method
Ito transparent electrode made of composite oxides (ITO) film of indium-tin is made on base material.
But the indium used in ITO is rare metal, and it is at high price, therefore, it is desirable to not use indium.Also, also
It is the problem of materials'use efficiency is excessively poor etc, saturating for ITO there are the production interval time of vacuum vapour deposition, sputtering method is long
There are big problems as high cost for prescribed electrode.
Therefore, it is had become a top priority instead of the exploitation of the transparent electrode of ito transparent electrode.
In contrast, the convection current by using liquid internal, the silver nanoparticle that will contain in liquid have been recorded in patent document 2
Particle buildup is transparent made of the peripheral portion of film makes the small annular patterns being made of Nano silver grain be connected with each other
Conductive film.
The convection current by using liquid internal has been recorded in patent document 3, and the carbon nanotube contained in liquid has been gathered in
The peripheral portion of film and with the electrically conducting transparent of multiple small annular patterns made of the interconnection being made of carbon nanotube
Film.
Existing technical literature
Patent document
Patent document 1:Japanese Patent No. 4325343
Patent document 2:WO2011/051952
Patent document 3:Japanese Unexamined Patent Application Publication 2011-502034 bulletins
Invention content
In method for forming pattern described in patent document 1, it is difficult to make the further graph thinning of pattern line-width, in addition, in shape
When the linear pattern of growth, the possibility that a part for pattern disconnects is got higher, therefore there are projects in terms of stability.Also, also
It is easy to remain in the project outside the pattern formation specified position of thin thread part in the presence of the solid constituent not conveyed by convection current.
In method for forming pattern described in patent document 2,3, it is difficult to make the further graph thinning of annular patterns line width, separately
Outside, the pattern that thin thread part is remained in there is also the solid constituent not conveyed by convection current is formed outside specified position, is made the transparency, is led
The problem of electrically reducing.
Therefore, the issue of the present invention is to provide a kind of coating film-forming methods, above-mentioned coating film-forming methods can stablize shape
At the pattern for including the filament with thin line width, the solid constituent outside the pattern formation specified position of thin thread part can be reduced
Residual.
In addition, another project of the present invention is to provide the base material (transparent electrode) with transparent conductive film, has above-mentioned band
The device and electronic equipment of the base material of transparent conductive film, the above-mentioned base material with transparent conductive film has to carry out with same resistance value
When comparing, the excellent characteristic of the transparency can be improved.
In addition other projects of the invention are shown by following record.
The above subject is solved by following invention.
1. the liquid containing functional material is coated on base material and forms pattern, makes figure by a kind of coating film-forming methods
Case is dry and when forming above-mentioned functional material and being selectively piled up in the film of edge part,
By make aforesaid liquid contain the solvent high with the compatibility of above-mentioned functional material and with above-mentioned functional material
The low solvent of compatibility, to make above-mentioned functional material be piled up in the above-mentioned edge part of above-mentioned film.
2. the coating film-forming methods recorded according to above-mentioned 1, wherein the solvent low with the compatibility of above-mentioned functional material
Boiling point is higher than the solvent high with the compatibility of above-mentioned functional material.
3. the coating film-forming methods recorded according to above-mentioned 1 or 2, wherein relative to the total amount of aforesaid liquid, with above-mentioned function
Property material the low solvent of compatibility containing ratio be 10 weight of weight %~40 % range.
4. the coating film-forming methods recorded according to above-mentioned any one of 1~3, wherein in dry aforesaid liquid, in heating
State base material.
5. the coating film-forming methods recorded according to above-mentioned any one of 1~4, wherein above-mentioned film passes through mode of printing shape
At.
6. the coating film-forming methods recorded according to above-mentioned any one of 1~5, wherein above-mentioned film passes through drop spray method
It is formed.
7. the coating film-forming methods recorded according to above-mentioned any one of 1~6, wherein above-mentioned functional material is electric conductivity
Material or conductive material precursor.
8. the coating film-forming methods recorded according to above-mentioned any one of 1~7, wherein disperseed with water system in aforesaid liquid
In the case that state contains above-mentioned functional material, water, methanol, second are selected from the high solvent of the compatibility of above-mentioned functional material
Alcohol, 1- propyl alcohol, isopropanol, the solvent low with the compatibility of above-mentioned functional material are selected from n,N-Dimethylformamide, N, N- bis-
Methylacetamide, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dipropyl two
Alcohol monomethyl ether, dipropylene glycol monoethyl ether, 1,3 butylene glycol, 1,4- butanediols, 1,2- hexylene glycols.
9. the coating film-forming methods recorded according to above-mentioned 8, wherein high solvent is with the compatibility of above-mentioned functional material
Water, the solvent low with the compatibility of above-mentioned functional material are selected from diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, 1,3- fourths two
Alcohol.
10. the coating film-forming methods recorded according to above-mentioned any one of 1~7, wherein with organic solvent in aforesaid liquid
It is in the case that dispersity contains above-mentioned functional material, high solvent selects oneself with the compatibility of above-mentioned functional material
Alkane, heptane, octane, hexamethylene, toluene, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), n-butyl alcohol, 2- butanol, isobutanol, 1-
Amylalcohol, the solvent low with the compatibility of above-mentioned functional material are selected from nonane, decane, dimethylbenzene, 1- octanols, sec-n-octyl alcohol, positive nonyl
Alcohol, tridecanol, ethylene glycol monomethyl ether acetate, Dipropylene glycol mono-n-butyl Ether, Tri(propylene glycol)butyl ether,mixture of isomers, cyclohexanone, phenol, benzene first
Alcohol.
11. the coating film-forming methods recorded according to above-mentioned any one of 1~10, wherein the parent with above-mentioned functional material
It is 19 (MPa) with the difference of the SP values of the solvent that property is high and the solvent low with the compatibility of above-mentioned functional material1/2More than.
12. a kind of base material with transparent conductive film in substrate surface there is transparent conductive film, the transparent conductive film to contain
The above-mentioned film that the coating film-forming methods recorded by above-mentioned any one of 1~11 are formed.
13. a kind of device has above-mentioned 12 base materials with transparent conductive film recorded.
14. a kind of electronic equipment has above-mentioned 13 devices recorded.
Description of the drawings
Fig. 1 is the figure illustrated to an example of coating film-forming methods of the present invention
Fig. 2 is the figure that an example of the principle formed to film of the present invention illustrates
Fig. 3 is the enlarged plan view of an example of the cyclic annular film for indicating to be formed by the present invention
Fig. 4 is the iv-iv line amplification sectional views in Fig. 3
Fig. 5 is the major part enlarged plan view of an example of the parallel lines film for indicating to be formed by the present invention
Fig. 6 is the vi-vi line sectional views in Fig. 5
Fig. 7 is the figure for illustrating embodiment
Fig. 8 is the figure for illustrating embodiment
Specific implementation mode
Hereinafter, being illustrated to mode for carrying out the present invention.
It, will be affine including at least functional material, with the functional material in coating film-forming methods of the present invention
The high solvent (hereinafter, sometimes referred to as high-affinity solvent) of property and the solvent low with the compatibility of the functional material are (hereinafter, have
When referred to as low compatibility solvent) liquid be coated on base material and form pattern, make it dry and form functional material choosing
It is piled up in selecting property the film of edge part, in this regard, illustrating referring to Fig.1.
Fig. 1 is the figure illustrated to an example of coating film-forming methods of the present invention.
As an example of coating film-forming methods of the present invention, Fig. 1 (a1)~Fig. 1 (a4) expressions form cricoid
The case where film.
Fig. 1 (a1) and Fig. 1 (a2) is indicated by including at least functional material, high-affinity solvent and low compatibility solvent
Liquid and formed pattern (coated pattern) the case where, Fig. 1 (a1) be vertical view, Fig. 1 (a2) be sectional view.
On the other hand, Fig. 1 (a3) and Fig. 1 (a4) indicates the case where film formed by the liquid of dry Fig. 1 (a1),
Fig. 1 (a3) is vertical view, and Fig. 1 (a4) is sectional view.
Circular pattern 2 is formed on base material 1 in the present invention, when as shown, overlooking, in the dry pattern 2, because of liquid
Body includes functional material, high-affinity solvent and low compatibility solvent, promotes the accumulation of the functional material on edge part, shape
At the cricoid film 3a for making functional material selectively be deposited in relative to central portion edge part.
In addition, an example as coating film-forming methods of the present invention, Fig. 1 (b1)~Fig. 1 (b4) indicates to be formed
The case where film of parallel line shaped.
Fig. 1 (b1) and Fig. 1 (b2) expressions will be including at least functional material, high-affinity solvent and low compatibility solvent
Liquid be coated on base material and formed pattern (coated pattern) the case where, Fig. 1 (b1) is vertical view, and Fig. 1 (b2) is sectional view.
On the other hand, Fig. 1 (b3) and Fig. 1 (b4) indicates the case where film formed by the liquid of dry Fig. 1 (b1),
Fig. 1 (b3) is vertical view, and Fig. 1 (b4) is sectional view.
Linear pattern 2 is formed in the present invention, when as shown, overlooking on base material 1, in the dry pattern 2, because of liquid
Body includes functional material, high-affinity solvent and low compatibility solvent, promotes the accumulation of the functional material of edge part, is formed
Functional material is set selectively to be deposited in the linear parallel lines film 3b of edge part relative to central portion.
Fig. 2 is the figure that an example of the principle formed to film of the present invention illustrates.
In the present invention, because also containing high-affinity solvent and low compatibility solvent while pattern 2 contains functional material,
So during pattern 2 is dried on base material 1, compared with the case where only containing high-affinity solvent, liquid is to work(
The compatibility of energy property material reduces.At this point, the drying of pattern 2 of the configuration on base material 1 is in edge part (reference faster than central portion
Fig. 2 (a)), thus promote the accumulation of the part of the functional material of alienation due to the reduction of compatibility in the edge part of pattern 2
(with reference to Fig. 2 (b)).
Thus the immobilization of the contact line (edge part) of pattern 2 is happened at the drying initial stage of pattern 2, inhibits with thereafter
Contraction of the dry pattern 2 in substrate surface direction.Due to the effect, the liquid of pattern 2 is lost with replenishing edge part drying
Part liquid mode formed from convection current from central portion to edge part (with reference to Fig. 2 (c)).
Because the convection current is easy to happen at dry initial stage, the functional material in pattern 2 is swimmingly conveyed to edge
Portion promotes further accumulation.Thereby, it is possible to the thin thread part pattern lines for the functional material for making to be formed in edge part,
The residual outside the thin thread part of solid constituent can be reduced.As a result, the transparency that can be got both well in transparent conductive film
With the effect of electric conductivity.
Also, the immobilization of the edge part of pattern 2 occurs at dry initial stage, therefore to preventing in the drying process because by liquid
The influence of the surface tension of body and being punctured into caused by spherical power swells also effectively.Thereby, it is possible in defined position
It is stably formed thin thread part pattern, especially to easy ting produce the linear parallel lines film 3b's swelled in forming drying process
In situation effectively.As a result, in the formation of the thin thread part pattern of functional material, the graph thinning and stabilization of the line width that can get both
Property.
Should be with explanation, in above principle explanation, as comparison other, the solvent for having enumerated formation pattern 2 only contains
The case where high-affinity solvent, but only containing low compatibility solvent the case where be equally also not achieved the present invention function and effect.Only
When containing low compatibility solvent, no matter because of the dry degree carried out, the compatibility between functional material and liquid is all low,
So functional material steadily becomes the state of self aggregation each other.As a result, generating self aggregation (accumulation) in the edge of film
The problems such as position other than portion.
In the present invention, forming the liquid of pattern 2 can contain functional material as dissolution system, can also be used as point
Granular media system is contained.
In dissolution system and dispersion, although being (single point of molecular cell there are the dispersal unit of functional material
Subelement or polymerized unit) or particle unit as difference, but be collectively formed dispersity this point be identical.No matter
It is which kind of system, when liquid is high to the compatibility of functional material, compared with the mutual combination of functional material, liquid and function
Property material between combination be in stabilized trend, be easy to keep dispersity.On the other hand, parent of the liquid to functional material
When low with property, with liquid compared with the combination between functional material, the mutual combination of functional material is in stabilized trend,
Functional material is easy aggregation each other.That is, if it is dissolution system, it is easy to be precipitated, if it is dispersion, is easy solidifying
It is poly-.
In the present invention, " high solvent (the high-affinity solvent) with the compatibility of functional material " expression makes with molecular cell
The functional material that (single molecular cell or polymerized unit) or particle unit are scattered in the solvent is easy to keep its dispersity
The solvent of (the case where especially being disperseed with molecular cell (single molecular cell or polymerized unit) is referred to as dissolved state),
" solvent (low compatibility solvent) low with the compatibility of functional material " indicates the dispersity for being difficult to keep functional material
Solvent.
In the present invention, as high-affinity solvent, the higher the better with the compatibility of functional material, molten as low compatibility
The lower agent the better with the compatibility of functional material.
When pattern 2 contains functional material as dissolution system,
(A) it is used as " high-affinity solvent ", can used " to molecular cell (single molecular cell or polymerized unit) point
Scattered functional material (functional material dissolved) is easy to keep (A-1) solvent of its dispersity (dissolved state) ",
(B) it is used as " low compatibility solvent ", can used " to molecular cell (single molecular cell or polymerized unit) point
Scattered functional material (functional material dissolved) is difficult to keep (B-1) solvent of its dispersity (dissolved state) ".
Its relationship is above-mentioned (A-1) solvent compared with above-mentioned (B-1) solvent, more to the solubility (25 DEG C) of functional material
It is high.Specifically, the solubility (25 DEG C) to functional material of above-mentioned (A-1) solvent is preferably 30 weight % or more, it is more excellent
It is selected as 50 weight % or more, further preferably 70 weight % or more.
In addition, the solubility (25 DEG C) to functional material of above-mentioned (B-1) solvent is preferably 5 weight % hereinafter, more excellent
3 weight % are selected as hereinafter, further preferably 1 weight % or less.
On the other hand, when pattern 2 contains functional material as dispersion,
(A) it is used as " high-affinity solvent ", can uses and " functional material disperseed with particle unit is easy to keep it
(A-2) solvent of dispersity ",
(B) it is used as " low compatibility solvent ", can uses and " it is difficult to keep to the functional material disperseed with particle unit
(B-2) solvent of dispersity ".
Its relationship is above-mentioned (A-2) solvent with above-mentioned (B-2) solvent compared with, to the particle of functional material it is dispersed more
High (particle of the functional material disperseed not free settling).Specifically, above-mentioned (A-2) solvent is disperseed preferably in the solvent
The functionality of 30 weight % of containing ratio or more, more preferably dispersion 50 weight % or more, further preferably dispersion 70 weight % or more
After the particle (particle identical with the particle used in coating fluid) of material, sedimentation is can't see within 1 hour at 25 DEG C
Solvent.
In addition, above-mentioned (B-2) solvent is that dispersion preferably comprises 5 weight % of rate or less, more preferably 3 weights of dispersion in the solvent
It measures % or less, further preferably disperse the particle of 1 weight % functional materials below (with the particle phase used in coating fluid
Same particle) after, the solvent of sedimentation can be confirmed within 1 hour at 25 DEG C.
In the present invention, preferably the boiling point of low compatibility solvent is higher than high-affinity solvent.As a result, in the dried of pattern 2
Cheng Zhong, high-affinity solvent are dried prior to low compatibility solvent, so consolidating for line can be steadily in contact earlier
Fixedization can significantly more obtain the effect of the present invention.The use of boiling point is more preferably that 100 DEG C of solvents below are made in the present invention
For high-affinity solvent, using the solvent that boiling point is 150 DEG C or more as low compatibility solvent.
In the present invention, relative to the total amount for the liquid for forming pattern 2, the containing ratio of low compatibility solvent is preferably 10 weights
Measure the range of the weight of %~40 %.If the containing ratio of low compatibility solvent is less than 10 weight %, pattern 2 is done on base material 1
In dry process, the edge part of pattern 2 is difficult to that the reduction of compatibility advantageously occurs, and functional material is locally precipitated sometimes
Promotion becomes inadequate.If the containing ratio of low compatibility solvent is more than 40 weight %, the mistake dry on base material 1 of pattern 2
Central portion of the reduction until pattern 2 of compatibility exceedingly occurs for Cheng Zhong, it is difficult to which it is right caused by the immobilization by contact line to occur
The conveying of caused functional material is flowed, solid constituent remains in outside the thin thread part pattern forming position of edge part sometimes.
In addition, along with this, the precipitation of the part of functional material becomes unstable on the edge part of pattern 2 sometimes.It is low
In the range of 10 weight of weight %~40 % with dry progress parent can occur for the containing ratio of compatibility solvent well
With the reduction of property, can more suitably get both pattern 2 edge part promotion functions material part precipitation effect and
The remaining effect of solid constituent outside thin thread part pattern position is reduced, the effect of the present invention can be significantly more obtained.
In the present invention, in dry pattern 2, preferred heated substrate 1.Using heat drying, promotes the drying of pattern 2, make
The difference of central portion and the evaporation capacity of edge part becomes larger, and the poor of evaporation capacity of high-affinity solvent, low compatibility solvent is also made also to become
Greatly, while promoting the immobilization of edge part of pattern 2, promote convection current of the central portion to edge part out of film.As a result, can
Enough effects for significantly more obtaining the present invention.
In the present invention, pattern forming method particularly preferably all meets the condition of following (ア)~(エ).
The liquid that (ア) forms pattern 2 on base material includes at least functional material, high-affinity solvent and low compatibility
Solvent.
(イ) above-mentioned low compatibility solvent boiling point compared with above-mentioned high-affinity solvent is high.
The containing ratio of the total amount of (ウ) relative to aforesaid liquid, above-mentioned low compatibility solvent is 10 weight of weight %~40 %
Range.
(エ) heats above-mentioned base material in the above-mentioned pattern 2 of drying.
In the present invention, the condition by all meeting above-mentioned (ア)~(エ) can obtain most significant effect.
All when meeting the condition of above-mentioned (ア)~(エ), in the drying process, the edge of the pattern 2 more than the evaporation capacity
Portion, the fast high-affinity solvent of rate of drying first evaporate, and the ratio of components of the low compatibility solvent of slow drying speed locally increases.Its
As a result, being drastically reduced to the compatibility of functional material on the edge part of pattern 2, functional material accumulation, at dry initial stage
The immobilization of the contact line of pattern 2 occurs.
As described above, if low compatibility solvent is less than 10 weight %, while compatibility reduces, pattern 2 connects
It is just preferential to touch line retrogressing, it becomes difficult to promote the immobilization of contact line.On the other hand, if low compatibility solvent is more than 40 weights
% is measured, then the reduction of compatibility will expand into the central portion of pattern 2, therefore right caused by end immobilization of the obstruction by pattern 2
Stream, functional material are difficult to be transported to the edge part of pattern 2, and the thin thread part pattern that solid constituent is easy to remain on edge part is formed
Outside position.
By being selected in above-mentioned containing ratio range, promote solid constituent in the accumulation of the part of the edge part of pattern 2,
Do not hinder convection current caused by the end immobilization by pattern 2 simultaneously, therefore functional material is transported to edge part, thus, it is possible to
The remaining reduction of solid constituent suitably to get both outside graph thinning and the thin thread part pattern position of filament width.In addition, by adding
Hot substrate 1 to make the central portion of pattern 2, the evaporation capacity difference of edge part become larger, therefore can promote to use high-affinity simultaneously
The convection current of edge part immobilization and pattern 2 caused by solvent and low compatibility solvent, therefore can significantly more obtain this hair
Bright effect.
In the present invention, functional material is not particularly limited, for example, preferable exemplary semiconductor material, dielectric material,
Insulating material, photoelectric conversion material, optical material etc..In addition, as the functional material that transparent conductive film utilizes, preference
Show the conductive materials such as electrically conductive microparticle, electric conductive polymer, organometallic complex, inorganic metal salt, electroless plating catalyst
Equal conductive materials precursor.
The high-affinity solvent and low compatibility solvent used in the present invention is not particularly limited, can be suitably used with
The relationship of functional material meets the solvent of the condition (condition of solubility or the condition of sedimentation) of above-mentioned compatibility.It can make
It uses a kind or the solvent that is used in combination of two or more is as high-affinity solvent, the solvent that can be used alone or in combination with two or more kinds is as low
Compatibility solvent.
It may be preferably exemplified as high-affinity solvent for example, functional material is the water system dispersion nano grain of silver period of the day from 11 p.m. to 1 a.m
Water, methanol, ethyl alcohol, 1- propyl alcohol, isopropanol etc. may be exemplified n,N-Dimethylformamide, N, N- bis- as low compatibility solvent
Methylacetamide, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dipropyl two
Alcohol monomethyl ether, dipropylene glycol monoethyl ether, 1,3 butylene glycol, 1,4- butanediols, 1,2- hexylene glycols etc..They can use a kind or
Combine two or more use.
In addition, for example, functional material is that the organic solvent system dispersion nano grain of silver period of the day from 11 p.m. to 1 a.m can as high-affinity solvent
Preferably to illustrate hexane, heptane, octane, hexamethylene, toluene, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), n-butyl alcohol, 2- fourths
It is pungent to may be preferably exemplified nonane, decane, dimethylbenzene, 1- octanols, 2- as low compatibility solvent for alcohol, isobutanol, 1- amylalcohols etc.
Alcohol, n-nonyl alcohol, tridecanol, ethylene glycol monomethyl ether acetate, Dipropylene glycol mono-n-butyl Ether, Tri(propylene glycol)butyl ether,mixture of isomers, cyclohexanone, benzene
Phenol, benzyl alcohol etc..They can use a kind or combine two or more use.
In addition, from more stably play the present invention effect from the viewpoint of, in preferred pattern 2 high-affinity solvent with it is low
Compatibility solvent is mixed with the degree for not generating phase separation mutually at least.It should be noted that even if will produce originally in selection
In the case of the combination of the solvent of phase separation, as long as the additive of their compatibility can be concocted by addition (such as to height
The compatibility solvent compound affinity with both low compatibility solvents) etc. so that two solvents is mixed, so that it may with appropriate
Ground uses.
In the case of containing such additive in pattern 2, carried out with not damaging the amount of range of the effect of the present invention
Addition.Additive remains in the first-class viewpoint of base material and considers after preventing drying, it is also preferred that using that can pass through the removings such as dry
Additive.
Meet the condition (condition of solubility or the condition of sedimentation) of above-mentioned compatibility in the relationship with functional material
In solvent, the high-affinity solvent that uses and the more preferable high-affinity solvent of low compatibility solvent are water, from organic in the present invention
Low compatibility solvent is selected in solvent.As a result, it is possible to expand solvent to the difference of the compatibility of functional material, it is further able to
Expand high-affinity solvent, low compatibility solvent evaporation capacity difference, therefore can significantly more obtain the effect of the present invention.
In addition, for the compatibility of the high-affinity solvent and low compatibility solvent and functional material that are used in the present invention
For, the condition (condition of solubility or the condition of sedimentation) for the compatibility stated is closed in conjunction with the relation character with functional material,
The solubility parameter (SP values) of solvent can also be used to indicate.
The solubility parameter (SP values) of solvent refers to the value indicated by the square root of molecule inner injection energy, polymer handbook
Have in (Polymer HandBook) (second edition) section IV solubility parameter value (Solubility Parameter Values)
It records in detail, uses the value.Unit is (MPa)1/2, refer to the value at 25 DEG C.It should be noted that for it is countless according to records, can be with
With R.F.Fedors, Polymer Engineering Science, the method described in 14, p147 (1967) is calculated.
The high-affinity solvent and low compatibility solvent used in the present invention by with the difference of the SP values of each solvent be 19
(MPa)1/2More than, more preferably 22 (MPa)1/2More than, further preferably 25 (MPa)1/2Above mode is selected, energy
Enough effects for significantly more obtaining the present invention.
The difference of SP values as high-affinity solvent of the present invention and low compatibility solvent is 19 (MPa)1/2More than
(hereinafter, omitting the record of the unit of SP values.) solvent type, for example, functional material be water system disperse the nano grain of silver period of the day from 11 p.m. to 1 a.m,
Water (47.9) is may be preferably exemplified as high-affinity solvent, as low compatibility solvent, may be preferably exemplified diethylene glycol list
Butyl ether (20.9), triethylene glycol monomethyl ether (21.9), 1,3 butylene glycol (23.7).They can use a kind or combine two or more
It uses.
In addition, within the scope of the effect of the invention, pattern 2 can contain the various additions such as surfactant
Agent.
By using surfactant, such as in using drop spray mode come the case where forming pattern 2 etc., can adjust
Whole surface tension etc. and realize the stabilisation etc. sprayed.It as surfactant, is not particularly limited, silicon systems surface can be used
Activating agent etc..Silicon-based surfactant refer to dimethyl polysiloxane side chain or end through silicon systems surface made of polyether-modified
Activating agent, for example, the commercially available KF-351A for having SHIN-ETSU HANTOTAI's chemical industry system, KF-642, BYK Chemie BYK347, BYK348
Deng.Relative to the total amount for the liquid for forming pattern 2, the additive amount of surfactant is preferably 1 weight % or less.
The base material 1 used in the present invention is not particularly limited, but can for example enumerate glass, plastics (polyethylene, polypropylene,
Acrylic acid, polyester, polyamide etc.), metal (copper, nickel, aluminium, iron etc. or their alloy), ceramics etc..
Base material 1 is preferably transparent, but is not necessarily limited to this.According to the present invention, because the conductive film on base material 1 is arranged
The transparency of (such as cyclic annular film 3a, parallel lines film 3b or one kind or two or more aggregate constituted by them) is excellent,
So no matter base material 1 it is transparent/opaque, various uses can be used in.
In addition, the base material 1 as the present invention can preferably make from the viewpoint of the flowing (convection current) for never interfering liquid
With being not easy to absorb the base material of liquid.As being not easy to absorb the base material of liquid, specifically, may be preferably exemplified following base material, i.e.,
It is 0≤L≤3ml/m to the uptake L of the liquid that the base material is impregnated in the base material after the liquid 1 minute2Range.This
In, uptake L is defined as being worth, that is, takes the state that liquid is fully eliminated after the substrate weight before liquid infiltration and dipping
Substrate weight difference, increased the weight of part divided by the density of liquid, by obtained value further divided by substrate surface
It is worth obtained by product.As base material 1, it is preferable to use the base materials that surface has the coating for not absorbing liquid.
In the present invention, the method that pattern 2 is formed on base material 1 can generate convection current only to have in drying process
The method that pattern 2 is formed in the state of the mobility of degree.Such as preferably enumerate mode of printing etc..
As mode of printing, general known method can be used, silk screen print method, letterpress are may be preferably exemplified
Method, gravure printing method, flexographic printing process, flexographic plate print process etc..
In the present invention, pattern 2 is preferably formed by drop spray mode, may be preferably exemplified ink-jet mode, dispensing mode,
Spray pattern etc..Pattern 2 is formed each other by being integrated on base material 1 alternatively, it is also possible to spray drop, thereby, it is possible to
Carry out the digital pattern of thread pattern.As a result, using the pattern formed by the present invention as the case where transparent conductive film etc.
In, obtain the effect that can freely design the transparency and electric conductivity.
As ink-jet mode, commonly known method can be used, may be preferably exemplified piezo electrics, heat foamable mode and
Electrostatic attraction mode etc., above-mentioned piezo electrics make ink flow path deform by spray droplet of ink by the vibration of piezoelectric element；On
It states thermal mode and heater is set in ink flow path, the heater is made to generate heat and generate bubble, according to oily caused by bubble
Pressure change in black flow path and spray droplet of ink；Above-mentioned electrostatic attraction mode makes the ink in ink flow path charge and utilize
The electrostatic attraction of ink sprays droplet of ink.It should be noted that in this specification, " ink " is used sometimes for convenience's sake
Such statement illustrates, and refers to the liquid for being used to form pattern 2, also includes the liquid without containing pigment dye.
In the present invention, the drying means of film is not particularly limited, such as can enumerate to 1 surface of base material equipped with pattern 2
The method that is thermally dried in advance heats 1 surface of base material for assigning pattern 2, using accumulation in the heat on 1 surface of base material
The method being dried can also combine them.In the drying process when heated substrate, the surface temperature of base material 1 is preferably
40 DEG C~150 DEG C of range.
The heating device used when as heated substrate 1, is not particularly limited, such as can enumerate air-heater, heating plate, face
The heaters such as board heating apparatus combine device made of them etc..
Next, the cyclic annular film formed to the coating film-forming methods that are related to by present invention mentioned above is preferred
Mode illustrates.
Fig. 3 is to indicate that the coating film-forming methods being related to through the invention form an example of cyclic annular film on base material
Enlarged plan view.Fig. 4 is the iv-iv line amplification sectional views in Fig. 3, is the cricoid thin thread part edge that will contain in cyclic annular film
The figure that diameter is cut off in the direction orthogonal with forming face.
In the present invention, as shown, ring-type film 3a is made of thin thread part 31 and film section 32, thin thread part 31 passes through function
Property material stacking constituted in edge part, film section 32 remains on center side a little by functional material by constitutes, this this
It is preferred in invention.
In the present invention, the line width w for constituting the thin thread part 31 of cyclic annular film 3a is preferably 10 μm or less.If it is 10 μm with
Under, then be generally can not visuognosis level, so to transparent conductive film improve the transparency from the viewpoint of and it is more preferable.
If also considering the stability of thin thread part 31, the line width w of thin thread part 31 is preferably 2 μm~10 μm of range.
It should be noted that in the present invention, the width w of thin thread part 31 is defined as functional material inside by the thin thread part
Thickness be the most thin thinnest part height be set as z, further by y is set as from the height outstanding of the thin thread part 31 of the z when, y
Half height at thin thread part 31 width.For example, when cyclic annular film 3a has above-mentioned film section 32, this can be made thin
The height of the thinnest part in film portion 32 is z.It should be noted that the height of the thinnest part of functional material in the film section 32 is
When 0, the line width w of thin thread part is defined as the width of the thin thread part 31 at the height of the half of height h of the thin thread part 31 away from 1 surface of base material
Degree.
In the present invention, it is superfine as described above to constitute the line width w of the thin thread part 31 of cyclic annular film 3a, therefore from transparent
From the viewpoint of ensuring sectional area, realization resistance lowering in conductive film, the height h of the thin thread part 31 away from 1 surface of base material is preferably high.Tool
The height h of thin thread part 31 is preferably the range of 50nm~5 μm for body.
In addition, in the present invention, from the viewpoint of the stability for improving cyclic annular film 3a, h/w ratios are respectively preferably 0.05
~1 range.
In addition, from further increasing in transparent conductive film from the viewpoint of the transparency of cyclic annular film 3a, it is preferably cyclic annular to apply
In film 3a, the height z of the most thin thinnest part of thickness of the functional material in the film section 32, specifically film section is most
The height z of thin part is preferably 10nm ranges below.In order to realize the balance of the get both transparency and stability, most preferably 0
Has film section in the range of ＜ z≤10nm.
In addition, in order to realize further resistance lowering and the transparency as transparent conductive film etc. with cyclic annular film 3a on the way
Raising, the h/z ratios of thin thread part 31 are respectively preferably 5 or more, more preferably 10 or more, particularly preferably 20 or more.
The diameter R of cyclic annular film 3a can be for example adjusted by the formation range of pattern 2, preferably in 10 μm~300 μ
The range of m adjusts.It should be noted that in the present invention, diameter R is defined as the distance between each maximum protruding portion of thin thread part 31.
In addition, preferred its line width w of thin thread part 31 for constituting cyclic annular film 3a is sufficiently fine compared with diameter R.
Cyclic annular film 3a particularly preferably of the present invention at least has the condition for all meeting following (ア)~(エ)
Pattern.
The height of thin thread part 31 is set as h by (ア), when the height of the thinnest part of cyclic annular film 3a central portions is set as z, 5
≤h/z
When the width of thin thread part 31 is set as w by (イ), w≤10 μm
When the diameter of cyclic annular film 3a is set as R by (ウ), 10 μm≤R≤300 μm
When the height of thin thread part 31 is set as h by (エ), 5 μm of 50nm ＜ h ＜
Next, the preferred side to the parallel lines film formed by above-mentioned coating film-forming methods of the present invention
Formula illustrates.
Fig. 5 is to indicate that the coating film-forming methods being related to through the invention form an example of parallel lines film on base material
The major part enlarged plan view of son.Fig. 6 is the vi-vi line sectional views in Fig. 5, is to put down include 1 group in parallel lines film
The figure that line is cut off along the direction orthogonal with line segment direction.
In the present invention, 2 line segments (thin thread part) 34,35 that parallel lines 33 are constituted in parallel lines film 3b are not necessarily mutually
Completely self-contained island.As shown, 2 line segments 34,35 are formed, film section 36 as the non-individual body connected by film section 36
Between the line segment 34,35, formed with the height lower than the height of the line segment 34,35, this is also preferred in the present invention.
In the present invention, line width W1, W2 for constituting the line segment 34,35 of parallel lines 33 is respectively preferably 10 μm or less.If it is
10 μm hereinafter, then become generally can not visuognosis level, therefore from improve the transparency from the viewpoint of preferably.If also examined
Consider the stability of each line segment 34,35, then line width W1, W2 of each line segment 34,35 is respectively preferably 2 μm~10 μm of range.
It should be noted that in the present invention, width W1, W2 of line segment 34,35 are defined as the functionality between the line segment 34,35
The height of the most thin thinnest part of the thickness of material is set as Z, further by from the projecting height of the line segment 34,35 of the Z be set as Y1,
When Y2, the width of the line segment 34,35 at the height of the half of Y1, Y2.For example, when parallel lines 33 have above-mentioned film section 36,
The height of the thinnest part in the film section 36 can be set as Z.It should be noted that the functional material between each line segment 34,35 is most
When the height of thin part is 0, line width W1, W2 of line segment 34,35 is defined as height h1, h2 of the line segment 34,35 away from 1 surface of base material
The width of line segment 34,35 at the height of half.
In the present invention, line width W1, W2 of line segment 34,35 for constituting parallel lines 33 is superfine as described above, therefore from true
It protects from the viewpoint of sectional area, realization resistance lowering, height h1, h2 of the line segment 34,35 away from 1 surface of base material is preferably high.Specifically,
Height h1, h2 of line segment 34,35 is preferably the range of 50nm~5 μm.
In addition, in the present invention, from the viewpoint of the stability for improving parallel lines 33, h1/W1 ratios, h2/W2 are more excellent than respectively
It is selected as 0.05~1 range.
In addition, from the viewpoint of the graph thinning for further increasing parallel lines film 3b, for parallel lines 33, in line segment
34, the height Z of the most thin thinnest part of the thickness of 35 functional materials, the specifically thinnest part of film section 36 height
Z is preferably 10nm ranges below.In order to realize the balance of the get both transparency and stability, the most preferably model in 0 ＜ Z≤10nm
Has film section 36 in enclosing.
In addition, in order to improve the further graph thinning of parallel lines film 3b, the h1/Z ratios of parallel lines 33, h2/Z scores
It You Xuanwei not 5 or more, more preferably 10 or more, particularly preferably 20 or more.
The interval I of line segment 34,35 can be suitably adjusted, and preferably adjust the range at 10 μm~300 μm.It should be noted that
In the present invention, the interval I of line segment 34,35 is defined as the distance between each maximum protruding portion of line segment 34,35.
In addition, in the present invention, identical shape (sectional area of same degree) preferably is assigned to line segment 34 and line segment 35, is had
For body, the height h1 and h2 of line segment 34 and line segment 35 are preferably the value being substantially equal.Equally it is also preferred that line segment 34 and line segment
35 line width W1 and W2 is the value being substantially equal.
In the present invention, " parallel lines ", " parallel " not necessarily indicates proper parallel, indicates at least in line segment direction
Certain length L in line segment 34,35 uncombined meanings.Line segment 34,35 is real preferably at least in the certain length L of line segment direction
It is parallel in matter.
In the present invention, the length L of the line segment direction of line segment 34,35 is preferably 5 times or more of the interval I of line segment 34,35, more
Preferably 10 times or more.Length L and interval I can be set with the formation length and formation width of corresponding pattern (linear liquid) 2
It is fixed.
In addition, the line segment 34,35 for constituting parallel lines 33, preferably its line width W1, W2 is almost equal, and line width W1,
W2 is sufficiently fine compared with parallel wire spacing (interval I).
In addition, in the parallel lines film 3b of the present invention, the line segment 34 and line segment 35 that constitute parallel lines 33 are preferably formed simultaneously.
Parallel lines film 3b of the present invention at least has particularly preferable as parallel lines 33 constitutes the parallel lines 33
Each line segment 34,35 all meets the parallel lines of the condition of following (ア)~(エ).
The height for each line segment for constituting above-mentioned parallel lines is set as h1, h2 by (ア), by the thinnest part between each line segment
When height is set as Z, 5≤h1/Z, and 5≤h2/Z
When the width for each line segment for constituting above-mentioned parallel lines is set as W1, W2 by (イ), W1≤10 μm, and W2≤10 μm
When distance between each line segment for constituting above-mentioned parallel lines is set as I by (ウ), 10 μm≤I≤300 μm
When the height for each line segment for constituting above-mentioned parallel lines is set as h1, h2 by (エ), 5 μm of 50nm ＜ h1 ＜, and 50nm ＜
5 μm of h2 ＜
More than, the shape for the film that mainly cyclic annular film and parallel lines film are illustrated, but formed by the present invention
It is not limited to these.According to the present invention, by assigning arbitrary shape to pattern 2, can be formed in its edge part has arbitrarily
Pattern film.
The band electrically conducting transparent of the film of substrate surface is formed in including at least the coating film-forming methods being related to through the invention
The base material of film has the excellent characteristic that can improve the transparency in the case where being compared with same resistance value.
The purposes of base material of the present invention with transparent conductive film is not particularly limited, and can be used for various electronic equipments
The various devices being had.
From the viewpoint of the effect for significantly playing the present invention, the base material of the present invention with transparent conductive film is preferred
Purposes various modes such as can function properly as liquid crystal, plasma, organic electroluminescent or Flied emission display
With transparent electrode or touch panel, mobile phone, Electronic Paper, various solar cells, various electroluminescent Light modulating devices etc.
The middle transparent electrode used.
More particularly it relates to the base material with transparent conductive film be preferably used as the transparent electrode of device.As
Device is not particularly limited, such as may be preferably exemplified touch panel sensor etc..In addition, as having these devices
Electronic equipment is not particularly limited, such as may be preferably exemplified smart mobile phone, tablet terminal etc..
Embodiment
Hereinafter, the embodiment of the present invention is illustrated, but the present invention is not limited to these embodiments.
＜ solvents ＞
The abbreviation and boiling point of the solvent used in following embodiments and comparative example are as follows.These solvents are to functional material
Compatibility is shown in table 1,2.
Water：100℃
Diethylene glycol monobutyl ether (DEGBE)：213 DEG C of boiling point
Triethylene glycol monomethyl ether (TEGME)：245 DEG C of boiling point
1,3 butylene glycol (1,3-BD)：208 DEG C of boiling point
Ethylene glycol (EG)：197 DEG C of boiling point
(Examples 1 to 6, comparative example 1)
Utilize ink gun (Konica Minolta corporation " KM512L "；Standard drop amount 42pl), use group shown in table 1
At ink, make drop be attached to using letter photoelectricity gas meter dress Co. Ltd. system PS-1M carried out Corona discharge Treatment band it is saturating
The above-mentioned transparent hard-coating layer surface of the PET film (base material) of bright hard conating, forms circular pattern (coated pattern).The dry figure
Case makes solid constituent be piled up in edge part and forms the small annular patterns (film) of 70 μm of multiple diameters.These ring-type figures
Arranges and form whole pattern (Fig. 7) to the clathrate that case is spaced by 282 μm.Here, adjacent annular patterns are each other on side
The part of edge overlaps, combines.
The result that total light transmittance and electric conductivity are measured to obtained pattern is shown in table 1.
(embodiment 7)
By screen printing mode, using the ink formed shown in table 2, with the μ of line width/interval width=70 μm/211
M is transparent in the band with different surfaces energy for having carried out Corona discharge Treatment using letter photoelectricity gas meter dress Co. Ltd. system PS-1M
The transparent hard-coating layer surface of the PET film (base material) of hard conating forms the pattern (coated pattern) of striated.The dry pattern, makes
Solid constituent is piled up in edge part and forms the pattern (film) (Fig. 8) of small striated.
The result that total light transmittance and electric conductivity are measured to obtained pattern is shown in table 2.
(embodiment 8~13, comparative example 2)
Utilize ink gun (Konica Minolta corporation " KM512L "；Standard drop amount 42pl), use group shown in table 1
At ink so that drop is attached to using letter photoelectricity gas meter with 211 μm of nozzle column direction spacing, 50 μm of scanning direction point spacing
Dress Co. Ltd. system PS-1M has carried out the transparent hard-coating layer of the PET film (base material) with transparent hard-coating layer of Corona discharge Treatment
Surface.Each drop is integrated each other on base material, forms the pattern (coated pattern) of striated similarly to Example 7.Pass through
The dry pattern makes solid constituent be piled up in edge part and forms the pattern (film) (Fig. 8) of small striated.
The result that total light transmittance and electric conductivity are measured to obtained pattern is shown in table 2.
＜ drying conditions ＞
Base material heating means：After film is formed, with heater plate base material.
Substrate surface temperature：70℃
＜ assay methods ＞
Transmitance (total light transmittance) shown in table 1,2 is to use Tokyo electricity color corporation AUTOMATICHAZEMETER
(MODEL TC-HIIIDP) is measured to be worth obtained by total light transmittance.It should be noted that being to use pattern-free film (transparent conductive film)
Base material be modified, the value measured as the total light transmittance of the pattern film (transparent conductive film) of making.
The evaluation of sheet resistance (surface resistance) shown in table 1,2 is as follows：It is forged using the heating of 120 DEG C of heating plate progress, 1h
It burns, configures extraction electrode later, be measured using three and electrical gauge Co. Ltd. system CD770.
The evaluation for the ratio that breaks shown in table 2 uses light based on the thread pattern between randomly selecting 1000 extraction electrodes
Learn microscope, the result observed the generation ratio of the broken string of filament.
Symbol description
1：Base material
2：Pattern
3：Film
3a：Cyclic annular film
31：Thin thread part
32：Film section
3b：Parallel lines film
33：(a pair) parallel lines
34、35：Line segment (thin thread part)
36：Film section
Claims (17)
1. a kind of coating film-forming methods, the liquid for containing functional material with the state dispersed or dissolved is coated on base material and
The pattern of formation is dried, when being selectively piled up in the film of edge part to form the functional material,
The functional material is conductive material,
Contain the solvent high with the compatibility of the functional material and affine with the functional material by the liquid
The low solvent of property, to make the functional material be piled up in the edge part of the film,
Relative to the total amount of the liquid, the containing ratio of the solvent low with the compatibility of the functional material be 10 weight %~
The range of 40 weight %.
2. coating film-forming methods according to claim 1, wherein formed at least has the film conduct of line segment in a part
The film.
3. coating film-forming methods according to claim 1, wherein being formed at least in a part there is the film of parallel lines to make
For the film.
4. coating film-forming methods according to claim 3, wherein form the pattern by ink-jet mode.
5. coating film-forming methods according to any one of claims 1 to 4, wherein affine with the functional material
Property low solvent boiling point be higher than the solvent high with the compatibility of the functional material.
6. coating film-forming methods according to any one of claims 1 to 4, wherein in the drying liquid, heat institute
State base material.
7. coating film-forming methods according to any one of claims 1 to 4, wherein the film passes through mode of printing shape
At.
8. coating film-forming methods according to any one of claims 1 to 4, wherein the film passes through drop spray method
It is formed.
9. coating film-forming methods according to any one of claims 1 to 4, wherein disperseed with water system in the liquid
When state contains the functional material, water, methanol, ethyl alcohol, 1- are selected from the high solvent of the compatibility of the functional material
Propyl alcohol, isopropanol, the solvent low with the compatibility of the functional material are selected from n,N-Dimethylformamide, N, N- dimethyl second
Amide, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dipropylene glycol list first
Ether, dipropylene glycol monoethyl ether, 1,3 butylene glycol, 1,4- butanediols, 1,2- hexylene glycols.
10. coating film-forming methods according to claim 9, wherein the high solvent with the compatibility of the functional material
For water, the solvent low with the compatibility of the functional material is selected from diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, 1,3- fourths
Glycol.
11. coating film-forming methods according to any one of claims 1 to 4, wherein with organic solvent in the liquid
When being that dispersity contains the functional material, with the high solvent of the compatibility of the functional material be selected from hexane, heptane,
Octane, hexamethylene, toluene, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), n-butyl alcohol, 2- butanol, isobutanol, 1- amylalcohols, with
The solvent that the compatibility of the functional material is low is selected from nonane, decane, dimethylbenzene, 1- octanols, sec-n-octyl alcohol, n-nonyl alcohol, 13
Alkanol, ethylene glycol monomethyl ether acetate, Dipropylene glycol mono-n-butyl Ether, Tri(propylene glycol)butyl ether,mixture of isomers, cyclohexanone, phenol, benzyl alcohol.
12. coating film-forming methods according to any one of claims 1 to 4, wherein affine with the functional material
Property high solvent and the solvent low with the compatibility of the functional material SP values difference be 19 (MPa)1/2More than.
13. coating film-forming methods according to any one of claims 1 to 4, which is characterized in that the functional material is
Water system disperses Nano silver grain,
The high-affinity solvent be it is one kind or two or more in water, methanol, ethyl alcohol, 1- propyl alcohol, isopropanol,
The low compatibility solvent is selected from N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, diethylene glycol monomethyl ether, two
Ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, 1,3-
It is one kind or two or more in butanediol, 1,4- butanediols, 1,2- hexylene glycols.
14. coating film-forming methods according to any one of claims 1 to 4, which is characterized in that the functional material is
Organic solvent system disperses Nano silver grain,
The high-affinity solvent is selected from hexane, heptane, octane, hexamethylene, toluene, acetone, methyl ethyl ketone, methyl tert-butyl
It is one kind or two or more in base ketone, n-butyl alcohol, 2- butanol, isobutanol, 1- amylalcohols,
The low compatibility solvent is selected from nonane, decane, dimethylbenzene, 1- octanols, sec-n-octyl alcohol, n-nonyl alcohol, tridecanol, second two
1 kind or 2 kinds in alcohol monobutyl ether-acetate, Dipropylene glycol mono-n-butyl Ether, Tri(propylene glycol)butyl ether,mixture of isomers, cyclohexanone, phenol, benzyl alcohol with
On.
15. a kind of base material with transparent conductive film, it includes to pass through to have transparent conductive film, the transparent conductive film in substrate surface
The film that coating film-forming methods described in any one of claim 1~14 are formed.
16. a kind of device, with the base material with transparent conductive film described in claim 15.
17. a kind of electronic equipment has the device described in claim 16.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2013-144814 | 2013-07-10 | ||
| JP2013144814 | 2013-07-10 | ||
| PCT/JP2014/068511 WO2015005457A1 (en) | 2013-07-10 | 2014-07-10 | Coating film formation method, base material with transparent conducting film, device and electronic apparatus |
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| CN105377449B true CN105377449B (en) | 2018-09-04 |
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| Country | Link |
|---|---|
| JP (1) | JP6536401B2 (en) |
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| WO2015111731A1 (en) * | 2014-01-24 | 2015-07-30 | コニカミノルタ株式会社 | Pattern formation method, substrate provided with transparent electroconductive film, device, and electronic instrument |
| KR102003625B1 (en) * | 2015-03-02 | 2019-07-24 | 코니카 미놀타 가부시키가이샤 | A pattern forming method, a substrate provided with a transparent conductive film, a device and an electronic device |
| JP6413978B2 (en) * | 2015-08-21 | 2018-10-31 | コニカミノルタ株式会社 | Functional fine line pattern precursor forming method, functional fine line pattern forming method, transparent conductive film forming method, device manufacturing method and electronic device manufacturing method, functional thin line pattern, substrate with transparent conductive film, Devices and electronic equipment |
| JP6717316B2 (en) * | 2015-09-29 | 2020-07-01 | コニカミノルタ株式会社 | Method for forming functional thin line pattern and functional thin line pattern |
| JP6658418B2 (en) * | 2016-09-09 | 2020-03-04 | コニカミノルタ株式会社 | Method of forming conductive pattern |
| WO2018110198A1 (en) * | 2016-12-16 | 2018-06-21 | コニカミノルタ株式会社 | Method for forming transparent electroconductive film, and plating liquid for electroplating |
| JP6769327B2 (en) * | 2017-02-10 | 2020-10-14 | 日信化学工業株式会社 | Ink composition and printed matter |
| CN107135602A (en) * | 2017-05-16 | 2017-09-05 | 华南师范大学 | A kind of low-temperature sintering prepares the high method for leading Nano silver grain flexible conductive circuit |
| TWI829765B (en) * | 2018-09-25 | 2024-01-21 | 日商日產化學股份有限公司 | Coating composition |
| CN112349871B (en) * | 2019-12-09 | 2023-02-07 | 广东聚华印刷显示技术有限公司 | Metal grid electrode and preparation method thereof |
| CN112331796A (en) * | 2019-12-20 | 2021-02-05 | 广东聚华印刷显示技术有限公司 | Grid electrode, preparation method thereof and light-emitting device |
| CN111970851A (en) * | 2020-08-25 | 2020-11-20 | 深圳市景旺电子股份有限公司 | Liquid waterproof glue flow choking method |
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| GB2373095A (en) * | 2001-03-09 | 2002-09-11 | Seiko Epson Corp | Patterning substrates with evaporation residues |
| US20040265550A1 (en) * | 2002-12-06 | 2004-12-30 | Glatkowski Paul J. | Optically transparent nanostructured electrical conductors |
| JP2004230690A (en) * | 2003-01-30 | 2004-08-19 | Takiron Co Ltd | Antistatic transparent resin sheet |
| JP4325343B2 (en) * | 2003-09-25 | 2009-09-02 | セイコーエプソン株式会社 | Film forming method and device manufacturing method |
| JP4096868B2 (en) * | 2003-11-25 | 2008-06-04 | セイコーエプソン株式会社 | Film forming method, device manufacturing method, and electro-optical device |
| KR100895521B1 (en) * | 2007-10-12 | 2009-04-30 | (주)탑나노시스 | Carbon nanotube conductive layer using spray coating and preparing method thereof |
| JP2009224078A (en) * | 2008-03-14 | 2009-10-01 | Kyoto Univ | Transparent conductive film and its manufacturing method |
| KR20120104565A (en) * | 2009-11-02 | 2012-09-21 | 이슘 리서치 디벨롭먼트 컴퍼니 오브 더 히브루 유니버시티 오브 예루살렘, 엘티디. | Transparent conductive coatings for optoelectronic and electronic devices |
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| Publication number | Publication date |
|---|---|
| WO2015005457A1 (en) | 2015-01-15 |
| CN105377449A (en) | 2016-03-02 |
| JPWO2015005457A1 (en) | 2017-03-02 |
| JP6536401B2 (en) | 2019-07-03 |
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