JP6521513B2 - Electrode and touch panel - Google Patents

Description

  The present invention relates to an electrode and a touch panel.

  With the development of computers, computer aids have also been developed. In personal computers, portable transmission devices, and other personal information processing devices, text and graphic processing are performed by various input devices such as a keyboard and a mouse.

  However, with the rapid development of the information society, the applications of computers tend to expand further, and it is becoming difficult to drive devices efficiently only with a keyboard and a mouse. Therefore, there is a growing need for a device that can be easily operated by anyone with few erroneous operations.

  In addition, technologies relating to input devices are attracting attention for technologies relating to high reliability, durability, innovation, design and processing, etc. beyond the level at which general functions are satisfied. In order to achieve such an object, a touch panel has been developed as an input device capable of inputting information such as text and graphics.

The touch panel is an electronic organizer, a liquid crystal display, a PDP (Plasma Display).
Panel) is a device provided on a display surface of a flat display device such as El (Electroluminescence) and a display such as a CRT (Cathode Ray Tube), and used by a user to select desired information while looking at the display.

  Types of touch panels are classified into resistive film type, electrostatic capacity type, electromagnetic type, surface acoustic wave type and infrared type. Such touch panels take into consideration signal amplification problems, differences in resolution, difficulty in design and processing techniques, optical characteristics, electrical characteristics, mechanical characteristics, environmental characteristics, input characteristics, durability, economy, etc. Adopted for electronic products. The touch panels currently used in the widest range of fields are resistive touch panels and capacitive touch panels.

  Moreover, the method of forming an electrode pattern using a metal is developed regarding a touch panel. When the electrode pattern is formed of metal, the electrode pattern has excellent electrical conductivity. In addition, the touch panel is required to have excellent visibility as well as excellent electrical conductivity. As methods for improving the visibility of the touch panel, methods described in Patent Documents 1 and 2 are known.

Such an electrode pattern may arrange two or more electrode patterns electrically separated from each other adjacently. In this case, since there is no electrode pattern between the electrode patterns adjacent to each other, the light transmittance of this portion is higher than that of the surrounding electrode pattern formed portion, and as a result, the contrast of the display screen becomes uneven. There is a possibility that the visibility may be reduced.
In the invention described in Patent Document 3, in order to improve the visibility of the portion between the electrode patterns adjacent to each other, the arrangement pattern and number of the grids of the first electrode and the second electrode adjacent to each other are predetermined. By forming in accordance with the rules, visibility is improved.

JP, 2014-63465, A JP, 2014-63468, A JP, 2014-81766, A

In the configurations described in Patent Documents 1 and 2, high printing accuracy is required in order to form an electrode pattern. Then, in order to make printing precision high, it is possible to extend the interval of the sides of an electrode pattern. However, there is no problem even if the distance between the sides of the electrode pattern is extended except for those requiring particularly high resolution, but if the distance between the sides is too wide, it is easy for humans to visually check the electrode pattern (visibility Worse). Therefore, it may not be sufficient to widen the interval between the sides of the electrode pattern indiscriminately.
Further, in the configurations described in Patent Documents 1 and 2, an electrical short circuit is likely to occur between adjacent electrode patterns and a dummy electrode pattern, and such a short circuit between the electrode pattern and the dummy electrode pattern is assured The touch panel which can be controlled is desired.
In addition, in the configuration described in Patent Document 3, it is necessary to form an electrode pattern in a special shape in order to form an array pattern or number of grids of the first electrode and the second electrode in accordance with a predetermined rule. There is a concern that the manufacturing cost is high and the productivity of the touch panel is reduced.

  This invention is made in view of the said situation, Comprising: It aims at providing the electrode and touch panel which are easy to form and can improve the visibility of an electrode pattern.

The electrode of the present invention is an electrode formed on the electrode formation surface and having at least a first electrode pattern area and a second electrode pattern area constituted by strip electrodes , the first electrode pattern area and the second electrode pattern area being An adjacent and electrically separated via a predetermined separation area along a predetermined direction of the electrode formation surface, and extending in the separation area with an inclination with respect to the extension direction of the strip electrode; A conductor separated from the electrode is disposed.

  The touch panel according to the present invention is characterized by comprising a transparent substrate and the electrode according to the above-mentioned formed on the transparent substrate.

  According to the present invention, it is possible to provide an electrode and a touch panel which can be easily formed and can improve the visibility of the electrode pattern.

It is a schematic plan view which shows the electrode for touchscreens of 1st embodiment, and a touchscreen. It is sectional drawing which follows the A-A 'line | wire of FIG. It is the principal part expansion perspective view which expanded D area | region of FIG. It is a principal part expansion perspective view which shows the electrode for touch panels of 2nd embodiment, and a touch panel. It is a principal part expansion perspective view showing the electrode for touch panels of a third embodiment, and a touch panel.

An embodiment of the electrode and touch panel of the present invention will be described.
The present embodiment is specifically described in order to better understand the spirit of the invention, and does not limit the present invention unless otherwise specified. Further, in the drawings used in the following description, for the sake of easy understanding of the features of the present invention, the main parts may be enlarged for convenience, and the dimensional ratio of each component may be the same as the actual one. Not necessarily.
Hereinafter, as an embodiment of the electrode of the present invention, an electrode for a touch panel and a touch panel including the electrode will be described as an example.

First Embodiment
FIG. 1 is a schematic plan view showing a touch panel provided with electrodes for the touch panel in the first embodiment. FIG. 2 is a cross-sectional view taken along the line AA 'of FIG. FIG. 3 is an enlarged plan view of a region surrounded by a dotted line D in FIG.
The touch panel 10 according to the present embodiment includes a transparent base (substrate) 20 and a touch panel electrode (electrode) 50 formed on an electrode forming surface 20 a which is one surface of the transparent base 20. The touch panel electrode 50 includes a pattern electrode formed by intersecting a plurality of strip electrodes 30 with each other, and a conductor 40. In the lower part (lower layer) of the transparent base material (substrate) 20, for example, a liquid crystal display panel (not shown) or the like is disposed.

  In the strip electrode 30, a plurality of strip electrodes 30a extending along the X direction in the figure and a plurality of strip electrodes 30b extending along the Y direction in the figure intersect at a predetermined angle to form a grid-like touch panel An electrode 50 is formed. That is, a grid-like touch panel electrode 50 is formed by connecting a large number of rectangular unit electrode patterns S. In the present embodiment, the crossing angle between the plurality of strip electrodes 30a extending along the X direction and the plurality of strip electrodes 30b extending along the Y direction is, for example, 90 degrees. That is, the strip electrode 30a and the strip electrode 30b are orthogonal to each other, and constitute the touch panel electrode 50 having a mesh (mesh) structure (mesh structure).

  The touch panel electrode 50 includes a first electrode pattern area E1 and a second electrode pattern area E2 arranged along a predetermined direction of the electrode forming surface 20a on the electrode forming surface 20a, and the first electrode pattern area E1 and the first electrode pattern area E1. It has the separation area E3 which is an area where the two-electrode pattern area E2 is separated. In the present embodiment, the predetermined direction in which the first electrode pattern area E1 and the second electrode pattern area E2 are separated is the X direction in the drawing. Further, the separation region E3 is a region in which the first electrode pattern region E1 and the second electrode pattern region E2 extend to a portion separated by a predetermined distance.

  The first electrode pattern area E1 and the second electrode pattern area E2 formed separately from each other are electrically separated from each other. That is, the strip electrodes 30 in the first electrode pattern area E1 and the strip electrodes 30 in the second electrode pattern area E2 are not connected to each other. The first electrode pattern area E1 and the second electrode pattern area E2 may be electrode patterns to which a voltage is actually applied or may be dummy electrode patterns.

  A large number of conductors 40 are disposed in a separation area E3 provided between the first electrode pattern area E1 and the second electrode pattern area E2. The conductor 40 has a band-shaped conductor having a region extending at least in a predetermined direction of the electrode forming surface 20 a, in the present embodiment, in an angle direction inclined with respect to the X direction, and separated from the strip electrode 30. It is. In the present embodiment, the conductor 40 is formed in a rectangular shape extending in a direction inclined at an angle θ with respect to the X direction, and the angle θ is set to 45 °, for example.

According to the touch panel 10 having such a configuration, it extends in the direction inclined at an angle θ with respect to the X direction to the separation region E3 in which the first electrode pattern region E1 and the second electrode pattern region E2 are electrically separated from each other. By forming the conductor 40, it is possible to prevent the visibility of the separated region E3 in which the electrode pattern does not exist from being lowered compared to the peripheral portion. Thereby, an image etc. which are displayed on touch panel 10 can be seen more clearly, and it becomes possible to improve the visibility of touch panel 10.
Moreover, in addition to the effect of improving the visibility described above, in the present embodiment, the conductor 40 for improving the visibility of the separated region E3 is the first direction of the electrode forming surface 20a, that is, the first in the present embodiment. In order to avoid a short circuit when forming the first electrode pattern area E1 and the second electrode pattern area E2 by inclining with respect to the X direction which is the separation direction between the electrode pattern area E1 and the second electrode pattern area E2. Space can be secured. As a result, even if the conductor 40 is formed in the separation area E3, it is possible to reliably prevent a short circuit between the first electrode pattern area E1 and the second electrode pattern area E2.

As the transparent substrate 20, for example, polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), polyethylene naphthalate (PEN), polyether sulfone (PES), cyclic olefin copolymer (COC), tri- Acetyl cellulose (Triacetylcellulose (TAC) film, polyvinyl alcohol (PVA) film, Polyimide (PI) film, Polystyrene (PS), Biaxially oriented polystyrene (K resin containing biaxially oriented PS; BOPS), Glass Or the base material which consists of tempered glass etc. is mentioned.
Further, in order to improve the adhesion between the transparent substrate 20 and the touch panel electrode 50, the transparent substrate 20 may be subjected to high frequency treatment or primer treatment.

The strip electrode 30 and the conductor 40 are made of, for example, a conductive ink used to form a conductive circuit. As the conductive ink, for example, a polymer type conductive ink, a silver ink composition, a commercially available metal paste, a metal nanoink, a metal complex ink and the like are used.
In addition, as the conductive ink, it is preferable to use one including metal particles whose particle diameter is smaller than the width and thickness of the strip electrode 30 and the conductor 40. In addition, since the conductor 40 does not participate in the resistance value of the touch panel electrode 50, the conductor 40 may be formed using an ink whose resistance value is high.
The strip electrode 30 and the conductor 40 are not limited to the formation using the conductive ink. For example, known methods for forming a conductor can be employed, such as formation of a conductor by etching, formation of a conductor by evaporation of a conductive material, formation of a conductor by sputtering, and the like.

  As the polymer type conductive ink, for example, conductive particles such as silver powder, gold powder, platinum powder, aluminum powder, palladium powder, rhodium powder, carbon powder (carbon black, carbon nanotubes, etc.) blended in a resin composition Can be mentioned.

When a thermosetting resin is used as the resin composition, the polymer type conductive ink becomes a thermosetting type capable of forming a coating film forming a conductive circuit at 200 ° C. or less, for example, about 100 to 150 ° C.
Further, as the polymer type conductive ink in the present embodiment, besides the thermosetting type, known ones such as a photocurable type, a penetration drying type, and a solvent volatilization type may be used.

  The photocurable polymer type conductive ink contains a photocurable resin in the resin composition, and since the curing time is short, the production efficiency can be improved. As the photocurable polymer type conductive ink, for example, 60% by mass of conductive fine particles in a thermoplastic resin alone, or a blend resin composition of a thermoplastic resin and a crosslinkable resin (in particular, a crosslinkable resin of polyester and isocyanate, etc.) % Or more and polyester resin in an amount of 10% by mass or more, ie, solvent volatile type or cross-linked / thermoplastic combination type (however, thermoplastic type is 50% by mass or more), thermoplastic resin Or a blend resin composition of a thermoplastic resin and a crosslinkable resin (in particular, a crosslink resin based on polyester and isocyanate) in which 10% by mass or more of a polyester resin is blended, that is, crosslinkable or crosslinkable / thermal The plasticizing type is preferably used.

As the silver ink composition, for example, one obtained by blending a forming material of metallic silver described later is used.
In the present embodiment, a conductive circuit is formed by subjecting the silver ink composition deposited on the electrode forming surface 20 a of the transparent substrate 20 to solidification processing.
The solidification process is carried out by heating (baking) the silver ink composition deposited on the electrode forming surface 20a of the transparent base 20 as described later.

In the silver ink composition, the content of silver derived from the forming material of metallic silver is preferably 5% by mass or more, and more preferably 10% by mass or more. With such a range, the conductive circuit formed by the method to be described later becomes more excellent in quality. The upper limit of the content of silver is not particularly limited as long as the effects of the present embodiment are not impaired, but it is preferably 25% by mass in consideration of handleability and the like.
In the present specification, “silver derived from the forming material of metallic silver” means silver in the forming material of metallic silver blended at the time of production of the silver ink composition, unless otherwise specified. It is a concept including both of the silver constituting the forming material of metallic silver and the silver itself and the silver itself in the decomposition product formed by decomposition of the forming material of metallic silver after compounding.

The metal silver forming material is decomposed by heating or the like to form metal silver.
In the present embodiment, one of the forming materials of metallic silver may be used alone, or two or more thereof may be used in combination. When using 2 or more types together, the combination and ratio can be adjusted arbitrarily.

[Silver carboxylate]
As a forming material of metallic silver, silver carboxylate having a group represented by the formula "-COOAg" can be exemplified.
The silver carboxylate is not particularly limited as long as it has a group represented by the formula "-COOAg". For example, the number of groups represented by the formula "-COOAg" may be only one or two or more. Further, the position of the group represented by the formula "-COOAg" in silver carboxylate is not particularly limited.

  The silver carboxylate is a silver β-ketocarboxylate represented by the following general formula (1) (hereinafter sometimes abbreviated as “β-ketocarboxylate silver (1)”) and the following general formula (2) It is preferable that it is 1 or more types selected from the group which consists of silver carboxylate (Hereinafter, it may abbreviate as "silver carboxylate (2).").

  In the present specification, the description “simple silver carboxylate” is not limited to “silver β-ketocarboxylate (1)” and “silver carboxylate (2)” unless specifically stated otherwise. It is intended to mean “silver carboxylate having a group represented by the formula“ -COOAg ””.

(Wherein R is an aliphatic hydrocarbon group having 1 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, or a phenyl group, a hydroxyl group, an amino group, or a general formula “R ¹ -CY” ₂ - "," CY ₃ - "," ^R 1 -CHY - "," ^{R 2} O - "," ^R 5 ^{R 4} N -, "" ^(R _{3 O)} 2 CY- "or" ^R 6 -C A group represented by (CYO) -CY _2- ";
Y is each independently a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom; R ¹ is an aliphatic hydrocarbon group having 1 to 19 carbon atoms or a phenyl group; R ² is an aliphatic having 1 to 20 carbon atoms R ³ is an aliphatic hydrocarbon group having 1 to 16 carbon atoms; R ⁴ and R ⁵ are each independently an aliphatic hydrocarbon group having 1 to 18 carbon atoms; R ⁶ is carbon An aliphatic hydrocarbon group of the number 1 to 19, a hydroxyl group or a group represented by the formula "AgO-";
X each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a phenyl group or a benzyl group in which one or more hydrogen atoms may be substituted by a substituent, a cyano group, an N- A phthaloyl 3-aminopropyl group, a 2-ethoxyvinyl group, or the general formula "R ⁷ O-", "R ⁷ S-", "R ⁷ -C (= O)-" or "R ⁷ -C (= O) -O- "is a group represented by
R ⁷ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a thienyl group, or a phenyl or diphenyl group in which one or more hydrogen atoms may be substituted by a substituent. )

(Wherein R ⁸ is an aliphatic hydrocarbon group having 1 to 19 carbon atoms, a carboxy group or a group represented by the formula “—C (= O) —OAg”, and the aliphatic hydrocarbon group is a methylene group) And one or more of the methylene groups may be substituted with a carbonyl group.

(Β-ketocarboxylic acid silver (1))
The β-ketocarboxylic acid silver (1) is represented by the above general formula (1).
In the formula, R is an aliphatic hydrocarbon group having 1 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, a phenyl group, a hydroxyl group, an amino group, or a general formula “R ¹ -CY ₂ - "," CY ₃ - "," ^R 1 -CHY - "," ^{R 2} O - "," ^R 5 ^{R 4} N -, "" ^(R _{3 O)} 2 CY- "or" ^R 6 -C ( = O) -CY ₂ - "is a group represented by.

The aliphatic hydrocarbon group having 1 to 20 carbon atoms in R may be linear, branched or cyclic (aliphatic cyclic group), and when it is cyclic, it may be either monocyclic or polycyclic. .
The aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. As preferable said aliphatic hydrocarbon group in R, an alkyl group, an alkenyl group, and an alkynyl group can be illustrated.

Examples of the linear or branched alkyl group for R include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n -Pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4- Methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group 1-ethyl-1-methylpropyl group, n-heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group 4-methylhexyl group, 5-methylhexyl group, 1,1-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group Group, 4,4-dimethylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 4-ethylpentyl group, 2,2,3-trimethylbutyl group, 1-propylbutyl group, n-octyl group, isooctyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3- Ethylhexyl group, 4-ethylhexyl group, 5-ethylhexyl group, 1,1-dimethylhexyl group, 2,2-dimethylhexyl group, 3 3-dimethylhexyl, 4,4-dimethylhexyl, 5,5-dimethylhexyl, 1-propylpentyl, 2-propylpentyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl And pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and icosyl group can be exemplified.
As the cyclic alkyl group for R, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, isobornyl group, 1-adamantyl group, 2- Examples include an adamantyl group and a tricyclodecyl group.

As the alkenyl group for R, a vinyl group (ethenyl group, -CH = CH ₂ ), an allyl group (2-propenyl group, -CH ₂ -CH = CH ₂ ), a 1-propenyl group (-CH = CH-CH) _3), isopropenyl _{(-C (CH 3) = CH} 2), 1- butenyl group _{(-CH = CH-CH 2 -CH} 3), 2- butenyl group _{(-CH 2 -CH = CH-CH} 3 1) a single bond (C—C) between carbon atoms of the alkyl group in R, such as 3-butenyl group (—CH ₂ —CH ₂ —CH = CH ₂ ), cyclohexenyl group, cyclopentenyl group, etc. Can be exemplified by a group substituted by a double bond (C = C).
As the alkynyl group for R, one single bond (C—C) between carbon atoms of the alkyl group for R such as ethynyl group (—C≡CH), propargyl group (—CH ₂ —C≡CH), etc. Can be exemplified as a group substituted with a triple bond (C≡C).

  In the aliphatic hydrocarbon group having 1 to 20 carbon atoms in R, one or more hydrogen atoms may be substituted with a substituent, and preferable examples of the substituent include a fluorine atom, a chlorine atom, and a bromine atom . Also, the number and position of substituents are not particularly limited. And when the number of substituents is plural, these plural substituents may be same or different. That is, all substituents may be the same, all substituents may be different, and only some of the substituents may be different.

In the phenyl group in R, one or more hydrogen atoms may be substituted by a substituent, and preferred examples of the substituent include saturated or unsaturated monovalent aliphatic hydrocarbon groups having 1 to 16 carbon atoms And a monovalent group in which the aliphatic hydrocarbon group is bonded to an oxygen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group (-OH), a cyano group (-C≡N), a phenoxy group (-O- C ₆ H ₅ ) and the like can be exemplified, and the number and position of substituents are not particularly limited. And when the number of substituents is plural, these plural substituents may be same or different.
As said aliphatic hydrocarbon group which is a substituent, the thing similar to the said aliphatic hydrocarbon group in R can be illustrated except a point which carbon number is 1-16.

Y in R is each independently a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom. And, in the general formulas "R ¹ -CY _2- ", "CY _3- " and "R ⁶ -C (= O) -CY _2- ", plural Y's may be the same or different from each other. Good.

R ¹ in R is an aliphatic hydrocarbon group having 1 to 19 carbon atoms or a phenyl group (C ₆ H _5- ), and the aliphatic hydrocarbon group in R ¹ has 1 to 19 carbon atoms The same aliphatic hydrocarbon groups as R in R can be exemplified except for the point.
R ² in R is an aliphatic hydrocarbon group having 1 to 20 carbon atoms can be exemplified by those similar to the aliphatic hydrocarbon group for R.
R ³ in R is an aliphatic hydrocarbon group of 1 to 16 carbon atoms, except a carbon number of 1-16, it can be exemplified the same as the aliphatic hydrocarbon group for R.
R ⁴ and R ⁵ in R are each independently an aliphatic hydrocarbon group having 1 to 18 carbon atoms. That is, R ⁴ and R ⁵ may be the same as or different from each other, and the same as the above-mentioned aliphatic hydrocarbon group in R can be exemplified except that the carbon number is 1 to 18.
R ⁶ in R is an aliphatic hydrocarbon group having 1 to 19 carbon atoms, a hydroxyl group or a group represented by the formula “AgO—”, and as the aliphatic hydrocarbon group in R ⁶ , it has 1 to 1 carbon atoms The same aliphatic hydrocarbon group as that in R can be exemplified except for the point of 19.

Among the above, R is preferably a linear or branched alkyl group, a group represented by the general formula "R ⁶ -C (= O) -CY _2- ", a hydroxyl group or a phenyl group . And R ⁶ is preferably a linear or branched alkyl group, a hydroxyl group or a group represented by the formula “AgO—”.

In the general formula (1), X each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a phenyl group or benzyl group in which one or more hydrogen atoms may be substituted by a substituent Group (C ₆ H ₅ -CH _2- ), cyano group, N-phthaloyl-3-aminopropyl group, 2-ethoxyvinyl group (C ₂ H ₅ -O-CH = CH-), or the general formula “R ⁷ O - "," ^{R 7} S - "," ^R 7 -C (= O) - "or" a group represented by ^R 7 -C (= O) -O-. "
As a C1-C20 aliphatic hydrocarbon group in X, the thing similar to the said aliphatic hydrocarbon group in R can be illustrated.

As a halogen atom in X, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be illustrated.
In the phenyl group and benzyl group in X, one or more hydrogen atoms may be substituted by a substituent, and preferred examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a nitro group can be exemplified a (-NO ₂₎ or the like, the number and position of the substituent is not particularly limited. And when the number of substituents is plural, these plural substituents may be same or different.

R ^{7 in} X is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a thienyl group (C ₄ H ₃ S—), or a phenyl group or diphenyl in which one or more hydrogen atoms may be substituted by a substituent group (biphenyl _{group, C 6 H 5 -C 6 H} 4 -) it is. The aliphatic hydrocarbon group for R ^7, except a carbon number of 1-10, can be exemplified the same as the aliphatic hydrocarbon group for R. Further, examples of the substituent of the phenyl group and a diphenyl group in R ^7, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) can be exemplified the like, the number and position of the substituent is not particularly limited. And when the number of substituents is plural, these plural substituents may be same or different.
When R ⁷ is a thienyl group or a diphenyl group, the bonding position with these adjacent groups or atoms (oxygen atom, sulfur atom, carbonyl group, carbonyloxy group) in X is not particularly limited. For example, the thienyl group may be either a 2-thienyl group or a 3-thienyl group.

In the general formula (1), two X may be bonded as a single group via a double bond to a carbon atom sandwiched by two carbonyl groups, and such as It can be exemplified groups represented by _{"= CH-C 6 H 4 -NO} 2 ".

  Among the above, X is preferably a hydrogen atom, a linear or branched alkyl group, or a benzyl group, and at least one of X is preferably a hydrogen atom.

The silver β-ketocarboxylate (1) is selected from silver 2-methylacetoacetate (CH ₃ -C (3O) -CH (CH ₃ ) -C (= O) -OAg), silver acetoacetate (CH ₃ -C (CH ₃ -C) _{= O) -CH 2 -C (=} O) -OAg), 2- ethylacetoacetate silver _{(CH 3 -C (= O)} -CH (CH 2 CH 3) -C (= O) -OAg), propionylacetate silver _{(CH 3 CH 2 -C (=} O) -CH 2 -C (= O) -OAg), 2-n- Buchiruaseto silver acetate _{(CH 3 -C (= O)} -CH (CH 2 CH 2 CH 2 CH ₃ ) -C (= O) -OAg), silver 2-benzylacetoacetate (CH ₃ -C (= O) -CH (CH ₂ C ₆ H ₅ ) -C (= O) -OAg), benzoylacetic acid Silver (C ₆ H ₅ -C (= O) -CH ₂ -C (= O) -OAg), silver pivaloylacetoacetate ((C H ₃ ) ₃ C—C (= O) —CH ₂ —C (= O) —CH ₂ —C (= O) —OAg), silver isobutyrylacetoacetate ((CH ₃ ) ₂ CH—C (== _{O) -CH 2 -C (= O} ) -CH 2 -C (= O) -OAg), or acetone dicarboxylic silver _{(AgO-C (= O)} -CH 2 -C (= O) -CH 2 - It is preferable that it is C (= O) -OAg).

  Silver (beta) -ketocarboxylic acid (1) can reduce more the density | concentration of the raw material and impurity which remain | survive in the conductor (metallic silver) formed by post-processes, such as a drying process and a heating (baking) process. As the amount of the raw materials and the impurities is smaller, for example, the contact between the formed metal silvers becomes better, the conduction becomes easier, and the resistivity is lowered.

  Silver β-ketocarboxylate (1) decomposes at a low temperature of preferably 60 ° C. to 210 ° C., more preferably 60 ° C. to 200 ° C., without using a reducing agent known in the art as described later. It is possible to form metallic silver. And by using together with a reducing agent, it decomposes | disassembles at lower temperature and forms metallic silver.

  In the present embodiment, silver β-ketocarboxylate (1) may be used alone or in combination of two or more. When using 2 or more types together, the combination and ratio can be adjusted arbitrarily.

(Silver carboxylate (2))
Silver carboxylate (2) is represented by the said General formula (2).
In the formula, R ⁸ is a C 1-19 aliphatic hydrocarbon group, a carboxy group (—COOH) or a group represented by the formula “—C (= O) —OAg”.
As said aliphatic hydrocarbon group in R < ⁸ >, the thing similar to the said aliphatic hydrocarbon group in R can be illustrated except the point which carbon number is 1-19. However, the aliphatic hydrocarbon group for R ⁸ preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms.

When the aliphatic hydrocarbon group for R ⁸ has a methylene group (—CH ₂ —), one or more of the methylene groups may be substituted with a carbonyl group. The number and position of the methylene group which may be substituted by the carbonyl group are not particularly limited, and all the methylene groups may be substituted by the carbonyl group. Here, "methylene group" is not only a group represented by the single formula "-CH _2- " but also one of an alkylene group in which a plurality of groups represented by the formula "-CH _2- " are connected. The group represented by the formula “—CH ₂ —” of

Silver carboxylate (2) is silver pyruvate (CH ₃ -C (= O) -C (= O) -OAg), silver acetate (CH ₃ -C (= O) -OAg), silver butyrate (CH ₃₎ -(CH ₂ ) ₂ -C (= O) -OAg), silver isobutyrate ((CH ₃ ) ₂ CH-C (= O) -OAg), silver 2-ethylhexanoate (CH _3- (CH ₂₎ ) _3- CH (CH ₂ CH ₃ ) -C (= O) -OAg), silver neodecanoate (CH _3- (CH ₂ ) ₅ -C (CH ₃ ) ₂ -C (= O) -OAg), oxalic acid is preferably a silver (AgO-C (= O) -C (= O) -OAg), or malonate silver _{(AgO-C (= O)} -CH 2 -C (= O) -OAg). Also, 2 of the silver oxalate (AgO-C (= O) -C (= O) -OAg) and malonic silver _{(AgO-C (= O)} -CH 2 -C (= O) -OAg) Of the groups represented by the formula “—COOAg”, one in which one is a group represented by the formula “—COOH” (HO—C (= O) —C (= O) —OAg, HO _{-C (= O) -CH 2 -C} (= O) -OAg) it is also preferred.

  Similarly to silver β-ketocarboxylate (1), silver carboxylate (2) is a raw material or an impurity remaining in a conductor (metallic silver) formed by post treatment such as drying treatment or heating (baking) treatment. The concentration can be further reduced. And by using together with a reducing agent, it decomposes | disassembles at lower temperature and forms metallic silver.

  In the present embodiment, one kind of silver carboxylate (2) may be used alone, or two or more kinds may be used in combination. When using 2 or more types together, the combination and ratio can be adjusted arbitrarily.

[Nitrogen-containing compounds]
The silver ink composition further includes an amine compound having a carbon number of 25 or less, a quaternary ammonium salt, ammonia, and the like, in addition to the material forming metal silver, particularly when the material forming metal silver is the silver carboxylate. A compound comprising one or more nitrogen-containing compounds (hereinafter sometimes simply referred to as “nitrogen-containing compounds”) selected from the group consisting of amine compounds or ammonium salts formed by the reaction of ammonia with acid. Is preferred.

  Hereinafter, an amine compound having a carbon number of 25 or less, an "amine compound", a quaternary ammonium salt having a carbon number of 25 or less is a "quaternary ammonium salt", and an amine compound having a carbon number of 25 or less reacts with an acid Is sometimes abbreviated as "an ammonium salt derived from an amine compound", and an ammonium salt formed by reaction of ammonia with an acid as "an ammonium salt derived from ammonia".

(Amine compound, quaternary ammonium salt)
The amine compound has 1 to 25 carbon atoms, and may be any of a primary amine, a secondary amine and a tertiary amine. The quaternary ammonium salt has 4 to 25 carbon atoms. The amine compound and the quaternary ammonium salt may be either linear or cyclic. Further, the number of nitrogen atoms constituting an amine site or an ammonium salt site (for example, nitrogen atoms constituting an amino group (—NH ₂ ) of a primary amine) may be one or two or more.

  Examples of the primary amine include monoalkylamines, monoarylamines, mono (heteroaryl) amines, diamines and the like in which one or more hydrogen atoms may be substituted by a substituent.

  The alkyl group constituting the monoalkylamine may be linear, branched or cyclic and may be the same as the alkyl group in R, and may be linear or branched having 1 to 19 carbon atoms. It is preferable that it is a chain | strand-shaped alkyl group or a C3-C7 cyclic alkyl group.

  Specific examples of preferable monoalkylamines include n-butylamine, n-hexylamine, n-octylamine, n-dodecylamine, n-octadecylamine, sec-butylamine, tert-butylamine, 3-aminopentane, 3 -Methylbutylamine, 2-aminooctane, 2-ethylhexylamine, 1,2-dimethyl-n-propylamine can be exemplified.

  As an aryl group which comprises the said monoarylamine, a phenyl group, 1-naphthyl group, 2-naphthyl group etc. can be illustrated, and it is preferable that carbon number is 6-10.

The heteroaryl group which comprises the said mono (hetero aryl) amine has a hetero atom as an atom which comprises aromatic ring frame | skeleton, As said hetero atom, a nitrogen atom, a sulfur atom, an oxygen atom, a boron atom Can be illustrated. Further, the number of the hetero atoms constituting the aromatic ring skeleton is not particularly limited, and may be one or two or more. When two or more, these heteroatoms may be the same or different. That is, these heteroatoms may all be the same, all be different, or only some may be different.
The heteroaryl group may be monocyclic or polycyclic, and the number of ring members (number of atoms constituting the ring skeleton) is not particularly limited, but is preferably a 3- to 12-membered ring.

  The heteroaryl group is a monocyclic group having 1 to 4 nitrogen atoms, such as pyrrolyl group, pyrrolinyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrimidyl group, pyrazinyl group, pyridazinyl group, triazolyl group, tetrazolyl group And a pyrrolidinyl group, an imidazolidinyl group, a piperidinyl group, a pyrazolidinyl group, and a piperazinyl group can be exemplified. A 3- to 8-membered ring is preferable, and a 5- to 6-membered ring is more preferable.

As said heteroaryl group, as a monocyclic thing which has one oxygen atom, a furanyl group can be illustrated, It is preferable that it is a 3- to 8-membered ring, and it is more preferable that it is a 5- to 6-membered ring.
Examples of the heteroaryl group as the monocyclic group having one sulfur atom include a thienyl group, preferably a 3- to 8-membered ring, and more preferably a 5- to 6-membered ring.
Examples of the heteroaryl group as the monocyclic group having 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms include an oxazolyl group, an isoxazolyl group, an oxadiazolyl group, and a morpholinyl group, and has a 3- to 8-membered ring. It is preferable that it is a 5- to 6-membered ring.
Examples of the heteroaryl group as the monocyclic group having 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms include thiazolyl group, thiadiazolyl group and thiazolidinyl group, and it is a 3- to 8-membered ring It is more preferable that it is a 5- or 6-membered ring.
Examples of the heteroaryl group which is a cyclic group having 1 to 5 nitrogen atoms include indolyl group, isoindolyl group, indolizinyl group, benzimidazolyl group, quinolyl group, isoquinolyl group, indazolyl group, benzotriazolyl group, tetrazo group. Examples thereof include a zolopyridyl group, a tetrazolopyridazinyl group and a dihydrotriazolopyridazinyl group, preferably a 7- to 12-membered ring, and more preferably a 9- to 10-membered ring.
Examples of the above-mentioned heteroaryl group which is a cyclic group having 1 to 3 sulfur atoms include a dithianaphthalenyl group and a benzothiophenyl group, and a 7- to 12-membered ring is preferable, and a 9 to 10-membered ring is preferable. More preferably, it is a ring.
Examples of the above-mentioned heteroaryl group which is a polycyclic group having 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms include benzoxazolyl group and benzooxadiazolyl group, each having a 7- to 12-membered ring. It is preferable that it is a 9- to 10-membered ring.
As the above-mentioned heteroaryl group, as a polycyclic group having 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms, benzothiazolyl group and benzothiadiazolyl group can be exemplified, and it is a 7- to 12-membered ring Preferably, a 9 to 10-membered ring is more preferred.

The said diamine should just have two amino groups, and the positional relationship of two amino groups is not specifically limited. As the preferable diamine, in the monoalkylamine, monoarylamine or mono (heteroaryl) amine, one hydrogen atom other than a hydrogen atom constituting an amino group (—NH ₂ ) is substituted by an amino group Can be illustrated.
The diamine preferably has 1 to 10 carbon atoms, and more preferably ethylene diamine, 1,3-diaminopropane and 1,4-diaminobutane.

  Examples of the secondary amine include dialkylamines, diarylamines, di (heteroaryl) amines and the like in which one or more hydrogen atoms may be substituted by a substituent.

The alkyl group constituting the dialkylamine is the same as the alkyl group constituting the monoalkylamine, and is a linear or branched alkyl group having 1 to 9 carbon atoms, or 3 to 7 carbon atoms. It is preferably a cyclic alkyl group. Also, two alkyl groups in one dialkylamine molecule may be the same or different.
Specific examples of the preferred dialkylamine include N-methyl-n-hexylamine, diisobutylamine and di (2-ethylhexyl) amine.

  The aryl group which comprises the said diarylamine is the same as that of the aryl group which comprises the said monoarylamine, and it is preferable that carbon number is 6-10. Also, two aryl groups in one molecule of diarylamine may be the same as or different from each other.

  The heteroaryl group constituting the di (heteroaryl) amine is the same as the heteroaryl group constituting the mono (heteroaryl) amine, and is preferably a 6- to 12-membered ring. Also, two heteroaryl groups in one molecule of di (heteroaryl) amine may be the same as or different from each other.

  Examples of the tertiary amine include trialkylamines and dialkyl monoarylamines in which one or more hydrogen atoms may be substituted by a substituent.

The alkyl group constituting the trialkylamine is the same as the alkyl group constituting the monoalkylamine, and is a linear or branched alkyl group having 1 to 19 carbon atoms, or 3 to 7 carbon atoms. It is preferable that it is a cyclic alkyl group of In addition, three alkyl groups in one trialkylamine molecule may be the same as or different from each other. That is, all of the three alkyl groups may be the same, all may be different, or only some of them may be different.
Specific examples of preferable trialkylamines include N, N-dimethyl-n-octadecylamine and N, N-dimethylcyclohexylamine.

The alkyl group constituting the dialkyl monoarylamine is the same as the alkyl group constituting the monoalkyl amine, and is a linear or branched alkyl group having 1 to 6 carbon atoms, or 3 to 3 carbon atoms. It is preferable that it is 7 cyclic alkyl groups. In addition, two alkyl groups in one dialkyl monoarylamine molecule may be the same as or different from each other.
The aryl group constituting the dialkyl monoarylamine is the same as the aryl group constituting the monoarylamine, and preferably has 6 to 10 carbon atoms.

In the present embodiment, examples of the quaternary ammonium salt include halogenated tetraalkyl ammonium and the like in which one or more hydrogen atoms may be substituted by a substituent.
The alkyl group constituting the halogenated tetraalkylammonium is the same as the alkyl group constituting the monoalkylamine, and preferably has 1 to 19 carbon atoms.
In addition, four alkyl groups in one halogenated tetraalkylammonium molecule may be the same as or different from each other. That is, all four alkyl groups may be the same, all may be different, or only some may be different.
As a halogen which comprises the said halogenated tetraalkyl ammonium, a fluorine, chlorine, a bromine, and an iodine can be illustrated.
As preferable said tetraalkyl ammonium halide, dodecyl trimethyl ammonium bromide can be illustrated specifically.

So far, the chain amine compound and quaternary organic ammonium salt have been mainly described, but in the amine compound and quaternary ammonium salt, the nitrogen atom constituting the amine site or the ammonium salt site has a ring skeleton structure ( The heterocyclic compound may be a part of the heterocyclic skeleton structure). That is, the amine compound may be a cyclic amine, and the quaternary ammonium salt may be a cyclic ammonium salt. At this time, the ring (a ring containing a nitrogen atom constituting an amine moiety or an ammonium salt moiety) may be monocyclic or polycyclic, and the number of ring members (number of atoms constituting a ring skeleton) is also particularly limited. And may be either an aliphatic ring or an aromatic ring.
If it is a cyclic amine, a pyridine can be illustrated as a preferable thing.

  In the above-mentioned primary amine, secondary amine, tertiary amine and quaternary ammonium salt, "a hydrogen atom which may be substituted by a substituent" means a nitrogen atom constituting an amine site or an ammonium salt site Is a hydrogen atom other than a hydrogen atom bonded to The number of substituents at this time is not particularly limited, and may be one or two or more, and all of the hydrogen atoms may be substituted with substituents. When the number of substituents is plural, these plural substituents may be the same or different. That is, the plurality of substituents may be all the same, all different, or only some of them may be different. Also, the position of the substituent is not particularly limited.

Examples of the substituent in the amine compound and quaternary ammonium salt, an alkyl group, an aryl group, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a trifluoromethyl group (-CF ₃₎ or the like can be mentioned. Here, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be exemplified.

  When the alkyl group constituting the monoalkylamine has a substituent, such an alkyl group is a linear or branched alkyl group having 1 to 9 carbon atoms or an aryl group as a substituent, or a substituent Is preferably a cyclic alkyl group having 3 to 7 carbon atoms and having an alkyl group having 1 to 5 carbon atoms, and as a monoalkylamine having such a substituent, specifically, 2-phenylethylamine And benzylamine and 2,3-dimethylcyclohexylamine.

  In addition, one or more hydrogen atoms of the above-mentioned aryl group and alkyl group which are substituents may be further substituted by a halogen atom, and as a monoalkylamine having a substituent substituted by such a halogen atom, And 2-bromobenzylamine. Here, as said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be illustrated.

  When the aryl group constituting the monoarylamine has a substituent, such an aryl group is preferably an aryl group having 6 to 10 carbon atoms having a halogen atom as a substituent, and a monoaryl having such a substituent Specifically as an amine, a bromophenylamine can be illustrated. Here, as said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be illustrated.

  When the alkyl group constituting the dialkylamine has a substituent, such an alkyl group is preferably a linear or branched alkyl group having 1 to 9 carbon atoms, having a hydroxyl group or an aryl group as a substituent, Specific examples of the dialkylamine having such a substituent include diethanolamine and N-methylbenzylamine.

The above-mentioned amine compounds are n-propylamine, n-butylamine, n-hexylamine, n-octylamine, n-dodecylamine, n-octadecylamine, sec-butylamine, tert-butylamine, 3-aminopentane, 3-methyl Butylamine, 2-aminooctane, 2-ethylhexylamine, 2-phenylethylamine, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, N-methyl-n-hexylamine, diisobutylamine, N-methylbenzylamine Preferably, di (2-ethylhexyl) amine, 1,2-dimethyl-n-propylamine, N, N-dimethyl-n-octadecylamine or N, N-dimethylcyclohexylamine.
In addition, the component in the silver ink composition (the second mixture) is dispersed more uniformly at the time of carbon dioxide supply described later, and the quality is stabilized, so that the amine compound has a branched alkyl group. Is preferred.

(Ammonia salt derived from amine compound)
In the present embodiment, the ammonium salt derived from the amine compound is an ammonium salt formed by reacting the amine compound with an acid, and the acid may be an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid, or an organic compound such as acetic acid It may be an acid, and the type of acid is not particularly limited.

  Examples of the ammonium salt derived from the amine compound include n-propylamine hydrochloride, N-methyl-n-hexylamine hydrochloride, N, N-dimethyl-n-octadecylamine hydrochloride and the like, but are not limited thereto. .

(Ammonia-derived ammonium salt)
In the present embodiment, the ammonium salt derived from ammonia is an ammonium salt formed by reacting ammonia with an acid, and as the acid, the same as the ammonium salt derived from the amine compound can be exemplified.
Although ammonium chloride etc. can be illustrated as said ammonium salt derived from ammonia, It is not limited to this.

  In the present embodiment, one kind of each of the amine compound, the quaternary ammonium salt, the ammonium salt derived from the amine compound and the ammonium salt derived from ammonia may be used alone, or two or more kinds may be used in combination. It is also good. When using 2 or more types together, the combination and ratio can be adjusted arbitrarily.

  And, as the nitrogen-containing compound, one selected from the group consisting of the amine compound, quaternary ammonium salt, ammonium salt derived from amine compound and ammonium salt derived from ammonia may be used alone, Two or more may be used in combination. When using 2 or more types together, the combination and ratio can be adjusted arbitrarily.

In the silver ink composition, the blending amount of the nitrogen-containing compound is preferably 0.4 to 15 moles, and more preferably 0.8 to 5 moles per mole of the blending amount of the silver carboxylate.
By defining the blending amount of the nitrogen-containing compound as described above, the stability of the silver ink composition is further improved, and the quality of the conductive circuit is further improved. Furthermore, the conductive circuit can be formed more stably without heat treatment at high temperature.

[Reductant]
The silver ink composition may further contain a reducing agent in addition to the above-mentioned forming material of metallic silver. By blending the reducing agent, the silver ink composition can more easily form metallic silver, and can form metallic silver (conductor) having sufficient conductivity even by heat treatment at a low temperature, for example.

And, the reducing agent is one or more selected from the group consisting of oxalic acid, hydrazine and a compound represented by the following general formula (3) (hereinafter sometimes abbreviated as “compound (3)”) It is preferable that it is a reducing compound (Hereinafter, it may only be abbreviated as a "reducing compound").
H-C (= O) -R ²¹ (3)
(Wherein, R ²¹ represents an alkyl group having 20 or less carbon atoms, an alkoxy group or an N, N-dialkylamino group, a hydroxyl group or an amino group).

(Reducing compound)
The reducing compound is one selected from the group consisting of oxalic acid (HOOC-COOH), hydrazine (H ₂ N-NH ₂ ), and a compound (compound (3)) represented by the general formula (3) It is the above thing. That is, only one kind or two or more kinds of reducing compounds may be blended, and when two or more kinds are used in combination, the combination and ratio thereof can be arbitrarily adjusted.

In the formula, R ²¹ is an alkyl group having 20 or less carbon atoms, an alkoxy group or an N, N-dialkylamino group, a hydroxyl group or an amino group.
The alkyl group having 20 or less carbon atoms in R ²¹ has 1 to 20 carbon atoms, and may be linear, branched or cyclic, and is the same as the alkyl group in R of the general formula (1) Can be illustrated.

The alkoxy group having 20 or less carbon atoms in R ²¹ has 1 to 20 carbon atoms, and can be exemplified by a monovalent group formed by bonding the alkyl group in R ^{21 to} an oxygen atom.

The N, N-dialkylamino group having 20 or less carbon atoms in R ²¹ has 2 to 20 carbon atoms, and the two alkyl groups bonded to the nitrogen atom may be identical to or different from each other. Each alkyl group has 1 to 19 carbon atoms. However, the total value of carbon number of these two alkyl groups is 2-20.
The alkyl group bonded to the nitrogen atom may be linear, branched or cyclic, and the alkyl in R of the general formula (1) except that it has 1 to 19 carbon atoms The same thing as a group can be illustrated.

Hydrazine (H ₂ N—NH ₂ · H ₂ O) may be used as the reducing compound.

The reducing compounds are formic acid (H-C (= O) -OH), methyl formate (H-C (= O) -OCH 3), ethyl formate _{(H-C (= O)} -OCH 2 CH 3) , Butyl formate (H-C (= O) -O (CH ₂ ) ₃ CH ₃ ), propanal (H-C (= O) -CH ₂ CH ₃ ), butanal (H-C (= O)-( CH ₂ ) ₂ CH ₃ ), hexanal (H—C (= O) — (CH ₂ ) ₄ CH ₃ ), formamide (H—C (= O) —NH ₂ ), N, N-dimethylformamide (H— _{C (= O) -N (CH} 3) 2) or is preferably oxalic acid.

  In the silver ink composition, the compounding amount of the reducing agent is preferably 0.04 to 3.5 moles, preferably 0.06 to 2.5 moles, per mole of the compounding amount of the forming material of the metal silver. Is more preferred. By defining in this way, the silver ink composition can form the conductive circuit more easily and more stably.

[alcohol]
The silver ink composition is preferably one in which an alcohol is further blended in addition to the forming material of the metallic silver.

The alcohol is preferably an acetylene alcohol represented by the following general formula (4) (hereinafter sometimes abbreviated as "acetylene alcohol (4)").
Acetylene alcohol (4) is suitable as a component for forming a black layer by the above-described heat treatment of the silver ink composition.

(Wherein, R ′ and R ′ ′ each independently represent an alkyl group having 1 to 20 carbon atoms, or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent).

(Acetylene alcohol (4))
The acetylene alcohol (4) is represented by the general formula (4).
In the formula, R ′ and R ′ ′ each independently represent an alkyl group having 1 to 20 carbon atoms, or a phenyl group in which one or more hydrogen atoms may be substituted by a substituent.
The alkyl group having 1 to 20 carbon atoms in R ′ and R ′ ′ may be linear, branched or cyclic, and when it is cyclic, it may be monocyclic or polycyclic. As said alkyl group in R 'and R'', the thing similar to the said alkyl group in R can be illustrated.

  The substituted or unsubstituted hydrogen atom of the phenyl group in R ′ and R ′ ′ is, for example, a saturated or unsaturated monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms, and the aliphatic carbon Examples include monovalent groups formed by bonding a hydrogen group to an oxygen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, a cyano group, a phenoxy group, etc., and the hydrogen atom of the phenyl group in R may be substituted It is the same as the above-mentioned substituent. The number and position of substituents are not particularly limited, and when the number of substituents is plural, the plural substituents may be the same or different.

  R ′ and R ′ ′ are each preferably an alkyl group having 1 to 20 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 10 carbon atoms.

  Examples of preferable acetylene alcohol (4) include 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-butyn-3-ol and 3-methyl-1-pentyn-3-ol.

  In the silver ink composition, the compounding amount of the acetylene alcohol (4) is preferably 0.03 mol to 0.7 mol per 1 mol of the compounding amount of the material forming the metal silver, and 0.05 mol to 0. More preferably, it is 5 moles. By setting this range, the stability of the silver ink composition is further improved. Moreover, in the solidification process mentioned later by setting it as such a range, in a conductive circuit, it becomes easy to form a black layer and a metallic-glossy color layer.

  The alcohols may be used alone or in combination of two or more. When using 2 or more types together, the combination and ratio can be adjusted arbitrarily.

The silver ink composition may be one in which other components other than the forming material of the metallic silver, the nitrogen-containing compound, the reducing agent and the alcohol are blended.
The other components can be optionally selected according to the purpose, and are not particularly limited. Preferred examples include solvents other than alcohols, and can be optionally selected according to the types and amounts of the compounding components.
In the silver ink composition, the ratio of the blending amount of the other components to the total amount of the blending components is preferably 10% by mass or less, and more preferably 5% by mass or less.
The other components may be used alone or in combination of two or more. When using 2 or more types together, the combination and ratio can be adjusted arbitrarily.

  The components in the silver ink composition may be all dissolved or some or all may not be dissolved, but it is preferable that the undissolved components be uniformly dispersed.

The silver ink composition is obtained by blending the forming material of the metallic silver and components other than the forming material of the metallic silver.
At the time of blending each component, all the components may be added and then mixed, or some of the components may be sequentially added and mixed, or all the components may be sequentially added and mixed. Good.
The mixing method is not particularly limited, and may be appropriately selected from known methods such as a method of mixing by rotating a stirrer or a stirring blade, a method of mixing using a mixer, a method of adding and mixing ultrasonic waves, .

The temperature at the time of compounding is not particularly limited as long as each compounded component is not deteriorated, but is preferably -5 ° C to 30 ° C.
Further, the compounding time (mixing time) is not particularly limited as long as each compounded component is not deteriorated, but it is preferably 5 minutes to 120 minutes.

[carbon dioxide]
The silver ink composition may further be supplied with carbon dioxide. Such a silver ink composition has a high viscosity, and, for example, printing methods that require thickening of the ink, such as flexographic printing, screen printing, gravure printing, gravure offset printing, pad printing, etc. Suitable for application.

Carbon dioxide may be supplied at any time during production of the silver ink composition.
And in this embodiment, carbon dioxide is supplied to the 1st mixture which the formation material of the said metallic silver and a nitrogen-containing compound are blended, for example, and it is set as a 2nd mixture, to the 2nd mixture, Furthermore, it is preferable to mix | blend the said reducing agent and to manufacture a silver ink composition. Moreover, when mix | blending the said alcohol or another component, these can be mix | blended at the time of manufacture of any one or both of a 1st mixture and a 2nd mixture, and can be selected arbitrarily according to the objective.

  The first mixture can be produced by the same method as the above silver ink composition except that the blending components are different.

  In the first mixture, all of the compounding components may be dissolved, or some of the components may be dispersed without being dissolved, but it is preferable that all of the compounding components be dissolved, and the solution be dissolved. It is preferable that the component which is not carried out is disperse | distributed uniformly.

  Although the compounding temperature at the time of 1st mixture manufacture is not specifically limited unless each compounding component degrades, It is preferable that it is -5 degreeC-30 degreeC. Moreover, although the compounding time may be suitably adjusted according to the kind of compounding component, and temperature at the time of compounding, it is preferable that they are 0.5 hour-12 hours, for example.

The carbon dioxide (CO ₂ ) supplied to the first mixture may be either gaseous and solid (dry ice), and may be both gaseous and solid. By supplying carbon dioxide, it is inferred that the carbon dioxide dissolves into the first mixture and acts on the components in the first mixture to increase the viscosity of the obtained second mixture.

  The supply of carbon dioxide gas may be performed by various known methods of blowing the gas into the liquid, and a suitable supply method may be appropriately selected. For example, the method of immersing one end of the pipe in the first mixture, connecting the other end to the carbon dioxide gas supply source, and supplying the carbon dioxide gas to the first mixture through the pipe can be exemplified. At this time, carbon dioxide gas may be supplied directly from the end of the pipe, but for example, a large number of void portions that can be gas flow paths, such as porous ones, are provided to diffuse the introduced gas. A gas diffusion member that can be released as a minute air bubble may be connected to the end of the pipe, and carbon dioxide gas may be supplied through the gas diffusion member. Alternatively, carbon dioxide gas may be supplied while stirring the first mixture in the same manner as in the preparation of the first mixture. By doing this, carbon dioxide can be efficiently supplied.

  The amount of carbon dioxide gas supplied may be appropriately adjusted according to the amount of the first mixture supplied and the viscosity of the target silver ink composition or the second mixture, and is not particularly limited. For example, in order to obtain about 100 g to about 1000 g of a silver ink composition having a viscosity (by ultrasonic wave viscometer) of 5 Pa · s or more at 20 ° C. to 25 ° C., 100 L or more of carbon dioxide gas is preferably supplied. It is more preferable to supply 200 L or more. In addition, although the viscosity in 20 degreeC-25 degreeC of silver ink composition was demonstrated here, the temperature at the time of use of a silver ink composition is not limited to 20 degreeC-25 degreeC, It can select arbitrarily.

The flow rate of carbon dioxide gas may be appropriately adjusted in consideration of the required supply amount of carbon dioxide gas, but it is preferably 0.5 mL / min or more per 1 g of the first mixture, and 1 mL / min or more. It is more preferable that Although the upper limit value of the flow rate is not particularly limited, it is preferably 40 mL / min per 1 g of the mixture in consideration of handleability and the like.
The carbon dioxide gas supply time may be appropriately adjusted in consideration of the required carbon dioxide gas supply amount and flow rate.

  The temperature of the first mixture at the time of carbon dioxide gas supply is preferably 5 ° C. to 70 ° C., more preferably 7 ° C. to 60 ° C., and particularly preferably 10 ° C. to 50 ° C. By setting the content to the lower limit value or more, carbon dioxide can be more efficiently supplied, and by setting the content to the upper limit value or less, a silver ink composition of better quality with few impurities can be obtained.

  The flow rate and supply time of carbon dioxide gas, and the temperature at the time of carbon dioxide gas supply may be adjusted to a suitable range while mutually considering the respective values. For example, even if the temperature is set lower, the carbon dioxide gas flow rate may be set higher, the carbon dioxide gas supply time may be set longer, or both may be performed efficiently. It can supply carbon.

  In addition, even if the flow rate of carbon dioxide gas is set to a small value, carbon dioxide can be efficiently provided by increasing the temperature or setting the supply time of carbon dioxide gas longer or both of them. Can be supplied. That is, a silver ink of good quality is obtained by flexibly combining the flow rate of carbon dioxide gas and the numerical values in the above numerical range exemplified as the temperature at the time of carbon dioxide gas supply while also considering the carbon dioxide gas supply time. The composition is obtained efficiently.

The supply of carbon dioxide gas is preferably performed while stirring the first mixture. By so doing, the supplied carbon dioxide gas can diffuse more uniformly into the first mixture, and carbon dioxide can be supplied more efficiently.
The stirring method at this time may be the same as that of the mixing method at the time of production of the above silver ink composition without using carbon dioxide.

The supply of dry ice (solid carbon dioxide) may be performed by adding dry ice to the first mixture. Dry ice may be added all at once, or may be divided and added stepwise (continuously across a time zone in which addition is not performed).
The amount of dry ice used may be adjusted in consideration of the above-mentioned supply amount of carbon dioxide gas.
During and after the addition of dry ice, the first mixture is preferably stirred, for example, in the same manner as in the preparation of the above silver ink composition without carbon dioxide. By doing this, carbon dioxide can be efficiently supplied.
The temperature during stirring may be the same as during carbon dioxide gas supply. In addition, the stirring time may be appropriately adjusted according to the stirring temperature.

  The viscosity of the second mixture may be appropriately adjusted depending on the purpose, such as the handling method of the silver ink composition or the second mixture, and is not particularly limited. For example, when the silver ink composition is applied to a printing method using a high viscosity ink such as a screen printing method or an intaglio printing (gravure printing) method, the viscosity of the second mixture at 20 ° C. to 25 ° C. It is preferable that it is 3 Pa.s or more according to a system viscometer. In addition, although the viscosity in 20 degreeC-25 degreeC of a 2nd mixture was demonstrated here, the temperature at the time of use of a 2nd mixture is not limited to 20 degreeC-25 degreeC, It can select arbitrarily.

The second mixture further contains the reducing agent to form a silver ink composition.
The silver ink composition at this time can be manufactured by the same method as the above-mentioned silver ink composition which does not use carbon dioxide except that blending components are different. Then, in the obtained silver ink composition, all of the compounding components may be dissolved, or some of the components may be dispersed without being dissolved, but all of the compounding components are dissolved. It is preferable that the undissolved components be uniformly dispersed.

  Although the temperature at the time of the said mixing | blending of a reducing compound is not specifically limited unless each mixing | blending component degrades, It is preferable that it is -5 degreeC-60 degreeC. Moreover, although the compounding time may be suitably adjusted according to the kind of compounding component, and temperature at the time of compounding, it is preferable that they are 0.5 hour-12 hours, for example.

  The other components may be compounded at the time of production of any of the first mixture and the second mixture, as described above, or may be compounded at the time of production of both. That is, in the process of producing the silver ink composition via the first mixture and the second mixture, the ratio of the blending amount of the other components to the total amount of the blending components other than carbon dioxide ([other components (mass) It is preferable that it is 10 mass% or less, and it is more preferable that it is 10 mass% or less [/ the formation material of metallic silver, a nitrogen-containing compound, a reducing agent, alcohol, and other components (mass)] x 100) Preferably, the silver ink composition sufficiently exhibits its effect even if it has no mass, that is, it does not contain other components.

  For example, when the reducing agent is blended, the resulting blend (silver ink composition) is relatively exothermic. And, when the temperature at the time of blending the reducing agent is high, this blend is in the same state as at the time of heat treatment of the silver ink composition described later, so the decomposition accelerating action of the silver carboxylate by the reducing agent It is speculated that formation of metallic silver may be initiated in at least a portion of the silver carboxylate. A silver ink composition containing such metallic silver may be able to form a conductive circuit by performing post-treatment under milder conditions than a silver ink composition not containing metallic silver at the time of forming the conductive circuit.

  Also, even when the compounding amount of the reducing agent is sufficiently large, it may be possible to form a conductive circuit by performing post-treatment under mild conditions as well. As described above, by adopting the conditions for promoting the decomposition of the silver carboxylate, the conductive circuit can be subjected to the heat treatment at a lower temperature as the post-treatment, or to the drying treatment only at the normal temperature without performing the heat treatment. It can be formed. In addition, a silver ink composition containing such metallic silver can be handled in the same manner as a silver ink composition not containing metallic silver, and the handling property is not particularly inferior.

  In the present embodiment, it is preferable to mix the reducing agent while dropping, and further suppressing the fluctuation of the dropping speed tends to further reduce the surface roughness of the conductive circuit.

  Moreover, in the present embodiment, it is also preferable to supply carbon dioxide to a mixture in which the metal silver forming material, the alcohol, and the nitrogen-containing compound are blended to produce a silver ink composition. In this case, as the method of supplying carbon dioxide, the same method as described above can be adopted.

  The silver ink composition to which carbon dioxide is supplied is, for example, at 20 ° C. to 25 ° C. when the silver ink composition is applied to a printing method using a high viscosity ink such as a screen printing method or a flexographic printing method. The viscosity (by an ultrasonic viscometer) is preferably 1 Pa · s or more.

  In the conductive circuit forming step, the conductive circuit is adjusted by adjusting the amount of the silver ink composition deposited on the electrode forming surface 20a of the transparent substrate 20 or the compounding amount of the forming material of the metal silver in the silver ink composition. You can adjust the thickness of the

  When the silver ink composition deposited on the electrode-forming surface 20a of the transparent substrate 20 is subjected to solidification, it may be carried out by a known method. For example, the drying may be performed under normal pressure, reduced pressure and blowing conditions. It may be carried out in any manner, and may be carried out under the atmosphere or under an inert gas atmosphere. The drying temperature is also not particularly limited, and any of heat drying and normal temperature drying may be used. As a preferable drying method when the heat treatment is unnecessary, a method of drying in the atmosphere at 18 ° C. to 30 ° C. can be exemplified.

  When the silver ink composition deposited on the electrode forming surface 20a of the transparent substrate 20 is subjected to a heating (baking) treatment, the conditions may be appropriately adjusted according to the type of the compounding component of the silver ink composition. In general, the heating temperature is preferably 50 ° C. to 500 ° C., and more preferably 70 ° C. to 300 ° C. The heating time may be adjusted according to the heating temperature, but usually, it is preferably 5 seconds to 12 hours, and more preferably 1 minute to 5 hours. Among the forming materials of the metal silver, the silver carboxylate, in particular, the silver β-ketocarboxylate (1), for example, is different from the forming material of the metal silver such as silver oxide, and a reducing agent known in the relevant field is used Even if not, it decomposes at low temperature. And, reflecting such decomposition temperature, the silver ink composition can form metallic silver at a much lower temperature than that of the conventional one, as described above.

  The method of heat treatment of the silver ink composition is not particularly limited, and for example, heating by an electric furnace, heating by a thermal head of a thermal type, heating by far infrared irradiation, heating by spraying a high heat gas, and the like can be performed. The heat treatment of the silver ink composition may be performed under the atmosphere, may be performed under an inert gas atmosphere, or may be performed under humidified conditions. And you may carry out under any pressure and pressure reduction.

  When the heat treatment of the silver ink composition is performed under humidified conditions, it is preferably performed in an atmosphere with a relative humidity of 10% or more, more preferably in an atmosphere with a relative humidity of 60% or more, and a relative humidity of 80% It is particularly preferable to carry out under the above atmosphere, and it may be carried out by spraying high pressure steam heated to 100 ° C. or higher. By heat treatment under humidified conditions as described above, a conductive circuit with low resistance (excellent conductivity) can be formed in a short time.

  The heat treatment of the silver ink composition may be performed in two steps. For example, in the heat treatment in the first stage, the silver ink composition is mainly dried instead of the formation of the conductive circuit, and in the second heat treatment, the formation of the conductive circuit may be completed to the end.

  In the first-step heat treatment, the heating temperature may be appropriately adjusted according to the type of the compounding component of the ink composition, but is preferably 50 ° C. to 500 ° C., and preferably 70 ° C. to 300 ° C. More preferable. The heating time may be adjusted according to the heating temperature, but generally, it is preferably 5 seconds to 12 hours, and more preferably 1 minute to 5 hours.

  In the second heat treatment, the heating temperature may be appropriately adjusted according to the type of the compounding component of the ink composition so that the conductive circuit is formed well, but it is 60 ° C. to 350 ° C. Preferably, the temperature is 70 ° C to 250 ° C. The heating time may be adjusted according to the heating temperature, but usually, it is preferably 1 minute to 12 hours, and more preferably 1 minute to 10 hours.

  According to the touch panel 10 including the touch panel electrode 50 of the present embodiment configured as described above, the separation area E3 extending between the first electrode pattern area E1 and the second electrode pattern area E2 is at least in the X direction. A conductor having a region extending at an inclined angle, for example, a conductor 40 extending in a direction inclined at an angle θ with respect to the X direction is formed. As a result, the visibility of the separated region E3 in which the electrode pattern does not exist can be prevented from being lower than the peripheral portion in which the electrode pattern exists. Thereby, an image etc. which are displayed on touch panel 10 can be seen more clearly, and it becomes possible to improve the visibility of touch panel 10.

Second Embodiment
FIG. 4: is a principal part enlarged plan view which shows the touch panel provided with the electrode for touch panels of 2nd embodiment of this invention. In the following description of the second embodiment, the same components as those of the touch panel provided with the touch panel electrode of the first embodiment described above are denoted by the same reference numerals, and the description thereof is omitted.
The touch panel 60 according to the present embodiment includes a transparent substrate (substrate) 20 and a touch panel electrode (electrode) 70 formed on an electrode forming surface 20 a which is one surface of the transparent substrate 20. The touch panel electrode 70 includes a pattern electrode formed by intersecting a plurality of strip electrodes 80 with each other, and a conductor 90. In the strip electrode 80, a plurality of strip electrodes 80a extending along the X direction in the figure and a plurality of strip electrodes 80b extending along the Y direction intersect at a predetermined angle, for example, 90.degree. The electrode 70 is formed.

  The touch panel electrode 70 is a first electrode pattern area E1, which is two electrode pattern areas spaced apart in a predetermined direction, for example, an X direction in the figure, via a predetermined separation area E3 on the electrode formation surface 20a. And a second electrode pattern area E2. A large number of conductors 90 are disposed in a separation area E3 provided between the first electrode pattern area E1 and the second electrode pattern area E2. The conductor 90 according to the present embodiment is a strip-shaped conductor including at least a region extending in an angular direction inclined with respect to the X direction which is a predetermined direction of the electrode forming surface 20 a and spaced from the strip electrode 80. is there. In the present embodiment, the conductor 90 has a hook shape including a region extending along the Y direction which is a direction inclined at an angle of 90 ° with respect to the X direction and a region extending in the X direction from both ends of this region. It consists of a formed conductor.

  According to the touch panel 60 having such a configuration, the separation region E3 in which the first electrode pattern region E1 and the second electrode pattern region E2 are electrically separated from each other includes a region extending in a direction inclined with respect to the X direction By forming the hook-shaped conductor 90, it is possible to prevent the visibility of the separated region E3 in which the electrode pattern is not present from being lower than that of the peripheral portion. Thus, an image etc. displayed on the touch panel 60 can be seen more clearly, and the visibility of the touch panel 60 can be improved.

Third Embodiment
FIG. 5: is a principal part enlarged plan view which shows the touch panel provided with the electrode for touch panels of 3rd embodiment of this invention. In the following description of the second embodiment, the same components as those of the touch panel provided with the touch panel electrode of the first embodiment described above are denoted by the same reference numerals, and the description thereof is omitted.
The touch panel 100 of the present embodiment includes a transparent substrate (substrate) 20 and a touch panel electrode (electrode) 110 formed on an electrode forming surface 20 a which is one surface of the transparent substrate 20. The touch panel electrode 110 includes a pattern electrode formed by intersecting a plurality of strip electrodes 120 with each other, and a conductor 130. The strip electrode 120 has a plurality of strip electrodes 120a extending along the X direction in the figure and a plurality of strip electrodes 120b extending along the Y direction intersecting at a predetermined angle, for example 90 °, to form a grid touch panel The electrode 110 is formed.

  The touch panel electrode 110 is a first electrode pattern area E1, which is two electrode pattern areas spaced apart in a predetermined direction, for example, an X direction in the figure, via a predetermined separation area E3 on the electrode formation surface 20a. And a second electrode pattern area E2. A large number of conductors 130 are disposed in a separation area E3 provided between the first electrode pattern area E1 and the second electrode pattern area E2. The conductor 130 of the present embodiment is a point-like conductor arranged in an angle direction inclined with respect to the X direction which is a predetermined direction of the electrode forming surface 20 a. In the present embodiment, one conductor 130 is formed of a set of three point-like conductors (point-like conductor groups).

  According to the touch panel 100 having such a configuration, the arrangement direction of three sets of point-like conductors in the separation region E3 in which the first electrode pattern region E1 and the second electrode pattern region E2 are electrically separated from each other By forming the conductors 130 arranged in a direction inclined with respect to the X direction, it is possible to prevent the visibility of the separated region E3 where the electrode pattern does not exist from being lowered compared to the peripheral portion. Thus, an image or the like displayed on the touch panel 100 can be seen more clearly, and the visibility of the touch panel 100 can be improved.

  As mentioned above, although embodiment of the electrode of this invention and the touch panel which applied this electrode was described, this invention is not limited to this, It can change suitably in the range which does not deviate from the technical idea of the invention.

  For example, the conductor may be made of a mixture of strip and dot. The conductor may be parallel to the predetermined direction as long as the conductor includes at least a region extending in a direction inclined at an arbitrary angle with respect to the predetermined direction of the electrode formation surface.

  The conductors are preferably formed randomly as well as regularly. Here, the term “random” means that a plurality of conductors are formed in random directions with each other as long as the extending direction of the conductors is inclined with respect to the predetermined direction, or the formation position in the separated region E3. Without regularly forming at random positions.

  In addition, at least a part of the conductor may be present in the separation area E3, and the other part may extend to the first electrode pattern area E1 or the second electrode pattern area E2. Further, the shapes of the individual conductors do not have to be identical to each other, and conductors having different shapes may be randomly arranged.

  Further, the crossing angle between the strip electrode extending along the X direction and the strip electrode extending along the Y direction can be crossed at any angle other than a right angle. When the crossing angle is other than 90 °, each unit electrode pattern has a rhombic shape.

  Moreover, it is also preferable that an insulating layer is further formed so as to cover the strip-shaped electrode and the conductor formed on the electrode formation surface of the transparent base material.

  In addition, although the electrode for touch panels and the touch panel using the same were illustrated as an application example of an electrode in embodiment mentioned above, the electrode of this invention is not limited to for touch panels. For example, the present invention can be applied to electromagnetic wave shields that require transparency, various transparent electrodes, and the like.

  Moreover, although the example which made the electrode formation surface one side of the transparent base material is mentioned in embodiment mentioned above, both surfaces of a transparent base material can also be made into an electrode formation surface. In this case, the patterns of the electrodes formed by the one electrode formation surface and the other electrode formation surface may be the same as or different from each other. Alternatively, a plurality of electrodes may be stacked and stacked to form an electrode of a capacitive touch panel.

10: touch panel, 20: transparent substrate, 30: band-like electrode, 40: conductor, 50: electrode for touch panel (electrode).

Claims (2)

An electrode having at least a first electrode pattern area and a second electrode pattern area which are formed on an electrode forming surface and formed of strip electrodes ,
The first electrode pattern area and the second electrode pattern area are adjacent to and electrically separated from each other via a predetermined separation area along a predetermined direction of the electrode formation surface,
An electrode characterized in that a conductor which is inclined to the extension direction of the strip electrode and is spaced from the strip electrode is disposed in the separation region.       A touch panel comprising: a transparent substrate; and the electrode according to claim 1 formed on the transparent substrate.

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