JP2012166546A - Ink receiving layer, coating liquid for forming ink receiving layer, ink receiving layer forming method, and conductive pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of forming a conductive material which is excellent in conductivity and adhesion, by forming an ink receiving layer with good fixability on a substrate and patterning and baking metal particulate dispersion on the substrate.SOLUTION: An ink receiving layer (R) is formed on a surface of a substrate (K) to form a conductive pattern thereon by heating and baking a coated or patterned conductive ink (I) that includes a reduction solvent (A) containing metal fine particles (P) and polyhydric alcohol (S1). The ink receiving layer (R) is formed by bonding non-conductive inorganic particles (G) whose surfaces are liquid-repellent treated with a silane coupling agent (C) having a fluoroalkyl group, with a hydrophilic binder (B). The ink receiving layer (R) has an uneven surface according to the inorganic particles (G). The hydrophilic binder (B) present on the ink receiving layer (R) has a hydroxyl group.

Description

  The present invention relates to an ink receiving layer formed on the surface of a substrate and capable of forming a conductive pattern by heating and baking after applying or patterning the conductive ink, the ink receiving layer forming coating liquid, and the ink receiving layer. The present invention relates to a method for forming a layer and a method for forming a conductive pattern.

Conventionally, a droplet discharge method is known as a method for forming a fine wiring pattern such as a circuit pattern on a printed wiring board. This method is a method of forming a wiring pattern by discharging a functional liquid containing a pattern forming component from a droplet discharge head onto a substrate. According to this method, since a photolithography process is not required, there is an advantage that the process is greatly simplified. In this pattern formation, a method of forming a conductive pattern of metal fine particles by performing patterning using a metal fine particle dispersion as a functional liquid containing a pattern forming component, followed by firing is known.
In recent years, from the viewpoint of cost reduction and migration resistance, it has been desired to use a dispersion solution in which fine particles of base metal such as copper are used for conductive ink discharged by a droplet discharge method such as an inkjet process. However, since the base metal is a metal that is easily oxidized, there is a problem that it is difficult to form a conductive pattern that is oxidized during firing and has excellent conductivity and adhesion.

  On the other hand, when forming a conductive pattern using a metal fine particle dispersion, a thin film layer (receiving layer) for receiving the metal fine particle dispersion is provided on the substrate surface for the purpose of improving adhesion to the substrate and patterning. It has been proposed. The receiving layer of a general metal fine particle dispersion has a porous structure composed of inorganic particles and a binder, and the metal fine particles in the metal fine particle dispersion are received by absorbing the solvent of the dispersion into the porous layer. The structure remains on the surface of the layer. Patent Document 1 discloses a method of forming a conductive pattern by forming a microvoid-type receiving layer above a substrate, providing a liquid material containing conductive fine particles on the receiving layer, and subsequently performing heat treatment. ing. Specifically, there is a method in which the receiving layer formed above the substrate absorbs only the liquid component and the conductive fine particles remain on the surface of the receiving layer, so that the conductive pattern can be efficiently thickened. It is disclosed. The receiving layer used here is formed by applying a mixture of at least one of porous silica particles, alumina, and alumina hydrate and a binder. Further, the surface of the receiving layer is made liquid repellent so that the liquid state is prevented from spreading on the substrate before being absorbed by the receiving layer.

  In order to facilitate the formation of a thick conductive pattern, the receiving layer used in Patent Document 1 prevents the wetting and spreading of the liquid material by liquid-repellent treatment on the surface of the receiving layer and improves the patternability. Since the porous receiving layer has a structure in which the liquid component in the dispersion is absorbed into the receiving layer, the metal fine particle dispersion containing a solvent that exhibits a reducing effect on the conductive fine particles during the heat treatment Even if the patterning is performed, it is difficult to effectively exert the reducing effect in the receiving layer. Therefore, the metal fine particles cannot be sintered in a reducing atmosphere by the reducing solvent in the conductive ink. Patent Document 1 includes gold, silver, copper, palladium, and nickel as metallic conductive fine particles. However, when trying to use copper fine particles or the like that are actually base metals, if a reducing atmosphere cannot be formed by containing a reducing solvent in the ink, a reducing gas such as hydrogen gas is used. It is necessary to fire in the atmosphere used. Therefore, the example of Patent Document 1 only gives an example using gold fine particles as metal fine particles.

  Patent Document 2 discloses an ink jet recording paper provided with a colorant receiving layer containing ultrafine silica, a silane coupling agent, a hydrophilic binder, and a cationic resin. Specifically, an ink jet recording paper excellent in water resistance, maintainability, white background, and coating strength is disclosed by configuring the receiving layer that absorbs the water-soluble dye as described above. The color material receiving layer used in Patent Document 2 is based on the premise that it is a receiving layer that improves image quality by having high ink absorptivity and high drying properties. It has a structure to absorb. For this reason, when the receptor layer disclosed in Patent Document 2 is used, even if an ink containing a reducing solvent is used, a reducing effect is exerted on the conductive fine particles during heating and baking. I can't.

Patent Document 3 discloses a wiring board on which an organic film containing a resin, a fine particle of silicon oxide, a compound having a perfluoroether chain or a perfluoroalkyl chain is formed. The organic film has a liquid-repellent surface, Moreover, it is described that wetting and spreading of the metal fine particle dispersion can be prevented by giving the surface an appropriate roughness. The organic film described in Patent Document 3 retains the metal fine particle dispersion due to the irregular shape on the surface of the organic film, and has reducibility because there are very few or no hydrophilic groups on the surface of the organic film. The adhesion to the polyhydric alcohol dispersion medium is low, and it is difficult to improve the adhesion when forming a conductive pattern by firing.
That is, in the receiving layers disclosed in Patent Document 1 and Patent Document 2, the solvent of the metal fine particle dispersion is absorbed in the receiving layer, so that the metal fine particles and the solvent of the dispersion are separated during firing, During firing, the reducing action of the reducing substance in the dispersion is not fully demonstrated, and the oxidation and reduction of the surface of the metal fine particles does not proceed rapidly. Can not form. Moreover, in the receiving layer disclosed in Patent Document 3, the adhesion of the reducing dispersion and metal fine particles to the receiving layer is not sufficient, and as a result, the adhesion of the conductive pattern after firing can be improved. There is a problem that it is difficult. If the adhesiveness of the conductive pattern to the ink receiving layer is low, the conductive pattern is easily peeled off due to an external impact or a thermal stress generated when a current is passed through the conductive pattern. In particular, since thermal stress is concentrated at the interface between the ink receiving layer and the conductive pattern, if the adhesiveness at the interface is low, peeling due to long-term use tends to occur, leading to a decrease in long-term reliability of the conductive pattern.

JP 2004-6578 A Japanese Patent Laid-Open No. 2001-10209 JP 2005-191330 A

  The present invention improves the above-described problems of the prior art, and an ink receiving layer capable of forming a conductive pattern having good conductivity and adhesion formed on a substrate, and the ink receiving layer forming coating solution Another object of the present invention is to provide a method for forming the ink receiving layer and a method for forming a conductive pattern.

As a result of intensive studies in view of the above problems, the present inventors have bonded non-conductive inorganic particles surface-treated with a silane coupling agent having a liquid repellent fluoroalkyl group to each other with a hydrophilic binder. The present inventors have found that the above problem can be solved by providing an ink receiving layer having the above structure on the substrate surface, and have completed the present invention.
That is, the gist of the present invention is the invention described in the following (1) to (13).
(1) Applying or patterning a conductive ink (I) formed on the surface of a substrate (K) and containing a metal fine particle (P) and a reducing solvent (A) containing a polyhydric alcohol (S1) component And an ink receiving layer (R) capable of forming a conductive pattern by heating and baking,
The ink receiving layer (R) is formed by bonding non-conductive inorganic particles (G) having a surface repellent with a silane coupling agent (C) having a fluoroalkyl group and bonded with a hydrophilic binder (B). In the layer
Volume ratio of nonconductive inorganic particles (G) to the total amount of nonconductive inorganic particles (G) and hydrophilic binder (B) (solid content) in the ink receiving layer (R) ([G / (B + G)] × 100) is 50 to 90 (volume%),
The surface of the ink receiving layer (R) has a concavo-convex shape based on the non-conductive inorganic particles (G),
The hydrophilic binder (B) present in the ink receiving layer (R) has a hydroxyl group;
An ink receiving layer (hereinafter sometimes referred to as a first embodiment).
(2) The ink receiving layer according to (1), wherein the silane coupling agent (C) is a silane coupling agent having a fluoroalkyl group having 9 to 17 fluorine atoms.
(3) The ink receiving layer according to (1) or (2), wherein the hydrophilic binder (B) is polyvinyl alcohol.
(4) The non-conductive inorganic particles (G) are one or two selected from alumina particles and silica particles having an average primary particle diameter of 10 to 1000 nm, and the thickness of the ink receiving layer (R). The ink-receiving layer according to any one of (1) to (3), wherein is from 1 to 100 μm.

(5) When the non-conductive inorganic particles (G) are heated or baked after (i) applying or patterning the conductive ink (I) on the ink receiving layer (R), the polyhydric alcohol (S1) It consists of catalytic non-conductive inorganic particles (G1) having a catalytic action to promote decomposition,
Or (ii) Catalytic non-conductive inorganic particles (G1) and non-catalytic non-conductive inorganic particles (G2) having no catalytic action, and catalytic non-conductive in the non-conductive inorganic particles (G) The proportion of the inorganic particles (G1) is 0.1% by mass or more,
The ink receiving layer according to any one of (1) to (3).
(6) The non-conductive inorganic particles (G) are composed of catalytic non-conductive inorganic particles (G1) and non-catalytic non-conductive inorganic particles (G2), and the non-conductive inorganic particles (G) The proportion of the catalytic non-conductive inorganic particles (G1) is 0.1 to 5.0% by mass,
The ink receiving layer according to (5).
(7) The average particle diameter of the catalytic non-conductive inorganic particles (G1) in the non-conductive inorganic particles (G) is 1-1000 nm.
The ink receiving layer according to (5) or (6).
(8) The catalytic non-conductive inorganic particles (G1) are one or two selected from alumina and titania.
The ink receiving layer according to any one of (5) to (7).
(9) The ink receiving layer (R) includes (i) non-conductive inorganic particles (G) that have been surface-treated in advance with a silane coupling agent (C) having a fluoroalkyl group, and a hydrophilic binder (B). A solution or a solution containing (ii) non-conductive inorganic particles (G), a silane coupling agent (C) having a fluoroalkyl group, and a hydrophilic binder (B) as an ink-receiving layer-forming coating solution, The ink receiving layer according to any one of (1) to (8), wherein the ink receiving layer is a layer formed after coating a coating liquid for forming a receiving layer on a substrate (K).

(10) A coating liquid for forming an ink-receiving layer, comprising particles whose surfaces of non-conductive inorganic particles (G) are treated with a silane coupling agent (C) and a hydrophilic binder (B),
(I) One or two non-conductive inorganic particles (G) selected from particles having an average particle size of 10 to 1000 nm of primary particles, or
(Ii) The non-conductive inorganic particles (G) promote the decomposition of the polyhydric alcohol (S1) when the conductive ink (I) is applied or patterned on the ink receiving layer (R) and then heated and baked. Catalytic non-conductive inorganic particles (G1) having catalytic action and non-catalytic non-conductive inorganic particles (G2) having no catalytic action, and catalytic non-conductive in non-conductive inorganic particles (G) Non-catalytic non-conductive inorganic particles (G1) having a proportion of 0.1 to 5.0% by mass and catalytic non-conductive inorganic particles (G1) having an average particle diameter of 1 to 1000 nm. The average particle size of G2) is 10 to 1000 nm,
The silane coupling agent (C) is a silane coupling agent having a fluoroalkyl group having 9 to 17 fluorine atoms,
The ratio of the total solid content in the ink receiving layer forming coating solution ([total solid content / ink receiving layer forming coating solution] mass ratio) is 0.08 to 0.3,
The volume ratio ([G / (B + G)] × 100) of the nonconductive inorganic particles (G) to the total amount of the nonconductive inorganic particles (G) and the hydrophilic binder (B) (solid content) is 50 to 90 ( volume%),
And the use ratio ([C / G] mass ratio) of the silane coupling agent (C) to the non-conductive inorganic particles (G) is 0.0002 to 0.02.
A coating liquid for forming an ink-receiving layer (hereinafter sometimes referred to as a second embodiment).
(11) A coating liquid for forming an ink receiving layer containing non-conductive inorganic particles (G), a silane coupling agent (C), and a hydrophilic binder (B),
(I) One or two non-conductive inorganic particles (G) selected from particles having an average particle size of 10 to 1000 nm of primary particles, or
(Ii) The non-conductive inorganic particles (G) promote the decomposition of the polyhydric alcohol (S1) when the conductive ink (I) is applied or patterned on the ink receiving layer (R) and then heated and baked. Catalytic non-conductive inorganic particles (G1) having catalytic action and non-catalytic non-conductive inorganic particles (G2) having no catalytic action, and catalytic non-conductive in non-conductive inorganic particles (G) Non-catalytic non-conductive inorganic particles (G1) having a proportion of 0.1 to 5.0% by mass and catalytic non-conductive inorganic particles (G1) having an average particle diameter of 1 to 1000 nm. The average particle size of G2) is 10 to 1000 nm,
The silane coupling agent (C) is a silane coupling agent having a fluoroalkyl group having 9 to 17 fluorine atoms,
The ratio of the total solid content in the ink receiving layer forming coating solution ([total solid content / ink receiving layer forming coating solution] mass ratio) is 0.08 to 0.3,
The volume ratio ([G / (B + G)] × 100) of the nonconductive inorganic particles (G) to the total amount of the nonconductive inorganic particles (G) and the hydrophilic binder (B) (solid content) is 50 to 90 ( volume%),
And the ratio ([C / G] mass ratio) of the silane coupling agent (C) to the non-conductive inorganic particles (G) is 0.0002 to 0.02.
A coating liquid for forming an ink-receiving layer (hereinafter sometimes referred to as a third aspect).

(12) A method for forming an ink receiving layer (hereinafter referred to as a fourth method), characterized in that the ink receiving layer forming coating liquid described in (10) or (11) is applied on a substrate (K) and then dried. May be referred to as an aspect).
(13) A conductive ink (I) containing fine metal particles (P) and a reducing solvent (A) is applied or patterned on the ink receiving layer (R) according to any one of (1) to (9). A method of forming a conductive pattern, characterized in that the metal fine particles (P) are sintered by heating and baking after the formation (hereinafter, sometimes referred to as a fifth aspect).

(A) The ink receiving layer (R) described in (1) to (9) above, the ink receiving layer (R) obtained from the ink receiving layer forming coating liquid described in (10) to (11) above, and The ink receiving layer (R) obtained by the method of forming an ink receiving layer described in (12) above applies or patterns the conductive ink (I) containing the reducing solvent (A) and the metal fine particles (P). In this case, since the non-conductive inorganic particles (G) having liquid repellency on the surface form irregularities on the surface of the ink receiving layer (R), wetting and spreading of the conductive ink (I), and metal fine particles The patterning property is improved by suppressing the diffusion of (P). Further, since the reducing solvent (A) in the conductive ink (I) is excellent in adhesion to the hydrophilic binder (B) in the ink receiving layer (R), the conductive ink (I) is heated and baked. Adhesiveness of the conductive pattern after bonding is improved.
Furthermore, by using the non-conductive inorganic particles (G1) having a catalytic action for promoting the decomposition of the polyhydric alcohol (S1) in the reducing solvent (A) as the non-conductive inorganic particles (G), Sintering of the metal fine particles (P) in the ink (I) in the vicinity of the surface of the non-conductive inorganic particles is promoted, and as a result, a conductive pattern with more excellent adhesion to the ink receiving layer can be formed.
(B) In the method for forming a conductive pattern described in (13) above, the reducing solvent (A) is present in the conductive ink (I) on the ink receiving layer (R) when the conductive ink (I) is baked. By doing so, an atmosphere of a reducing liquid and a reducing gas is formed, so that a highly conductive conductive pattern can be formed through a firing process at a relatively low temperature. Further, in the firing step, the metal fine particles (P) in the conductive ink (I) adhere to the irregularities formed from the non-conductive inorganic particles (G) on the surface of the ink receiving layer (R), thereby adhering the conductive pattern. Can be improved.

FIG. 1 is a cross-sectional view for explaining the concept of the ink receiving layer (R) of the present invention. FIG. 2 is a conceptual diagram illustrating a method for forming a conductive pattern using the ink receiving layer (R) of the present invention.

Hereinafter, the ink receiving layer (R) (first aspect), the ink receiving layer forming coating liquid (second and third aspects), the ink receiving layer (R) forming method (fourth aspect), and the conductivity A pattern forming method (fifth aspect) will be described.
[1] Ink-receiving layer (R), ink-receiving layer-forming coating liquid, and method for forming ink-receiving layer (R) (first to fourth aspects)
The ink receiving layer (R) (first aspect) of the present invention is an ink receiving layer (first aspect) in which an ink receiving layer forming coating liquid (second and third aspects) described below is applied to the surface of a substrate (K). R) is formed by the formation method (fourth embodiment).

(1) Ink-receiving layer-forming coating solution (second and third embodiments)
The “ink receiving layer forming coating solution” for forming the ink receiving layer (R) on the substrate (K) is:
(I) A coating liquid for forming an ink-receiving layer, comprising particles whose surfaces of non-conductive inorganic particles (G) are treated with a silane coupling agent (C) and a hydrophilic binder (B),
(I) One or two non-conductive inorganic particles (G) selected from alumina particles and silica particles having an average primary particle size of 10 to 1000 nm, or
(Ii) The non-conductive inorganic particles (G) promote the decomposition of the polyhydric alcohol (S1) when the conductive ink (I) is applied or patterned on the ink receiving layer (R) and then heated and baked. Catalytic non-conductive inorganic particles (G1) having catalytic action and non-catalytic non-conductive inorganic particles (G2) having no catalytic action, and catalytic non-conductive in non-conductive inorganic particles (G) Non-catalytic non-conductive inorganic particles (G1) having a proportion of 0.1 to 5.0% by mass and catalytic non-conductive inorganic particles (G1) having an average particle diameter of 1 to 1000 nm. The average particle size of G2) is 10 to 1000 nm,
The silane coupling agent (C) is a silane coupling agent having a fluoroalkyl group having 9 to 17 fluorine atoms,
The ratio of the total solid content in the ink receiving layer forming coating solution ([total solid content / ink receiving layer forming coating solution] mass ratio) is 0.08 to 0.3,
The volume ratio ([G / (B + G)] × 100) of the nonconductive inorganic particles (G) to the total amount of the nonconductive inorganic particles (G) and the hydrophilic binder (B) (solid content) is 50 to 90 ( volume%),
And the use ratio ([C / G] mass ratio) of the silane coupling agent (C) to the non-conductive inorganic particles (G) is 0.0002 to 0.02.
It is characterized by being (2nd aspect), or
(II) A coating liquid for forming an ink receiving layer containing non-conductive inorganic particles (G), a silane coupling agent (C), and a hydrophilic binder (B),
(I) One or two non-conductive inorganic particles (G) selected from alumina particles and silica particles having an average primary particle size of 10 to 1000 nm, or
(Ii) The non-conductive inorganic particles (G) promote the decomposition of the polyhydric alcohol (S1) when the conductive ink (I) is applied or patterned on the ink receiving layer (R) and then heated and baked. Catalytic non-conductive inorganic particles (G1) having catalytic action and non-catalytic non-conductive inorganic particles (G2) having no catalytic action, and catalytic non-conductive in non-conductive inorganic particles (G) Non-catalytic non-conductive inorganic particles (G1) having a proportion of 0.1 to 5.0% by mass and catalytic non-conductive inorganic particles (G1) having an average particle diameter of 1 to 1000 nm. The average particle size of G2) is 10 to 1000 nm,
The silane coupling agent (C) is a silane coupling agent having a fluoroalkyl group having 9 to 17 fluorine atoms,
The ratio of the total solid content in the ink receiving layer forming coating solution ([total solid content / ink receiving layer forming coating solution] mass ratio) is 0.08 to 0.3,
The volume ratio ([G / (B + G)] × 100) of the nonconductive inorganic particles (G) to the total amount of the nonconductive inorganic particles (G) and the hydrophilic binder (B) (solid content) is 50 to 90 ( volume%),
And the ratio ([C / G] mass ratio) of the silane coupling agent (C) to the non-conductive inorganic particles (G) is 0.0002 to 0.02.
(Third aspect).

(A) Non-conductive inorganic particles (G)
Examples of non-conductive inorganic particles (G) used in the ink receiving layer (R) include inorganic particles such as alumina, titania, zirconia, silica, colloidal silica, colloidal alumina, and the like. These non-conductive inorganic particles (G) can be used as primary particles or in the form of secondary agglomerated particles, and the primary particle size of the non-conductive inorganic particles (G). No particular limitation is imposed on the particle size of the ink-receiving layer (R), and a primary particle size of about 10 μm can be used as long as the particle size is smaller than the thickness of the ink receiving layer (R). It is preferable to use inorganic particles.
When the primary particle diameter of the non-conductive inorganic particles (G) is 10 nm or more, an increase in the amount of the silane coupling agent (C) on the surface of the inorganic particles due to an increase in the specific surface area of the inorganic particles is suppressed. It can be expected that the bonding between the layers is promoted and the film strength of the ink receiving layer (R) is improved. On the other hand, when the thickness is 1000 nm or less, the flatness of the surface of the ink receiving layer (R) is improved. It becomes possible to improve the patterning property of I).
Non-conductive inorganic particles (G) are selected from alumina particles and silica particles from the viewpoint of easy availability, low cost, and excellent surface affinity with metal fine particles (P). It is preferable to use 1 type or 2 types.
Further, when porous inorganic particles are used as the non-conductive inorganic particles (G), the irregularities on the surface of the inorganic particles increase, and the area to be fixed to the metal fine particles (P) increases. Can be improved. Even if porous inorganic particles are used, the surface of the inorganic particles (G) is subjected to a liquid repellent treatment with the silane coupling agent (C), so that the reducing solvent (A) in the conductive ink (I) is the ink. It is not absorbed into the receiving layer.

Further, among the non-conductive inorganic particles (G), the polyhydric alcohol in the reducing solvent (A) when the conductive ink (I) is applied or patterned on the ink receiving layer and then heated and baked. There are catalytic non-conductive inorganic particles (G1) such as alumina particles and titania particles that have catalytic action to promote decomposition of (S1), while zirconia, silica, colloidal silica, etc. that do not have such catalytic action Of non-catalytic non-conductive inorganic particles (G2).
The non-conductive inorganic particles (G) are composed of catalytic non-conductive inorganic particles (G1) and non-catalytic non-conductive inorganic particles (G2) having no catalytic action, and the non-conductive inorganic particles (G) The proportion of the non-catalytic non-conductive inorganic particles (G1) is 0.1 to 5.0% by mass, and the non-catalytic non-conductive non-conductive inorganic particles (G1) have an average particle size of 1 to 1000 nm. The average particle size of the conductive inorganic particles (G2) is preferably 10 to 1000 nm.
The adhesion between the ink receiving layer (R) and the conductive pattern is such that the conductive ink (I) enters the uneven shape formed by the non-conductive inorganic particles (G) on the surface of the ink receiving layer (R). When sintering occurs, the conductive pattern plays a role like a wedge and is considered to be caused by an anchor effect in which mechanical coupling occurs. At this time, when the catalytic non-conductive inorganic particles (G1) are used as the non-conductive inorganic particles (G), the sintering of the conductive pattern portion that plays the role of a wedge in the vicinity of the inorganic particles is promoted. Mechanical strength is improved. As a result, the bond due to the anchor effect is strengthened, so that the adhesion of the conductive pattern to the ink receiving layer (R) is improved.
The interface between the non-conductive inorganic particles (G) and the conductive pattern is a portion where thermal stress generated when a current flows in the conductive pattern is concentrated. Become. By improving the adhesion at the interface between the non-conductive inorganic particles (G) and the conductive pattern in the ink receiving layer (R), it is possible to form a highly reliable conductive pattern that can withstand long-term use.
Since the catalytic action of the catalytic non-conductive inorganic particles (G1) is affected by the surface area of the particles, the smaller the particle diameter, the larger the catalytic action per unit weight. Therefore, the particle size of the catalytic non-conductive inorganic particles (G1) is preferably 1 to 1000 nm. If the particle diameter is less than 1 nm, the bonding between the inorganic particles may be inhibited, and the film strength of the ink receiving layer (R) may be reduced. On the other hand, if the particle diameter exceeds 1000 nm, the above catalytic action is sufficiently exerted. There is a risk of being lost. From such a viewpoint, the particle diameter of the catalytic non-conductive inorganic particles (G1) is more preferably 1 to 100 nm, further preferably 1 nm or more and 10 nm or less.

Non-conductive inorganic particles (G) are composed of catalytic non-conductive inorganic particles (G1), or non-catalytic non-conductive non-catalytic non-catalytic non-conductive particles and catalytic non-conductive inorganic particles (G1). It is preferably composed of inorganic particles (G2), and the proportion of the catalytic non-conductive inorganic particles (G1) in the non-conductive inorganic particles (G) is preferably 0.1% by mass or more. Furthermore, the non-conductive inorganic particles (G) are composed of catalytic non-conductive inorganic particles (G1) and non-catalytic non-conductive inorganic particles (G2), and the catalytic properties in the non-conductive inorganic particles (G). More preferably, the proportion of the non-conductive inorganic particles (G1) is 0.1 to 5.0% by mass.
When the proportion of the catalytic non-conductive inorganic particles (G1) is 0.1% by mass or more and the metal fine particles (P) are fired, a catalytic activity that promotes the decomposition of the polyhydric alcohol (S1) is expressed, It becomes possible to reinforce the adhesiveness of the conductive pattern at 5.0% by mass or less.

(B) Silane coupling agent having fluoroalkyl group (C)
The silane coupling agent (C) used in the present invention is a silane coupling agent represented by the following general formula (I) or a compound represented by the general formula (II) obtained by hydrolyzing the silane coupling agent. It is.
_{X-Si-Y 3 (I} )
X-Si (OH) ₃ (II)
However, in the general formulas (I) and (II), X is a fluoroalkyl group containing 9 to 17 fluorine atoms, and Y is a hydrolyzable alkoxy group having 1 to 3 carbon atoms bonded to a silicon atom. Or it is a halogen atom.
Since X is a fluoroalkyl group containing a fluorine atom, the presence of this fluoroalkyl group on the surface of the non-conductive inorganic particles (G) in the ink receiving layer (R) results in a conductive containing the reducing solvent (A). It becomes possible to continue the liquid repellency of the ink (I) on the ink receiving layer (R). Since the non-conductive inorganic particles (G) and the reducing solvent (A) coexist on the ink receiving layer (R), a reduction effect is exhibited when the fine metal particles (P) are sintered by firing, and the conductivity is good. A pattern can be formed. Further, since the ink solvent (reducing solvent (A)) is repelled on the ink receiving layer (R), the flow of the conductive ink (I) is prevented and the patterning property is improved. The reason why the liquid repellency of the ink solvent is manifested in this way is that a fluoroalkyl group having a low surface tension is present on the surface of the ink receiving layer (R), so that the conductive ink (I) and the ink receiving layer (R). It is presumed that a difference in surface tension occurs and the contact angle of the conductive ink (I) increases.

As such X, a fluoroalkyl group containing an arbitrary fluorine atom can be used, but a C4-10 fluoroalkyl group containing 9 to 17 fluorine atoms is preferred. Examples thereof include nanofluorohexyltriethoxysilane and (heptadecafluoro-1,1,2,2, -tetrahydrodecyl) trichlorosilane. When the number of fluorine atoms in the fluoroalkyl group is less than 9, the effect of repelling ink becomes small, and the patterning property and liquid repellency are lowered. On the other hand, when the number of fluorine atoms in the fluoroalkyl group exceeds 17, the silane coupling agent is desirably not used because there is a great concern about adverse environmental effects. The number of carbon atoms in the fluoroalkyl group is determined to some extent by the number of fluorine atoms contained in the fluoroalkyl group. For example, in the above-mentioned nanofluorohexyltriethoxysilane, the number of carbon atoms is six.
Y in a position opposite to X is a hydrolyzable C 1-3 alkoxy group or a halogen atom that is bonded to a silicon atom.
The Y or (OH) group is formed on the substrate after the solution containing the silane coupling agent (C) represented by the general formula [I] or the compound represented by the general formula [II] is applied on the substrate (K). (K) Since the dehydration condensation reaction occurs with the (OH) group present on the surface, the adhesion of the ink receiving layer (R) to the substrate (K) having the (OH) group on the surface is improved. In addition, the OH group on the surface of the alumina particle and Si of the silane coupling agent (C) are bonded by a hydrolysis reaction, and a silanol group containing a fluoroalkyl group is formed on the surface of the alumina particle.

(C) Non-conductive inorganic particles (G) surface-treated with a silane coupling agent (C)
The non-conductive inorganic particles (G) surface-treated with the silane coupling agent (C) are a ratio of the silane coupling agent (C) to the non-conductive inorganic particles (G) in a solvent such as water and ethanol ( The surface treatment can be performed by blending at a ratio of [C / G] mass ratio) of 0.0002 to 0.02 described later.
After the surface treatment, a non-conductive inorganic particle (G) surface-treated with the silane coupling agent (C) can be obtained by performing a centrifugal separation treatment.
The surface treatment of the nonconductive inorganic particles (G) with the silane coupling agent (C) in the third aspect will be described later.

(D) Hydrophilic binder (B)
The hydrophilic binder (B) used in the ink receiving layer (R) is not particularly limited, but a water-soluble solvent is preferable as a solvent used in the coating liquid of the ink receiving layer (R). Considering that the adhesion of the reducing solvent (A) having an (OH) group that is a hydrophilic group is improved, a hydrophilic polymer is preferable. Examples of such hydrophilic polymers include polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, polyacrylamide, polyurethane, and the like, and these hydrophilic polymers can be used in combination of two or more.
The hydrophilic binder (B) used in the present invention is more preferably polyvinyl alcohol. The polybilyl alcohol includes, in addition to ordinary polyvinyl alcohol obtained by hydrolyzing polyvinyl acetate, modified polyvinyl alcohol such as polyvinyl alcohol having a cation-modified terminal and anion-modified polyvinyl alcohol having an anionic group. In consideration of handling and high versatility, it is preferable to use ordinary polyvinyl alcohol.

As the normal polyvinyl alcohol, those having an average polymerization degree of 1000 or more are preferably used, and those having an average polymerization degree of 1000 to 2400 are particularly preferable. The saponification degree is preferably 70 to 100%, particularly preferably 80 to 99.5%.
The hydrophilic binder (B) improves the film strength of the receiving layer by bonding the non-conductive inorganic particles (G) to each other at the time of forming the ink receiving layer (R), and in the coating solution for forming the ink receiving layer. Since the non-conductive inorganic particles (G) are adhered on the substrate (K), the adhesion between the ink receiving layer (R) and the substrate (K) is also improved. Further, since the hydrophilic polymer has a high affinity with a molecule having a hydrophilic group such as an (OH) group, the polyhydric alcohol (S1) containing a plurality of (OH) groups in the reducing solvent (A). As a result, the conductive ink (I) and the metal fine particles (P) are fixed to the surface of the ink receiving layer (R), and a conductor pattern with high adhesion can be produced.
When polyvinyl alcohol is used in the present invention, the OH group in polyvinyl alcohol that does not contribute to the bonding of non-conductive inorganic particles (G) and the improvement of the adhesion of the reducing solvent (A) is a liquid-repellent silane coupling. Since it is treated with the agent (C), in addition to the liquid repellency effect on the surface of the non-conductive inorganic particles (G), it is possible to further improve the liquid repellency of the ink receiving layer (R).

(E) Composition of ink receiving layer forming coating solution (e-1) When non-surface non-conductive inorganic particles (G) are used Non-conductive inorganic particles not surface-treated with silane coupling agent (C) The composition of the coating liquid for forming the ink receiving layer when (G) is used will be described below.
In addition, it is preferable to use water or a hydrophilic solvent as the solvent of the coating liquid for forming the ink receiving layer.
(I) Ratio of total solids The ratio of total solids in the ink receiving layer forming coating liquid ([total solids / ink receiving layer forming liquid] mass ratio) is 0.08 to 0.3. It is preferable. When the mass ratio is less than 0.08, the concentration of the inorganic particles in the coating solution decreases, and it may be difficult to produce a dense ink-receiving layer when the coating film is dried. Liquid repellency decreases. On the other hand, if the mass ratio exceeds 0.3, the viscosity of the coating liquid increases and the coating property is lowered, so that it may be difficult to produce a uniform ink receiving layer.

(Ii) Ratio of non-conductive inorganic particles (G) and hydrophilic binder (B) Non-conductive inorganic with respect to the total amount of non-conductive inorganic particles (G) and hydrophilic binder (B) in the receiving layer (R) The volume ratio ([G / (B + G)] × 100) of the particles (G) is 50 to 90 (volume%).
When the volume ratio is less than 50 (volume%), non-conductive inorganic particles (G) treated with the silane coupling agent (C) present on the surface of the non-conductive inorganic particles (G) are reduced, The liquid repellency at the tank surface becomes insufficient and the patterning property is lowered. Moreover, the hydrophilic binder (B) covers most of the nonconductive inorganic particles (G), and the surface of the nonconductive inorganic particles (G) is treated with a silane coupling agent (C) containing a fluoroalkyl group. On the other hand, when the volume ratio exceeds 90 (volume%), the hydrophilic binder (B) that binds the inorganic particles and the non-conductive inorganic particles (G) to the substrate (K) is formed. If the amount is too small, it may be difficult to produce a receiving layer having high film strength.
(Iii) Ratio of non-conductive inorganic particles (G) and silane coupling agent (C) The ratio of silane coupling agent (C) to non-conductive inorganic particles (G) ([C / G] mass ratio) is 0. .0002 to 0.02 is preferable.
If the mass ratio is less than 0.0002, sufficient ink repellency may not be imparted to the ink receiving layer (R). On the other hand, when the mass ratio exceeds 0.02, the silane coupling agent (C) becomes excessive, and the film strength of the ink receiving layer (R) may be lowered.
(E-2) When using surface-treated non-conductive inorganic particles (G) Coating for forming an ink receiving layer when using non-conductive inorganic particles (G) surface-treated with a silane coupling agent (C) As for the composition of the liquid, since the ink receiving layer (R) similar to that described in (e) -1 is basically formed, the ratio of the silane coupling agent (C) is small, so that the silane What is necessary is just to select the conditions used as a result similar to the case where the nonelectroconductive inorganic particle (G) which is not surface-treated with a silane coupling agent (C) is used except a coupling agent (C).

(2) Method for forming ink receiving layer (R) (fourth embodiment)
The method for forming the ink receiving layer (R) is characterized in that the ink receiving layer forming coating solution is applied onto the substrate (K) and then dried.
(A) Substrate (K) The substrate (K) used in the present invention is not particularly limited, and an inorganic material substrate such as a glass substrate, a resin substrate, or the like can be widely used. Examples of the resin substrate include polyester resin, polycarbonate resin, polyamide resin, polyimide resin, polyamideimide resin, polyetherimide resin, and polycycloolefin resin. Among these, it is preferable to use a polyimide resin, a polyamideimide resin, or a polyester resin from the viewpoints of heat resistance, mechanical characteristics, thermal characteristics, and the like, and among these, a polyimide resin is particularly preferable.
In addition, when using a glass substrate, it is desirable to perform an acid washing | cleaning, water washing, and a drying process in this order beforehand. When using a resin substrate, it is preferable to surface-treat the surface beforehand by one or more operations selected from corona treatment, electron beam irradiation, plasma treatment, and etching treatment.
The ink receiving layer forming coating solution is preferably applied onto the substrate (K) so that the solid content is 0.005 to 1000 g / m ² .

(B) Method for applying ink-receiving layer forming coating solution As a method for applying the ink-receiving layer forming coating solution, a known method can be used. For example, there are a bar coating method, a spin coating method, a spray coating method, an air knife coating method and the like. The ink receiving layer (R) can be formed on the substrate (K) by drying after applying the ink receiving layer forming coating solution. The drying step is preferably performed by heat treatment. Although the heat treatment conditions depend on the thermal stability of the silane coupling agent (C) and other materials, for example, it is preferably 100 ° C. or lower and about 0.5 to 1 hour. The thickness of the ink receiving layer (R) after the drying step is preferably 1 to 100 μm, and more preferably 1 to 10 μm from the viewpoints of flex resistance and transparency.

(3) Ink receiving layer (R) (first embodiment)
As shown in FIG. 1, the ink receiving layer (R) of the first embodiment is formed on the surface of the substrate (K) and contains a reducing solvent (A) containing fine metal particles (P) and a polyhydric alcohol (S1). Ink-receiving layer (R) capable of forming a conductive pattern by heating and baking after coating or patterning of conductive ink (I) containing A layer formed by bonding non-conductive inorganic particles (G) with a hydrophilic binder (B), the surface of which is subjected to a liquid repellent treatment with a silane coupling agent (C) having a group, and an ink receiving layer ( The surface of R) has a concavo-convex shape based on non-conductive inorganic particles (G), and the hydrophilic binder (B) present on the surface of the ink receiving layer (R) has a hydroxyl group. To do.
The ink receiving layer (R) not only has excellent adhesion to the substrate (K), but also has a pattern formed using the conductive ink (I) containing the reducing solvent (A) and the metal fine particles (P). At the time of formation, patterning properties are improved by suppressing wetting and spreading of the ink and diffusion of the metal fine particles (P). The surface of the ink receiving layer (R) has liquid repellency with respect to the conductive ink (I) and has a concavo-convex shape based on the non-conductive inorganic particles (G), and the solvent of the conductive ink (I). Ingredients can be retained on the surface. Further, the adhesion property of the reducing solvent (A) in the conductive ink (I) to the hydrophilic binder (B) in the ink receiving layer (R) is improved, so that the conductive ink (I) and the metal fine particles are improved. The adhesion of (P) is improved. Furthermore, as non-conductive inorganic particles (G), catalytic non-conductive inorganic particles (such as alumina particles and titania particles having catalytic action for promoting the decomposition of the polyhydric alcohol (S1) in the reducing solvent (A) ( By using G1), sintering of the metal fine particles (P) in the conductive ink (I) on the surface of the nonconductive inorganic particles is promoted, and a conductive pattern having excellent adhesion to the ink receiving layer (R) is obtained. Can be formed.

[2] Method for forming conductive pattern (fifth aspect)
The conductive pattern is formed by applying or patterning a conductive ink (I) containing metal fine particles (P) and a reducing solvent (A) on the ink receiving layer (R) described in the fourth aspect. Thereafter, the metal fine particles (P) are sintered by heating and firing.
A method for forming a conductive pattern will be described with reference to FIGS.
FIG. 1 is a cross-sectional view for explaining the concept of the ink receiving layer (R). The ink receiving layer (R) 12 is formed on the substrate (K) 11, and the ink receiving layer (R) A conductive pattern 13 is formed.
FIG. 2 is a conceptual diagram illustrating a method for forming a conductive pattern.
(A1) in FIG. 2 is a conceptual diagram in which the ink receiving layer (R) is formed on the substrate (K), and the ink receiving layer (R) 12 is formed on the substrate (K) 11, In (A2), which is a partial enlarged view of the surface of the ink receiving layer (R) of (A1), the surface of the non-conductive inorganic particles (G) 15 has silane coupling groups 16 and non-conductive inorganic particles ( G) 15 are bonded to each other by a hydrophilic binder (B) 17.

(B1) in FIG. 2 is a conceptual diagram in which the conductive ink (I) is patterned on the ink receiving layer (R), and the conductive ink (I) 14 is patterned on the ink receiving layer (R) 12. The surface of the non-conductive inorganic particles (G) 15 in (B2) is an enlarged view of a portion where the conductive ink (I) 14 is patterned on the ink receiving layer (R) 12 in (B1). In addition, the fine metal particles (P) 19 are held in the reducing solvent (A) 18 in a dispersed state.
(C1) in FIG. 2 is a conceptual diagram in which the metal fine particles (P) in the conductive ink (I) are sintered on the ink receiving layer (R) to form a conductive pattern. R) The conductive pattern 13 is formed on 12, and is an enlarged view of the portion where the conductive pattern of (C1) is formed. In (C2), the conductive pattern 13 is sintered on the surface of the nonconductive inorganic particles (G) 15. Metal fine particles (P) 19 are held in a state where a pattern is formed.
The conductive ink (I) is an ink in which metal fine particles (P) are dispersed in a reducing solvent (A), and a dispersant can be blended for improving dispersibility.

(1) Metal fine particles (P)
The metal fine particles (P) are not particularly limited, but gold, silver, copper, platinum, palladium, tungsten, nickel, iron, cobalt, tantalum, bismuth, lead, indium, tin, zinc, titanium, and One type or two or more types of fine particles selected from aluminum are listed. Among these, one type or two or more types selected from silver, copper, platinum, palladium, tungsten, nickel, iron, cobalt, and tantalum are selected. These fine particles are preferred.
The particle diameter of the metal fine particles (P) in the conductive ink (I) is preferably 10 μm or less, more preferably 500 nm or less, and even more preferably 1 to 500 nm in order to form a precise conductive material.
The conductive ink (I) can be obtained by dispersing the metal fine particles (P) in the reducing solvent (A) described below. The concentration of the metal fine particles (P) in the conductive ink (I) is 2-70 mass% is preferable. If the concentration of the metal fine particles (P) is less than 2% by mass, there is a risk that the mechanical strength of the conductive material after firing is reduced. On the other hand, if the concentration exceeds 70% by mass, the reducing solvent (A) has a problem. It may be difficult to obtain high dispersibility.

(2) Reducing solvent (A)
As the reducing solvent (A) contained in the conductive ink (I), it is preferable to use a single or a mixed solvent containing a plurality of polyhydric alcohols (S1) having two or more hydroxyl groups in the molecule. .
Preferred polyhydric alcohols (S1) include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2 -Butene-1,4-diol, 2,3-butanediol, pentanediol, hexanediol, octanediol, glycerol, 1,1,1-trishydroxymethylethane, 2-ethyl-2-hydroxymethyl-1,3 -Propanediol, 1,2,6-hexanetriol, 1,2,3-hexanetriol, 1,2,4-butanetriol, threitol, erythritol, pentaerythritol, pentitol, xylitol, ribitol, arabitol, hexitol, Mannitol, sorbitol , Dulcitol, glyceraldehyde, dioxyacetone, threose, erythrulose, erythrose, arabinose, ribose, ribulose, xylose, xylulose, lyxose, glucose, fructose, mannose, idose, sorbose, gulose, talose, tagatose, galactose, allose, alt There may be mentioned one or more selected from the group consisting of loose, lactose, isomaltose, glucoheptose, heptose, maltotriose, lactulose, and trehalose. Among these, those having a high melting point can be used by mixing with other polyhydric alcohols (S1).

These polyhydric alcohols (S1) generate hydrogen radicals at the time of thermal decomposition accompanying the firing of the ink, and the hydrogen radicals exhibit a function of reducing or preventing oxidation of the oxide film on the surface of the metal fine particles (P). Even with fine metal particles, it is possible to form a highly conductive metal film with good sinterability. In addition, since the polyhydric alcohol (S1) has a hydroxyl group which is a hydrophilic group, it has a high affinity for the hydrophilic binder (B) and is attached to the hydrophilic binder (B) in the ink receiving layer (R). This improves the adhesion between the conductive ink (I) and the metal fine particles (P). As a result, the adhesion of the conductor pattern produced when baked to the ink receiving layer (R) is improved, and a conductor pattern having excellent adhesion can be produced.
As a component of the reducing solvent (A), in addition to the polyhydric alcohol (S1), an organic solvent (S2) having an amide group described below, an ether compound (S3), an alcohol (S4), and a ketone compound (S5), an amine compound (S6), etc. can be mix | blended.

Examples of the organic solvent (S2) having an amide group include N-methylacetamide, N-methylformamide, N-methylpropanamide, formamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, Examples thereof include one or more selected from N, N-dimethylformamide, 1-methyl-2-pyrrolidone, hexamethylphosphoric triamide, 2-pyrrolidinone, ε-caprolactam, and acetamide.
The other component of the reducing solvent (A) is represented by the general formula R ¹ —O—R ² (wherein R ¹ and R ² are each an independent alkyl group having 1 to 4 carbon atoms). An ether compound (S3), an alcohol (S4) represented by the general formula R ³ —OH (wherein R ³ is an alkyl group and has 1 to 4 carbon atoms), R ⁴ —C (= ^{O) -R 5 (R 4,} R 5 are each independently an alkyl group, number of carbon atoms is 1 to 2) an amine based compound (S5), and the general formula ^R 6 -. (N ^{-R 7) -R 8 (R 6} , R 7, R 8 are each independently an alkyl group, or hydrogen, carbon atoms is 0-2.) amine compounds represented by (S6) is It can be illustrated.

  Specific examples of the ether compound (S3) include diethyl ether, methyl propyl ether, dipropyl ether, diisopropyl ether, methyl t-butyl ether, t-amyl methyl ether, divinyl ether, ethyl vinyl ether, and allyl ether. Examples of the alcohol (S4) include one selected from methanol, ethanol, 1-propanol, 2-propanol, 2-butanol, and 2-methyl 2-propanol. 1 or 2 or more types can be exemplified, and specific examples of the ketone compound (S5) include one or more selected from acetone, methyl ethyl ketone, and diethyl ketone, and the amine type As a specific example of the compound (S6), triethyl Min, and / or diethylamine can be exemplified.

(3) Dispersant The fine solvent (P) can be mixed with the reducing solvent (A).
The dispersant covers at least a part of the surface of the metal fine particles (P) in the reducing solvent (A) and exerts an action of dispersing the metal fine particles (P) in a state where the secondary aggregation property is low. Preferred as the dispersant is a water-soluble polymer compound, an amine polymer such as polyvinylpyrrolidone or polyethyleneimine; a hydrocarbon polymer having a carboxylic acid group such as polyacrylic acid or carboxymethylcellulose; polyacrylamide Such as acrylamide; polyvinyl alcohol, polyethylene oxide, starch, and one or more selected from gelatin and gelatin.

  Specific examples of the water-soluble polymer compounds exemplified above include polyvinylpyrrolidone (molecular weight: 1000 to 500,000), polyethyleneimine (molecular weight: 100 to 100,000), carboxymethylcellulose (carboxymethyl of hydroxyl group Na salt of alkali cellulose) Substitution degree: 0.4 or more, molecular weight: 1000 to 100,000, polyacrylamide (molecular weight: 100 to 6,000,000), polyvinyl alcohol (molecular weight: 1000 to 100,000), polyethylene glycol (molecular weight) : 100-50,000), polyethylene oxide (molecular weight: 50,000-900,000), gelatin (average molecular weight: 61,000-67,000), water-soluble starch and the like.

The number average molecular weight of each polymer compound is shown in the parentheses, and those within such molecular weight range can be suitably used as the organic protective film of the present invention. In addition, these 2 or more types can also be mixed and used.
Further, the addition amount of the dispersant is preferably 0.01 to 30 as a mass ratio ([dispersant / metal fine particle (P)] mass ratio) to the metal fine particles (P) present in the dispersion solution. If the additive ratio of the dispersant exceeds 30, the viscosity of the solution may increase. On the other hand, if it is less than 0.01, the particles may be coarsened or the particles may form a strong aggregate due to the crosslinking effect. A more preferable addition ratio is 0.5 to 10.
In the conductive ink (I) thus obtained, the metal fine particles (P) are dispersed in the reducing solvent (A) in a state where at least a part of the surface is covered with the dispersant. Although the mechanism by which such a dispersant disperses the metal fine particles (P) has not been completely elucidated, when a polymer dispersant is used, for example, an unshared electron pair of a functional group present in the polymer is removed. It is expected that a repulsive force is generated in which the atomic portion is adsorbed on the surface of the metal fine particles (P) to form a molecular layer and the metal fine particles (P) do not approach each other.

(4) Improvement of dispersibility of metal fine particles (P) In order to further improve the dispersibility of the metal fine particles (P) in the conductive ink (I), it is desirable to employ a stirring means. As a stirring method of the dispersion solution, a known stirring method can be adopted, but an ultrasonic irradiation method is preferably adopted.
The ultrasonic irradiation time is not particularly limited and can be arbitrarily selected. For example, when the ultrasonic irradiation time is arbitrarily set between 5 and 60 minutes, the average secondary aggregation size tends to be smaller as the irradiation time is longer. Further, when the ultrasonic wave irradiation time is lengthened, the dispersibility is further improved.

(5) Method for Forming Conductive Pattern A patterned liquid film is formed on the ink receiving layer (R) by discharging, applying or transferring the conductive ink (I). The method for forming the pattern is not particularly limited, and methods such as screen printing, mask printing, spray coating, bar coating, knife coating, spin coating, ink jet printing, and dispenser printing can be used.
According to the present invention, it is possible to form a dense pattern having a line width of 25 μm and a line spacing of about 25 μm. Moreover, a known method can be adopted for these discharge, application, or transfer means.
When forming a patterned liquid film, the ink receiving layer (R) may be used at room temperature or in a heated state.
The patterned liquid film can be baked in a furnace in a non-oxidizing gas atmosphere or a reducing gas atmosphere at a relatively low temperature of, for example, about 200 ° C. to form a conductive pattern.

Although the said baking conditions are based also on application | coating thickness, it is about 20 to 40 minutes at 190-250 degreeC, for example, Preferably it is about 20-40 minutes at 190-220 degreeC.
The conductive pattern thus obtained has good conductivity, and its electric resistance value is 1.0 Ωcm or less, for example, about 1.0 × 10 ⁻⁵ Ωcm to 1 × 10 ⁻³ Ωcm. It is possible to achieve. Furthermore, since the conductive pattern exhibits an anchor effect by being fixed to the non-conductive inorganic particles (G) above the ink receiving layer (R), it has excellent adhesion to the ink receiving layer (R).

The present invention will be described more specifically with reference to examples. The present invention is not limited to these examples.
The evaluation method of a present Example and a comparative example is described below.
(1) Evaluation of substrate adhesion of ink receiving layer The substrate adhesion of the ink receiving layer formed on the substrate was evaluated by the following method.
A tape peeling test of the ink receiving layer was performed according to JIS D0202-1988.
The drawing pattern of the evaluation sample was separated by 10 mm in total, using cellophane tape (manufactured by Nichiban Co., Ltd., trade name: cellotape (registered trademark) No. 405), and then peeled after being adhered to the film. The evaluation results are shown in Table 1.
In addition, evaluation criteria were represented by the following criteria from the number of squares that do not peel out of 10 squares.
○: The peeled square is 1 square or less Δ: The peeled square is 2 to 4 squares ×: 5 squares or more are peeled

(2) Evaluation of pattern of conductive ink The pattern of conductive ink was evaluated by the following method.
(A) Ink liquid repellency The ink contact angle (α) when a small amount of ink droplets were dropped on the ink receiving layer was evaluated.
A contact angle meter was used for the evaluation. The liquid repellency was evaluated according to the following criteria.
○: α ≧ 60 degrees Δ: 30 degrees ≦ α <60 degrees ×: α <30 degrees (b) Printability The spread width X when the commercially available inkjet media print width is set to 1 is obtained, and the conductivity is determined according to the following criteria. The printability of the ink to the ink receiving layer was evaluated. The spread width X was obtained by observing the obtained wiring material with a digital microscope.
○: 0.1 ≦ X ≦ 1.2
Δ: 1.2 <X ≦ 1.5
×: 1.5 <X

(3) Evaluation of conductive pattern The performance of each wiring material obtained was evaluated by the following method.
(A) Adhesiveness A tape peeling test of the conductive pattern was performed in accordance with JIS D0202-1988.
The drawing pattern of the evaluation sample was separated by 10 mm in total, using cellophane tape (manufactured by Nichiban Co., Ltd., trade name: cellotape (registered trademark) No. 405), and then peeled after being adhered to the film.
Judgment was expressed according to the following criteria from the number of squares not peeled out of 10 squares.
◎: No peeling ○: The peeled square is 1 to 2 squares Δ: The peeled square is 3 to 4 squares ×: The peeled square is 5 squares or more

(B) Conductivity In accordance with JIS D0202-1988, the volume resistivity of the conductive pattern is evaluated by the direct current four-terminal method (use measuring machine: Keithley, Digital Multimeter DMM2000 type (four-terminal electrical resistance measurement mode)). did. The judgment was expressed by the following criteria.
○: Volume resistivity is 100 μΩ · cm or less Δ: Volume resistivity is more than 100 μΩ · cm, 200 μΩ · cm or less ×: Volume resistivity is more than 200 μΩ · cm

[Example 1]
(1) Formation of ink receiving layer The following materials (a) to (d) were used for forming the ink receiving layer.
1.5 parts by mass of polyvinyl alcohol (b) below is dissolved in 83 parts by mass of ion-exchanged water (c) below, heated to 90 ° C., and then 13.5 parts by mass of alumina particles (a) below are added. Thus, a dispersion solution of alumina particles was prepared. Thereafter, this dispersion solution was cooled to room temperature, and then 2 parts by mass of the following (d) silane coupling agent was added to prepare a coating solution for forming an ink receiving layer. Next, this coating solution is applied onto a glass substrate (manufactured by Matsunami Glass Industry Co., Ltd., trade name: Micro Slide Glass) washed by dipping in ethanol by drop coating, and dried at room temperature for 12 hours. An ink receiving layer was formed. The volume ratio of the alumina particles to the total amount of alumina particles and polyvinyl alcohol in the formed ink receiving layer was 70% by volume.
(A) Alumina particles having an average primary particle size of 700 nm (manufactured by Sumitomo Chemical Co., Ltd., trade name: AA-07, Sumiko Random)
(B) Polyvinyl alcohol (Kuraray Co., Ltd., trade name: PVA117)
(C) Ion-exchanged water (d) Nonafluorohexyltriethoxysilane (manufactured by Gelest, trade name: SIN 6597-65)

(2) Formation of conductive pattern Copper fine particles covered with an organic dispersant composed of a water-soluble polymer were prepared by the following procedure.
10 ml of an aqueous copper acetate solution in which 0.2 g of copper acetate ((CH ₃ COO) ₂ Cu · H ₂ O) is dissolved in 10 ml of distilled water as a raw material for copper fine particles, and 5.0 mol / liter (l) as a metal ion reducing agent Thus, 100 ml of an aqueous sodium borohydride solution in which sodium borohydride and distilled water were mixed was prepared. Thereafter, 0.5 g of polyvinyl pyrrolidone (PVP, number average molecular weight of about 3500) as a water-soluble polymer for forming a protective film is added to the sodium borohydride aqueous solution, and the mixture is stirred and dissolved. Then, 10 ml of the aqueous copper acetate solution was added dropwise.
As a result of reacting this mixed liquid with sufficient stirring for about 60 minutes, a fine particle dispersion in which copper fine particles having a primary particle diameter of 5 to 10 nm were dispersed in an aqueous solution was obtained.
Next, 5 ml of chloroform as an aggregation accelerator was added to 100 ml of the copper fine particle dispersion obtained by the above method and stirred well. After stirring for several minutes, the reaction solution was supplied to a centrifuge, and copper fine particles were collected by precipitation. Thereafter, the obtained copper fine particles and 30 ml of distilled water were added to a test tube, and after thoroughly stirring using an ultrasonic homogenizer, water washing for recovering the copper fine particle components with a centrifuge was performed three times. The obtained copper fine particles and 30 ml of 1-butanol were similarly added to the test tube and stirred well, and then alcohol washing for recovering the copper fine particles with a centrifuge was performed three times.
The copper fine particles recovered by the above steps are dispersed in 10 ml of a mixed organic solvent consisting of 50% by volume of N-methylacetamide, 10% by volume of triethylamine and 40% by volume of glycerin as a mixed organic solvent, and an ultrasonic homogenizer is used for 1 hour. Then, ultrasonic vibration was applied to the dispersion and stirred well to prepare a conductive ink containing copper fine particles.
The conductive ink is printed on the surface of the ink receiving layer formed on the glass substrate by a screen printing method (pattern: line width 200 μm, length 50 mm, thickness 10 μm), and at 200 ° C. in the presence of nitrogen gas. The conductive pattern was produced by baking for 30 minutes.

[Example 2]
(1) Formation of ink receiving layer A coating liquid for forming an ink receiving layer was prepared in the same manner as in Example 1. This coating liquid was applied onto a polyimide film (trade name: Kapton, manufactured by Toray DuPont Co., Ltd.) by drop coating, and dried at room temperature for 12 hours to form an ink receiving layer on the polyimide film.
(2) Formation of conductive pattern A conductive pattern was produced on the surface of the ink receiving layer formed on the polyimide film in the same manner as in Example 1.
(3) Evaluation of ink receiving layer and conductive pattern The obtained ink receiving layer and conductive pattern were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 1.

[Example 3]
(1) Formation of ink receiving layer A coating solution for forming an ink receiving layer was prepared in the same manner as in Example 2. This coating liquid was applied onto a polyimide film (trade name: Kapton, manufactured by Toray DuPont Co., Ltd.) by drop coating, and dried at room temperature for 12 hours to form an ink receiving layer on the polyimide film.
(2) Formation of conductive pattern The same as Example 1 except that a mixed organic solvent composed of 65% by volume of N-methylacetamide, 5% by volume of trimethylamine, 25% by volume of glycerin, and 5% by volume of ethanol was used as the mixed organic solvent. A conductive ink was prepared by dispersing copper fine particles in 10 ml by the method described above and applying ultrasonic vibration to the dispersion using an ultrasonic homogenizer for 1 hour.
The conductive ink is put in an inkjet head (Mect, manufactured by MICROJET (registered trademark) Model MJ-040), and a predetermined pattern (line width: 100 μm, long) is formed on the surface of the ink receiving layer formed on the substrate. 20 mm in thickness and 3 μm in thickness). After drying at 120 ° C. for 30 minutes in a nitrogen atmosphere, heat treatment was further performed at 220 ° C. for 1 hour in a nitrogen atmosphere to produce a conductive pattern.
(3) Evaluation of ink receiving layer and conductive pattern The obtained ink receiving layer and conductive pattern were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 1.

[Example 4]
(1) Formation of ink receiving layer In the ink receiving layer forming method described in Example 2, the ink receiving layer was formed by changing polyvinyl alcohol to 2.5 parts by mass and alumina particles to 12.5 parts by mass. The volume ratio of the alumina particles to the total amount of alumina particles and polyvinyl alcohol in the ink receiving layer produced by this method was 60% by volume.
(2) Formation of conductive pattern A conductive pattern was formed on the surface of the ink receiving layer in the same manner as in Example 3.
(3) Evaluation of ink receiving layer and conductive pattern The obtained ink receiving layer and conductive pattern were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 1.

[Comparative Example 1]
(1) Formation of ink receiving layer In the ink receiving layer forming method described in Example 2, the ink receiving layer was formed by changing polyvinyl alcohol to 4.3 parts by mass and alumina particles to 10.7 parts by mass. The volume ratio of the alumina particles to the total amount of alumina particles and polyvinyl alcohol in the ink receiving layer produced by this method was 45% by volume.
(2) Formation of conductive pattern A conductive pattern was formed on the surface of the ink receiving layer in the same manner as in Example 3.
(3) Evaluation of ink receiving layer and conductive pattern The obtained ink receiving layer and conductive pattern were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 1.

[Example 5]
(1) Formation of ink receiving layer In the ink receiving layer forming method described in Example 2, the ink receiving layer was formed by changing polyvinyl alcohol to 1.1 parts by mass and alumina particles to 13.9 parts by mass. The volume ratio of the alumina particles to the total amount of alumina particles and polyvinyl alcohol in the ink receiving layer produced by this method was 80% by volume.
(2) Formation of conductive pattern A conductive pattern was formed on the surface of the ink receiving layer in the same manner as in Example 3.
(3) Evaluation of ink receiving layer and conductive pattern The obtained ink receiving layer and conductive pattern were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 1.

[Comparative Example 2]
(1) Formation of ink receiving layer In the ink receiving layer forming method described in Example 2, the ink receiving layer was formed by changing polyvinyl alcohol to 0.2 parts by mass and alumina particles to 14.8 parts by mass. The volume ratio of the alumina particles to the total amount of alumina particles and polyvinyl alcohol in the ink receiving layer produced by this method was 95% by volume.
(2) Formation of conductive pattern A conductive pattern was formed on the surface of the ink receiving layer in the same manner as in Example 3.
(3) Evaluation of ink receiving layer and conductive pattern The obtained ink receiving layer and conductive pattern were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 2.

[Example 6]
(1) Formation of ink receiving layer The following materials (a) to (d) were used for forming the ink receiving layer.
1.5 parts by mass of polyvinyl alcohol (b) below was dissolved in 48.5 parts by mass of ion exchange water (c) below heated at 90 ° C. to prepare an aqueous solution of polyvinyl alcohol.
Subsequently, 13.5 parts by mass of the following (a) alumina particles are dispersed in 34.5 parts by mass of ion-exchanged water (c), and then 2 parts by mass of (d) the silane coupling agent are added to obtain alumina particles. A dispersion was prepared. A coating liquid for forming an ink receiving layer was prepared by mixing an aqueous polyvinyl alcohol solution and an alumina particle dispersion liquid cooled to room temperature. Next, an ink receiving layer was produced on the polyimide film by the method described in Example 2 using this coating solution. The volume ratio of the alumina particles to the total amount of alumina particles and polyvinyl alcohol in the ink receiving layer produced by this method was 70% by volume.
(A) Alumina particles having an average primary particle size of 700 nm (manufactured by Sumitomo Chemical Co., Ltd., trade name: AA-07, Sumiko Random)
(B) Polyvinyl alcohol (Kuraray Co., Ltd., trade name: PVA117)
(C) Ion-exchanged water (d) Nonafluorohexyltriethoxysilane (manufactured by Gelest, trade name: SIN 6597-65)
(2) Formation of conductive pattern A conductive pattern was formed on the surface of the ink receiving layer in the same manner as in Example 3.
(3) Evaluation of ink receiving layer and conductive pattern The obtained ink receiving layer and conductive pattern were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 2.

[Example 7]
(1) Formation of ink receiving layer The following materials (a) to (d) were used for forming the ink receiving layer.
2.5 parts by mass of the following (b) polyvinyl alcohol was dissolved in 47.5 parts by mass of ion-exchanged water (c) below, which was heated to 90 ° C., to prepare an aqueous solution of polyvinyl alcohol. Subsequently, 12.5 parts by mass of alumina particles of the following (A) are dispersed in 35.5 parts by mass of ion-exchanged water of (C), and then 2 parts by mass of the silane coupling agent (D) are added to obtain alumina particles. A dispersion was prepared. A coating liquid for forming an ink receiving layer was prepared by mixing an aqueous polyvinyl alcohol solution and an alumina particle dispersion liquid cooled to room temperature. Next, an ink receiving layer was produced on the polyimide film by the method described in Example 2 using this coating solution. The volume ratio of the alumina particles to the total amount of alumina particles and polyvinyl alcohol in the ink receiving layer produced by this method was 60% by volume.
(A) Alumina particles having an average primary particle size of 700 nm (manufactured by Sumitomo Chemical Co., Ltd., trade name: AA-07, Sumiko Random)
(B) Polyvinyl alcohol (Kuraray Co., Ltd., trade name: PVA117)
(C) Ion-exchanged water (d) Nonafluorohexyltriethoxysilane (manufactured by Gelest, trade name: SIN 6597-65)
(2) Formation of conductive pattern A conductive pattern was formed on the surface of the ink receiving layer in the same manner as in Example 3.
(3) Evaluation of ink receiving layer and conductive pattern The obtained ink receiving layer and conductive pattern were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 2.

[Comparative Example 3]
A conductive pattern was produced in the same manner as in Example 1 except that the ink receiving layer was not formed on the glass substrate.
The performance of the obtained ink receiving layer and conductive pattern was evaluated in the same manner as in Example 1. In Comparative Example 3, since the ink receiving layer was not formed, the substrate adhesion of the ink receiving layer was not evaluated. The ink repellency and printability were evaluated on a glass substrate on which no ink receiving layer was formed.
The evaluation results are shown in Table 2.

[Comparative Example 4]
A conductive pattern was produced in the same manner as in Example 2 except that the ink receiving layer was not formed on the polyimide film.
The performance of the obtained ink receiving layer and conductive pattern was evaluated in the same manner as in Example 1. In Comparative Example 4, since the ink receiving layer was not formed, the substrate adhesion of the ink receiving layer was not evaluated. The ink repellency and printability were evaluated on a polyimide substrate on which no ink receiving layer was formed.
The evaluation results are shown in Table 2.

[Comparative Example 5]
A conductive pattern was produced in the same manner as in Example 1 except that the silane coupling agent was not added to the coating solution for forming the ink receiving layer on the polyimide film.
The performance of the obtained ink receiving layer and conductive pattern was evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 2.

[Example 8]
(1) Formation of ink receiving layer The following materials (a) to (d) were used for forming the ink receiving layer.
1.5 parts by mass of polyvinyl alcohol (b) below is dissolved in 83 parts by mass of ion-exchanged water (c) below, heated to 90 ° C., and then 13.5 parts by mass of silica particles (a) below are added. Thus, a dispersion solution of silica particles was prepared. Thereafter, this dispersion solution was cooled to room temperature, and then 2 parts by mass of the following (d) silane coupling agent was added to prepare a coating solution for forming an ink receiving layer. Next, this coating solution is applied onto a glass substrate (manufactured by Matsunami Glass Industry Co., Ltd., trade name: Micro Slide Glass) washed by dipping in ethanol by drop coating, and dried at room temperature for 12 hours. An ink receiving layer was formed. The volume ratio of silica particles to the total amount of silica particles and polyvinyl alcohol in the formed ink receiving layer was 70% by volume.
(A) Silica particles having a primary particle size of 30 nm (Tokuyama Corporation, trade name: QS-09, Leoroseal)
(B) Polyvinyl alcohol (Kuraray Co., Ltd., trade name: PVA117)
(C) Ion-exchanged water (d) Nonafluorohexyltriethoxysilane (manufactured by Gelest, trade name: SIN 6597-65)
(2) Formation of conductive pattern A conductive pattern was formed on the surface of the ink receiving layer in the same manner as in Example 3.
(3) Evaluation of ink receiving layer and conductive pattern The obtained ink receiving layer and conductive pattern were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 3.

[Example 9]
(1) Formation of ink receiving layer The following materials (a) to (e) were used for forming the ink receiving layer.
1.5 parts by mass of the polyvinyl alcohol of the following (C) is dissolved in 83 parts by mass of the ion-exchanged water of the following (D) heated to 90 ° C., followed by 13 parts by mass of the silica particles of the following (A) and the following (b) The dispersion solution was prepared by adding 0.5 parts by mass of alumina particles of Thereafter, the dispersion solution was cooled to room temperature, and then 2 parts by mass of the following silane coupling agent (e) was added to prepare an ink-receiving layer coating solution. Next, this coating solution is applied onto a glass substrate (manufactured by Matsunami Glass Industry Co., Ltd., trade name: Micro Slide Glass) washed by dipping in ethanol by drop coating, and dried at room temperature for 12 hours. An ink receiving layer was formed. The volume ratio of silica particles to the total amount of alumina particles, silica particles, and polyvinyl alcohol in the formed ink receiving layer was 70% by volume. Further, the weight ratio of the alumina particles to the total amount of the alumina particles and the silica particles was 3.7% by mass.

(A) Silica particles having a primary particle diameter of 30 nm (Tokuyama Corporation, trade name: QS-09, Leoroseal)
(B) Alumina particles having an average particle diameter of 700 nm (manufactured by Sumitomo Chemical Co., Ltd., trade name: AA-07, Sumiko Random)
(C) Polyvinyl alcohol (Kuraray Co., Ltd., trade name: PVA117)
(D) Ion-exchanged water (e) Nonafluorohexyltriethoxysilane (manufactured by Gelest, trade name: SIN 6597-65)
(2) Formation of conductive pattern A conductive pattern was formed on the surface of the ink receiving layer in the same manner as in Example 3.
(3) Evaluation of ink receiving layer and conductive pattern The obtained ink receiving layer and conductive pattern were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 3.

[Example 10]
(1) Formation of ink receiving layer The following materials (a) to (e) were used for forming the ink receiving layer.
1.5 parts by mass of the polyvinyl alcohol of the following (C) is dissolved in 83 parts by mass of the ion-exchanged water of the following (D) heated to 90 ° C., followed by 13 parts by mass of the silica particles of the following (A) and The dispersion solution was prepared by adding 0.5 parts by mass of alumina particles of Thereafter, the dispersion solution was cooled to room temperature, and then 2 parts by mass of the following silane coupling agent (e) was added to prepare a coating solution for forming an ink receiving layer. Next, this coating solution is applied onto a glass substrate (manufactured by Matsunami Glass Industry Co., Ltd., trade name: Micro Slide Glass) washed by dipping in ethanol by drop coating, and dried at room temperature for 12 hours. An ink receiving layer was formed. The volume ratio of silica particles to the total amount of alumina particles, silica particles, and polyvinyl alcohol in the formed ink receiving layer was 70% by volume. Further, the weight ratio of the alumina particles to the total amount of the alumina particles and the silica particles was 3.7% by mass.

(A) Silica particles having a primary particle diameter of 30 nm (Tokuyama Corporation, trade name: QS-09, Leoroseal)
(B) Alumina particles having an average particle diameter of 10 μm (manufactured by Sumitomo Chemical Co., Ltd., trade name: AA-10, Sumicorundum)
(C) Polyvinyl alcohol (Kuraray Co., Ltd., trade name: PVA117)
(D) Ion-exchanged water (e) Nonafluorohexyltriethoxysilane (manufactured by Gelest, trade name: SIN 6597-65)
(2) Formation of conductive pattern A conductive pattern was formed on the surface of the ink receiving layer in the same manner as in Example 3.
(3) Evaluation of ink receiving layer and conductive pattern The obtained ink receiving layer and conductive pattern were evaluated in the same manner as in Example 1.
The evaluation results are shown in Table 3.

[Evaluation results of Examples 1 to 10 and Comparative Examples 1 to 5]
The evaluation results of Examples 1 to 10 and Comparative Examples 1 to 5 are shown in Table 1, Table 2, and Table 3.
In Examples 1, 2, and 3, it can be seen that the ink-receiving layer formed on the substrate has good substrate adhesion, and the ink repellency and printability of the conductive ink pattern are also good. It can also be seen that the conductive materials of Examples 1, 2, and 3 obtained by baking after forming the pattern of the conductive ink have good adhesion and conductivity.
In Examples 4 and 5, the function of a good ink receiving layer is expressed as in Example 3. However, by changing the blending ratio of the constituent materials of the receiving layer, the substrate adhesion and printability of the receiving layer are changed. Some changes were observed.
On the other hand, it can be seen that in Comparative Examples 1 and 2 in which the ratio of the material constituting the receiving layer is outside the definition of the present application, an ink receiving layer for producing an appropriate conductor pattern cannot be formed. That is, in the ink receiving layer of Example 6 having a low ratio of polyvinyl alcohol to alumina particles, the ink receiving layer had a low film strength, and an ink receiving layer capable of producing a conductive pattern could not be obtained. Further, in Comparative Example 1 in which the ratio of polyvinyl alcohol to alumina particles is high, although the ink receiving layer can be produced, the ink liquid repellency and the conductive pattern adhesion are reduced.

When preparing the ink receiving layer coating solution, the alumina particles previously treated with a silane coupling agent were prepared, followed by the addition of an aqueous polyvinyl alcohol solution to prepare the coating solution for forming the ink receiving layer. In Examples 6 and 7, ink receiving layers having functions similar to those of Example 3 and Example 4 were obtained.
In Comparative Examples 3 and 4 where no ink receiving layer was formed, the ink repellency and printability were poor. In Comparative Example 3, a conductive pattern that can be evaluated could not be obtained, and in Comparative Example 4, a conductive pattern having low adhesion and low conductivity was obtained.
Further, in Comparative Example 5 in which no silane coupling agent was blended, the liquid repellency of the ink was lowered, so that a conductive pattern that could be evaluated could not be obtained.
From Examples 3, 8, 9, and 10, it was confirmed that when the alumina particles exhibiting a catalytic action for decomposing polyhydric alcohol were used as the non-conductive inorganic particles, the adhesion of the conductive pattern was good. The In Example 8, when silica particles having no catalytic action for decomposing polyhydric alcohol were used as the non-conductive inorganic particles, the improvement effect was lower than alumina particles having a catalytic effect. In Example 9, the addition of several mass% alumina particles to silica as non-conductive inorganic particles has resulted in improved adhesion, and catalytic properties that promote the decomposition of polyhydric alcohols. It can be seen that the adhesion of the conductive pattern is improved by the addition of the non-conductive inorganic particles. On the other hand, in Example 10, as the catalytic non-conductive inorganic particles, when alumina particles having a particle diameter exceeding 1000 nm were added to silica, no further improvement in adhesion was exhibited, and the particles had catalytic action. However, it can be seen that when the particle size is large, the improvement effect by the catalytic action is low.

11 Substrate (K)
12 Ink receiving layer (R)
13 Conductive Pattern 14 Conductive Ink (I)
15 Non-conductive inorganic particles (G)
16 Silane coupling group 17 Hydrophilic binder (B)
18 Reducing solvent (A)
19 Metal fine particles (P)

Claims (13)

The conductive ink (I) formed on the surface of the substrate (K) and containing the fine metal particles (P) and the reducing solvent (A) containing the polyhydric alcohol (S1) component is applied or patterned, and then heated. An ink receiving layer (R) capable of forming a conductive pattern by firing,
The ink receiving layer (R) is formed by bonding non-conductive inorganic particles (G) having a surface repellent with a silane coupling agent (C) having a fluoroalkyl group and bonded with a hydrophilic binder (B). In the layer
Volume ratio of nonconductive inorganic particles (G) to the total amount of nonconductive inorganic particles (G) and hydrophilic binder (B) (solid content) in the ink receiving layer (R) ([G / (B + G)] × 100) is 50 to 90 (volume%),
The surface of the ink receiving layer (R) has a concavo-convex shape based on the non-conductive inorganic particles (G),
The hydrophilic binder (B) present in the ink receiving layer (R) has a hydroxyl group;
An ink receiving layer.   2. The ink receiving layer according to claim 1, wherein the silane coupling agent (C) is a silane coupling agent having a fluoroalkyl group having 9 to 17 fluorine atoms.   The ink receiving layer according to claim 1, wherein the hydrophilic binder (B) is polyvinyl alcohol.   The non-conductive inorganic particles (G) are one or two selected from alumina particles and silica particles having an average primary particle diameter of 10 to 1000 nm, and the thickness of the ink receiving layer (R) is 1 to 2. The ink receiving layer according to claim 1, wherein the ink receiving layer is 100 μm. The non-conductive inorganic particles (G) promote decomposition of the polyhydric alcohol (S1) when heated or baked after applying or patterning (i) the conductive ink (I) on the ink receiving layer (R). Consisting of catalytic non-conductive inorganic particles (G1) having a catalytic action,
Or (ii) Catalytic non-conductive inorganic particles (G1) and non-catalytic non-conductive inorganic particles (G2) having no catalytic action, and catalytic non-conductive in the non-conductive inorganic particles (G) The proportion of the inorganic particles (G1) is 0.1% by mass or more,
The ink receiving layer according to claim 1. The non-conductive inorganic particles (G) are composed of catalytic non-conductive inorganic particles (G1) and non-catalytic non-conductive inorganic particles (G2). The proportion of the conductive inorganic particles (G1) is 0.1 to 5.0% by mass.
The ink receiving layer according to claim 5. The average particle diameter of the catalytic non-conductive inorganic particles (G1) in the non-conductive inorganic particles (G) is 1-1000 nm.
The ink receiving layer according to claim 5 or 6. The catalytic non-conductive inorganic particles (G1) are one or two selected from alumina and titania.
The ink receiving layer according to claim 5. A solution containing (i) non-conductive inorganic particles (G) surface-treated in advance with a silane coupling agent (C) having a fluoroalkyl group, and a hydrophilic binder (B), or (Ii) A solution containing non-conductive inorganic particles (G), a silane coupling agent (C) having a fluoroalkyl group, and a hydrophilic binder (B) is used as a coating solution for forming an ink receiving layer, and the ink receiving layer is formed. The ink receiving layer according to any one of claims 1 to 8, wherein the ink receiving layer is a layer formed after the coating liquid is applied on the substrate (K). A coating liquid for forming an ink-receiving layer, comprising particles whose surfaces of non-conductive inorganic particles (G) are treated with a silane coupling agent (C) and a hydrophilic binder (B),
(I) One or two non-conductive inorganic particles (G) selected from particles having an average particle size of 10 to 1000 nm of primary particles, or
(Ii) The non-conductive inorganic particles (G) promote the decomposition of the polyhydric alcohol (S1) when the conductive ink (I) is applied or patterned on the ink receiving layer (R) and then heated and baked. Catalytic non-conductive inorganic particles (G1) having catalytic action and non-catalytic non-conductive inorganic particles (G2) having no catalytic action, and catalytic non-conductive in non-conductive inorganic particles (G) Non-catalytic non-conductive inorganic particles (G1) having a proportion of 0.1 to 5.0% by mass and catalytic non-conductive inorganic particles (G1) having an average particle diameter of 1 to 1000 nm. The average particle size of G2) is 10 to 1000 nm,
The silane coupling agent (C) is a silane coupling agent having a fluoroalkyl group having 9 to 17 fluorine atoms,
The ratio of the total solid content in the ink receiving layer forming coating solution ([total solid content / ink receiving layer forming coating solution] mass ratio) is 0.08 to 0.3,
The volume ratio ([G / (B + G)] × 100) of the nonconductive inorganic particles (G) to the total amount of the nonconductive inorganic particles (G) and the hydrophilic binder (B) (solid content) is 50 to 90 ( volume%),
And the use ratio ([C / G] mass ratio) of the silane coupling agent (C) to the non-conductive inorganic particles (G) is 0.0002 to 0.02.
A coating liquid for forming an ink receiving layer, wherein A coating liquid for forming an ink receiving layer containing non-conductive inorganic particles (G), a silane coupling agent (C), and a hydrophilic binder (B),
(I) One or two non-conductive inorganic particles (G) selected from particles having an average particle size of 10 to 1000 nm of primary particles, or
(Ii) The non-conductive inorganic particles (G) promote the decomposition of the polyhydric alcohol (S1) when the conductive ink (I) is applied or patterned on the ink receiving layer (R) and then heated and baked. Catalytic non-conductive inorganic particles (G1) having catalytic action and non-catalytic non-conductive inorganic particles (G2) having no catalytic action, and catalytic non-conductive in non-conductive inorganic particles (G) Non-catalytic non-conductive inorganic particles (G1) having a proportion of 0.1 to 5.0% by mass and catalytic non-conductive inorganic particles (G1) having an average particle diameter of 1 to 1000 nm. The average particle size of G2) is 10 to 1000 nm,
The silane coupling agent (C) is a silane coupling agent having a fluoroalkyl group having 9 to 17 fluorine atoms,
The ratio of the total solid content in the ink receiving layer forming coating solution ([total solid content / ink receiving layer forming coating solution] mass ratio) is 0.08 to 0.3,
The volume ratio ([G / (B + G)] × 100) of the nonconductive inorganic particles (G) to the total amount of the nonconductive inorganic particles (G) and the hydrophilic binder (B) (solid content) is 50 to 90 ( volume%),
And the ratio ([C / G] mass ratio) of the silane coupling agent (C) to the non-conductive inorganic particles (G) is 0.0002 to 0.02.
A coating liquid for forming an ink receiving layer, wherein   A method for forming an ink receiving layer, comprising: applying the ink receiving layer forming coating solution according to claim 10 or 11 onto a substrate (K) and then drying the coating.   A conductive ink (I) containing metal fine particles (P) and a reducing solvent (A) is applied or patterned on the ink receiving layer (R) according to any one of claims 1 to 9, and then heated and baked. Then, the method for forming a conductive pattern is characterized in that the metal fine particles (P) are sintered.

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