JP6178150B2 - Electronics - Google Patents

Description

  The present invention relates to a laminate including a substrate, a conductive layer, and an overcoat layer, and an electronic device using the laminate.

  A laminate in which a base material, a conductive layer, and an overcoat layer are laminated in this order is widely used in various fields. For example, if the conductive layer is patterned, a circuit is used in the field of electronic equipment. Used as a substrate. In such a laminate, the overcoat layer is mainly provided for protecting the conductive layer by suppressing alteration or breakage, and various types of overcoat layers have been studied depending on the material of the conductive layer. .

  For example, for suppressing corrosion of metal circuit by sulfide, an overcoat layer (see Patent Document 1) from a cured product of a composition containing an essential component of a curable silicone rubber composition and an inorganic ion exchanger, A hydrolyzable silyl group and / or silanol group, 50 mol% or more in the monomer component is methyl methacrylate, and the weight average molecular weight and silicon atom content are in a specific range (meth) An overcoat layer (see Patent Document 2) is disclosed from a cured product of a composition mainly composed of an acrylic resin.

JP-A-2005-120155 JP 2003-188503 A

  However, since the overcoat layer disclosed in Patent Document 1 has a low hardness, it cannot be said that the protective action of the circuit (conductive layer) is sufficient, and the circuit ( There is a problem that the conductive layer) is easily disconnected. Moreover, although the overcoat layer disclosed in Patent Document 2 has a sufficient circuit protection effect, there is a problem that the laminate is likely to warp because the linear expansion coefficient is larger than that of the base material. .

  The present invention has been made in view of the above circumstances, and includes a laminate including a base material, a conductive layer, and an overcoat layer, having a high protective effect on the conductive layer and suppressing warpage, and the laminate. It is an object to provide an electronic device.

To solve the above problem,
The present invention comprises a substrate, conductive layer and the overcoat layer are laminated in this order using the name Ru laminate, the substrate an electronic apparatus having a housing, conforming to JIS K 5600-5-4 pencil hardness of the overcoat layer according to hardness tests is not less than HB, the overcoat layer is provided an electronic apparatus characterized in that it contains cellulose nanofibers.
In the electronic device of the present invention, the overcoat layer is preferably formed using one or more selected from the group consisting of urethane acrylate resins and epoxy acrylate resins .

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body which was provided with the base material, the conductive layer, and the overcoat layer, and the protective effect of the conductive layer was high, and curvature was suppressed, and the electronic device using this laminated body are provided.

It is a schematic sectional drawing which illustrates the layered product concerning the present invention. It is a schematic sectional drawing which illustrates the laminated body provided with the contact | adherence layer based on this invention. It is a schematic sectional drawing for demonstrating the manufacturing method of the laminated body which concerns on this invention.

<< Laminate >>
In the laminate according to the present invention, a base material, a conductive layer, and an overcoat layer are laminated in this order, and the pencil hardness of the overcoat layer according to a hardness test in accordance with JIS K 5600-5-4 is HB or more. And the overcoat layer contains cellulose nanofiber (hereinafter sometimes abbreviated as “CNF”).
Such a laminate has a high protective effect of the conductive layer because the overcoat layer has the above hardness (pencil hardness), and the overcoat layer contains CNF as a fiber, so that Warpage is remarkably suppressed.

FIG. 1 is a schematic cross-sectional view illustrating a laminated body according to the present invention.
In the laminate 1 shown here, a conductive layer 12 is laminated on a base material 11, and an overcoat layer 13 is laminated on the conductive layer 12. The conductive layer 12 is covered with an overcoat layer 13 on the substrate 11 and is configured so that there is no exposed portion. In addition, the conductive layer 12 is patterned into a predetermined shape on the substrate 11, and an overcoat is applied to a portion of the surface (one main surface) 11 a of the substrate 11 where the conductive layer 12 is not laminated. Layer 13 is laminated in direct contact. Here, although the conductive layer 12 or the overcoat layer 13 is laminated on the entire surface 11a of the substrate 11, the laminated body 1 is configured so that there is no exposed portion of the conductive layer 12. For example, the overcoat layer 13 may not be laminated on a portion of the surface 11a of the substrate 11 where the conductive layer 12 is not laminated, and the portion may be exposed.
The laminated body 1 shows an example of the laminated body according to the present invention, and the laminated body according to the present invention is not limited to this. For example, the conductive layer 12 is formed on the entire surface 11a of the substrate 11. It may be laminated.

<Base material>
Although the base material 11 can select arbitrary shapes according to the objective, It is preferable that it is plate shape, film shape, or sheet shape, and it is preferable that thickness is 0.05-5 mm, 0.1-3 mm It is more preferable that

The material of the substrate 11 is not particularly limited and may be selected according to the purpose. However, it is preferable to have heat resistance that does not change when the conductive layer is formed by heat treatment of the silver ink composition described later.
Specifically, the material of the substrate 11 is polyethylene (PE), polypropylene (PP), polycycloolefin, polyvinyl chloride (PVC), ethylene-vinyl acetate copolymer, polyvinyl alcohol, vinylon, polyvinylidene chloride (PVDC). ), Polymethylpentene (PMP), polystyrene (PS), polyvinyl acetate (PVAc), polymethyl methacrylate (PMMA), polyethyl methacrylate (PEMA), polybutyl methacrylate (PBMA), polymethyl acrylate ( PMA), polyethyl acrylate (PEA), polybutyl acrylate (PBA), AS resin, ABS resin, polyamide (PA), polyimide (PI), polyamideimide (PAI), polyacetal, polyethylene terephthalate (PET), glycol Modified poly Tylene terephthalate (PET-G), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyphenylene sulfide (PPS), polysulfone (PSF), Polyethersulfone (PES), polyetherketone (PEK), polyetheretherketone (PEEK), polycarbonate (PC), polyurethane, polyphenylene ether (PPE), modified polyphenylene ether (m-PPE), polyarylate, epoxy resin, Examples thereof include synthetic resins such as melamine resin, phenol resin, and urea resin.
In addition to the above, the material of the substrate 11 can be exemplified by ceramics such as glass and silicon; papers such as fine paper, thin paper, glassine paper, and sulfuric acid paper.
The substrate 11 may be a combination of two or more materials such as glass epoxy resin and polymer alloy.

The substrate 11 may be composed of a single layer, or may be composed of two or more layers. When the base material 11 consists of multiple layers, these multiple layers may be the same as or different from each other. That is, all the layers may be the same, all the layers may be different, or only some of the layers may be different. And when several layers differ from each other, the combination of these several layers is not specifically limited. Here, the plurality of layers being different from each other means that at least one of the material and the thickness of each layer is different from each other.
In addition, when the base material 11 consists of multiple layers, it is good to make it the thickness of the total of each layer be the thickness of said preferable base material 11.

<Conductive layer>
The material of the conductive layer 12 is not particularly limited as long as it has conductivity. However, from the viewpoint that a conductive layer having a low resistance value can be easily formed, a single metal such as silver or copper, or an alloy (hereinafter, these are summarized). In other words, it is preferably abbreviated as “metal”), more preferably silver, and particularly preferably formed using a metal silver forming material described later.

  The shape of the conductive layer 12 is not particularly limited. For example, the shape of the conductive layer 12 when the laminate 1 is viewed in plan so that the surface 11a of the substrate 11 is looked down from above is arbitrarily set according to the purpose. it can.

  Although the thickness of the conductive layer 12 can be arbitrarily set according to the purpose, it is preferably 0.01 to 5 μm, and more preferably 0.05 to 3 μm. When the thickness of the conductive layer 12 is equal to or more than the lower limit, the conductivity can be further improved, and the structure of the conductive layer 12 can be more stably maintained. Moreover, the laminated body 1 can be made thinner by the thickness of the conductive layer 12 being equal to or less than the upper limit value.

  The conductive layer 12 may be composed of a single layer, or may be composed of two or more layers. When the conductive layer 12 includes a plurality of layers, the plurality of layers may be the same as or different from each other, and can be configured in the same manner as in the case of the substrate 11. For example, the conductive layer 12 composed of a plurality of layers may be configured such that the total thickness of the respective layers is equal to the thickness of the preferable conductive layer 12 described above.

<Overcoat layer>
The overcoat layer 13 has a pencil hardness of HB or higher according to a hardness test in accordance with JIS K 5600-5-4, has a sufficient hardness, and has a high protective effect on the conductive layer 12. Here, the “protective action of the conductive layer” means an action of suppressing deterioration or breakage of the conductive layer. The “degeneration of the conductive layer” means a clear change in the material of the conductive layer, such as oxidation and sulfurization, to the extent that the conductive layer cannot fully perform its function. Further, “damage of the conductive layer” means structural destruction of the conductive layer caused by external force during normal handling of the laminate. In the laminate according to the present invention, since the overcoat layer 13 has a sufficient hardness, not only the damage of the conductive layer 12 is suppressed, but also the conductive layer 12 and an alteration cause substance (for example, oxygen, sulfide) Since contact with hydrogen and sulfurous acid is highly suppressed, alteration of the conductive layer 12 is also suppressed.

  Conventionally, the difference in the linear expansion coefficient (thermal expansion coefficient) between the overcoat layer and the substrate is large, so that the environmental temperature changes during storage or use of the laminate, or the overcoat layer is heated during formation. In such a case, the difference between the heating temperature at this time and the environmental temperature after manufacturing the laminate increases, resulting in a temperature difference with time in the laminate and warping of the entire laminate. On the other hand, in the laminate 1 according to the present invention, since the overcoat layer 13 contains CNF, the difference in the linear expansion coefficient between the overcoat layer 13 and the substrate 11 is reduced. Even if a temperature difference occurs in the laminate over time, the warpage of the entire laminate is significantly suppressed.

The material other than CNF of the overcoat layer 13 is not particularly limited as long as it has the above hardness, and may be either an organic compound or an inorganic compound, and may be both an organic compound and an inorganic compound. From the viewpoint of easier formation, an organic compound is preferable, and various resins are more preferable.
Moreover, the material other than CNF of the overcoat layer 13 may be one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio can be arbitrarily adjusted according to the purpose.

  In particular, the overcoat layer 13 is preferably formed using at least one selected from the group consisting of urethane acrylate resins and epoxy acrylate resins, in addition to CNF, and selected from the group consisting of urethane acrylate resins and epoxy acrylate resins. Those formed by polymerizing one or more of the above are more preferable.

  The urethane acrylate resin used for the formation of the overcoat layer 13 is preferably a urethane acrylate resin having an isocyanate skeleton (hereinafter sometimes referred to as “isocyanate skeleton-containing urethane acrylate resin”). It is more preferable that it is a urethane acrylate resin (hereinafter sometimes referred to as “alicyclic isocyanate skeleton-containing urethane acrylate resin”).

  The epoxy acrylate resin used to form the overcoat layer 13 is preferably a bisphenol A type epoxy acrylate resin.

  When the material other than CNF of the overcoat layer 13 is a polymer of various resins (hereinafter sometimes abbreviated as “base resin”), the weight average molecular weight of the base resin subjected to polymerization is 3000 or less. It is preferably 2000 or less, more preferably 1500 or less. Here, the weight average molecular weight is determined on the basis of polystyrene conversion by GPC (gel permeation chromatography). For example, using an analyzer such as “HLC-8120GPC” manufactured by Tosoh Corporation, a TSK gel or the like is used. It can be determined by analysis using a column, eluent such as N, N-dimethylformamide (DMF). By using such a base resin, the overcoat layer 13 has a higher protective effect on the conductive layer 12.

The base resin is preferably a urethane acrylate resin, and more preferably an alicyclic isocyanate skeleton-containing urethane acrylate resin, in that the effect of suppressing migration when a voltage is applied to the conductive layer 12 is high.
Here, “migration” is a phenomenon in which the constituent components of the conductive layer move from the conductive layer surface to the outside of the conductive layer and move. When the conductive layer is a silver layer, metallic silver moves. . Migration is likely to occur under high humidity conditions. For example, in a line and space pattern of a conductive layer, migration is likely to occur between adjacent lines.

The overcoat layer 13 is preferably insulating, and preferably has a surface resistance value of 1 × 10 ⁸ (Ω / □) or more in accordance with JIS K 6911.

  Although the thickness of the overcoat layer 13 can be arbitrarily set according to the purpose, it is preferably 0.5 to 50 μm, and more preferably 0.7 to 30 μm. When the thickness of the overcoat layer 13 is not less than the lower limit value, the protective effect of the conductive layer 12 is further increased. Moreover, the laminated body 1 can be made thinner by the thickness of the overcoat layer 13 being the said upper limit or less.

  The overcoat layer 13 may be composed of a single layer or may be composed of two or more layers. When the overcoat layer 13 includes a plurality of layers, the plurality of layers may be the same as or different from each other, and can be configured in the same manner as the substrate 11. For example, the overcoat layer 13 composed of a plurality of layers may be configured such that the total thickness of each layer is equal to the preferred thickness of the overcoat layer 13.

  The laminate according to the present invention is not limited to that shown in FIG. 1, and other configurations may be added or some configurations may be appropriately changed within a range not impairing the effects of the present invention. For example, another layer other than the conductive layer 12 and the overcoat layer 13 may be provided on the substrate 11, and the other layer may be used to improve the adhesion between the substrate 11 and the conductive layer 12. An adhesion layer provided between these layers can be exemplified.

  FIG. 2 is a schematic cross-sectional view illustrating a laminated body provided with an adhesion layer according to the present invention. 2 that are the same as those shown in FIG. 1 are assigned the same reference numerals as in FIG. 1, and detailed descriptions thereof are omitted. The same applies to the following drawings.

The laminated body 2 shown here is provided with an adhesion layer 14 between the base material 11 and the conductive layer 12, and is the same as the laminated body 1 except for this point.
The adhesion layer 14 is laminated on the entire surface 11 a of the base material 11, the conductive layer 12 is laminated on a part of the surface 14 a of the adhesion layer 14, and the adhesion layer is formed in a portion where the conductive layer 12 is not laminated. 14, an overcoat layer 13 is laminated in direct contact therewith. Here, the adhesion layer 14 is laminated on the entire surface 11a of the substrate 11, but in the laminate 2, the entire back surface (the other main surface) 12b of the conductive layer 12 is the adhesion layer. 14 is preferably in contact with the surface 14a. Further, for example, the adhesion layer 14 may be laminated not only on the entire surface 11a of the substrate 11 but on a part thereof. In this case, the adhesion layer 14 may be patterned, and the surface 11a of the substrate 11 may be patterned. Among them, the overcoat layer 13 may be laminated in direct contact with a portion where the adhesion layer 14 is not laminated, or may be exposed without being laminated.

<Adhesion layer>
The material of the adhesion layer 14 may be appropriately adjusted according to the types of the base material 11 and the conductive layer 12, and is not particularly limited, and examples thereof include the same materials as those of the overcoat layer 13 other than CNF.
The material of the adhesion layer may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio can be arbitrarily adjusted according to the purpose.
When the material of the adhesion layer 14 is, for example, a resin, a preferable example of such a resin is a urethane acrylate resin, which is described as a urethane acrylate resin having a polycarbonate skeleton (hereinafter referred to as “polycarbonate skeleton-containing urethane acrylate resin”). More preferably).

  Although the thickness of the contact | adherence layer 14 can be set arbitrarily according to the objective, it is preferable that it is 0.5-50 micrometers, and it is more preferable that it is 0.7-30 micrometers. The adhesiveness of the base material 11 and the conductive layer 12 improves more because the thickness of the contact | adherence layer 14 is more than the said lower limit. Moreover, when the thickness of the adhesion layer 14 is equal to or less than the upper limit value, the stacked body 2 can be made thinner.

  The adhesion layer 14 may be composed of a single layer, or may be composed of two or more layers. When the adhesion layer 14 includes a plurality of layers, the plurality of layers may be the same as or different from each other, and can be configured in the same manner as the substrate 11. For example, the adhesion layer 14 composed of a plurality of layers may be configured such that the total thickness of each layer is the thickness of the preferable adhesion layer 14 described above.

<Method for producing laminate>
The laminated body which concerns on this invention can be manufactured with the manufacturing method which has the process of forming a conductive layer on a base material, and the process of forming an overcoat layer on the said conductive layer, for example.
FIG. 3 is a schematic cross-sectional view for explaining a method of manufacturing the laminate 1 shown in FIG.

[Step of forming conductive layer on substrate]
In order to manufacture the laminated body 1, first, as shown in FIG.3 (b), the conductive layer 12 is formed on the surface (one main surface) 11a of the base material 11. As shown in FIG.
The method for forming the conductive layer 12 may be appropriately selected according to the material of the conductive layer 12.
For example, a composition for forming the conductive layer 12 (hereinafter, sometimes abbreviated as “composition for conductive layer”) is prepared, and this is attached to a desired location on the surface 11a of the substrate 11, The conductive layer 12 can be formed by appropriately selecting post-treatment such as drying treatment and heating (firing) treatment as necessary. The heat treatment may be performed also as a drying treatment.
Further, a composition for the conductive layer is prepared, and this is adhered to a predetermined portion or the entire surface of the surface 11a of the substrate 11, and a post-treatment such as a drying treatment or a heating (firing) treatment is appropriately selected as necessary. After forming a conductive layer (a conductive layer before patterning, not shown), the conductive layer 12 can be formed by patterning the conductive layer into a desired shape by a known method such as etching. .
In addition, a conductive film (not shown) made of a desired material such as a conductive foil is fixed by a method of heat-sealing on the surface 11a of the substrate 11 or a method of bonding on the surface 11a using an adhesive, The conductive layer 12 can be formed by patterning the conductive film into a desired shape by a known method such as etching. Here, as said adhesive agent, well-known things, such as a polyester-type thing and the polyurethane containing an epoxy resin, can be used suitably, for example.

[Step of forming overcoat layer on conductive layer]
Next, as illustrated in FIG. 3C, the laminate 1 is obtained by forming the overcoat layer 13 on the conductive layer 12.
The formation method of the overcoat layer 13 may be appropriately selected according to the material of the overcoat layer 13.
For example, a composition for forming the overcoat layer 13 (hereinafter sometimes abbreviated as “coating composition”) is prepared, and this is desired on the substrate 11 so as to cover the conductive layer 12. The overcoat layer 13 can be formed by adhering to the portion and performing post-treatment as necessary. The post-treatment at this time may be appropriately selected according to the type of the coating composition. For example, it is cured as a material for forming the overcoat layer 13 other than CNF (hereinafter sometimes abbreviated as “coat material”). In the case where a monomer, oligomer or polymer (where the oligomer and polymer correspond to the above-mentioned “base resin”) is blended, ultraviolet irradiation treatment or heat treatment may be performed. Moreover, you may further pattern the formed overcoat layer by well-known methods, such as an etching, as needed.

Hereinafter, a method for forming the conductive layer 12 and the overcoat layer 13 will be described in more detail.
First, the method for forming the conductive layer 12 will be described in more detail.
When the material of the conductive layer 12 is a metal, a metal ink composition containing a metal forming material is prepared as a composition for the conductive layer, and this is adhered to the surface 11 a of the substrate 11. The conductive layer 12 is preferably formed by appropriately selecting post-treatment such as drying treatment or heating (firing) treatment.
The metal forming material in the metal ink composition may be only one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio can be arbitrarily adjusted.

The metal forming material only needs to have a corresponding metal atom (element) and generate a metal by structural change such as decomposition, metal salt, metal complex, organometallic compound (compound having a metal-carbon bond). Etc. can be illustrated. In particular, the metal forming material is preferably a metal compound having an organic group, and the metal compound may be either a compound having a metal-carbon bond or a compound having no metal-carbon bond.
By using a metal forming material, a metal is generated from the material, and the conductive layer 12 including the metal is formed. In this case, the conductive layer 12 is mainly composed of the metal, and the ratio of the metal is sufficiently high so that it can be regarded as consisting of only the metal, and the ratio of the metal in the conductive layer 12 is preferably Is 99% by mass or more.

  As the metal ink composition, a liquid one is preferable, and one in which the metal forming material is uniformly dispersed is preferable.

Hereinafter, a method for forming the conductive layer 12 in the case where a silver ink composition containing a metal silver forming material is used as the metal ink composition will be described. The same applies to the case where the metal species is other than silver. The conductive layer 12 can be formed by the method.
The metallic silver forming material is decomposed by heating or the like to form metallic silver.

[Silver carboxylate]
Examples of the metal silver forming material include silver carboxylate having a group represented by the formula “—COOAg”.
The silver carboxylate is not particularly limited as long as it has a group represented by the formula “—COOAg”. For example, the number of groups represented by the formula “—COOAg” may be only one, or two or more. Further, the position of the group represented by the formula “—COOAg” in the silver carboxylate is not particularly limited.

The silver carboxylate is represented by the following general formula (1) β-ketocarboxylate silver (hereinafter sometimes abbreviated as “β-ketocarboxylate (1)”) and the following general formula (4). It is preferably one or more selected from the group consisting of silver carboxylates (hereinafter sometimes abbreviated as "silver carboxylate (4)").
In the present specification, the simple description of “silver carboxylate” is not limited to “silver β-ketocarboxylate (1)” and “silver carboxylate (4)”, unless otherwise specified. It is intended to mean “silver carboxylate having a group represented by the formula“ —COOAg ””.

（式中、Ｒは１個以上の水素原子が置換基で置換されていてもよい炭素数１〜２０の脂肪族炭化水素基若しくはフェニル基、水酸基、アミノ基、又は一般式「Ｒ^１−ＣＹ^１ _２−」、「ＣＹ^１ _３−」、「Ｒ^１−ＣＨＹ^１−」、「Ｒ^２Ｏ−」、「Ｒ^５Ｒ^４Ｎ−」、「（Ｒ^３Ｏ）_２ＣＹ^１−」若しくは「Ｒ^６−Ｃ（＝Ｏ）−ＣＹ^１ _２−」で表される基であり；
Ｙ^１はそれぞれ独立にフッ素原子、塩素原子、臭素原子又は水素原子であり；Ｒ^１は炭素数１〜１９の脂肪族炭化水素基又はフェニル基であり；Ｒ^２は炭素数１〜２０の脂肪族炭化水素基であり；Ｒ^３は炭素数１〜１６の脂肪族炭化水素基であり；Ｒ^４及びＲ^５はそれぞれ独立に炭素数１〜１８の脂肪族炭化水素基であり；Ｒ^６は炭素数１〜１９の脂肪族炭化水素基、水酸基又は式「ＡｇＯ−」で表される基であり；
Ｘ^１はそれぞれ独立に水素原子、炭素数１〜２０の脂肪族炭化水素基、ハロゲン原子、１個以上の水素原子が置換基で置換されていてもよいフェニル基若しくはベンジル基、シアノ基、Ｎ−フタロイル−３−アミノプロピル基、２−エトキシビニル基、又は一般式「Ｒ^７Ｏ−」、「Ｒ^７Ｓ−」、「Ｒ^７−Ｃ（＝Ｏ）−」若しくは「Ｒ^７−Ｃ（＝Ｏ）−Ｏ−」で表される基であり；
Ｒ^７は、炭素数１〜１０の脂肪族炭化水素基、チエニル基、又は１個以上の水素原子が置換基で置換されていてもよいフェニル基若しくはジフェニル基である。）

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

（式中、Ｒ^８は炭素数１〜１９の脂肪族炭化水素基、カルボキシ基又は式「−Ｃ（＝Ｏ）−ＯＡｇ」で表される基であり、前記脂肪族炭化水素基がメチレン基を有する場合、１個以上の該メチレン基はカルボニル基で置換されていてもよい。）

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

(Silver β-ketocarboxylate (1))
The β-ketocarboxylate silver (1) is represented by the general formula (1).
In the formula, R represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a phenyl group, a hydroxyl group, an amino group, or a general formula “R ¹ -CY ¹ ” in which one or more hydrogen atoms may be substituted with a substituent. " _2- ", "CY ¹ _3- ", "R ¹ -CHY ^1- ", "R ² O-", "R ⁵ R ⁴ N-", "(R ³ O) ₂ CY ^1- " or "R ^6- C (═O) —CY ¹ ₂ — ”.

  The aliphatic hydrocarbon group having 1 to 20 carbon atoms in R may be any of linear, branched and cyclic (aliphatic cyclic group), and when it is cyclic, it may be monocyclic or polycyclic. . Further, the aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. Preferred examples of the aliphatic hydrocarbon group for R include an alkyl group, an alkenyl group, and an alkynyl group.

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

Examples of the alkenyl group in R include a vinyl group (ethenyl group, —CH═CH ₂ ), an allyl group (2-propenyl group, —CH ₂ —CH═CH ₂ ), and a 1-propenyl group (—CH═CH—CH). ₃ ), isopropenyl group (—C (CH ₃ ) ═CH ₂ ), 1-butenyl group (—CH═CH—CH ₂ —CH ₃ ), 2-butenyl group (—CH ₂ —CH═CH—CH _3). ), 3-butenyl group (—CH ₂ —CH ₂ —CH═CH ₂ ), cyclohexenyl group, cyclopentenyl group and the like, one single bond (C—C) between carbon atoms of the alkyl group in R Is a group in which is substituted with a double bond (C═C).
As the alkynyl group in R, one single bond (C—C) between carbon atoms of the alkyl group in R, such as ethynyl group (—C≡CH), propargyl group (—CH ₂ —C≡CH) and the like. ) Is substituted with a triple bond (C≡C).

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

The phenyl group in R may have one or more hydrogen atoms substituted with a substituent, and the preferred substituent is a saturated or unsaturated monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms. , A monovalent group formed by bonding the aliphatic hydrocarbon group to an oxygen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group (—OH), a cyano group (—C≡N), a phenoxy group (—O— C ₆ H ₅ ) and the like can be exemplified, and the number and position of substituents are not particularly limited. When the number of substituents is plural, the plural substituents may be the same as or different from each other.
Examples of the aliphatic hydrocarbon group that is a substituent include the same aliphatic hydrocarbon groups as those described above for R except that the number of carbon atoms is 1 to 16.

Y ^{1 in} R is independently a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom. In the general formulas “R ¹ —CY ¹ ₂ —”, “CY ¹ ₃ —” and “R ⁶ —C (═O) —CY ¹ ₂ —”, a plurality of Y ¹ may be the same as each other. May be different.

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

R is, among these, a linear or branched alkyl group, the general formula ^{"R 6 -C (= O) -CY} 1 2 - " group represented by be a hydroxyl group or a phenyl group preferable. R ⁶ is preferably a linear or branched alkyl group, a hydroxyl group, or a group represented by the formula “AgO—”.

In the general formula (1), each X ¹ is independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a phenyl group in which one or more hydrogen atoms may be substituted with a substituent, or A benzyl group (C ₆ H ₅ —CH ₂ —), a cyano group, an N-phthaloyl-3-aminopropyl group, a 2-ethoxyvinyl group (C ₂ H ₅ —O—CH═CH—), or a general formula “R ⁷ O— ”,“ R ⁷ S— ”,“ R ⁷ —C (═O) — ”or“ R ⁷ —C (═O) —O— ”.
Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms in X ¹ include those similar to the aliphatic hydrocarbon group in R.

Examples of the halogen atom in X ¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In the phenyl group and benzyl group in X ¹ , one or more hydrogen atoms may be substituted with a substituent. Preferred examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), nitro group (-NO ₂₎ or the like can be exemplified, the number and position of the substituent is not particularly limited. When the number of substituents is plural, the plural substituents may be the same as or different from each other.

R ⁷ in X ¹ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a thienyl group (C ₄ H ₃ S—), a phenyl group in which one or more hydrogen atoms may be substituted with a substituent, or diphenyl group (biphenyl _{group, C 6 H 5 -C 6 H} 4 -) is. Examples of the aliphatic hydrocarbon group for R ⁷ include those similar to the aliphatic hydrocarbon group for R except that the aliphatic hydrocarbon group has 1 to 10 carbon atoms. Further, examples of the substituent of the phenyl group and a diphenyl group in R ^7, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) can be exemplified the like, the number and position of the substituent is not particularly limited. When the number of substituents is plural, the plural substituents may be the same as or different from each other.
When R ⁷ is a thienyl group or a diphenyl group, there are no particular limitations on the bonding position of these groups with an adjacent group or atom (oxygen atom, sulfur atom, carbonyl group, carbonyloxy group) in X ¹ . For example, the thienyl group may be a 2-thienyl group or a 3-thienyl group.

In the general formula (1), two X ^{1 s} may be bonded as one group through a double bond with a carbon atom sandwiched between two carbonyl groups. A group represented by the formula “═CH—C ₆ H ₄ —NO ₂ ” can be exemplified.

X ¹ is preferably a hydrogen atom, a linear or branched alkyl group, a benzyl group, or a group represented by the general formula “R ⁷ —C (═O) —” among the above. It is preferable that at least one X ¹ is a hydrogen atom.

β-ketocarboxylate silver (1) is silver 2-methylacetoacetate (CH ₃ —C (═O) —CH (CH ₃ ) —C (═O) —OAg), silver acetoacetate (CH ₃ —C (= O) —CH ₂ —C (═O) —OAg), silver 2-ethylacetoacetate (CH ₃ —C (═O) —CH (CH ₂ CH ₃ ) —C (═O) —OAg), silver propionyl acetate _{(CH 3 CH 2 -C (=} O) -CH 2 -C (= O) -OAg), isobutyryl silver acetate _{((CH 3) 2 CH-} C (= O) -CH 2 -C (= O) - OAg), silver pivaloyl acetate ((CH ₃ ) ₃ C—C (═O) —CH ₂ —C (═O) —OAg), silver 2-n-butylacetoacetate (CH ₃ —C (═O) —CH _{(CH 2 CH 2 CH 2 CH} 3) -C (= O) -OAg), 2- benzyl acetoacetate silver _(CH 3 -C ( _{= O) -CH (CH 2 C} 6 H 5) -C (= O) -OAg), silver benzoylacetate _{(C 6 H 5 -C (=} O) -CH 2 -C (= O) -OAg), Silver pivaloyl acetoacetate ((CH ₃ ) ₃ C—C (═O) —CH ₂ —C (═O) —CH ₂ —C (═O) —OAg), silver isobutyryl acetoacetate ((CH ₃ ) _{2 CH-C (= O) -CH} 2 -C (= O) -CH 2 -C (= O) -OAg), 2- acetyl pivaloyl silver acetate _{((CH 3) 3 C-} C (= O) _{-CH (-C (= O) -CH} 3) -C (= O) -OAg), 2- acetyl isobutyryl silver acetate _{((CH 3) 2 CH-} C (= O) -CH (-C ( _{= O) -CH 3) -C (} = O) -OAg), or acetone dicarboxylic silver _{(AgO-C (= O)} -CH 2 -C (= O) -CH 2 -C ( O) -OAg), preferably silver 2-methylacetoacetate, silver acetoacetate, silver 2-ethylacetoacetate, silver propionylacetate, silver isobutyrylacetate, silver pivaloylacetate, silver 2-n-butylacetoacetate, 2-benzyl Silver acetoacetate, silver benzoyl acetate, silver pivaloyl acetoacetate, silver isobutyryl acetoacetate, or silver acetone dicarboxylate is more preferable.

  The β-ketocarboxylate (1) can further reduce the concentration of the remaining raw materials and impurities in the conductor (metal silver) formed by post-treatment such as drying treatment or heating (firing) treatment. The smaller the raw materials and impurities, for example, the better the contact between the formed metal silvers, the easier the conduction, and the lower the resistivity.

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

  In this invention, (beta) -ketocarboxylate (1) may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together, the combination and ratio can be adjusted arbitrarily.

(Silver carboxylate (4))
The carboxylate silver (4) is represented by the general formula (4). In the formula, R ⁸ is an aliphatic hydrocarbon group having 1 to 19 carbon atoms, a carboxy group (—COOH) or a formula “—C (═O ) -OAg ".
Examples of the aliphatic hydrocarbon group for R ⁸ include those similar to the aliphatic hydrocarbon group for R except that the aliphatic hydrocarbon group has 1 to 19 carbon atoms. However, the aliphatic hydrocarbon group for R ⁸ preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms.

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

Silver carboxylate (4) is silver pyruvate (CH ₃ —C (═O) —C (═O) —OAg), silver acetate (CH ₃ —C (═O) —OAg), silver butyrate (CH _{3 - (CH 2) 2 -C (} = O) -OAg), isobutyric acid silver _{((CH 3) 2 CH-} C (= O) -OAg), hexane silver 2-ethylhexyl _(CH 3 - _{(CH 2} ) ₃ —CH (CH ₂ CH ₃ ) —C (═O) —OAg), silver neodecanoate (CH ₃ — (CH ₂ ) ₅ —C (CH ₃ ) ₂ —C (═O) —OAg), Shu It is preferably silver oxide (AgO—C (═O) —C (═O) —OAg) or silver malonate (AgO—C (═O) —CH ₂ —C (═O) —OAg). Also, 2 of the silver oxalate (AgO-C (= O) -C (= O) -OAg) and malonic silver _{(AgO-C (= O)} -CH 2 -C (= O) -OAg) Of the groups represented by the formula “—COOAg”, one is a group represented by the formula “—COOH” (HO—C (═O) —C (═O) —OAg, HO) _{-C (= O) -CH 2 -C} (= O) -OAg) it is also preferred.

  As in the case of silver β-ketocarboxylate (1), silver carboxylate (4) is also a conductor (metal silver) formed by post-treatment such as drying treatment or heating (firing) treatment. The concentration can be further reduced. And by using together with a reducing agent, it decomposes at a lower temperature to form metallic silver.

  In this invention, silver carboxylate (4) may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together, the combination and ratio can be adjusted arbitrarily.

In the silver ink composition, the content of silver derived from the metal silver forming material is preferably 5% by mass or more, and more preferably 10% by mass or more. By being in such a range, the formed conductive layer 12 becomes more excellent in quality. The upper limit of the silver content is not particularly limited as long as the effects of the present invention are not impaired, but it is preferably 25% by mass in consideration of handling properties and the like.
In the present specification, “silver derived from a metallic silver forming material” means silver in the metallic silver forming material blended during the production of the silver ink composition, unless otherwise specified. The concept includes both silver that subsequently constitutes a material for forming metallic silver, and silver and silver itself in the decomposition product produced by decomposition of the material for forming metallic silver after blending.

[Nitrogen-containing compounds]
The silver ink composition, in particular, when the metal silver forming material is the silver carboxylate, in addition to the metal silver forming material, an amine compound having a carbon number of 25 or less, a quaternary ammonium salt, ammonia, and the above A compound in which one or more nitrogen-containing compounds selected from the group consisting of an ammonium salt formed by reacting an amine compound or ammonia with an acid (hereinafter sometimes simply referred to as “nitrogen-containing compound”) is preferable. .
Hereinafter, an amine compound having 25 or less carbon atoms is referred to as “amine compound”, a quaternary ammonium salt having 25 or less carbon atoms is referred to as “quaternary ammonium salt”, and an ammonium salt obtained by reacting an amine compound having 25 or less carbon atoms with an acid. Is sometimes abbreviated as “ammonium salt derived from an amine compound”, and an ammonium salt formed by reacting ammonia with an acid is sometimes abbreviated as “ammonium salt derived from ammonia”.

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

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

The alkyl group constituting the monoalkylamine may be linear, branched or cyclic, and examples thereof are the same as the alkyl group in R, and are linear or branched having 1 to 19 carbon atoms. It is preferably a chain alkyl group or a cyclic alkyl group having 3 to 7 carbon atoms.
Specific examples of preferable monoalkylamine include n-butylamine, n-hexylamine, n-octylamine, n-dodecylamine, n-octadecylamine, sec-butylamine, tert-butylamine, 3-aminopentane, 3 Examples include -methylbutylamine, 2-aminooctane, 2-ethylhexylamine, and 1,2-dimethyl-n-propylamine.

  Examples of the aryl group constituting the monoarylamine include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and the like, and preferably has 6 to 10 carbon atoms.

The heteroaryl group constituting the mono (heteroaryl) amine has a heteroatom as an atom constituting the aromatic ring skeleton, and the heteroatom includes a nitrogen atom, a sulfur atom, an oxygen atom, and a boron atom. Can be illustrated. Moreover, the number of the said hetero atom which comprises an aromatic ring frame is not specifically limited, One may be sufficient and two or more may be sufficient. When there are two or more, these heteroatoms may be the same or different from each other. That is, these heteroatoms may all be the same, may all be different, or may be partially different.
The heteroaryl group may be monocyclic or polycyclic, and the number of ring members (the number of atoms constituting the ring skeleton) is not particularly limited, but is preferably a 3- to 12-membered ring.

Examples of the monoaryl group having 1 to 4 nitrogen atoms as the heteroaryl group include pyrrolyl group, pyrrolinyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrimidyl group, pyrazinyl group, pyridazinyl group, triazolyl group, and tetrazolyl group. , A pyrrolidinyl group, an imidazolidinyl group, a piperidinyl group, a pyrazolidinyl group, and a piperazinyl group are preferable, and a 3- to 8-membered ring is preferable, and a 5- to 6-membered ring is more preferable.
Examples of the monoaryl group having one oxygen atom as the heteroaryl group include a furanyl group, preferably a 3- to 8-membered ring, and more preferably a 5- to 6-membered ring.
Examples of the monoaryl group having one sulfur atom as the heteroaryl group include a thienyl group, preferably a 3- to 8-membered ring, and more preferably a 5- to 6-membered ring.
Examples of the monoaryl group having 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms as the heteroaryl group include an oxazolyl group, an isoxazolyl group, an oxadiazolyl group, and a morpholinyl group. It is preferable that it is a 5- to 6-membered ring.
Examples of the monoaryl group having 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms as the heteroaryl group include a thiazolyl group, a thiadiazolyl group, and a thiazolidinyl group, and a 3- to 8-membered ring. Preferably, it is a 5-6 membered ring.
Examples of the polyaryl group having 1 to 5 nitrogen atoms as the heteroaryl group include indolyl group, isoindolyl group, indolizinyl group, benzimidazolyl group, quinolyl group, isoquinolyl group, indazolyl group, benzotriazolyl group, tetra Examples include a zolopyridyl group, a tetrazolopyridazinyl group, and a dihydrotriazolopyridazinyl group, preferably a 7-12 membered ring, and more preferably a 9-10 membered ring.
Examples of the polyaryl group having 1 to 3 sulfur atoms as the heteroaryl group include a dithiaphthalenyl group and a benzothiophenyl group, preferably a 7 to 12 membered ring, preferably a 9 to 10 membered ring. More preferably, it is a ring.
Examples of the polyaryl group having 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms as the heteroaryl group include a benzoxazolyl group and a benzooxadiazolyl group. It is preferable that it is a 9-10 membered ring.
Examples of the polyaryl group having 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms as the heteroaryl group include a benzothiazolyl group and a benzothiadiazolyl group, and is a 7 to 12 membered ring. Preferably, it is a 9-10 membered ring.

The diamine only needs to have two amino groups, and the positional relationship between the two amino groups is not particularly limited. As the preferred diamine, in the monoalkylamine, monoarylamine or mono (heteroaryl) amine, one hydrogen atom other than the hydrogen atom constituting the amino group (—NH ₂ ) is substituted with an amino group. The thing can be illustrated.
The diamine preferably has 1 to 10 carbon atoms, and more preferable examples include ethylenediamine, 1,3-diaminopropane, and 1,4-diaminobutane.

  Examples of the secondary amine include dialkylamine, diarylamine, di (heteroaryl) amine and the like in which one or more hydrogen atoms may be substituted with a substituent.

The alkyl group that constitutes the dialkylamine is the same as the alkyl group that constitutes the monoalkylamine, and is a linear or branched alkyl group having 1 to 9 carbon atoms, or 3 to 7 carbon atoms. A cyclic alkyl group is preferred. Two alkyl groups in one molecule of dialkylamine may be the same as or different from each other.
Specific examples of preferable dialkylamine include N-methyl-n-hexylamine, diisobutylamine, and di (2-ethylhexyl) amine.

  The aryl group constituting the diarylamine is the same as the aryl group constituting the monoarylamine, and preferably has 6 to 10 carbon atoms. Two aryl groups in one molecule of diarylamine may be the same as or different from each other.

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

  Examples of the tertiary amine include trialkylamine and dialkylmonoarylamine in which one or more hydrogen atoms may be substituted with a substituent.

The alkyl group constituting the trialkylamine is the same as the alkyl group constituting the monoalkylamine, and is a linear or branched alkyl group having 1 to 19 carbon atoms, or 3 to 7 carbon atoms. The cyclic alkyl group is preferably. Further, the three alkyl groups in one molecule of trialkylamine may be the same as or different from each other. That is, all three alkyl groups may be the same, all may be different, or only a part may be different.
Preferable examples of the trialkylamine include N, N-dimethyl-n-octadecylamine and N, N-dimethylcyclohexylamine.

The alkyl group constituting the dialkyl monoarylamine is the same as the alkyl group constituting the monoalkylamine, and is a linear or branched alkyl group having 1 to 6 carbon atoms, or 3 to 3 carbon atoms. 7 is a cyclic alkyl group. Two alkyl groups in one molecule of dialkyl monoarylamine may be the same or different from each other.
The aryl group constituting the dialkyl monoarylamine is the same as the aryl group constituting the monoarylamine, and preferably has 6 to 10 carbon atoms.

In the present invention, examples of the quaternary ammonium salt include halogenated tetraalkylammonium, in which one or more hydrogen atoms may be substituted with a substituent.
The alkyl group constituting the halogenated tetraalkylammonium is the same as the alkyl group constituting the monoalkylamine, and preferably has 1 to 19 carbon atoms. Further, the four alkyl groups in one molecule of the tetraalkylammonium halide may be the same as or different from each other. That is, all four alkyl groups may be the same, all may be different, or only a part may be different.
Examples of the halogen constituting the halogenated tetraalkylammonium include fluorine, chlorine, bromine and iodine.
Specific examples of the preferred tetraalkylammonium halide include dodecyltrimethylammonium bromide.

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

  In the primary amine, secondary amine, tertiary amine and quaternary ammonium salt, the “hydrogen atom optionally substituted with a substituent” means a nitrogen atom constituting an amine moiety or an ammonium salt moiety. A hydrogen atom other than a hydrogen atom bonded to. The number of substituents at this time is not particularly limited, and may be one or two or more, and all of the hydrogen atoms may be substituted with a substituent. When the number of substituents is plural, the plural substituents may be the same as or different from each other. That is, the plurality of substituents may all be the same, may all be different, or only some may be different. Further, the position of the substituent is not particularly limited.

Examples of the substituent in the amine compound and the quaternary ammonium salt include an alkyl group, an aryl group, a halogen atom, a cyano group, a nitro group, a hydroxyl group, and a trifluoromethyl group (—CF ₃ ). Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

When the alkyl group constituting the monoalkylamine has a substituent, the alkyl group has an aryl group as a substituent, a linear or branched alkyl group having 1 to 9 carbon atoms, or a substituent Preferably, a cyclic alkyl group having 3 to 7 carbon atoms having an alkyl group having 1 to 5 carbon atoms is preferable, and specific examples of monoalkylamine having such a substituent include 2-phenylethylamine , Benzylamine, and 2,3-dimethylcyclohexylamine.
In addition, the aryl group and the alkyl group which are substituents may further have one or more hydrogen atoms substituted with halogen atoms, and as monoalkylamines having such substituents substituted with halogen atoms, And 2-bromobenzylamine. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  When the aryl group constituting the monoarylamine has a substituent, the aryl group is preferably an aryl group having 6 to 10 carbon atoms having a halogen atom as the substituent, and monoaryl having such a substituent. Specific examples of the amine include bromophenylamine. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

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

The amine compound is n-propylamine, n-butylamine, n-hexylamine, n-octylamine, n-dodecylamine, n-octadecylamine, sec-butylamine, tert-butylamine, 3-aminopentane, 3-methyl. Butylamine, 2-aminooctane, 2-ethylhexylamine, 2-phenylethylamine, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, N-methyl-n-hexylamine, diisobutylamine, N-methylbenzylamine Di (2-ethylhexyl) amine, 1,2-dimethyl-n-propylamine, N, N-dimethyl-n-octadecylamine or N, N-dimethylcyclohexylamine is preferred.
As will be described later, when the silver ink composition is prepared by supplying carbon dioxide, the components in the silver ink composition (second mixture) are more uniformly dispersed during the carbon dioxide supply. In view of stable quality, the amine compound preferably has a branched alkyl group.

(Ammonium salts derived from amine compounds)
In the present invention, the ammonium salt derived from the amine compound is an ammonium salt obtained by reacting the amine compound with an acid, and the acid may be an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid, or an organic acid such as acetic acid. However, the type of acid is not particularly limited.
Examples of the ammonium salt derived from the amine compound include, but are not limited to, n-propylamine hydrochloride, N-methyl-n-hexylamine hydrochloride, N, N-dimethyl-n-octadecylamine hydrochloride and the like. .

(Ammonium salt derived from ammonia)
In the present invention, the ammonium salt derived from ammonia is an ammonium salt formed by reacting ammonia with an acid, and examples of the acid include the same ones as in the case of the ammonium salt derived from the amine compound.
Examples of the ammonium salt derived from ammonia include ammonium chloride, but are not limited thereto.

In the present invention, the amine compound, the quaternary ammonium salt, the ammonium salt derived from the amine compound and the ammonium salt derived from ammonia may be used singly or in combination of two or more. . When using 2 or more types together, the combination and ratio can be adjusted arbitrarily.
And as said nitrogen-containing compound, you may use individually by 1 type selected from the group which consists of said amine compound, quaternary ammonium salt, ammonium salt derived from an amine compound, and ammonium salt derived from ammonia, More than one species may be used in combination. When using 2 or more types together, the combination and ratio can be adjusted arbitrarily.

In the silver ink composition, the compounding amount of the nitrogen-containing compound is preferably 0.4 to 15 mol, and more preferably 0.8 to 5 mol, per mol of the silver carboxylate.
By defining the blending amount of the nitrogen-containing compound as described above, the silver ink composition is further improved in stability and the quality of the conductive layer (conductor, metallic silver) is further improved. Furthermore, the conductive layer can be formed more stably without performing heat treatment at a high temperature.

[Reducing agent]
The silver ink composition preferably contains a reducing agent in addition to the metal silver forming material. By blending a reducing agent, the silver ink composition can more easily form metallic silver. For example, a conductive layer (conductor, metallic silver) having sufficient conductivity can be formed even by heat treatment at a low temperature. .

The reducing agent is one or more reducing compounds selected from the group consisting of oxalic acid, hydrazine and a compound represented by the following general formula (5) (hereinafter sometimes abbreviated as “compound (5)”). (Hereinafter, sometimes simply abbreviated as “reducing compound”).
HC (= O) -R ²¹ (5)
(In the formula, R ²¹ represents an alkyl group having 20 or less carbon atoms, an alkoxy group, an N, N-dialkylamino group, a hydroxyl group, or an amino group.)

(Reducing compounds)
The reducing compound is one or more selected from the group consisting of oxalic acid (HOOC-COOH), hydrazine (H ₂ N—NH ₂ ) and the compound represented by the general formula (5) (compound (5)). belongs to. That is, the reducing compound to be blended may be only one kind, or two or more kinds. When two or more kinds are used in combination, the combination and ratio can be arbitrarily adjusted.

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

The alkoxy group having 20 or less carbon atoms in R ²¹ has 1 to 20 carbon atoms, and examples thereof include monovalent groups formed by bonding the alkyl group in R ^{21 to} an oxygen atom.

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

As the reducing compound, hydrazine may be a monohydrate (H ₂ N—NH ₂ .H ₂ O).

The reducing compound includes formic acid (HC (═O) —OH), methyl formate (HC—═O) —OCH ₃ ), ethyl formate (HC—═O) —OCH ₂ CH ₃ ). , Butyl formate (HC (═O) —O (CH ₂ ) ₃ CH ₃ ), propanal (HC (═O) —CH ₂ CH ₃ ), butanal (HC (═O) — ( CH _{2) 2} CH _3), hexanal (H-C (= O) - (CH 2) 4 CH 3), formamide _{(H-C (= O)} -NH 2), N, N- dimethylformamide (H- C (═O) —N (CH ₃ ) ₂ ) or oxalic acid is preferred.

  In the silver ink composition, the compounding amount of the reducing agent is preferably 0.04 to 3.5 mol, and preferably 0.06 to 2.5 mol per 1 mol of the metal silver forming material. Is more preferable. By defining in this way, the silver ink composition can form a conductive layer more easily and more stably.

[alcohol]
The silver ink composition may further contain an alcohol in addition to the metal silver forming material.

  The alcohol is preferably an acetylene alcohol represented by the following general formula (2) (hereinafter sometimes abbreviated as “acetylene alcohol (2)”).

（式中、Ｒ’及びＲ’’は、それぞれ独立に炭素数１〜２０のアルキル基、又は１個以上の水素原子が置換基で置換されていてもよいフェニル基である。）

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

(Acetylene alcohol (2))
The acetylene alcohol (2) is represented by the general formula (2).
In the formula, R ′ and R ″ are each independently an alkyl group having 1 to 20 carbon atoms, or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent.
The alkyl group having 1 to 20 carbon atoms in R ′ and R ″ may be linear, branched or cyclic, and when it is cyclic, it may be monocyclic or polycyclic. Examples of the alkyl group in R ′ and R ″ include the same alkyl groups as in R.

  Examples of the substituent in which the hydrogen atom of the phenyl group in R ′ and R ″ may be substituted include a saturated or unsaturated monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms, the aliphatic carbonization Examples thereof include a monovalent group formed by bonding a hydrogen group to an oxygen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, a cyano group, a phenoxy group, and the like, and the hydrogen atom of the phenyl group in R may be substituted. This is the same as the substituent. And the number and position of a substituent are not specifically limited, When there are two or more substituents, these several substituents may mutually be same or different.

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

  Examples of preferable acetylene alcohol (2) include 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-butyn-3-ol, and 3-methyl-1-pentyn-3-ol.

  When acetylene alcohol (2) is used, the amount of acetylene alcohol (2) in the silver ink composition is preferably 0.03 to 0.7 mole per mole of the metal silver forming material. 0.05 to 0.3 mol is more preferable. By setting it as such a range, stability of a silver ink composition improves more.

  The said alcohol may be used individually by 1 type, and may use 2 or more types together. When two or more kinds are used in combination, the combination and ratio can be arbitrarily adjusted.

The silver ink composition may contain other components other than the metallic silver forming material, nitrogen-containing compound, reducing agent, and alcohol.
The other components in the silver ink composition can be arbitrarily selected according to the purpose, and are not particularly limited. Preferred examples thereof include solvents other than alcohol, and can be arbitrarily selected according to the type and amount of compounding components. it can.
One of these other components in the silver ink composition may be used alone, or two or more thereof may be used in combination. When two or more kinds are used in combination, the combination and ratio can be arbitrarily adjusted.
In the silver ink composition, the ratio of the blending amount of the other components to the total blending component is preferably 10% by mass or less, and more preferably 5% by mass or less.

  All of the components in the silver ink composition may be dissolved, or some or all of the components may not be dissolved, but the components that are not dissolved are preferably dispersed uniformly.

The silver ink composition is obtained by blending components other than the metallic silver forming material and the metallic silver forming material.
At the time of blending each component, all the components may be added and then mixed, or some components may be mixed while being sequentially added, or all components may be mixed while being sequentially added. Good. However, in this invention, it is preferable to mix | blend a reducing agent by dripping, and exists in the tendency which can further reduce the surface roughness of metal silver by suppressing the fluctuation | variation of dripping speed.
The mixing method is not particularly limited, and may be appropriately selected from known methods such as a method of mixing by rotating a stirrer or a stirring blade, a method of mixing using a mixer, a method of adding ultrasonic waves, and the like. .

The temperature at the time of blending is not particularly limited as long as each blending component does not deteriorate, but is preferably −5 to 60 ° C.
The blending time (mixing time) is not particularly limited as long as each blending component does not deteriorate, but it is preferably 5 minutes to 5 hours.

[carbon dioxide]
The silver ink composition may be further supplied with carbon dioxide. Such a silver ink composition has a high viscosity. For example, a flexographic printing method, a screen printing method, a gravure printing method, a gravure offset printing method, a pad printing method, etc. Suitable for application.

Carbon dioxide may be supplied at any time during the production of the silver ink composition.
In the present invention, for example, carbon dioxide is supplied to the first mixture in which the metal silver forming material and the nitrogen-containing compound are blended to form a second mixture, and if necessary, the second mixture It is preferable that a silver ink composition is produced by further blending the reducing agent with the mixture. Moreover, when mix | blending the said alcohol or another component, these can be mix | blended at the time of manufacture of any one or both of a 1st mixture and a 2nd mixture, and can be arbitrarily selected according to the objective.

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

  The first mixture may have all of the compounding components dissolved, or may be in a state of being dispersed without dissolving some of the components, but preferably all of the compounding components are dissolved and dissolved. It is preferable that the components not dispersed are uniformly dispersed.

  Although the compounding temperature at the time of manufacture of a 1st mixture is not specifically limited unless each compounding component deteriorates, it is preferable that it is -5-30 degreeC. Moreover, what is necessary is just to adjust a compounding time suitably according to the kind of compounding component, and the temperature at the time of a compounding, For example, it is preferable that it is 0.5 to 12 hours.

Carbon dioxide (CO ₂ ) supplied to the first mixture may be either gaseous or solid (dry ice), or both gaseous and solid. By supplying carbon dioxide, it is estimated that this carbon dioxide dissolves in the first mixture and acts on the components in the first mixture, thereby increasing the viscosity of the obtained second mixture.

  Carbon dioxide gas may be supplied by various known methods of blowing gas into the liquid, and a suitable supply method may be selected as appropriate. For example, a method in which one end of a pipe is immersed in the first mixture, the other end is connected to a carbon dioxide gas supply source, and the carbon dioxide gas is supplied to the first mixture through the pipe. At this time, the carbon dioxide gas may be supplied directly from the end of the pipe. For example, a plurality of voids that can serve as gas flow paths, such as a porous one, are provided to diffuse the introduced gas. A gas diffusion member that can be discharged as minute bubbles may be connected to the end of the pipe, and the carbon dioxide gas may be supplied through the gas diffusion member. Moreover, you may supply a carbon dioxide gas, stirring the 1st mixture by the method similar to the time of manufacture of a 1st mixture. By doing in this way, carbon dioxide can be supplied efficiently.

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

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

  The temperature of the first mixture at the time of supplying carbon dioxide gas is preferably 5 to 70 ° C, more preferably 7 to 60 ° C, and particularly preferably 10 to 50 ° C. When the temperature is equal to or higher than the lower limit value, carbon dioxide can be supplied more efficiently, and when the temperature is equal to or lower than the upper limit value, a silver ink composition having better quality with fewer impurities can be obtained.

  The flow rate and supply time of the carbon dioxide gas, and the temperature at the time of supplying the carbon dioxide gas may be adjusted to a suitable range while considering each value. For example, even if the temperature is set lower, the carbon dioxide gas flow rate is set higher, the carbon dioxide gas supply time is set longer, or both are performed efficiently. Can supply carbon. Moreover, even if the flow rate of carbon dioxide gas is set to a small value, the carbon dioxide gas can be efficiently produced by increasing the temperature, setting the carbon dioxide gas supply time longer, or both. Can supply. That is, a silver ink of good quality can be obtained by flexibly combining the numerical values in the above numerical range exemplified as the flow rate of carbon dioxide gas and the temperature at the time of carbon dioxide gas supply while considering the supply time of carbon dioxide gas. A composition is obtained efficiently.

The carbon dioxide gas is preferably supplied while stirring the first mixture. By doing in this way, the supplied carbon dioxide gas diffuses more uniformly in the first mixture, and carbon dioxide can be supplied more efficiently.
The stirring method at this time may be the same as in the case of the mixing method at the time of producing the above silver ink composition not using carbon dioxide.

The supply of dry ice (solid carbon dioxide) may be performed by adding dry ice to the first mixture. The total amount of dry ice may be added all at once, or may be added stepwise (continuously across a time zone during which no addition is performed).
What is necessary is just to adjust the usage-amount of dry ice in consideration of the supply amount of said carbon dioxide gas.
During and after the addition of dry ice, the first mixture is preferably stirred. For example, the first mixture is preferably stirred in the same manner as in the production of the above silver ink composition without using carbon dioxide. By doing in this way, carbon dioxide can be supplied efficiently.
The temperature at the time of stirring may be the same as that at the time of supplying carbon dioxide gas. Moreover, what is necessary is just to adjust stirring time suitably according to stirring temperature.

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

If necessary, the second mixture may be further blended with one or more selected from the group consisting of the reducing agent, alcohol and other components to form a silver ink composition.
The silver ink composition at this time can be manufactured by the same method as the above silver ink composition not using carbon dioxide except that the blending components are different. The obtained silver ink composition may have all of the compounding components dissolved therein or may be in a state where some of the components are dispersed without dissolving, but all of the compounding components are dissolved. Preferably, the undissolved component is preferably dispersed uniformly.

  The temperature at the time of blending the reducing agent is not particularly limited as long as each blended component does not deteriorate, but is preferably −5 to 60 ° C. Moreover, what is necessary is just to adjust a compounding time suitably according to the kind of compounding component, and the temperature at the time of a compounding, For example, it is preferable that it is 0.5 to 12 hours.

  As described above, the other components may be blended during the production of either the first mixture or the second mixture, or may be blended during the production of both. That is, in the process of producing the silver ink composition through the first mixture and the second mixture, the ratio of the blended amount of the other components to the total amount of blended components other than carbon dioxide ([other components (mass)] / [Formation material of metallic silver, nitrogen-containing compound, reducing agent, alcohol, and other components (mass)] × 100) is preferably 10% by mass or less, and more preferably 5% by mass or less. , 0 mass, that is, the silver ink composition exhibits its effect sufficiently even if other components are not blended.

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

  For example, when a reducing agent is blended, the resulting blend (silver ink composition) tends to generate heat relatively easily. And when the temperature at the time of mixing | blending of a reducing agent is high, since this compounding will be in the state similar to the time of the heat processing of the silver ink composition mentioned later, by the decomposition | disassembly acceleration | stimulation effect | action of the said metal silver formation material by a reducing agent It is presumed that the formation of metal silver may be started in at least a part of the metal silver forming material. Such a silver ink composition containing metallic silver forms a conductive layer (conductor) by performing post-treatment under milder conditions than the silver ink composition not containing metallic silver during the formation of the conductive layer. There are things you can do. In addition, even when the amount of the reducing agent is sufficiently large, the conductive layer may be formed by performing post-treatment under the same mild conditions. In this way, by adopting conditions that promote the decomposition of the metal silver forming material, the conductive layer can be subjected to post-treatment, such as a heat treatment at a lower temperature, or a drying treatment at normal temperature without performing the heat treatment. Can be formed. Moreover, the silver ink composition containing such metal silver can be handled in the same manner as the silver ink composition not containing metal silver, and the handleability is not particularly inferior.

A silver ink composition can be made to adhere on a base material by well-known methods, such as a printing method, the apply | coating method, and the immersion method, for example.
Examples of the printing method include screen printing method, flexographic printing method, offset printing method, dip printing method, ink jet printing method, dispenser printing method, gravure printing method, gravure offset printing method, pad printing method and the like.
Examples of the coating method include spin coaters, air knife coaters, curtain coaters, die coaters, blade coaters, roll coaters, gate roll coaters, bar coaters, rod coaters, gravure coaters, and other methods such as wire bars. It can be illustrated.

  In the step of forming the conductive layer, the amount of the silver ink composition to be deposited on the substrate 11 or the blending amount of the metal silver forming material in the silver ink composition is adjusted. The thickness can be adjusted.

  When the silver ink composition deposited on the substrate 11 is dried, it may be performed by a known method, for example, under normal pressure, reduced pressure, or blowing conditions, It may be performed in any of an inert gas atmosphere. Also, the drying temperature is not particularly limited, and may be either heat drying or room temperature drying. As a preferable drying method when the heat treatment is unnecessary, a method of drying in the atmosphere at 18 to 30 ° C. can be exemplified.

  When the silver ink composition deposited on the substrate 11 is heated (baked), the conditions may be adjusted as appropriate according to the type of compounding component of the silver ink composition. Usually, it is preferable that heating temperature is 60-200 degreeC, and it is more preferable that it is 70-180 degreeC. Although what is necessary is just to adjust a heating time according to heating temperature, Usually, it is preferable that it is 0.2 to 12 hours, and it is more preferable that it is 0.4 to 10 hours. Among the silver carboxylates, silver β-ketocarboxylate (1) is decomposed at a low temperature without using a reducing agent or the like known in the art, unlike metal silver forming materials such as silver oxide. Reflecting such decomposition temperature, the silver ink composition can form metallic silver at an extremely lower temperature than the conventional one as described above.

  The method for heat treatment of the silver ink composition is not particularly limited, and for example, it can be performed by heating with an electric furnace, heating with a thermal head, heating with far infrared irradiation, or the like. In addition, the heat treatment of the silver ink composition may be performed in the air or in an inert gas atmosphere. And you may carry out under any of normal pressure and pressure reduction.

  When the silver ink composition is used, the conductive layer 12 is a layer made of a conductor formed by the post-treatment of the silver ink composition, and contains metal silver as a main component. Here, “having metallic silver as a main component” means that the ratio of metallic silver is high enough to be regarded as consisting of metallic silver apparently, for example, the ratio of metallic silver in the conductor Is preferably 99% by mass or more.

Next, a method for forming the overcoat layer 13 will be described in more detail.
The overcoat layer 13 is a desired composition on the base material 11 so as to cover the conductive layer 12 as described above by preparing a coating composition in which the above coating material and CNF are blended. It is preferable to form the overcoat layer 13 by adhering to (by laminating on the conductive layer 12) and performing a post-treatment as necessary.
Each of the coating material and CNF in the coating composition may be one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio can be arbitrarily adjusted.

  The coating material is preferably a resin forming material (monomer or base resin), and more preferably one or more selected from the group consisting of urethane acrylate resins and epoxy acrylate resins as described above. As described above, the urethane acrylate resin is preferably an isocyanate skeleton-containing urethane acrylate resin, and more preferably an alicyclic isocyanate skeleton-containing urethane acrylate resin. The epoxy acrylate resin is preferably a bisphenol A type epoxy acrylate resin.

When the coating material is a resin forming material, the coating composition is preferably a mixture of a resin forming material, an initiator (polymerization initiator) and a solvent in addition to CNF.
The initiator may be appropriately selected from known ones according to the type of resin forming material, and is not particularly limited.
The solvent may be any solvent that does not inhibit the polymerization reaction. Cyclohexanone, toluene, ethanol, 2-propanol, propylene glycol monomethyl ether acetate (PGMAc), 3,5,5-trimethyl-2-cyclohexen-1-one ( What is necessary is just to select suitably from well-known things, such as isophorone) and 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol).

CNF blended at the time of preparing the coating composition is a fibrous substance (fibril) made of cellulose or a derivative thereof, and known substances such as those produced by various plants and bacteria can be used.
The plant is not particularly limited, and preferable examples include wood, wheat, rice, corn, cotton, sugar cane, straw, bamboo, potato, and cassava.

The average fiber width (diameter) of CNF is preferably 3.5 to 100 nm, and by being in such a range, the effect of suppressing the warp of the laminate becomes higher.
The average fiber length of CNF is preferably 0.8 μm or more, and more preferably 0.8 to 8 μm. The effect which suppresses the curvature of a laminated body becomes higher because the average fiber length of CNF is more than the said lower limit. Moreover, CNF is easily obtained by the method mentioned later because the average fiber length of CNF is below the said upper limit.
In addition, the average fiber width and the average fiber length of CNF, for example, the average value of the fiber width and the fiber length is calculated for 30 CNF arbitrarily selected in the CNF imaging data with a scanning electron microscope (SEM). Is required.

  Since the CNF has a small linear expansion coefficient (thermal expansion coefficient), as described above, the difference in the linear expansion coefficient between the overcoat layer 13 and the substrate 11 is small, and the temperature of the laminate is increased with time. Even if a difference arises, the curvature of the whole laminated body is suppressed notably. From the point that the effect of suppressing such warpage becomes higher, CNF preferably has a linear expansion coefficient of 0.1 to 5 ppm / ° C, and more preferably 0.1 to 3.

  CNF can be produced by a known method. For example, when obtaining CNF from a plant, using a homogenizer or grinder such as an ultrahigh pressure homogenizer, and a disaggregation step of stirring a plant raw material together with water to obtain a mixture of plant fibers and dispersion contained in the cell wall, CNF is obtained by the manufacturing method which has the defibrating process which loosens the fiber bundle of the obtained plant fiber.

  In the coating composition, the ratio of the amount of the resin forming material to the total amount of the compounding components is preferably 10 to 60% by mass, and more preferably 15 to 40% by mass. When the blending amount of the resin forming material is equal to or higher than the lower limit value, the protective action of the conductive layer by the overcoat layer is further increased, and when the blending amount of the resin forming material is equal to or lower than the upper limit value, the conductive layer The protective effect and the effect of suppressing the warpage of the laminate are more balanced.

  In the coating composition, the ratio of the amount of CNF to the total amount of the components is preferably 15 to 65% by mass, and more preferably 20 to 45% by mass. When the blending amount of CNF is equal to or higher than the lower limit value, the effect of suppressing the warpage of the laminate is further increased, and when the blending amount of CNF is equal to or less than the upper limit value, the protective effect of the conductive layer and the warpage of the laminate body are increased. The suppression effect is further balanced.

In the coating composition, the compounding amount of the initiator is preferably 0.01 to 0.1 times by mass, and 0.02 to 0.08 times by mass with respect to the compounding amount of the resin forming material. Is more preferable.
In the coating composition, the blending amount of the solvent (including the dispersion solvent when used) is preferably 20 to 60% by mass, and more preferably 30 to 50% by mass.

The coating composition may be formed by blending other components other than the resin forming material, CNF, initiator and solvent.
The other components in the coating composition can be arbitrarily selected according to the purpose and are not particularly limited.
The other components in the coating composition may be used singly or in combination of two or more. When two or more kinds are used in combination, the combination and ratio can be arbitrarily adjusted.
In the coating composition, the ratio of the amount of the other components to the total amount of the components is preferably 10% by mass or less, and more preferably 5% by mass or less.

The coating composition includes the coating material, CNF, and components other than these (coating material and CNF) as necessary (for example, an initiator, a solvent, etc. when the resin forming material is used as the coating material). It is obtained by blending.
At the time of blending each component, all the components may be added and then mixed, or some components may be mixed while being sequentially added, or all components may be mixed while being sequentially added. Good. Except for the difference in the blending components, the blending method and blending conditions of each component in the coating composition can be the same as in the silver ink composition.

In particular, in the present invention, CNF may be added as a solid in the production of the coating composition, but CNF is obtained from the point that a coating composition in which the blended components are more uniformly dispersed or dissolved is obtained. It is preferable to prepare a CNF dispersion in which is dispersed in a solvent in advance and add this CNF dispersion.
The CNF dispersion may be obtained by dispersing CNF in a dispersion solvent (dispersion medium) by a known method. For example, the liquid obtained by the defibrating step by the above-described CNF production method may be used as it is. Or what was post-processed as needed may be used as a CNF dispersion.
The dispersion solvent of the CNF dispersion may be any solvent that does not inhibit the polymerization reaction, and examples include those mentioned above as the solvent used in combination with the initiator.

  The coating composition can be attached to a desired location on the substrate 11 in the same manner as the silver ink composition.

  In the step of forming the overcoat layer, by adjusting the amount of the coating composition to be adhered to a desired location on the substrate 11, or the blending amount of the coating material and CNF in the coating composition, The thickness of the overcoat layer 13 can be adjusted.

  When the coating composition deposited on the substrate 11 is post-treated, it may be performed by a known method. For example, when the coating material is a resin forming material, ultraviolet irradiation treatment or heat treatment is performed. Can be done.

  When the laminate according to the present invention is a laminate in which an adhesion layer is provided between the substrate and the conductive layer (for example, the laminate 2 shown in FIG. 2), the laminate has, for example, an adhesion layer on the substrate. It can be manufactured by a manufacturing method including a step of forming, a step of forming a conductive layer on the adhesion layer, and a step of forming an overcoat layer on the conductive layer.

[Step of forming an adhesion layer on a substrate]
For the adhesion layer, for example, a composition for forming the adhesion layer (hereinafter sometimes abbreviated as “composition for adhesion layer”) is prepared, and this is adhered on the substrate, and later as necessary. It can be formed by processing.

The composition for the adhesion layer is obtained by the same method as in the case of the silver ink composition or the coating composition except that the blending components are different, and is applied on the substrate in the same manner as the silver ink composition. Can be attached.
The post-treatment at the time of forming the adhesion layer may be appropriately selected according to the type of the composition for the adhesion layer. For example, as the material for forming the adhesion layer, the same as the resin forming material at the time of forming the overcoat layer In the case of using, UV irradiation treatment or heat treatment may be performed.

[Step of forming conductive layer on adhesion layer, step of forming overcoat layer on conductive layer]
After the step of forming the adhesion layer on the base material, for example, a base material on which an adhesion layer is formed is used instead of the base material on which the adhesion layer is not formed, such as the base material 11 shown in FIG. Except for this, the conductive layer can be formed on the adhesion layer by the same method as the step of forming the conductive layer on the substrate described with reference to FIG.
Then, as shown in FIG. 3, the adhesive layer is not formed, and instead of the base material on which the conductive layer is formed, the base material on which the adhesive layer and the conductive layer are formed is used. The overcoat layer can be formed on the conductive layer by the same method as that described with reference to the step of forming the overcoat layer on the conductive layer.

  In the laminate according to the present invention, as described above, the protective effect of the conductive layer by the overcoat layer is high, and the alteration and breakage of the conductive layer are highly suppressed. Moreover, even if a temperature difference occurs with time, the warpage of the entire laminate is remarkably suppressed. As described above, the laminate according to the present invention is extremely useful as a component of various electronic devices because the quality and structure are stably maintained over a long period of time. For example, the laminated body can be used as a circuit board by using the patterned conductive layer as a circuit. Further, by using the patterned conductive layer as an antenna, the laminate can be used as an antenna structure, and the configuration is the same as that of a known data transmitter / receiver except that the antenna structure is used. Thus, a data receiving / transmitting body can be obtained. For example, in the laminated body 1 shown in FIG. 1, a non-contact type data receiving / transmitting body can be formed by providing an IC chip electrically connected to the conductive layer 12 on the substrate 11 to form an antenna portion.

<< Electronic equipment >>
The electronic apparatus according to the present invention is characterized in that the laminate is used and the base material is provided as a casing, for example, except that at least a part of the casing is constituted by the base material in the laminate. The configuration can be similar to that of a known electronic device. For example, the laminate can be used as a circuit board, and a mobile phone can be configured by combining a voice input unit, a voice output unit, an operation switch, a display unit, and the like in addition to the laminate. In addition, the conductive layer can be formed at a low temperature, and a wide variety of materials such as a base material can be selected. Therefore, the degree of freedom in design is greatly improved, and a more rational structure can be obtained.
For example, in the laminated body shown in FIG. 1, an example is shown in which the conductive layer is covered with an overcoat layer on the base material so that there is no exposed portion. The conductive layer inside may have an exposed portion without being covered with the overcoat layer for connection to other components.
The electronic device according to the present invention can maintain stable performance over a long period of time.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.

[Example 1]
<Manufacture of laminates>
(Manufacture of silver ink composition)
By adding silver 2-methylacetoacetate to 2-ethylhexylamine (1 molar amount relative to 2-methylacetoacetate silver described later) and stirring for 15 minutes so that the liquid temperature becomes 50 ° C. or lower, I got a thing. To this liquid, formic acid (0.8-fold molar amount with respect to silver 2-methylacetoacetate) was added dropwise over 30 minutes so that the temperature of the reaction solution was 50 ° C. or lower. After the formic acid was dropped, the reaction solution was further stirred at 25 ° C. for 1.5 hours to obtain a silver ink composition. Table 1 shows the mixing ratio of each component. In Table 1, “nitrogen-containing compound (molar ratio)” means the compounding amount (number of moles) of nitrogen-containing compound per mol of silver carboxylate ([number of moles of nitrogen-containing compound] / [silver carboxylate] Number of moles]). Similarly, the “reducing agent (molar ratio)” is the reductant compounding amount (mole number) per mol of silver carboxylate ([molar number of reducing agent] / [molar number of silver carboxylate]). means.

(Manufacture of adhesive layer composition)
UV curable polycarbonate skeleton-containing urethane acrylate resin (Nippon Gosei Co., Ltd. “UV3310B”), cyclohexanone (manufactured by Wako Pure Chemical Industries, Ltd.), and photoinitiator (manufactured by BASF Co., Ltd. “Irgacure”) 127 ”) was added and stirred at room temperature (25 ° C.) for 10 minutes to prepare an adhesive layer composition. In addition, the compounding quantity currently displayed by the mass% unit in Table 2 means the ratio of each compounding component with respect to the total amount of a compounding component.

(Manufacturing CNF)
CNF was produced by the following method with reference to the method described in the document “Masaya Nogi et al, Nanoscale, 2013, 5, 4395-4399”.
Using a stirrer (“ABS-BU” manufactured by Vita Mix), slush pulp (manufactured by Nippon Paper Chemical Co., Ltd.) in a state in which hardwood sulfite pulp is suspended at a concentration of 2% by mass is stirred at 3700 rpm for 5 minutes. did.
Next, the obtained agitated product (suspension) was diluted with water so that the concentration of the pulp was 0.5% by mass, and using an ultra-high pressure homogenizer (“HJP-25005E” manufactured by Sugino Machine Co.), This diluted suspension was made to collide with a ceramic ball from a nozzle having a diameter of 0.15 mm at a pressure of 245 MPa, and this operation was repeated 50 times.
Subsequently, the obtained suspension was subjected to suction filtration, and the obtained solid content was washed with ethanol to obtain CNF.
Table 4 shows properties such as physical properties of the obtained CNF. In addition, the physical properties of CNF in Table 4 were measured by the following methods.

(Measurement of average fiber width and average fiber length)
It calculated | required by the method described above using SEM.

(Measurement of linear expansion coefficient)
At the time of suction filtration at the time of CNF production, CNF remaining on the filter paper was left as it was at room temperature for 24 hours, and then peeled off from the filter paper to obtain a CNF sheet. And according to JIS K7197 "Linear expansion coefficient test method by thermomechanical analysis of plastics" using a thermomechanical measuring device ("TMA Q400" manufactured by TA Instruments), the obtained CNF sheet at 50 to 150 ° C. The linear expansion coefficient was measured.

(Measurement of Young's modulus)
The Young's modulus of the CNF sheet was measured using a dynamic viscoelasticity measuring device (“DMA Q800” manufactured by TA Instruments).

(Measurement of heat transfer coefficient)
The heat transfer coefficient of the CNF sheet was measured by a hot disk method in accordance with ISO / CD 22007-2 using a hot disk method thermophysical property measuring apparatus (“TPS 2500 S” manufactured by Kyoto Electronics Industry Co., Ltd.).

(Manufacture of coating composition)
CNF and ethanol were mixed so that the blending amounts shown in Table 3 were obtained, and CNF was sufficiently dispersed. Next, an alicyclic isocyanate skeleton-containing urethane acrylate resin (“U-6LPA” manufactured by Shin-Nakamura Chemical Co., Ltd.), cyclohexanone (Wako Pure Chemical Industries, Ltd.) so as to have the blending amounts shown in Table 3 with respect to the total amount of the obtained dispersion. And a photoinitiator (“Irgacure 127” manufactured by BASF) were added and stirred at room temperature (25 ° C.) for 10 minutes to prepare a coating composition. In addition, the compounding quantity currently displayed by the mass% unit in Table 3 means the ratio of each compounding component with respect to the total amount of a compounding component. Table 5 shows properties such as physical properties of the resin used. In Table 5, “viscosity” is a value measured using a rheometer “MCR301” manufactured by Anton Paar.

(Manufacture of laminates)
Using a bar coater (# 01), the adhesive layer composition obtained above was applied onto one main surface (surface) of a substrate (thickness 2 mm) made of polycarbonate / ABS resin alloy, and then placed in the oven. After the film was dried at 80 ° C. for 5 minutes, the coating film dried using an ozone-less high-pressure mercury lamp was irradiated with ultraviolet rays at a dose of 100 mJ / cm ² , and an adhesion layer was formed on the entire surface of the substrate. (Thickness 1 μm) was formed.

  Next, after applying the silver ink composition obtained above on the adhesion layer by a screen printing method, this is heated (baked) in an oven at 80 ° C. for 2 hours to form a silver layer as a conductive layer. (Thickness of 1 to 2 μm) was formed on the surface of the adhesion layer by patterning in a line shape so as to have a line width of 0.5 mm and a line length of 30 mm.

Next, the coating composition obtained above is applied onto the adhesive layer on which the conductive layer is formed by screen printing, and dried in an oven at 80 ° C. for 5 minutes, and then an ozone-less high-pressure mercury lamp is used. The coated and dried film is irradiated with ultraviolet rays at a dose of 500 mJ / cm ² (that is, a recommended dose), and the entire surface of the adhesion layer on which the conductive layer is formed (the surface of the conductive layer and the conductive layer are formed). An overcoat layer (thickness of 1 μm) was formed on the exposed surface of the adhesive layer that was not formed to obtain a laminate.

<Evaluation of laminate>
(Evaluation of warpage of laminate and hardness of overcoat layer)
About the obtained laminated body, the magnitude | size of curvature was measured based on JISX6305-01, and hardness (pencil hardness) was measured about the overcoat layer based on JISK5600-5-4. The results are shown in Table 6.

[Example 2]
<Manufacture and evaluation of laminate>
As shown in Table 3, in place of the alicyclic isocyanate skeleton-containing urethane acrylate resin, a bisphenol A type epoxy acrylate resin ("EB3700" manufactured by Daicel Chemical Industries, Ltd.) was used, and the ultraviolet irradiation dose during the overcoat layer formation was 800 mJ / cm. ^{2 A} laminate was produced and evaluated in the same manner as in Example 1 except that the recommended dose was set. The results are shown in Table 6. Table 5 shows properties such as physical properties of the resin used.

[Comparative Example 1]
<Manufacture and evaluation of laminate>
As shown in Table 3, a laminate was produced in the same manner as in Example 1 except that CNF and ethanol were not used, and the compounding amounts of alicyclic isocyanate skeleton-containing urethane acrylate resin, cyclohexanone and photoinitiator were changed. ,evaluated. The results are shown in Table 6.

[Comparative Example 2]
<Manufacture and evaluation of laminate>
As shown in Table 3, a laminate was produced in the same manner as in Example 2 except that CNF and ethanol were not used, and the blending amounts of bisphenol A type epoxy acrylate resin, cyclohexanone and photoinitiator were changed, and evaluated. did. The results are shown in Table 6.

[Comparative Example 3]
<Manufacture and evaluation of laminate>
As shown in Table 3, a laminate was produced and evaluated in the same manner as in Example 1 except that glass fiber was used instead of CNF as the fiber. The results are shown in Table 6. Table 4 shows properties such as physical properties of the glass fiber used. In addition, the physical property etc. of the glass fiber in Table 4 were measured by the same method as the case of CNF.

[Comparative Example 4]
<Manufacture and evaluation of laminate>
As shown in Table 3, laminates were produced and evaluated in the same manner as in Example 2 except that glass fibers were used instead of CNF. The results are shown in Table 6. The same glass fiber as in Comparative Example 3 was used.

  As is clear from the above results, in Examples 1 and 2 in which the alicyclic isocyanate skeleton-containing urethane acrylate resin or bisphenol A type epoxy acrylate resin was used as the base resin and CNF was used as the fiber, the overcoat layer had a sufficient hardness ( The conductive layer had a protective action), and the warpage of the laminate was also slightly suppressed.

On the other hand, in Comparative Examples 1 and 2 in which no fiber was used, the overcoat layer had sufficient hardness by using the alicyclic isocyanate skeleton-containing urethane acrylate resin or bisphenol A type epoxy acrylate resin as the base resin. However, the warpage of the laminate was large.
Moreover, in Comparative Examples 3 to 4 using glass fibers as the fibers, the warpage of the laminate was slightly suppressed, but the hardness of the overcoat layer was low. This is because the transparency of the glass fiber is low and the refractive index difference between the glass fiber and the base resin is large, so that when the coating composition is cured by irradiating the ultraviolet ray, the irradiated ultraviolet ray is a composition. It is presumed that the film did not spread evenly and unevenness in curing occurred.

  The present invention can be used for any laminate including a conductive layer on a substrate, and is particularly suitable for use in an electronic device such as a data receiver / transmitter or a mobile phone.

  1, 2 ... laminate, 11 ... base material, 11a ... surface of base material, 12 ... conductive layer, 12b ... back surface of conductive layer, 13 ... overcoat layer, 14 ... Adhesion layer, 14a ... Surface of adhesion layer

Claims (2)

Substrate, conductive layer and the overcoat layer is a laminated body ing are laminated in this order, said substrate an electronic apparatus having a housing,
The pencil hardness of the overcoat layer by a hardness test according to JIS K 5600-5-4 is HB or more,
The electronic device, wherein the overcoat layer contains cellulose nanofibers. The electronic device according to claim 1, wherein the overcoat layer is formed using at least one selected from the group consisting of a urethane acrylate resin and an epoxy acrylate resin.

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