JP6515418B2 - Laminate and electronic device - Google Patents

Description

  The present invention relates to a laminate in which a silver layer is provided on a substrate via a receiving layer, and an electronic device using the laminate.

  A laminate in which a silver layer is provided on a substrate via a receiving layer is widely used in various fields, for example, in the field of electronic devices such as communication devices if the silver layer is patterned. Is used as a circuit board. In such laminates, a receptive layer is provided to stably maintain the silver layer on the substrate.

  The silver layer usually prepares a silver ink composition containing metallic silver or its forming material, deposits the composition on a substrate (receptive layer), and heats the deposited composition as needed. It is formed by a (baking) method. And in recent years, since it is easy to form a silver layer with good characteristics, a method of forming metallic silver using a silver ink composition containing not a metallic silver itself but a forming material of metallic silver is widely used. It is coming. (See Patent Document 1)

  In addition, a method of forming a conductive layer formed on a substrate in a pattern by a method such as etching and performing electrolytic plating or electroless plating to thicken the conductive layer is generally performed. (See Patent Document 2).

Japanese Patent Publication No. 2010-500476 JP, 2012-237060, A

  The use of the metal silver layer disclosed in Patent Document 1 etc. as a conductive layer as a base for plating disclosed in Patent Document 2 etc. enables easy pattern formation without going through complicated etching steps. Therefore, depending on the conditions such as the type of metal silver layer forming material and film thickness, the adhesion of the conductive layer to the substrate may be lowered by passing through the electrolytic plating process in which the plating solution is immersed in the plating bath. There is a problem that there is a possibility.

  The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a laminate in which a copper layer is provided on a silver layer formed on a substrate, and an electronic device using the laminate. I assume.

In order to solve the above problems, the present invention comprises a substrate, a silver layer formed on one surface side of the substrate via a receptor layer, and a copper layer laminated on the silver layer. a laminate of the silver layer does not include a resin component as a binder, and 0.5μm or more thickness der is, the receiving layer has a nitrogen atom and a hydroxyl group, polyester having an aromatic group providing a laminate which is characterized that you have been formed using a.
Further, the present invention provides an electronic device using the laminate and including the base material as a housing.

  According to the present invention, the copper layer is provided on the base material via the silver layer not containing the resin as the binder, and the laminate in which the decrease in the adhesion of the conductive layer to the base material is suppressed even after the electrolytic plating step. And an electronic device using the stack.

It is a sectional view which illustrates a layered product concerning the present invention typically. It is sectional drawing for demonstrating typically the manufacturing method of the laminated body which concerns on this invention.

<< laminate >>
The laminate according to the present invention is a laminate in which a copper layer is provided on a substrate via a silver layer, and the silver layer contains no resin as a binder and has a thickness of 0.5 μm or more. It is characterized by

In the laminate, the silver layer is formed as a base layer when the copper layer is formed by electrolytic plating. That is, the silver layer functions as a conductive layer to be formed by electrolytic plating.
In the present invention, a silver layer may be formed directly on the substrate, or a silver layer may be laminated after forming a receptive layer to further improve the adhesion between the silver layer and the substrate. It is also good.

FIG. 1 is a cross-sectional view schematically illustrating a laminate according to the present invention.
The laminate 1 shown here comprises a silver layer 4 and a copper layer 5 on a substrate 2 with a receptor layer 3 interposed therebetween. That is, in the laminate 1, the receiving layer 3, the silver layer 4 and the copper layer 5 are laminated in this order on the base material 2.

<Base material>
The base material 2 can be selected in any shape according to the purpose, and for example, is preferably in the form of a film or a sheet, preferably 0.5 to 5000 μm in thickness, and 0.5 to 2500 μm. Is more preferred. When the thickness of the substrate 2 is at least the lower limit, the structure of the receiving layer can be held more stably, and when the thickness of the substrate 2 is at the upper limit or less, the receiving layer and the silver layer are formed. The handling at the time becomes better.

The material of the substrate 2 is not particularly limited and may be selected according to the purpose, but it is preferable to have heat resistance that does not deteriorate at the time of silver layer formation by heat treatment of a silver ink composition described later.
Specific examples of the material of the substrate 2 include polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polymethylpentene (PMP), polycycloolefin, polystyrene (PS) , Acrylic resin such as polyvinyl acetate (PVAc), polymethyl methacrylate (PMMA), AS resin, ABS resin, polyamide resin (PA), polyimide, polyamide imide (PAI), polyacetal, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyphenylene sulfide (PPS), polysulfone (PSF), polyethersulfone (PES) , Polyether ketone (PEK), polyether ether ketone (PEEK), polycarbonate (PC), polyurethane, polyphenylene ether (PPE), modified polyphenylene ether (m-PPE), polyarylate, epoxy resin, melamine resin, phenol resin, A synthetic resin such as urea resin can be exemplified.
Moreover, as a material of the base material 2, ceramics, such as glass and a silicon, and paper can be illustrated besides the above.
Moreover, the base material 2 may be a combination of two or more materials such as a glass epoxy resin and a polymer alloy.

The base material 2 may consist of a single layer, or may consist of two or more layers. When the substrate 2 is composed of a plurality of layers, the plurality of layers may be identical to or different from each other. That is, all layers may be the same, all layers may be different, or only some layers may be different. And when several layers mutually differ, the combination of these several layers is not specifically limited. Here, that the plurality of layers are different from each other means that at least one of the material and thickness of each layer is different from each other.
In addition, when the base material 2 consists of multiple layers, it is good for the total thickness of each layer to be the thickness of the above-mentioned preferable base material 2.

<Receptive layer>
As a material used for a receiving layer, what was formed, for example using polycarbonate frame | skeleton containing urethane (meth) acrylate is mentioned.
The polycarbonate skeleton-containing urethane (meth) acrylate is a base resin (prepolymer) and is not particularly limited, but one having a weight average molecular weight of 2,000 to 20,000 is preferable, and one having 2300 to 17,000 is more preferable. When the weight average molecular weight is in such a range, the effect of suppressing peeling of the silver layer after being placed under high temperature and high humidity conditions is further enhanced. In the present specification, the weight average molecular weight of a base resin or a base resin such as a polycarbonate skeleton-containing urethane (meth) acrylate is determined by GPC (gel permeation chromatography) based on polystyrene.

  The polycarbonate skeleton-containing urethane (meth) acrylate preferably has a pencil hardness of 2B or less according to JIS K 5600-5-4, and more preferably 6B or less of the coating film as the cured product thereof. .

The polycarbonate skeleton-containing urethane (meth) acrylate preferably has an elongation of 70 or more, more preferably 80 or more, in the following tensile test of a coating film as a cured product thereof.
(Tensile test)
A test piece of the coating film, which is a strip of 15 mm in width, is placed in an atmosphere with a relative humidity of 50% and a temperature of 23 ° C. according to JIS K 5600, with a distance between chucks of 25 mm and a tensile speed of 10 mm / min. The test is performed, and the measured value converted when the thickness of the test piece is 50 μm is taken as the elongation.

  The polycarbonate skeleton-containing urethane (meth) acrylate preferably has a viscosity of 40 Pa · s or less at 20 to 60 ° C., and more preferably 10 Pa · s or less. When the viscosity is in such a range, when the composition for the receiving layer described later is mixed with a solvent to be prepared, it is easy to stir and handling becomes better.

  It is preferable that the glass transition point (Tg) of the coating film which is the hardened | cured material of the said polycarbonate frame | skeleton containing urethane (meth) acrylate becomes -18-35 degreeC, and what becomes -15-30 degreeC is more preferable.

The polycarbonate skeleton-containing urethane (meth) acrylate preferably has a Young's modulus of 1 to 300 N / mm ^2, and more preferably 3 to 250 N / mm ² of the coating film as the cured product.

  As for the said polycarbonate frame | skeleton containing urethane (meth) acrylate, that from which the cure shrinkage rate of the coating film which is the hardened | cured material becomes 2 to 7% is preferable, and what becomes 3 to 6% is more preferable.

The polycarbonate skeleton-containing urethane (meth) acrylate preferably has a mechanical strength of ² to 50 N / mm ^2, and more preferably ³ to 45 N / mm ² , as a cured film thereof.

  The polycarbonate skeleton-containing urethane (meth) acrylate is preferably a urethane acrylate having a polycarbonate skeleton (hereinafter sometimes referred to as "polycarbonate skeleton-containing urethane acrylate").

  The receiving layer contains as a main component a polymer (cured resin) obtained by polymerizing a polycarbonate skeleton-containing urethane (meth) acrylate, and the content of the polymer is 90% by mass or more Preferably, it is 95 mass% or more.

As a material used for a receiving layer, the thing containing the resin which has a nitrogen atom and a hydroxyl group etc. is mentioned other than what was formed using polycarbonate frame | skeleton containing urethane (meth) acrylate. The resin having a nitrogen atom and a hydroxyl group has a nitrogen atom (N) as its component, and may have, for example, a nitrogen atom in the main chain or in a side chain. And may be in both the main chain and the side chain.
Further, the resin having a nitrogen atom and a hydroxyl group has a hydroxyl group (-OH), and for example, the hydroxyl group may be bonded to the main chain or may be bonded to the side chain, and the main chain and the side chain May be bound to both.
The nitrogen atom and the hydroxyl group contained in the resin having the nitrogen atom and the hydroxyl group may be only one or two or more per one molecule. And the positions of the nitrogen atom and the hydroxyl group in the resin are not particularly limited.

The resin having a nitrogen atom and a hydroxyl group may be obtained by polymerizing one kind of monomer, or may be obtained by polymerizing two or more kinds of monomers, and is obtained by polymerizing two or more kinds of monomers. In the case, the combination and ratio of these monomers can be arbitrarily adjusted.
Moreover, the monomer having a nitrogen atom and a hydroxyl group, which constitutes the resin having a nitrogen atom and a hydroxyl group, is not particularly limited, and the monomer having a nitrogen atom and the monomer having a hydroxyl group may be different from each other. The molecule may have both a nitrogen atom and a hydroxyl group.

The resin having a nitrogen atom and a hydroxyl group is preferably polyester.
The polyester may be a polymer (resin) having a structure obtained by the polymerization (polycondensation) of a polyvalent carboxylic acid such as a dicarboxylic acid and a polyvalent alcohol such as a diol, specifically, polyethylene terephthalate (PET) Although what has structures, such as polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), can be illustrated, it is not limited to these.
The polyester may be obtained by polymerizing other monomers besides the above-mentioned polyvalent carboxylic acid and polyhydric alcohol. And any of the said polyhydric carboxylic acid, polyhydric alcohol, and other monomers which comprise polyester may have a nitrogen atom and a hydroxyl group.

  The resin having a nitrogen atom and a hydroxyl group has a benzene ring skeleton (a group formed by removing one or more hydrogen atoms from benzene) in its structure, a naphthalene ring skeleton (a group formed by removing one or more hydrogen atoms from naphthalene) Etc. is preferable, and what has aromatic hydrocarbon ring frame | skeleton (aromatic hydrocarbon group) is more preferable. And as for polyester, what has aromatic ring frame | skeleton in the principal chain among the structures is preferable.

  The receptive layer 12 may contain, in addition to the resin, other components that do not correspond to this. The other components contained in the receiving layer 12 are not particularly limited and may be optionally selected according to the purpose. Examples thereof include pigments, dyes, and other resins other than the above-described resins.

Any of known pigments and dyes in the other components can be used.
The other resin in the other component is not particularly limited as long as it is other than the resin, and may be, for example, any of a thermoplastic resin and a thermosetting resin.

  The other components contained in the receptive layer 12 may be only one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof can be arbitrarily adjusted.

  The shape of the receptive layer when the laminate 1 is viewed in a plan view so as to look down on one main surface (the surface on which the silver layer 4 is formed) 2a of the substrate 2 is arbitrarily set according to the purpose It may be set in consideration of the shape of the silver layer 4 described later. For example, the receptive layer may be provided on the entire surface of the substrate 2, or only a part of the surface of the substrate 2 may be provided with a receptive layer, in which case the receptive layer is patterned. It may be

  The thickness of the receptive layer is preferably 0.001 to 20 μm, and more preferably 0.002 to 5 μm. When the thickness of the receptive layer is not less than the lower limit, the adhesion of the silver layer 4 is further improved, and when the thickness of the receptive layer is not more than the upper limit, the structure of the receptive layer is made more stable. It can hold.

<Silver Layer>
The shape of the silver layer 4 can be arbitrarily set according to the purpose when the laminate 1 is viewed from above so that one main surface 2 a of the substrate 2 is viewed from above, and the entire surface 3 a of the receptive layer 3 The silver layer 4 may be provided on the surface, or the silver layer 4 may be provided on only a part of the surface 3a of the receiving layer 3. In this case, the silver layer 4 may be patterned. . The patterned silver layer 4 is useful, for example, as a wiring.

  Although the thickness of the silver layer 4 can be set arbitrarily according to the objective, it is preferable that it is 0.5-5 micrometers, and it is more preferable that it is 1-3 micrometers. By the thickness of the silver layer 4 being more than the said lower limit, adhesiveness with the copper layer laminated | stacked can be improved more, and also the structure of the silver layer 4 can be maintained more stably. Moreover, the laminated body 1 can be thinned more because the thickness of the silver layer 4 is below the said upper limit.

  The silver layer 4 may be composed of a single layer, or may be composed of two or more layers. When the silver layer 4 is composed of a plurality of layers, the plurality of layers may be the same as or different from each other, and can be configured similarly to the case of the substrate 2. For example, in the silver layer 4 composed of a plurality of layers, the total thickness of each layer may be set to the above-mentioned preferable thickness of the silver layer 4.

  The silver layer 4 is excellent in conductivity, and for example, when it is formed using silver of β-ketocarboxylate described later as a forming material of metallic silver, the volume resistivity is preferably 30 μΩ · cm or less, more preferably 25 μΩ. It is possible to set it as cm or less, more preferably 20 μΩ · cm or less, particularly preferably 15 μΩ · cm or less. The volume resistivity of the silver layer 4 can be adjusted by the type of the forming material of metallic silver and the thickness of the silver layer 4 itself.

The layered product concerning the present invention is not limited to what is shown in Drawing 1, and in the range which does not impair the effect of the present invention, other composition may be added or some composition may be changed suitably. For example, the substrate 2 may be provided with other layers other than the receptive layer 3 and the silver layer 4 on the substrate 2, and as the other layers, an overcoat layer (not shown) covering the receptive layer 3 and the silver layer 4 Can be illustrated.
Moreover, although the thing provided with the silver layer 4 via the receptive layer 3 on one main surface 2a of the base material 2 as the laminated body 1 is shown here, the laminate according to the present invention is the base material 2 Similarly, the silver layer 4 may be provided on the other main surface 2 b of the above (on both main surfaces of the substrate 2) via the receptive layer 3.

  In the laminate according to the present invention, as described above, the receptive layer and the silver layer, and the receptive layer and the base material each have high adhesion even after the laminate passes through the plating step, and are obtained from the base material of the silver layer. Peeling is significantly suppressed. Such a laminate in which peeling of the silver layer from the base material is suppressed is extremely useful for application to various electronic devices such as circuit boards, antenna structures and the like, and particularly has such high peeling resistance. It is suitable for the application to the antenna structure which is required. However, the application of the laminate according to the present invention is not limited thereto.

<Copper layer>
The copper layer 5 is a conductive layer formed by known electrolytic copper plating, and the silver layer 4 functions as a conductive underlayer for electrolytic copper plating. The thickness of the copper layer 5 can be optionally set according to the purpose, but is preferably 0.5 to 50 μm, and more preferably 1 to 30 μm. Conductivity can be improved by the thickness of the silver layer 4 being more than the said lower limit, and also the structure of the silver layer 4 can be maintained more stably. Moreover, the laminated body 1 can be thinned more because the thickness of the silver layer 4 is below the said upper limit.

  The copper layer 5 is excellent in conductivity and can have a volume resistivity of preferably 20 μΩ · cm or less, more preferably 10 μΩ · cm or less, and further preferably 5 μΩ · cm or less. The resistance value of the laminate 1 can be adjusted, in particular, by the thickness of the copper layer 5.

<< Production method of laminates >>
The laminate according to the present invention includes, for example, a step of forming a receiving layer on a substrate (hereinafter sometimes abbreviated as a “receiving layer forming step”) and a step of forming a silver layer on the receiving layer ( Hereinafter, in a manufacturing method including “a silver layer forming step” and a step of forming a copper layer on the silver layer (hereinafter, “copper layer forming step” may be described) It can be manufactured.
FIG. 2 is a cross-sectional view for schematically illustrating a method of manufacturing the laminate 1 shown in FIG.

<Receptive layer formation process>
In order to produce the laminate 1, first, as shown in FIG. 2 (b), the receiving layer 3 is formed on the surface (one main surface) 2 a of the base material 2.
The receiving layer 3 has, for example, a composition in which a polycarbonate skeleton-containing urethane (meth) acrylate, which is a base resin for forming the polymer (hardened resin) as a main component thereof, a photopolymerization initiator and a solvent are blended. Product (hereinafter sometimes abbreviated as “composition for receiving layer”), which is deposited on the substrate 2 and formed by curing the polycarbonate skeleton-containing urethane (meth) acrylate by light irradiation . At this time, other treatments such as drying treatment and heat treatment may be performed as needed, and the heat treatment may be combined with the drying treatment.

  The photopolymerization initiator is not particularly limited, and may be a known one, and may be appropriately selected according to the type of polycarbonate skeleton-containing urethane (meth) acrylate.

  The solvent may be any solvent that does not inhibit the polymerization reaction, and may be appropriately selected from known solvents such as cyclohexanone, 1,2-dimethoxyethane (dimethyl cellosolve), propylene glycol monomethyl ether acetate and the like.

  The polycarbonate skeleton-containing urethane (meth) acrylate, the photopolymerization initiator and the solvent may be used alone or in combination of two or more, and when two or more are used in combination, a combination thereof and The ratio can be adjusted arbitrarily.

In the composition for a receptor layer, the ratio of the compounding amount of the polycarbonate skeleton-containing urethane (meth) acrylate to the total amount of the compounding components is preferably 30 to 70% by mass, and more preferably 40 to 60% by mass.
In the composition for a receptor layer, the ratio of the compounding amount of the photopolymerization initiator to the total amount of the compounding components is preferably 1 to 10% by mass, and more preferably 1 to 4% by mass.
In the composition for a receptor layer, the ratio of the compounding amount of the solvent to the total amount of the compounding components is preferably 15 to 65% by mass, and more preferably 25 to 60% by mass.

The composition for the receptor layer may be one in which, in addition to the polycarbonate skeleton-containing urethane (meth) acrylate, the photopolymerization initiator and the solvent, other components that do not correspond to these are further blended.
The other components can be arbitrarily selected according to the purpose and are not particularly limited. For example, as the other components, other base resins other than polycarbonate skeleton-containing urethane (meth) acrylate may be used as long as the effects of the present invention are not impaired.

  The other components in the composition for the receptor layer may be used alone or in combination of two or more. When two or more are used in combination, the combination and ratio thereof are optionally It can be adjusted.

In the composition for the receptor layer, the ratio of the blending amount of the other components to the total amount of the blending components is preferably 10% by mass or less, and more preferably 5% by mass or less.
And when using base resin other than polycarbonate frame | skeleton containing urethane (meth) acrylate as said base resin, the ratio of the compounding quantity of said other base resin with respect to the total compounding quantity of base resin in the composition for receptive layers is The content is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 2% by mass or less, and particularly preferably 1% by mass or less.
By the ratio of the compounding quantity of the said other component being below the said upper limit, the peeling inhibitory effect of the silver layer after putting on high temperature and high humidity conditions becomes higher.

  The composition for a receptor layer is obtained by blending a polycarbonate skeleton-containing urethane (meth) acrylate, a photopolymerization initiator, a solvent, and the above-mentioned other components as needed. After blending of the respective components, the obtained product may be used as it is as a composition for the receiving layer or, if necessary, it may be obtained as a composition for the receiving layer by carrying out a known purification operation.

At the time of blending each component, all the components may be added and then mixed, or some of the components may be sequentially added and mixed, or all the components may be sequentially added and mixed. Good.
The mixing method is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc .; a method of mixing using a mixer, a triple roll, a kneader, a bead mill, etc .; a method of adding ultrasonic waves and mixing, etc. It may be appropriately selected from known methods.

  In the composition for the receptor layer, all of the compounding components may be dissolved, or some of the components may be dispersed without being dissolved, but it is preferable that all of the compounding components be dissolved, It is preferable that the components which are not dissolved be uniformly dispersed. In order to disperse | distribute the component which is not melt | dissolved uniformly, it is preferable to apply the method of disperse | distributing using said 3 roll, kneader, bead mill etc., for example.

The temperature at the time of compounding is not particularly limited as long as each compounded component is not deteriorated, but 40 to 60 ° C. is preferable. Then, the temperature at the time of blending may be appropriately adjusted according to the type and amount of blending components so that the mixture obtained by blending has a viscosity that facilitates stirring.
The compounding time is not particularly limited as long as each compounded component does not deteriorate, but it is preferably 5 minutes to 12 hours, more preferably 1 to 6 hours, and still more preferably 2 to 4 hours. .

The composition for receptive layer can be deposited on the substrate 2 by a known method such as, for example, a printing method, a coating method, or an immersion method.
Examples of the printing method include screen printing, flexographic printing, offset printing, dip printing, ink jet printing, dispenser printing, gravure printing, gravure offset printing, pad printing and the like.
Examples of the coating method include spin coaters, air knife coaters, curtain coaters, die coaters, blade coaters, blade coaters, roll coaters, gate roll coaters, gate coaters, bar coaters, rod coaters, rod coaters, gravure coaters, and other wire coaters. It can be illustrated.

  In the receptive layer forming step, the amount of the composition for the receptive layer to be deposited on the substrate 2 or the blending amount of the polycarbonate skeleton-containing urethane (meth) acrylate in the composition for the receptive layer is adjusted. You can adjust the thickness.

  Drying processing and heat processing of the composition for receptive layer may be carried out by any known method, for example, under normal pressure, under reduced pressure or under blowing condition, under air and under inert gas atmosphere. It may be done either. The processing temperature is also not particularly limited, and may be appropriately set according to the purpose. For example, the drying process may be either a heating drying process or a normal temperature drying process, and in the case of the heating drying process, for example, it can be preferably performed under conditions of 60 to 100 ° C. for 2 to 10 minutes.

In order to polymerize (cure) the polycarbonate skeleton-containing urethane (meth) acrylate, the composition for the receptor layer deposited on the substrate 2 is irradiated with light by a known method. Irradiation light may be suitably selected according to the kind of polycarbonate frame | skeleton containing urethane (meth) acrylate, and it is preferable that it is an ultraviolet-ray normally. The light quantity at the time of light irradiation is preferably 200 to 1000 mJ / cm ² .

In the receptive layer forming step, the substrate 2 may be heat treated (annealed) before the composition for the receptive layer is attached. By subjecting the substrate 2 to heat treatment, when the composition for the receiving layer is subjected to heat treatment in this step, or when the silver ink composition is subjected to heat (baking) treatment in a silver layer forming step described later, The shrinkage of the material 2 is suppressed, and the dimensional stability is improved.
Although the conditions of the heat processing of the base material 2 before making the composition for receptive layers adhere may be suitably adjusted according to the kind of base material 2, and it is not specifically limited, It heats at 60-200 degreeC for 10 to 60 minutes. It is preferable to process, for example, it may be the same as the conditions of the heating (baking) process of the silver ink composition in the silver layer forming process.

In the present invention, the surface of the substrate 2 on which the receptive layer 3 is formed may be plasma-treated before the composition for the receptive layer is attached. By subjecting the substrate 2 to plasma treatment, bleeding of the silver ink composition may be suppressed on the receiving layer 3 in the silver layer forming step described later.
The plasma treatment may be performed by a known method. For example, in the case of atmospheric pressure plasma treatment, the treatment can be performed under conditions such as a voltage of 290 to 300 W and an air velocity of 1.0 to 5.0 m / min.

<Silver layer formation process>
Next, as shown in FIG. 2C, the silver layer 4 is formed on the surface (main surface) 3 a of the receiving layer 3 in order to manufacture the laminate 1.
Silver layer 4 prepares a composition for forming this (hereinafter sometimes abbreviated as “composition for silver layer”), adheres it to a desired location on receptive layer 3, and is dried It can form by performing post-processing, such as a heating (baking) process, selecting suitably. The heat treatment may be performed concurrently with the drying treatment.
In addition, silver layer 4 prepares a composition for silver layer, adheres this to a predetermined place or the entire surface on receptive layer 3, and selects and performs post-treatments such as drying treatment and heating (baking) treatment appropriately. After the silver layer (silver layer before patterning, not shown) is formed, the silver layer can be formed into a desired shape by a known method such as etching.

In the present invention, as the composition for the silver layer, a silver ink composition in which a forming material of metallic silver or metallic silver is blended is prepared, this is deposited on the receptive layer 3, and drying treatment or heating ( The silver layer 4 is preferably formed by appropriately selecting and performing post treatments such as baking treatment.
The forming material of metallic silver or metallic silver to be blended may be only one kind or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof can be arbitrarily adjusted.

The metallic silver to be blended is preferably in the form of particles or fibers (tubes, wires, etc.), more preferably nanoparticles or nanowires.
In the present specification, “nanoparticles” means particles having a particle size of 1 nm to less than 1000 nm, preferably 1 to 100 nm, and “nanowires” has a width of 1 nm to less than 1000 nm, preferably It means a wire that is 1 to 100 nm.

The forming material of the metal silver may have silver atoms (elements) and may generate metal silver by structural change such as decomposition, and a silver salt, a silver complex, an organic silver compound (compound having a silver-carbon bond) Etc. can be illustrated. The silver salt and the silver complex may be any of a silver compound having an organic group and a silver compound having no organic group. Among them, the forming material of metallic silver is preferably a silver salt.
By using a forming material of metallic silver, metallic silver is generated from such a material, and a silver layer 4 containing the metallic silver is formed. In this case, the silver layer 4 is mainly composed of metallic silver, and the proportion of metallic silver is high enough to be regarded as apparently consisting only of metallic silver, and the proportion of metallic silver in the silver layer 4 is Preferably, it is 99 mass% or more.

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

Hereinafter, the formation method of the silver layer 4 at the time of using what the formation material of metallic silver is mix | blended as a silver ink composition is demonstrated.
It is preferable that the metal silver forming material is decomposed by heating to form metal silver.

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

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

(Wherein R is an aliphatic hydrocarbon group having 1 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, or a phenyl group, a hydroxyl group, an amino group, or a general formula “R ¹ -CY 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 — ”a group represented by
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 a fat having 1 to 20 carbon atoms Group hydrocarbon group; 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 each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a phenyl group or a benzyl group in which one or more hydrogen atoms may be substituted 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 ( A group represented by = O) -O- ";
R ⁷ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a thienyl group, or a phenyl or diphenyl group in which one or more hydrogen atoms may be substituted by a substituent. )

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

(Β-ketocarboxylic acid silver (1))
The β-ketocarboxylic acid silver (1) is represented by the above general formula (1).
In the formula, R is an aliphatic hydrocarbon group having 1 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, a phenyl group, a hydroxyl group, an amino group, or a general formula “R ¹ -CY 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 - "a group represented by.

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

The linear or branched alkyl group for R is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n -Pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4- Methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group 1-ethyl-1-methylpropyl group, n-heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, -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, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 4-ethylpentyl, 2,2,3-trimethylbutyl, 1-propylbutyl, n -Octyl group, isooctyl group, 1-methyl heptyl group, 2-methyl heptyl group, 3-methyl heptyl group, 4-methyl heptyl group, 5-methyl heptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl Group, 4-ethylhexyl group, 5-ethylhexyl group, 1,1-dimethylhexyl group, 2,2-dimethylhexyl group, 3,3, -Dimethylhexyl 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.
As the cyclic alkyl group for R, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, isobornyl group, 1-adamantyl group, 2- Examples include adamantyl group and tricyclodecyl group.

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

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

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

Y ^{1 in} R is each independently a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom. Then, the general formula ^"R ₁ ^-CY 1 ₂ -", ^"CY _{1 3} -" and ^{"R 6 -C (= O) -CY} 1 2 - " In a plurality of ^{Y 1} are each, also identical to one another It 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 The same aliphatic hydrocarbon group as R in R can be exemplified except the point.
R ² in R is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, those similar to the aforementioned aliphatic hydrocarbon group for R can be exemplified.
R ³ in R is an aliphatic hydrocarbon group of 1 to 16 carbon atoms, except a carbon number of 1 to 16 include the same aliphatic hydrocarbon group for R can be exemplified.
R ⁴ and R ⁵ in R are each independently an aliphatic hydrocarbon group having 1 to 18 carbon atoms. That is, R ⁴ and R ⁵ may be the same as or different from each other, and the same as the above-mentioned aliphatic hydrocarbon group in R can be exemplified except that the carbon number is 1 to 18.
R ⁶ in R is an aliphatic hydrocarbon group having 1 to 19 carbon atoms, a hydroxyl group or a group represented by the formula “AgO—”, and as the aliphatic hydrocarbon group in R ⁶ , it has 1 to 1 carbon atoms The same aliphatic hydrocarbon group as that in R can be exemplified except for the point of 19.

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. And R ⁶ is preferably a linear or branched alkyl group, a hydroxyl group or a group represented by the formula “AgO—”.

In the general formula (1), X ¹ each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, or a phenyl group in which one or more hydrogen atoms may be substituted by a substituent 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, the same as the aliphatic hydrocarbon group for R can be exemplified.

The halogen atom in X ^1, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom can be exemplified.
In the phenyl group and the benzyl group in X ¹ , one or more hydrogen atoms may be substituted with a substituent, and 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. And when the number of substituents is plural, these plural substituents may be same or different.

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

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

Among the above, 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) —”. Preferably, at least one X ¹ is a hydrogen atom.

Silver β-ketocarboxylate (1) is selected from silver 2-methylacetoacetate (CH ₃ -C (= O) -CH (CH ₃ ) -C (= O) -OAg), silver acetoacetate (CH ₃ -C (= _{O) -CH 2 -C (= O} ) -OAg), 2- ethylacetoacetate silver _{(CH 3 -C (= O)} -CH (CH 2 CH 3) -C (= O) -OAg), propionyl silver 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 (OO) —OAg), caproyl acetate silver (CH ₃ (CH ₂ ) ₃ CH ₂ —C (= O) ) -CH ₂ -C (= O) -OAg), silver 2-n-butylacetoacetate (CH ₃ -C (= O) -CH (C) _{H 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), Pibaroiruaseto silver acetate _{((CH 3) 3 C-} C (= O) -CH 2 _{-C (= O) -CH 2 -C} (= O) -OAg), isobutyryl acetoacetate silver _{((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) - Ag), or is preferably acetone dicarboxylic silver _{(AgO-C (= O)} -CH 2 -C (= O) -CH 2 -C (= O) -OAg).

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

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

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

(Silver carboxylate (4))
Silver carboxylate (4) is represented by the above general formula (4), wherein R ⁸ is an aliphatic hydrocarbon group having 1 to 19 carbon atoms, a carboxy group (—COOH) or a formula “—C (CO ] -OAg "is a group represented by this.
As said aliphatic hydrocarbon group in R < ⁸ >, the thing similar to the said aliphatic hydrocarbon group in R can be illustrated except the point which carbon number is 1-19. However, the aliphatic hydrocarbon group for R ⁸ preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms.

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

Silver carboxylate (4), pyruvic silver _{(CH 3 -C (= O)} -C (= O) -OAg), silver acetate _{(CH 3 -C (= O)} -OAg), silver butyrate (CH ₃ -(CH ₂ ) ₂ -C (= O) -OAg), silver isobutyrate ((CH ₃ ) ₂ CH-C (= O) -OAg), silver 2-ethylhexanoate (CH _3- (CH ₂₎ ) _3- CH (CH ₂ CH ₃ ) -C (= O) -OAg), silver neodecanoate (CH _3- (CH ₂ ) ₅ -C (CH ₃ ) ₂ -C (= O) -OAg), oxalic acid silver (AgO-C (= O) -C (= O) -OAg), or is preferably a malonate silver _{(AgO-C (= O)} -CH 2 -C (= O) -OAg). Also, 2 of the silver oxalate (AgO-C (= O) -C (= O) -OAg) and malonic silver _{(AgO-C (= O)} -CH 2 -C (= O) -OAg) Of the groups represented by the formula “—COOAg”, one in which one is a group represented by the formula “—COOH” (HO—C (= O) —C (= O) —OAg, HO _{-C (= O) -CH 2 -C} (= O) -OAg) it is also preferred.

  Similarly to silver β-ketocarboxylate (1), silver carboxylate (4) is a raw material or an impurity remaining in a conductor (metallic silver) formed by post treatment such as drying treatment or heating (baking) treatment. The concentration can be further reduced. And by using together with a reducing agent, it decomposes | disassembles at lower temperature and forms metallic silver.

  In the present invention, one kind of silver carboxylate (4) may be used alone, or two or more kinds thereof may be used in combination. When using 2 or more types together, the combination and ratio can be adjusted arbitrarily.

The silver carboxylate is silver 2-methylacetoacetate, silver acetoacetate, silver 2-ethylacetoacetate, silver propionyl acetate, silver isobutyryl acetate, silver pivaloyl acetate, silver caproyl acetate, silver 2-n-butylacetoacetate, 2-benzylacetoate Silver acetate, silver benzoylacetate, silver pivaloylacetoacetate, silver isobutyrylacetoacetate, silver acetonedicarboxylate, silver pyruvate, silver acetate, silver acetate, silver isobutyrate, silver 2-ethylhexanoate, silver neodecanoate, oxalate It is preferable that it is 1 or more types selected from the group which consists of silver acid and silver malonate.
And, among these silver carboxylates, silver 2-methylacetoacetate and silver acetoacetate are excellent in compatibility with nitrogen-containing compounds (particularly, amine compounds) described later, and are particularly suitable for increasing the concentration of silver ink compositions. Listed as

In the silver ink composition, the content of silver derived from the forming material of the metallic silver is preferably 5% by mass or more, and more preferably 10% by mass or more. Within such a range, the formed conductor (metallic silver) is more excellent in quality. The upper limit of the content of silver 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 handleability and the like.
In the present specification, “silver derived from a forming material of metallic silver” means silver in the forming material of the metallic silver compounded at the time of production of a silver ink composition, unless otherwise specified. It is considered as a concept including both silver which constitutes the forming material of metallic silver after blending and silver and silver itself in a decomposition product formed by decomposition of the forming material of metallic silver after blending.

[Nitrogen-containing compounds]
The nitrogen-containing compound is an amine compound having 25 or less carbon atoms (hereinafter sometimes abbreviated as "amine compound"), a quaternary ammonium salt having 25 or less carbon atoms (hereinafter abbreviated as "quaternary ammonium salt") Ammonia, an ammonium salt formed by the reaction of an amine compound having 25 or less carbon atoms with an acid (hereinafter sometimes abbreviated as “an ammonium salt derived from an amine compound”), and ammonia reacts with an acid And one or more selected from the group consisting of ammonium salts (hereinafter sometimes abbreviated as "ammonia-derived ammonium salts"). That is, the nitrogen-containing compound to be blended may be only one kind or two or more kinds, and when two or more kinds are used in combination, the combination and ratio thereof can be arbitrarily adjusted.

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

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

The alkyl group constituting the monoalkylamine may be linear, branched or cyclic and may be the same as the alkyl group in R, and may be linear or branched having 1 to 19 carbon atoms. It is preferable that it is a chain | strand-shaped alkyl group or a C3-C7 cyclic alkyl group.
Specific examples of the preferred monoalkylamines include n-butylamine, n-hexylamine, n-octylamine, n-dodecylamine, n-octadecylamine, sec-butylamine, tert-butylamine, isobutylamine, 3-amino Examples include pentane, 3-methylbutylamine, 2-heptylamine (2-aminoheptane), 2-aminooctane, 2-ethylhexylamine and 1,2-dimethyl-n-propylamine.

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

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

The heteroaryl group is a monocyclic group having 1 to 4 nitrogen atoms, such as pyrrolyl group, pyrrolinyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrimidyl group, pyrazinyl group, pyridazinyl group, triazolyl group, tetrazolyl group And a pyrrolidinyl group, an imidazolidinyl group, a piperidinyl group, a pyrazolidinyl group and a piperazinyl group can be exemplified. A 3- to 8-membered ring is preferable, and a 5- to 6-membered ring is more preferable.
As said heteroaryl group, as a monocyclic thing which has one oxygen atom, a furanyl group can be illustrated, It is preferable that it is a 3- to 8-membered ring, and it is more preferable that it is a 5- to 6-membered ring.
Examples of the heteroaryl group as a monocyclic group having one sulfur atom include a thienyl group, preferably a 3- to 8-membered ring, and more preferably a 5- to 6-membered ring.
Examples of the heteroaryl group as the monocyclic group having 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms include an oxazolyl group, an isoxazolyl group, an oxadiazolyl group, and a morpholinyl group, and has a 3- to 8-membered ring. It is preferable that it is a 5- to 6-membered ring.
Examples of the heteroaryl group as the monocyclic group having 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms include thiazolyl group, thiadiazolyl group and thiazolidinyl group, and it is a 3- to 8-membered ring It is more preferable that it is a 5- or 6-membered ring.
Examples of the heteroaryl group which is a cyclic group having 1 to 5 nitrogen atoms include indolyl group, isoindolyl group, indolizinyl group, benzimidazolyl group, quinolyl group, isoquinolyl group, indazolyl group, benzotriazolyl group, tetrazo group. Examples thereof include a zolopyridyl group, a tetrazolopyridazinyl group and a dihydrotriazolopyridazinyl group, preferably a 7- to 12-membered ring, and more preferably a 9- to 10-membered ring.
Examples of the above-mentioned heteroaryl group which is a polycyclic group having 1 to 3 sulfur atoms include a dithianaphthalenyl group and a benzothiophenyl group, and a 7- to 12-membered ring is preferable, and a 9 to 10-membered ring is preferable. More preferably, it is a ring.
Examples of the above-mentioned heteroaryl group which is a polycyclic group having 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms include benzoxazolyl groups and benzooxadiazolyl groups, each having a 7- to 12-membered ring. It is preferable that it is a 9- to 10-membered ring.
Examples of the above-mentioned heteroaryl group which is a polycyclic group having 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms include benzothiazolyl group and benzothiadiazolyl group, and it is a 7- to 12-membered ring. Preferably, a 9 to 10-membered ring is more preferred.

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

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

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

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

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

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

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

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

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

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

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

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

When the alkyl group constituting the monoalkylamine has a substituent, the alkyl group is a linear or branched alkyl group having 1 to 9 carbon atoms or an aryl group as a substituent, or a substituent Is preferably a cyclic alkyl group having 3 to 7 carbon atoms and having an alkyl group having 1 to 5 carbon atoms, and as a monoalkylamine having such a substituent, specifically, 2-phenylethylamine And benzylamine and 2,3-dimethylcyclohexylamine.
In addition, one or more hydrogen atoms of the above-mentioned aryl group and alkyl group which are substituents may be further substituted by a halogen atom, and as a monoalkylamine having a substituent substituted by such a halogen atom, And 2-bromobenzylamine. Here, as said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be illustrated.

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

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

The above-mentioned amine compounds are n-propylamine, n-butylamine, n-hexylamine, n-octylamine, n-dodecylamine, n-octadecylamine, sec-butylamine, tert-butylamine, 3-aminopentane, 3-methyl Butylamine, 2-heptylamine, 2-aminooctane, 2-ethylhexylamine, 2-phenylethylamine, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, N-methyl-n-hexylamine, diisobutylamine, Preferred is N-methylbenzylamine, di (2-ethylhexyl) amine, 1,2-dimethyl-n-propylamine, N, N-dimethyl-n-octadecylamine or N, N-dimethylcyclohexylamine .
Among these amine compounds, 2-ethylhexylamine is excellent in compatibility with the silver carboxylate, is particularly suitable for increasing the concentration of the silver ink composition, and further reduces the surface roughness of the silver layer 4. Particularly suitable ones are mentioned.

(Ammonia salt derived from amine compound)
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 The type of acid is not particularly limited.
Examples of the ammonium salt derived from the amine compound include n-propylamine hydrochloride, N-methyl-n-hexylamine hydrochloride, N, N-dimethyl-n-octadecylamine hydrochloride and the like, but are not limited thereto. .

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

In the present invention, the amine compound, the quaternary ammonium salt, the ammonium salt derived from the amine compound and the ammonium salt derived from the 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 the nitrogen-containing compound, one selected from the group consisting of the amine compound, quaternary ammonium salt, ammonium salt derived from the amine compound and ammonium salt derived from the ammonia may be used alone, or More than 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 0.3 to 15 moles, and more preferably 0.3 to 5 moles per mole of the forming amount of the metal silver. preferable. When the compounding amount of the nitrogen-containing compound is in such a range, the stability of the silver ink composition is further improved, and the quality of the conductor (metallic silver) is further improved. Furthermore, the conductor can be formed more stably without heat treatment at high temperature.

[Reductant]
The silver ink composition is preferably one in which a reducing agent is further blended in addition to the forming material of the metallic silver. By blending the reducing agent, the silver ink composition can more easily form metallic silver, and can form, for example, a conductor (metallic silver) having sufficient conductivity 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, it may be simply abbreviated as "reducing compound") is preferable.
H-C (= O) -R ²¹ (5)
(Wherein, R ²¹ represents an alkyl group having 20 or less carbon atoms, an alkoxy group or an N, N-dialkylamino group, a hydroxyl group or an amino group).

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

The alkyl group having 20 or less carbon atoms in R ²¹ has 1 to 20 carbon atoms, and may be linear, branched or cyclic, and is the same as the alkyl group in R of the general formula (1) Can be illustrated.

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

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

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

Preferred examples of the reducing compound include: formic acid (H-C (= O) -OH); methyl formate (H-C (= O) -OCH ₃ ), ethyl formate (H-C (= O) -OCH) Formic acid esters such as ₂ CH ₃ ), butyl formate (H—C (= O) —O (CH ₂ ) ₃ CH ₃ ), etc .; propanal (H—C (= O) —CH ₂ CH ₃ ), butanal (H Aldehydes such as —C (CO) — (CH ₂ ) ₂ CH ₃ ), hexanal (H—C (= O) — (CH ₂ ) ₄ CH ₃ ), etc .; formamide (H—C (= O) —NH ₂ Formamides (groups represented by the formula “HC (= O)-N (-)-”) such as N, N-dimethylformamide (HC (= O)-N (CH ₃ ) ₂ ) And oxalic acid.

  In the silver ink composition, the compounding amount of the reducing agent is preferably 0.04 to 3.5 moles, preferably 0.06 to 2.5 moles, per mole of the compounding amount of the forming material of the metal silver. Is more preferred. When the compounding amount of the reducing agent is in such a range, the silver ink composition can form the conductor (metallic silver) more easily and more stably.

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

  It is preferable that the said alcohol is acetylene alcohols (Hereinafter, it may abbreviate as "acetylene alcohol (2).") Represented by following General formula (2).

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

(Acetylene alcohol (2))
The acetylene alcohol (2) is represented by the general formula (2).
In the formula, R ′ and R ′ ′ each independently represent an alkyl group having 1 to 20 carbon atoms, or a phenyl group in which one or more hydrogen atoms may be substituted by a substituent.
The alkyl group having 1 to 20 carbon atoms in R ′ and R ′ ′ may be linear, branched or cyclic, and when it is cyclic, it may be monocyclic or polycyclic. As said alkyl group in R 'and R'', the thing similar to the said alkyl group in R can be illustrated.

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

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

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

  When the acetylene alcohol (2) is used, it is preferable that the blending amount of the acetylene alcohol (2) in the silver ink composition is 0.03 to 0.7 mol per 1 mol of the blending amount of the forming material of the metal silver. More preferably, it is 0.05 to 0.3 mol. The stability of a silver ink composition improves more because the said compounding quantity of acetylene alcohol (2) is such a range.

  The alcohols may be used alone or in combination of two or more. In the case of using two or more kinds in combination, the combination and ratio thereof can be arbitrarily adjusted.

[Other ingredients]
The silver ink composition may be one in which other components other than the forming material of the metallic silver, the nitrogen-containing compound, the reducing agent and the alcohol are blended.
The other components in the silver ink composition can be optionally selected according to the purpose, and are not particularly limited. Preferred examples include solvents other than alcohols, and are optionally selected according to the type and amount of the compounding components it can.
The other components in the silver ink composition may be used alone or in combination of two or more. In the case of using two or more kinds in combination, the combination and ratio thereof can be arbitrarily adjusted.

  In the silver ink composition, the ratio of the blending amount of the other components to the total amount of the blending components is preferably 10% by mass or less, more preferably 5% by mass or less, 0 mass, that is, the other components Even if it does not mix, a silver ink composition fully expresses the effect.

  In the silver ink composition, all of the compounding components may be dissolved, or some or all of the components may be dispersed without being dissolved, but it is preferable that all of the compounding components be dissolved. The components which are not dissolved are preferably uniformly dispersed.

[Method of producing silver ink composition]
The silver ink composition can be obtained by blending the metal silver forming material and components other than the metal silver forming material. After blending of the respective components, the obtained product may be used as it is as a silver ink composition, or, if necessary, it may be used as a silver ink composition which is obtained by performing a known purification operation. In the present invention, in particular, when silver (1) of a β-ketocarboxylate is used as a material for forming the metallic silver, no impurity inhibiting the conductivity is generated at the time of blending each of the above components, or such Since the amount of generation of impurities can be suppressed to a very small amount, a conductor (metallic silver) having sufficient conductivity can be obtained even if a silver ink composition not subjected to a purification operation is used.

At the time of blending each component, all the components may be added and then mixed, or some of the components may be sequentially added and mixed, or all the components may be sequentially added and mixed. Good. However, in the present invention, the reducing agent is preferably blended by dropping, and by suppressing the fluctuation of the dropping speed, the surface roughness of the metallic silver tends to be further reduced.
The mixing method is not particularly limited, and a method of mixing by rotating a stirrer or a stirring blade, etc .; a method of mixing using a mixer, a triple roll, a kneader, a bead mill, etc .; a method of adding ultrasonic waves and mixing, etc. It may be appropriately selected from known methods.
In the case of uniformly dispersing undissolved components in the silver ink composition, it is preferable to apply the method of dispersing using, for example, the above-mentioned triple roll, kneader or bead mill.

The temperature at the time of blending is not particularly limited as long as each blended component does not deteriorate, but is preferably -5 to 60 ° C. Then, the temperature at the time of blending may be appropriately adjusted according to the type and amount of blending components so that the mixture obtained by blending has a viscosity that facilitates stirring.
Also, the blending time is not particularly limited as long as each blending component does not deteriorate, but it is preferably 10 minutes to 36 hours.

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

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

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

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

  Although the compounding temperature at the time of 1st mixture manufacture is not specifically limited unless each compounding component degrades, It is preferable that it is -5-30 degreeC. The blending time may be appropriately adjusted according to the type of blending component and the temperature at the time of blending, but preferably 0.5 to 12 hours, for example.

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

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

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

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

  It is preferable that it is 5-70 degreeC, as for the temperature of the 1st mixture at the time of carbon dioxide gas supply, it is more preferable that it is 7-60 degreeC, and it is especially preferable that it is 10-50 degreeC. Carbon dioxide can be more efficiently supplied when the temperature is equal to or higher than the lower limit, and a silver ink composition of better quality with few impurities can be obtained when the temperature is equal to or lower than the upper limit.

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

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

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

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

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

The temperature at which the reducing agent is mixed is not particularly limited as long as each compounded component is not deteriorated, but is preferably -5 to 60 ° C. Then, the temperature at the time of blending may be appropriately adjusted according to the type and amount of blending components so that the mixture obtained by blending has a viscosity that facilitates stirring.
The blending time may be appropriately adjusted according to the type of blending component and the temperature at the time of blending, but preferably 0.5 to 12 hours, for example.

  The other components may be compounded at the time of production of any of the first mixture and the second mixture as described above, or may be compounded at the time of production of both. That is, in the process of producing the silver ink composition via the first mixture and the second mixture, the ratio of the blending amount of the other components to the total amount of the blending components other than carbon dioxide ([other components (mass)] It is preferable that it is 10 mass% or less, and it is more preferable that it is [/ the [forming material of metallic silver, a nitrogen-containing compound, a reducing agent, alcohol, and other components (mass)] x 100)]. The silver ink composition sufficiently exhibits its effect even if it contains no mass, that is, no other components.

  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 the reducing agent is blended, the resulting blend (silver ink composition) is relatively exothermic. And when the temperature at the time of compounding of the reducing agent is high, this compound is in the same state as at the time of heat treatment of the silver ink composition described later, so the reducing agent promotes the decomposition of the forming material of the metal silver by the reducing agent. It is speculated that the formation of metallic silver may be initiated in at least part of the metallic silver forming material. A silver ink composition containing such metallic silver can sometimes form a conductor by performing post-treatment under milder conditions than a silver ink composition not containing metallic silver at the time of conductor formation. Also, even when the compounding amount of the reducing agent is sufficiently large, the conductor may be able to be formed by post-treatment similarly under mild conditions. As described above, by adopting the conditions for promoting the decomposition of the forming material of metallic silver, the conductor can be subjected to heat treatment at a lower temperature as a post-treatment, or only to a drying treatment at ordinary temperature without heat treatment. Can be formed. In addition, a silver ink composition containing such metallic silver can be handled in the same manner as a silver ink composition not containing metallic silver, and the handling property is not particularly inferior.

  The second mixture in the present invention has a viscosity higher than usual due to the supply of carbon dioxide as described above. On the other hand, at the time of blending the reducing agent into the second mixture, depending on the type of the second mixture or reducing agent, the formation of metallic silver starts in at least a part of the forming material of metallic silver as described above And silver metal may precipitate out. Here, when the viscosity of the second mixture is high, the aggregation of the deposited metal silver is suppressed, and the dispersibility of the metal silver in the obtained silver ink composition is improved. The conductor obtained by forming metallic silver by the method described later using such a silver ink composition is obtained by blending a reducing agent in a mixture having a low viscosity, that is, no carbon dioxide is supplied. The conductivity is higher (the volume resistivity is lower) and the surface roughness is smaller than those of the conductor using the above-described silver ink composition, which results in more preferable characteristics.

The silver ink composition can be deposited on the substrate by a known method such as, for example, a printing method, a coating method, or an immersion method.
Examples of the printing method include screen printing, flexographic printing, offset printing, dip printing, ink jet printing, dispenser printing, gravure printing, gravure offset printing, pad printing and the like.
Examples of the coating method include spin coaters, air knife coaters, curtain coaters, die coaters, blade coaters, blade coaters, roll coaters, gate roll coaters, gate coaters, bar coaters, rod coaters, rod coaters, gravure coaters, and other wire coaters. It can be illustrated.

  In the step of forming the silver layer 4 described above, the silver layer 4 is adjusted by adjusting the amount of the silver ink composition to be deposited on the substrate 2 or the compounding amount of the metal silver forming material in the silver ink composition. You can adjust the thickness of the

  When the silver ink composition deposited on the substrate 2 is subjected to a drying process, it may be carried out by a known method, for example, under normal pressure, under reduced pressure or under blast conditions, under the atmosphere and It may be performed under any inert gas atmosphere. The drying temperature is also not particularly limited, and any of heat drying and normal temperature drying may be used. As a preferable drying method when the heat treatment is unnecessary, a method of drying in the air at 18 to 30 ° C. can be exemplified.

  When the silver ink composition deposited on the substrate 2 is subjected to a heating (baking) treatment, the conditions may be appropriately adjusted according to the type of the compounding component of the silver ink composition. In general, the heating temperature is preferably 60 to 200 ° C., and more preferably 70 to 180 ° C. The heating time may be adjusted according to the heating temperature, but usually 0.2 to 12 hours is preferable, and 0.4 to 10 hours is more preferable. Among the forming materials of the metal silver, the silver carboxylate, particularly the silver β-ketocarboxylate (1), for example, is different from the forming material of metal silver such as silver oxide, and a reducing agent known in the relevant field is used Even if not, it decomposes at low temperature. And, reflecting such decomposition temperature, the silver ink composition can form metallic silver at a much lower temperature than that of the conventional one, as described above.

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

  In the case of producing a laminate according to the present invention in which another layer other than the receptor layer 3 and the silver layer 4 is provided on the substrate 2, the other layers may be formed at a predetermined timing in the above manufacturing method. The steps of forming the above may be added as appropriate.

The laminate according to the present invention is, as described above, because the conductivity of the silver layer is sufficiently high in addition to the suppression of peeling of the silver layer from the base material, as described later, various kinds of communication devices etc. It is extremely useful as a component of an electronic device.

<Copper layer formation process>
Next, as shown in FIG. 2D, the copper layer 5 is formed on the surface (main surface) 4 a of the silver layer 4 in order to manufacture the laminate 1.
The copper layer 5 can be formed by preparing a general plating solution and performing known electrolytic copper plating. The plating solution may contain additives such as brighteners, pit inhibitors, pH buffer materials and the like, and the type and amount of the additives are appropriately selected as necessary.

  The pH of the plating solution at the time of electrolysis is not particularly limited as long as it is the pH range of a general plating solution, and is appropriately adjusted.

  The temperature of the plating solution is not particularly limited as long as it is a temperature range of a general plating solution, and is appropriately adjusted.

The current density at the time of electrolytic plating may be any condition suitable for performing electrolysis on a cored bar using a plating solution, and is appropriately adjusted in accordance with the type of metal.
The time for applying the voltage at the current density is not particularly limited as long as it is a general range, and is appropriately adjusted in accordance with the thickness 1 μm to 50 μm of the target plating layer.

<< Electronic equipment, data transmitter / receiver, transparent conductive film >>
The wiring board is suitable for forming various electronic devices such as a data transmitter / receiver, a transparent conductive film, and the like.
For example, the electronic device can be configured to use the wiring board and include the base material as a housing (exterior material), except that at least a part of the housing is formed of the base material in the wiring board. And the same configuration as a known electronic device. For example, the flat or curved surface portion of the exterior material in an electronic device such as a mobile phone is used as the base material, the metal thin wire is directly formed on the exterior material (base material), and the metal thin wire is used as a circuit. A wiring board can be used as a circuit board. Then, for example, 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 with the wiring board. Moreover, the wiring board can be used as an antenna structure by using the patterned thin metal wire as an antenna.
The data transmitter / receiver can be configured to use the wiring board and include the thin metal wire as an antenna, and has the same configuration as a known data transmitter / receiver except that the wiring board is used as an antenna structure. can do. For example, in the laminate 1 shown in FIG. 1, a noncontact data transmitter / receiver can be configured by providing an IC chip electrically connected to the copper layer 5 on the base material 2 to form an antenna portion.
The transparent conductive film can be configured to use the wiring board and include the fine metal wires as ultrafine wires or ultrathin wires, except that the thin metal wires are provided as ultrafine wires and a known transparent conductive film. The same configuration can be made. For example, in addition to the wiring board, a touch panel or an optical display can be configured by combining with a transparent substrate or the like.
The width of the ultrathin wiring is preferably 0.1 μm to 10 μm, more preferably 0.1 μm to 5 μm, and particularly preferably 0.1 μm to 3 μm.
In addition, in the laminate, it is possible to form a silver layer at a low temperature, and it is possible to select a wide range of materials such as a substrate, so the degree of freedom in design is dramatically improved, making electronic devices more rational. It is also possible to make it a structure.
The electronic device according to the present invention can maintain high performance for a long time.
Further, in the laminate, depending on the required resistance value, the thickness of the copper layer, that is, the time of the plating step may be selected, and the printing accuracy may be deteriorated even when the extremely low resistance value can be obtained. (1), and the degree of freedom in design is dramatically improved, and it is possible to make the electronic device a more rational structure.

  Hereinafter, the present invention will be described in more detail by way of specific examples. However, the present invention is not limited at all to the examples shown below.

Example 1
<Production of laminates>
(Production of silver ink composition)
Add silver 2-methylacetoacetate to 2-ethylhexylamine (0.4 times the molar amount of silver 2-methylacetoacetate described later) in a beaker so that the solution temperature is 50 ° C or less, and then use a mechanical stirrer. The mixture was stirred for 15 minutes to obtain a liquid. Formic acid (0.7-fold molar amount with respect to silver 2-methylacetoacetate) was added dropwise to this liquid using a syringe pump over 30 minutes so that the temperature of the reaction solution became 50 ° C. or lower. After completion of the dropwise addition of formic acid, the reaction solution was further stirred at 25 ° C. for 1 hour to obtain a silver ink composition. The types and blending ratios of the respective blending components are shown in Table 1. In Table 1, “nitrogen-containing compound (molar ratio)” means the compounding amount (number of moles) of nitrogen-containing compound per mole of the compounding amount of the forming material of metal silver ([mole number of nitrogen-containing compound] / [metal The number of moles of silver forming material] is meant. Similarly, in the case of "reducing agent (molar ratio)", the compounding amount (number of moles) of reducing agent per mole of compounding amount of metal silver forming material ([mole number of reducing agent] / [mol of metal silver forming material] Means number]).

(Production of composition for receiving layer)
49 parts by mass of cyclohexanone (manufactured by Wako Pure Chemical Industries, Ltd.) and 49 parts by mass of UV curable polycarbonate skeleton-containing urethane acrylate (manufactured by Japan Synthetic Chemical Industry Co., Ltd. “UV-3310B”, weight average molecular weight 13000), 49 parts by mass 2 parts by mass of “IRGACURE 127” manufactured by BASF Japan Ltd. was added, and the mixture was stirred at 50 ° C. for 2 hours to prepare a composition for a receptor layer.

(Production of laminate)
Using the bar coater (bar No. 010), the composition for the receptor layer obtained above is one of the substrates made of polycarbonate resin ("Iupilon 1.5 NF 2000" manufactured by Mitsubishi Gas Chemical Co., Ltd., 1.5 mm thick) The composition is applied onto the main surface (surface) of the film, dried at 80 ° C. for 5 minutes in an oven, and then 800 mJ / cm ² of light is applied to the dried coating using an ozoneless high pressure mercury lamp. Then, the polycarbonate skeleton-containing urethane acrylate was cured by irradiation with ultraviolet light to form a receiving layer (thickness of 3 μm or less) on the entire surface of the substrate.

Subsequently, pad printing (Mishima company printing machine) was performed on the receiving layer using the silver ink composition obtained above.
(Printing conditions)
Pad: Silicone resin material Version: Metal plate, depth 40μm
Blade: Steel material triangle blade, thickness 0.9mm
Blade air setting pressure: 0.4MPa
Next, the obtained print pattern is dried in an oven at 80 ° C. for 1 minute, and further placed in a steam atmosphere at 80 ° C. and a relative humidity of 95% for 30 minutes by heating (baking) treatment. A 30 mm patterned silver layer (1 μm thick) was formed on the surface of the receiving layer.

  Next, the laminate obtained with the silver layer obtained above is immersed in a plating bath filled with a copper plating solution so that part of the silver layer is in contact with the feeding roller, and the thickness of the copper layer is 3 μm A copper layer was formed to obtain a laminate.

<Evaluation of laminate>
(Evaluation of adhesion)
About the laminated body, the adhesiveness of a silver layer and a base material (acceptor layer) was evaluated before and behind a plating process according to JISK5600-5-6. That is, after making cuts from the surface side in two directions orthogonal to each other in the silver layer and making a cross cut so that 25 regions having the same area are formed, and applying a tape to the surface of the silver layer after this cross cut, The tape was peeled off, and the number of regions where peeling of the silver layer from the substrate was not observed was confirmed among the 25 regions, and the adhesion between the silver layer and the substrate was evaluated based on the number. The results are shown in Table 2.

Example 2
A laminate was manufactured and evaluated in the same manner as in Example 1 except that the plating time was changed so that the thickness of the copper layer was 30 μm. The results are shown in Table 2.

[Example 3]
Except that the composition for the receptor layer is a resin containing a nitrogen atom and a hydroxyl group, “JELCON AC-3G” manufactured by Tojo Chemical Co., Ltd. is applied by spin coating (5 seconds at 3000 rpm, then 5 seconds at 6000 rpm) The laminate was manufactured and evaluated in the same manner as Example 1. The results are shown in Table 2.

Example 4
A laminate was manufactured and evaluated in the same manner as in Example 3 except that the plating time was changed to make the thickness of the copper layer be 30 μm. The results are shown in Table 2.

[Examples 5-8, 9-12]
Laminates were produced and evaluated in the same manner as in Examples 1 to 4 except that the blending amount of the silver ink composition was changed as shown in Table 1. The results are shown in Table 2

Comparative Example 1
A laminate was manufactured and evaluated in the same manner as in Example 1 except that the depth of the printing plate was changed to 5 μm, and the thickness of the silver layer was made to be 0.1 μm. The results are shown in Table 2.

Comparative Example 2
A laminate was manufactured and evaluated in the same manner as in Example 3 except that the depth of the printing plate was changed to 5 μm, and the thickness of the silver layer was made to be 0.1 μm. The results are shown in Table 2.

[Comparative examples 3 to 4]
Laminates were manufactured and evaluated in the same manner as Comparative Examples 1 and 2 except that the blending amount of the silver ink composition was changed as shown in Table 1. The results are shown in Table 2.

[Comparative Examples 5 to 6]
Laminates were manufactured and evaluated in the same manner as in Comparative Examples 1 and 2 except that the blending amount of the silver ink composition was changed as shown in Table 1, and the depth of the printing plate was changed to 10 μm. The results are shown in Table 2.

As is clear from the above results, in the laminates of Examples 1 to 12, the adhesion between the conductive layer and the substrate (receptive layer) satisfied the category 0 regardless of before or after the electrolytic copper plating step. However, in the laminates of Comparative Examples 1 to 6, although the conductive layer (silver layer) before electrolytic copper plating satisfies the classification 0, the conductive layer after electrolytic copper plating (silver layer + copper layer) The adhesion of the above was Class 5, and the conductive layer was peeled from the receiving layer at the interface with the receiving layer.
Thus, a clear difference was observed in the adhesion between the conductive layer and the substrate (adhesion layer) depending on the thickness of the silver layer which is the underlayer of electrolytic copper plating.

  The present invention is applicable to various electronic devices provided with a silver layer on a substrate.

DESCRIPTION OF SYMBOLS 1 laminated body 2 base material 2a one main surface 2b base material other main surface 3 base material 3 receiving layer 3 a receiving layer surface 4 silver layer 4 a silver surface 5 copper layer

Claims (2)

A laminate comprising a substrate, a silver layer formed on one side of the substrate via a receiving layer, and a copper layer laminated on the silver layer,
The silver layer is free of a resin component as a binder, Ri and 0.5μm or more thickness der,
It said receiving layer has a nitrogen atom and a hydroxyl group, a laminate, characterized that you have been formed by using a polyester having an aromatic group.   An electronic device comprising the base material as a casing, using the laminate according to claim 1.