JP2015182437A - Laminate and electronic apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate provided with a silver layer on a substrate through a reception layer, with the silver layer being small in resistance value even when the reception layer is formed by pad printing, and an electronic apparatus using the laminate.SOLUTION: In a laminate 1 provided with a silver layer 4 on a substrate 2 through a reception layer 3, the reception layer is formed with a photocurable resin composition comprising a photocurable resin and a modified polysiloxane having a photo-reactive group other than that of the photocurable resin. An electronic apparatus using the laminate 1 and provided with the substrate 2 as an enclosure is also provided.

Description

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

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

The silver layer is usually prepared by preparing a silver ink composition in which metallic silver or its forming material is blended, and depositing the composition on a substrate (receiving layer), and heating the deposited composition as necessary. It is formed by the method of (baking). In recent years, since it is easy to form a silver layer having good characteristics, a technique for forming metallic silver using a silver ink composition containing a metallic silver forming material instead of metallic silver itself has become widely used. It is coming.
Conventionally, silver oxide or the like has been widely used as a material for forming metallic silver, but it can form metallic silver with better characteristics. Β-ketocarboxylate silver has been disclosed as one that can form metallic silver quickly at low temperatures (see Patent Document 1).

On the other hand, what was formed using the composition which has an acrylic photocurable component as a main component as the said receiving layer when forming a conductive layer using a conductive ink composition is disclosed (patent document) 2).
Moreover, in order to improve the wettability with respect to the said base material, what mix | blended the surface conditioning agent is disclosed as a composition for forming the said receiving layer (refer patent document 3 and 4).
These compositions form a receiving layer on a substrate by adhering and curing on the substrate by various printing methods.

JP 2009-114232 A Japanese Patent No. 4023782 JP 2003-113350 A JP 2011-231170 A

  Usually, when a composition is deposited on a substrate by a pad printing method, a composition prepared by blending a surface conditioner as the composition is used in order to improve pad printing suitability. However, when the receiving layer is formed using a composition in which conventional surface conditioners including those described in Patent Documents 3 and 4 are blended, the silver layer formed using the silver ink composition is There is a problem that the resistance value becomes large.

  The present invention has been made in view of the above circumstances, and even if a silver layer is provided on a substrate via a receptor layer, and the receptor layer is formed by a pad printing method, the silver layer It is an object of the present invention to provide a laminate having a small resistance value and an electronic device using the laminate.

In order to solve the above-mentioned problems, the present invention is a laminate in which a silver layer is provided on a base material via a receptor layer, and the receptor layer includes a photocurable resin and a photocurable resin other than the photocurable resin. Provided is a laminate characterized in that it is formed using a photocurable resin composition comprising a modified polysiloxane having a photoreactive group.
In addition, the present invention provides an electronic apparatus using the laminate and including the base material as a casing.

  According to the present invention, even if a silver layer is provided on a substrate via a receiving layer, and the receiving layer is formed by a pad printing method, a laminate having a small resistance value of the silver layer, and An electronic device using the laminate is provided.

It is sectional drawing which illustrates typically the laminated body which concerns on this invention. It is sectional drawing for demonstrating the manufacturing method of the laminated body which concerns on this invention typically.

<< Laminate >>
The laminate according to the present invention is a laminate in which a silver layer is provided on a substrate via a receptor layer, and the receptor layer is abbreviated as a photocurable resin (hereinafter referred to as “base resin”). And a modified polysiloxane having a photoreactive group other than the photocurable resin (hereinafter sometimes abbreviated as “photoreactive modified polysiloxane”). It is formed using an object.

  In the laminate, the receiving layer improves the adhesion between the silver layer and the substrate. That is, the receiving layer and the silver layer, and the receiving layer and the base material each have high adhesion, and the silver layer provided via the receiving layer is one in which peeling from the base material is suppressed. Moreover, although a receiving layer can be formed by the pad printing method by using the said photocurable resin composition, the silver layer formed on it has a small resistance value. Thus, the compatibility between the pad printability of the photocurable resin composition and the high conductivity of the silver layer is achieved as a surface conditioner used during the preparation of the photocurable resin composition. This is due to the selection of the photoreactive modified polysiloxane.

FIG. 1 is a cross-sectional view schematically illustrating a laminate according to the present invention.
The laminated body 1 shown here includes a silver layer 4 on a base material 2 with a receiving layer 3 interposed therebetween. That is, the laminate 1 is obtained by laminating the receiving layer 3 and the silver layer 4 on the base material 2 in this order.

<Base material>
The base material 2 can select arbitrary shapes according to the objective, For example, it is preferable that it is a film form or a sheet form, it is preferable that thickness is 0.5-5000 micrometers, and it is 0.5-2500 micrometers. It is more preferable. When the thickness of the base material 2 is not less than the lower limit, the structure of the receiving layer can be more stably maintained, and when the thickness of the base material 2 is not more than the upper limit value, 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. However, it is preferable to have heat resistance that does not change when a silver layer is formed by heat treatment of a silver ink composition described later.
Specifically, the material of the substrate 2 is polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polymethylpentene (PMP), polycycloolefin, polystyrene (PS). , Acrylic resin such as polyvinyl acetate (PVAc) and polymethyl methacrylate (PMMA), AS resin, ABS resin, polyamide (PA), polyimide, polyamideimide (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, in addition to the above, ceramics such as glass and silicon, and paper can be exemplified.
The substrate 2 may be a combination of two or more materials such as glass epoxy resin and polymer alloy.

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

<Receptive layer>
The receiving layer 3 is formed using a photocurable resin composition in which the base resin and the photoreactive modified polysiloxane are blended.
In the photocurable resin composition, the base resin is a component (prepolymer) for forming a resin that is a main component of the receiving layer 3. The photoreactive modified polysiloxane is a resin forming material that functions as a surface conditioner.
The photocurable resin composition will be described in detail later.

  The receiving layer 3 is mainly composed of the base resin or a polymer (cured resin) obtained by polymerizing the base resin and the photoreactive modified polysiloxane, and the content of the polymer is It is preferably 90% by mass or more, and more preferably 95% by mass or more. When the content of the polymer is equal to or more than the lower limit, the effect of improving the pad printing suitability of the receiving layer 3 is improved while improving the adhesion between the silver layer 4 and the substrate 2.

  The shape of the receiving layer 3 when the laminate 1 is viewed in plan so that one main surface (the surface on which the receiving layer 3 is formed) 2a of the substrate 2 is looked down from above is arbitrarily selected according to the purpose. It can be set and may be set in consideration of the shape of the silver layer 4 described later. For example, the receiving layer 3 may be provided on the entire surface of the base material 2, or the receiving layer 3 may be provided on only a part of the surface of the base material 2. May be patterned.

  The thickness of the receiving layer 3 is preferably 0.001 to 20 μm, and more preferably 0.002 to 5 μm. When the thickness of the receiving layer 3 is not less than the lower limit, the adhesion of the silver layer 4 is further improved, and when the thickness of the receiving layer 3 is not more than the upper limit, the structure of the receiving layer is more stable. Can be held.

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

  Although the thickness of the silver layer 4 can be arbitrarily set according to the objective, it is preferable that it is 0.01-5 micrometers, and it is more preferable that it is 0.05-3 micrometers. When the thickness of the silver layer 4 is equal to or more than the lower limit, the conductivity can be further improved, and the structure of the silver layer 4 can be more stably maintained. Moreover, the laminated body 1 can be made thinner by the thickness of the silver layer 4 being the said upper limit or less.

  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 in the same manner as in the case of the substrate 2. For example, the silver layer 4 composed of a plurality of layers may be configured such that the total thickness of each layer is the thickness of the preferred silver layer 4 described above.

  The silver layer 4 is excellent in conductivity. For example, when formed using a silver β-ketocarboxylate described later as a metal silver forming material, the volume resistivity is preferably 100 μΩ · cm or less, more preferably 90 μΩ. It is possible to make it cm or less, more preferably 80 μΩ · cm or less, particularly preferably 70 μΩ · cm or less. The volume resistivity of the silver layer 4 can be adjusted by the type of metal silver forming material and the thickness of the silver layer 4 itself.

The laminate according to the present invention is not limited to that shown in FIG. 1, and other configurations may be added or some configurations may be appropriately changed within a range not impairing the effects of the present invention. For example, another layer other than the receiving layer 3 and the silver layer 4 may be provided on the substrate 2, and the other layer may be an overcoat layer (not shown) that covers the receiving layer 3 and the silver layer 4. ) Can be exemplified.
Moreover, although the thing provided with the silver layer 4 via the receiving layer 3 on one main surface 2a of the base material 2 as the laminated body 1 is shown here, the laminated body based on this invention is the base material 2. Similarly, the other main surface 2b may be provided with the silver layer 4 via the receiving layer 3 (on both main surfaces of the substrate 2).

  As described above, the laminate according to the present invention has both the pad printing suitability at the time of forming the receiving layer and the high conductivity of the silver layer, is excellent in practicality, and uses the silver layer as a conductive layer. It is extremely useful for application to various electronic devices such as circuit boards and antenna structures used. However, the use of the laminate according to the present invention is not limited to these.

<< Manufacturing Method of Laminate >>
The laminate according to the present invention includes, for example, a step of forming a receiving layer on a substrate (hereinafter, sometimes abbreviated as “receiving layer forming step”) and a step of forming a silver layer on the receiving layer ( Hereinafter, it may be abbreviated as “silver layer forming step”).
FIG. 2 is a cross-sectional view for schematically explaining the method for manufacturing the laminate 1 shown in FIG.

<Receptive layer forming step>
In order to manufacture the laminated body 1, first, as shown in FIG.2 (b), the receiving layer 3 is formed on the surface (one main surface) 2a of the base material 2. As shown in FIG.
The receiving layer 3 is prepared, for example, by preparing a photocurable resin composition in which the base resin and the photoreactive modified polysiloxane for forming the polymer (cured resin) that is the main constituent component are blended, It can be formed by adhering this onto the substrate 2 and curing the composition by light irradiation. At this time, other processes such as a drying process and a heating process may be performed as necessary, and the heating process may also serve as a drying process.
It is preferable that the photocurable resin composition further comprises a photopolymerization initiator and a solvent in addition to the base resin and the photoreactive modified polysiloxane.

[Base resin]
The base resin is not particularly limited as long as it is a photocurable resin that can constitute the receiving layer 3.
The base resin is preferably urethane (meth) acrylate.
In this specification, “(meth) acrylate” is a concept including both “acrylate” and “methacrylate”.

The urethane (meth) acrylate in the base resin preferably has a weight average molecular weight of 2000 to 20000, more preferably 2300 to 17000. When the weight average molecular weight is in such a range, the effect of improving the pad printing suitability of the receiving layer 3 is improved while the adhesion between the silver layer 4 and the substrate 1 is improved.
In addition, in this specification, "weight average molecular weight" is calculated | required on the polystyrene conversion reference | standard by GPC (gel permeation chromatography).

[Photoreactive modified polysiloxane]
The photoreactive modified polysiloxane is not particularly limited as long as it has a photoreactive group and has a modified polysiloxane skeleton, and may be appropriately selected in consideration of the type of the base resin used in combination. .

The photoreactive group possessed by the photoreactive modified polysiloxane is preferably a polymerizable group, and is not particularly limited as long as the target photoreaction is possible. Preferred examples of the photoreactive group include a polymerizable unsaturated double bond (C = C) between carbon atoms such as (meth) acryl group, ethenyl group (vinyl group), 2-propenyl group (allyl group) and the like. Examples thereof include an epoxy group (—CHOCH ₂ ) and the like.
In this specification, “(meth) acrylic group” is a concept including both “acrylic group” and “methacrylic group”.

  The photoreactive group possessed by the photoreactive modified polysiloxane is preferably one that reacts with the same reaction mechanism as the reactive group such as a polymerizable group possessed by the base resin. For example, when the base resin has a polymerizable unsaturated double bond between carbon atoms, the photoreactive modified polysiloxane also preferably has a polymerizable unsaturated double bond between carbon atoms.

  The number of photoreactive groups possessed by the photoreactive modified polysiloxane may be only one per molecule, or may be two or more. And when the photoreactive modified polysiloxane has two or more polymerizable groups per molecule, these polymerizable groups may be only one kind, may be two kinds or more, if two or more kinds, the combination and The ratio can be arbitrarily selected. However, it is preferable that these two or more polymerizable groups all react by the same reaction mechanism.

  The photoreactive modified polysiloxane is preferably a photoreactive modified polyalkylsiloxane having one or two alkyl groups directly bonded to one silicon atom (Si) constituting the main chain, More preferred is a photoreactive modified polydialkylsiloxane.

In the photoreactive modified polyalkylsiloxane, the alkyl group directly bonded to the silicon atom constituting the main chain may be linear, branched or cyclic, and if it is cyclic, it is monocyclic And any of polycyclic may be sufficient.
The linear or branched alkyl group preferably has 1 to 10 carbon atoms, and includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an 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, -Methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1,1-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3 , 3-dimethylpentyl group, 4,4-dimethylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 4-ethylpentyl group, 2,2,3-trimethylbutyl group, 1 -Propylbutyl group, n-octyl group, isooctyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 1-ethylhexyl group, 2- Ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 5-ethylhexyl group, 1,1-dimethylhexyl group, 2,2-di- Ethylhexyl group, 3,3-dimethyl hexyl group, 4,4-dimethyl hexyl group, 5,5-dimethyl hexyl group, 1-propyl pentyl group, 2-propyl pentyl group, nonyl group, decyl group and the like.
Among these, the linear or branched alkyl group preferably has 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
The cyclic alkyl group preferably has 3 to 10 carbon atoms, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, isobornyl group. Examples thereof include a group, 1-adamantyl group, 2-adamantyl group and tricyclodecyl group.

  In the photoreactive modified polyalkylsiloxane, the alkyl group directly bonded to the silicon atom constituting the main chain may be only one kind or two or more kinds. Can be arbitrarily selected. However, it is preferable that only one alkyl group is directly bonded to the silicon atom.

  The structure of the modified site of the photoreactive modified polysiloxane is not particularly limited, but from a polyether structure such as a polyalkyleneoxy group (for example, polyethyleneoxy group, polypropyleneoxy group), a polyester structure, or an aromatic ring of an aralkyl group. A divalent group in which one hydrogen atom is removed is preferable.

In the photoreactive modified polysiloxane, the modification site and the photoreactive group binding site are not particularly limited.
However, the photoreactive group binding site in the photoreactive modified polysiloxane is preferably at the end of the main chain. Moreover, it is preferable that the modification site | part in photoreactive modified polysiloxane is the terminal part of a polysiloxane chain. In the photoreactive modified polysiloxane, the photoreactive group is preferably bonded to the modified site.

  Preferred examples of the photoreactive modified polysiloxane include compounds represented by the following general formula (P) -1 or (P-2).

（式中、Ｚ^１及びＺ^２はそれぞれ独立に１価の光反応性基であり、Ｚ^１又はＺ^２が複数個存在する場合、これら複数個のＺ^１又はＺ^２は互いに同一でも異なっていてもよく；Ｒ^Ｐ１及びＲ^Ｐ２はそれぞれ独立に２価の変性基であり、Ｒ^Ｐ１又はＲ^Ｐ２が複数個存在する場合、これら複数個のＲ^Ｐ１又はＲ^Ｐ２は互いに同一でも異なっていてもよく；Ｒ^Ｐ３は連結基であり、複数個のＲ^Ｐ３は互いに同一でも異なっていてもよく；ｎｐは２以上の整数である。）

(Wherein, a monovalent photoreactive groups each Z ¹ and Z ² are independently if Z ¹ or Z ² there are a plurality, a plurality of Z ¹ or Z ² which are mutually the same or different at ^{best; R P1} and ^{R P2} are each independently a divalent modified ^{group, if R P1} or ^{R P2} there are a plurality, even these plurality of ^{R P1} or ^{R P2} are identical or different from each other Well; R ^P3 is a linking group, and a plurality of R ^P3 may be the same or different from each other; np is an integer of 2 or more.)

In the formula, Z ¹ and Z ² are each independently a monovalent photoreactive group and have been described above.
In the formula, R ^P1 and R ^P2 are each independently a divalent modifying group, which is the same as the modifying site described above.
In the formula, R ^P3 is a linking group, and a plurality (two) of R ^P3 may be the same or different from each other, and examples of the linking group include a hydrocarbon group.

  The photoreactive modified polysiloxane is preferably a polyether-modified polysiloxane or a polyester-modified polysiloxane, and more preferably a polyether-modified polyalkylsiloxane or a polyester-modified polyalkylsiloxane.

[Photopolymerization initiator]
The photopolymerization initiator is not particularly limited and may be a known one, and may be appropriately selected according to the types of the base resin and the photoreactive modified polysiloxane.

[solvent]
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.

  In the photocurable resin composition, each of the base resin, the photoreactive modified polysiloxane, the photopolymerization initiator, and the solvent may be used alone or in combination of two or more. When using more than one species in combination, their combination and ratio can be arbitrarily adjusted.

In the photocurable resin composition, the ratio of the blending amount of the base resin to the total amount of blending components is preferably 30 to 70% by mass, and more preferably 40 to 60% by mass.
In the photocurable resin composition, the ratio of the amount of the photoreactive modified polysiloxane to the total amount of the components is preferably 0.1 to 5% by mass, and preferably 0.1 to 3% by mass. Is more preferable.
In the photocurable resin composition, the ratio of the 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 photocurable resin composition, the ratio of the amount of the solvent to the total amount of the components is preferably 30 to 70% by mass, and more preferably 40 to 60% by mass.

[Other ingredients]
In addition to the base resin, the photoreactive modified polysiloxane, the photopolymerization initiator, and the solvent, the photocurable resin composition may further include other components not corresponding to these.
The other components can be arbitrarily selected according to the purpose and are not particularly limited. For example, as the other components, other resin forming materials other than the base resin and the photoreactive modified polysiloxane may be used as long as the effects of the present invention are not impaired.

  The other components in the photocurable resin composition may be used singly or in combination of two or more, in the case of using two or more in combination, Can be adjusted arbitrarily.

In the photocurable resin composition, the ratio of the amount of the other components to the total amount of the components is preferably 10% by mass or less, and more preferably 5% by mass or less.
And when using other resin forming materials other than the said base resin and photoreactive modified polysiloxane, the ratio of the compounding quantity of the said other resin forming material with respect to the total compounding quantity of the resin forming material in a photocurable resin composition ([Blending amount (mass) of other resin forming material] / [total blending amount (mass) of the base resin, photoreactive modified polysiloxane, and other resin forming material] × 100) is 10% by mass or less Is preferably 5% by mass or less, more preferably 2% by mass or less, and particularly preferably 1% by mass or less.
When the proportion of the other components is less than or equal to the upper limit, the effect of improving the pad printing suitability of the receiving layer 3 is improved while improving the adhesion between the silver layer 4 and the substrate 1. .

  The photocurable resin composition is blended with the base resin and the photoreactive modified polysiloxane. Preferably, in addition to these, a photopolymerization initiator and a solvent are blended, and the other components are blended as necessary. It is obtained by doing. After blending each component, the resulting product may be used as it is as a photocurable resin composition, or a product obtained by performing a known purification operation as necessary may be used as a photocurable resin composition. .

At the time of blending each component, all the components may be added and then mixed, or some components may be mixed while being added sequentially, or all components may be mixed while being added sequentially. Good.
The mixing method is not particularly limited, a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer, a three-roller, a kneader, a bead mill or the like; a method of mixing by adding ultrasonic waves, etc. What is necessary is just to select suitably from a well-known method.

  In the photocurable resin composition, all of the compounding components may be dissolved, or a part of the components may be dispersed without dissolving, but it is preferable that all of the compounding components are dissolved. The undissolved component is preferably dispersed uniformly. In the case of uniformly dispersing the undissolved component, for example, it is preferable to apply a method of dispersing using the above-described three-roll, kneader or bead mill.

The temperature at the time of blending is not particularly limited as long as each blending component does not deteriorate, but it is preferably 15 to 60 ° C. And the temperature at the time of mixing | blending is good to adjust suitably so that the mixture obtained by mix | blending may become the viscosity which is easy to stir according to the kind and quantity of a mixing | blending component.
Also, the blending time is not particularly limited as long as each blending component does not deteriorate, but it is preferably 5 minutes to 3 hours.

A photocurable resin composition can be made to adhere on the base material 2 by well-known methods, such as a printing method, the apply | coating method, and the immersion method, for example.
Examples of the printing method include screen printing method, flexographic printing method, offset printing method, dip printing method, ink jet printing method, dispenser printing method, gravure printing method, gravure offset printing method, pad printing method and the like.
Examples of the coating method include spin coaters, air knife coaters, curtain coaters, die coaters, blade coaters, roll coaters, gate roll coaters, bar coaters, rod coaters, gravure coaters, and other methods such as wire bars. It can be illustrated.
Especially, the photocurable resin composition in this invention is especially suitable for the application to a pad printing method. The reason is that, as described above, the photocurable resin composition is prepared using photoreactive modified polysiloxane as a surface conditioner, and has appropriate wettability to the substrate 2. It is.

  In the receiving layer forming step, for example, the thickness of the receiving layer 3 is adjusted by adjusting the amount of the photocurable resin composition to be deposited on the substrate 2 or the blending amount of the base resin in the photocurable resin composition. You can adjust the height.

  The drying treatment and heat treatment of the photocurable resin composition may be performed by any known method, for example, under normal pressure, reduced pressure, or blowing conditions, and may be performed in the atmosphere or in an inert gas atmosphere. You can do either of the following. The treatment temperature is not particularly limited, and may be set as appropriate according to the purpose. For example, the drying treatment may be either a heat drying treatment or a room temperature drying treatment. In the case of a heat drying treatment, for example, the drying treatment can be preferably performed at 60 to 100 ° C. for 2 to 10 minutes.

In order to cure the photocurable resin composition, the photocurable resin composition deposited on the substrate 2 may be irradiated with light by a known method. Irradiation light may be appropriately selected according to the type of the base resin and the like, and is usually preferably ultraviolet rays. The amount of light upon light irradiation is preferably 50 to 1000 mJ / cm ² .

  When the photocurable resin composition is deposited on the substrate 2 by pad printing or the like, that is, at the stage before curing, the photoreactive modified polysiloxane functions as a surface conditioner, while the receiving layer 3 is formed. That is, at the stage during curing of the photocurable resin composition, the photoreactive modified polysiloxane reacts with the base resin or a partially polymerized polymer in the middle of polymerization to finally form the receiving layer 3. After the formation, that is, after the curing of the photocurable resin composition, the photoreactive modified polysiloxane is taken into the polymer of the base resin, and the movement of the photoreactive modified polysiloxane in the receiving layer 3 is suppressed. It is speculated that. The photoreactive modified polysiloxane is suppressed from being released from the receiving layer 3 and is prevented from being mixed into the silver layer 4 to be described later, so that the silver layer 4 has high purity and does not have a low resistance value. I guess that. On the other hand, since the conventional surface conditioner is not taken into the polymer of the base resin, it remains free in the formed receiving layer even after the curing of the photocurable resin composition. For this reason, it is presumed that it is easy to be mixed into the silver layer, the purity of the silver layer is lowered, and the resistance value is increased.

In the receiving layer forming step, the substrate 2 may be heat-treated (annealed) before the photocurable resin composition is attached. By heat-treating the substrate 2, when the photocurable resin composition is heat-treated in this step, or when the silver ink composition is heat-treated (baked) in the silver layer forming step described later, Shrinkage of the base material 2 is suppressed and dimensional stability is improved.
The conditions for the heat treatment of the substrate 2 before attaching the photocurable resin composition may be appropriately adjusted according to the type of the substrate 2, and are not particularly limited, but are 60 to 200 ° C. for 10 to 60 minutes. It is preferable to heat-process, for example, it may be the same as the conditions of the heat (baking) process of the silver ink composition in a silver layer formation process.

Moreover, in this invention, you may plasma-process the formation surface of the receiving layer 3 of the base material 2 before making a photocurable resin composition adhere. By subjecting the substrate 2 to plasma treatment, bleeding of the silver ink composition may be suppressed on the receiving layer 3 in a 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, it can be performed under conditions of a voltage of 290 to 300 W, an air velocity of 1.0 to 5.0 m / min, and the like.

<Silver layer formation process>
In order to manufacture the laminate 1, the silver layer 4 is then formed on the surface (main surface) 3 a of the receiving layer 3 as shown in FIG.
The silver layer 4 is prepared by preparing a composition for forming the silver layer (hereinafter sometimes abbreviated as “composition for silver layer”), and attaching it to a desired location on the receiving layer 3. It can be formed by appropriately selecting post-treatment such as heat treatment (baking). The heat treatment may be performed also as a drying treatment.
In addition, the silver layer 4 is prepared by preparing a composition for the silver layer, adhering it to a predetermined portion or the entire surface of the receiving layer 3, and appropriately selecting post-treatment such as drying treatment or heating (firing) treatment. Then, after forming a silver layer (a silver layer before patterning, not shown), the silver layer may be patterned to have a desired shape by a known method such as etching.

In the present invention, as the silver layer composition, a silver ink composition prepared by blending metal silver or a metal silver forming material is prepared, and this is deposited on the receiving layer 3 for drying treatment or heating ( It is preferable to form the silver layer 4 by appropriately selecting post-treatment such as (baking) treatment.
The metallic silver or metallic silver forming material to be blended may be 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 (tube shape, wire shape, etc.), and more preferably nanoparticles or nanowires.
In the present specification, “nanoparticle” means a particle having a particle size of 1 nm or more and less than 1000 nm, preferably 1 to 100 nm, and “nanowire” means a width of 1 nm or more and less than 1000 nm, preferably It means a wire that is 1 to 100 nm.

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

  The silver ink composition is preferably in a liquid form, and preferably a metal silver forming material dispersed uniformly.

Hereinafter, a method for forming the silver layer 4 in the case where a silver ink composition containing a metallic silver forming material is used will be described.
The material for forming metallic silver is preferably one that decomposes by heating to form metallic silver.

[Silver carboxylate]
Examples of the metal silver forming material include silver carboxylate having a group represented by the formula “—COOAg”.
In this invention, silver carboxylate may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together, the combination and ratio can be adjusted arbitrarily.
The silver carboxylate is not particularly limited as long as it has a group represented by the formula “—COOAg”. For example, the number of groups represented by the formula “—COOAg” may be only one, or two or more. Further, the position of the group represented by the formula “—COOAg” in the silver carboxylate is not particularly limited.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

β-ketocarboxylate silver (1) is silver 2-methylacetoacetate (CH ₃ —C (═O) —CH (CH ₃ ) —C (═O) —OAg), silver acetoacetate (CH ₃ —C (= O) —CH ₂ —C (═O) —OAg), silver 2-ethylacetoacetate (CH ₃ —C (═O) —CH (CH ₂ CH ₃ ) —C (═O) —OAg), silver propionyl acetate _{(CH 3 CH 2 -C (=} O) -CH 2 -C (= O) -OAg), isobutyryl silver acetate _{((CH 3) 2 CH-} C (= O) -CH 2 -C (= O) - OAg), silver pivaloyl acetate ((CH ₃ ) ₃ C—C (═O) —CH ₂ —C (═O) —OAg), silver caproyl acetate (CH ₃ (CH ₂ ) ₃ CH ₂ —C (═O) _{) -CH 2 -C (= O)} -OAg), 2-n- Buchiruaseto silver acetate _{(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).

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

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

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

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

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

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

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

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

The silver carboxylate is silver 2-methylacetoacetate, silver acetoacetate, silver 2-ethylacetoacetate, silver propionylacetate, silver isobutyrylacetate, silver pivaloylacetate, silver caproylacetate, silver 2-n-butylacetoacetate, 2-benzylacetoacetate Silver acetate, silver benzoyl acetate, silver pivaloyl acetoacetate, silver isobutyryl acetoacetate, silver acetone dicarboxylate, silver pyruvate, silver acetate, silver butyrate, silver isobutyrate, silver 2-ethylhexanoate, silver neodecanoate, silver It is preferably at least one selected from the group consisting of silver oxide and silver malonate.
Among these silver carboxylates, silver 2-methylacetoacetate and silver acetoacetate are excellent in compatibility with the nitrogen-containing compounds (among others amine compounds) described later, and are particularly suitable for increasing the concentration of silver ink compositions. It is mentioned as a thing.

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

[Nitrogen-containing compounds]
The silver ink composition is preferably one in which a nitrogen-containing compound is further blended in addition to the metal silver forming material, particularly when the metal silver forming material is the silver carboxylate.
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 reacting an amine compound having 25 or less carbon atoms with an acid (hereinafter sometimes abbreviated as “ammonium salt derived from an amine compound”), and ammonia reacting with an acid. One or more selected from the group consisting of ammonium salts (hereinafter sometimes abbreviated as “ammonium salts derived from ammonia”). That is, the nitrogen-containing compound to be blended may be only one kind, or two or more kinds. When two or more kinds are used in combination, the combination and ratio can be arbitrarily adjusted.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  In the silver ink composition, the compounding amount of the nitrogen-containing compound is preferably 0.4 to 15 mol, more preferably 0.8 to 5 mol, per mol of the metal silver forming material. preferable. When the blending amount of the nitrogen-containing compound is within such a range, the silver ink composition is further improved in stability and the quality of the conductor (metal silver) is further improved. Furthermore, the conductor can be formed more stably without performing heat treatment at a high temperature.

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

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

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

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

The alkoxy group having 20 or less carbon atoms in R ²¹ has 1 to 20 carbon atoms, and examples thereof include monovalent groups in which the alkyl group in R ²¹ is bonded to an oxygen atom.

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

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

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

  In the silver ink composition, the compounding amount of the reducing agent is preferably 0.04 to 3.5 mol, and preferably 0.06 to 2.5 mol per 1 mol of the metal silver forming material. Is more preferable. When the blending amount of the reducing agent is within such a range, the silver ink composition can form a conductor (metal silver) more easily and more stably.

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

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

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

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

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

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

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

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

  When acetylene alcohol (2) is used, the amount of acetylene alcohol (2) in the silver ink composition is preferably 0.03 to 0.7 mole per mole of the metal silver forming material. 0.05 to 0.3 mol is more preferable. When the blending amount of acetylene alcohol (2) is within such a range, the stability of the silver ink composition is further improved.

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

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

  In the silver ink composition, the ratio of the blending amount of the other components to the total amount of the blending components is preferably 10% by mass or less, more preferably 5% by mass or less, and 0 mass, ie other components. Even if it is not added, the silver ink composition exhibits its effect sufficiently.

  In the silver ink composition, all the compounding components may be dissolved, or some or all of the components may be dispersed without dissolving, but it is preferable that all the compounding components are dissolved. The undissolved component is preferably dispersed uniformly.

[Method for producing silver ink composition]
The silver ink composition is obtained by blending components other than the metallic silver forming material and the metallic silver forming material. After the blending of each component, the resulting product may be used as it is as a silver ink composition, or a product obtained by performing a known purification operation as necessary may be used as a silver ink composition. In the present invention, in particular, when β-ketocarboxylate (1) is used as the material for forming the metal silver, impurities that impede conductivity are not generated at the time of blending the above components, or such Since the generation amount of impurities can be suppressed to a very small amount, a conductor (metal silver) having sufficient conductivity can be obtained even if a silver ink composition that has not been 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 components may be mixed while being added sequentially, or all components may be mixed while being added sequentially. Good. However, in this invention, it is preferable to mix | blend the said reducing agent by dripping, and exists in the tendency which can further reduce the surface roughness of metal silver by suppressing the fluctuation | variation of dripping speed | rate.
The mixing method is not particularly limited, a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer, a three-roller, a kneader, a bead mill or the like; a method of mixing by adding ultrasonic waves, etc. What is necessary is just to select suitably from a well-known method.
In the silver ink composition, when the undissolved component is uniformly dispersed, for example, a method of dispersing using the above-described three rolls, kneader, bead mill or the like is preferably applied.

The temperature at the time of blending is not particularly limited as long as each blending component does not deteriorate, but is preferably −5 to 60 ° C. And the temperature at the time of mixing | blending is good to adjust suitably so that the mixture obtained by mix | blending may become the viscosity which is easy to stir according to the kind and quantity of a mixing | blending component.
Further, 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 be further supplied with carbon dioxide. Such a silver ink composition has a high viscosity. For example, a flexographic printing method, a screen printing method, a gravure printing method, a gravure offset printing method, a pad printing method, etc. Suitable for application.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The temperature at the time of blending the reducing agent is not particularly limited as long as each blended component does not deteriorate, but is preferably −5 to 60 ° C. And the temperature at the time of mixing | blending is good to adjust suitably so that the mixture obtained by mix | blending may become the viscosity which is easy to stir according to the kind and quantity of a mixing | blending component.
Moreover, what is necessary is just to adjust a compounding time suitably according to the kind of compounding component, and the temperature at the time of a compounding, For example, it is preferable that it is 0.5 to 12 hours.

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

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

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

  The second mixture in the present invention has a higher viscosity than usual due to the supply of carbon dioxide as described above. On the other hand, when the reducing agent is blended into the second mixture, depending on the type of the second mixture or the reducing agent, formation of metallic silver is started in at least part of the metallic silver forming material as described above. Metallic silver may precipitate. Here, when the viscosity of the second mixture is high, the aggregation of the precipitated metallic silver is suppressed, and the dispersibility of the metallic silver in the obtained silver ink composition is improved. A conductor obtained by forming metallic silver by a 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, carbon dioxide is not supplied. In addition, it has higher electrical conductivity (lower volume resistivity), lower surface roughness, and more favorable characteristics than a conductor using a silver ink composition.

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

  In the step of forming the silver layer 4, the silver layer 4 is adjusted by adjusting the amount of the silver ink composition to be deposited on the substrate 2 or the amount of the metallic silver forming material in the silver ink composition. Can adjust the thickness.

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

  When the silver ink composition deposited on the substrate 2 is heated (baked), the conditions may be adjusted as appropriate according to the type of compounding component of the silver ink composition. Usually, it is preferable that heating temperature is 60-200 degreeC, and it is more preferable that it is 70-180 degreeC. Although what is necessary is just to adjust a heating time according to heating temperature, Usually, it is preferable that it is 0.2 to 12 hours, and it is more preferable that it is 0.4 to 10 hours. Among the silver metal forming materials, the silver carboxylate, particularly β-ketocarboxylate silver (1) is different from metal silver forming materials such as silver oxide, for example, using a reducing agent known in the art. Even if not, it decomposes at low temperature. Reflecting such decomposition temperature, the silver ink composition can form metallic silver at an extremely lower temperature than the conventional one as described above.

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

  In the case of manufacturing a laminate according to the present invention in which other layers other than the receiving layer 3 and the silver layer 4 are provided on the base material 2, in the manufacturing method described above, the other layers are provided at a predetermined timing. A step of forming the layer may be added as appropriate.

  As described above, the laminate according to the present invention has a small resistance value and a sufficiently high conductivity of the silver layer in addition to suppressing the peeling of the silver layer from the base material. It is extremely useful as a component of various electronic devices such as communication devices.

<< Electronic equipment >>
The electronic device according to the present invention is characterized in that the laminate is used and the base material is provided as a casing. For example, except that at least a part of the casing is configured by the base material in the laminate. The configuration can be similar to that of a known electronic device. For example, by using a patterned silver layer as a circuit, the stacked body can be used as a circuit board, and in addition to the stacked body, by combining a voice input unit, a voice output unit, an operation switch, a display unit, and the like. A mobile phone can be configured. Further, by using the patterned silver layer as an antenna, the laminate can be used as an antenna structure, and the configuration is the same as that of a known data transmitter / receiver except that the antenna structure is used. Thus, a new data receiving / transmitting body can be obtained. For example, in the laminated body 1 shown in FIG. 1, a non-contact type data receiving / transmitting body can be formed by providing an IC chip electrically connected to the silver layer 4 on the base material 2 to form an antenna portion.
In the laminate, the silver layer can be formed at a low temperature, and a wide range of materials such as a base material can be selected. This greatly improves the degree of freedom in design and makes electronic devices more rational. A structure is also possible.
The electronic device according to the present invention can maintain high performance over a long period of time.

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

[Example 1]
<Manufacture of laminates>
(Manufacture of silver ink composition)
Add 2-methyl acetoacetate silver to 2-ethylhexylamine (2.5 times molar amount relative to 2-methyl acetoacetate silver described later) in a beaker so that the liquid temperature is 50 ° C. or less. The mixture was stirred for 15 minutes to obtain a liquid material. To this liquid, formic acid (1.5-fold molar amount with respect to silver 2-methylacetoacetate) was added dropwise over 30 minutes using a syringe pump so that the temperature of the reaction solution was 50 ° C. or lower. After the formic acid was dropped, the reaction solution was further stirred at 25 ° C. for 1 hour to obtain a silver ink composition. Table 1 shows the types and blending ratios of each blending component. In Table 1, “nitrogen-containing compound (molar ratio)” means the compounding amount (number of moles) of nitrogen-containing compound per mol of compounding material of the metallic silver ([number of moles of nitrogen-containing compound] / [metal The number of moles of silver forming material]). Similarly, the “reducing agent (molar ratio)” is the amount (mole number) of the reducing agent per mole of the metal silver forming material ([mole number of reducing agent] / [mole of metal silver forming material). Number]).

(Production of photocurable resin composition)
As shown in Table 2, urethane acrylate (manufactured by Nippon Synthetic Chemical Industry "purple light UV-3310B", weight average molecular weight 13000) (100 parts by mass), cyclohexanone (manufactured by Wako Pure Chemical Industries, Ltd.) (100 parts by mass), light Polymerization initiator ("Irgacure 127" manufactured by BASF Japan) (5 parts by mass), surface conditioner mainly composed of polyether-modified polydimethylsiloxane having an acrylic group ("BYK-UV3500" manufactured by BYK Japan Japan) ( 1 part by mass) was added and stirred at 50 ° C. for 2 hours to prepare a photocurable resin composition as a solution. In addition, the compounding quantity of components other than said solvent is all solid content.

(Manufacture of laminates)
The photocurable resin composition obtained above is padded on one main surface (surface) of a base material (“EFN-800-4” manufactured by Sumitomo Bakelite Co., Ltd., thickness 2 mm) made of polycarbonate / ABS resin alloy. After coating with a printing method and drying in an oven at 80 ° C. for 5 minutes, using an ozone-less high-pressure mercury lamp, ultraviolet rays are applied to the dried coating film at an integrated dose of 100 mJ / cm ^2. Was applied to cure the composition to form a receiving layer (4 μm thick) on the entire surface of the substrate.

Subsequently, screen printing was performed on the receiving layer using the silver ink composition obtained above. As the screen plate, a stainless steel 500 mesh was used, and printing was performed under the condition of an emulsion thickness of 30 μm.
Next, the obtained printed pattern was heated (baked) in an oven at 80 ° C. for 1 hour to form a patterned silver layer (thickness: 1 μm) on the surface of the receiving layer.

<Evaluation of laminate>
(Measurement of volume resistivity of silver layer)
With respect to the formed silver layer, the line resistance value R (Ω), the cross-sectional area A (cm ² ), and the line length L (cm) are measured, and the volume resistance of the silver layer is determined by the equation “ρ = R × A / L”. The rate ρ (μΩ · cm) was calculated. The wire resistance value R is measured using a digital multimeter ("PC5000a" manufactured by Sanwa Denki Keiki Co., Ltd.), and the cross-sectional area A is measured using a shape measurement laser microscope ("VK-X100" manufactured by Keyence Corporation). did. The results are shown in Table 2.

<Manufacture and evaluation of laminate>
[Example 2, Comparative Examples 1-2]
A laminate was produced and evaluated in the same manner as in Example 1 except that instead of “BYK-UV3500”, the one shown in Table 2 was used as the surface conditioner. In Comparative Example 1, no surface conditioner was used. The results are shown in Table 2.
The surface conditioners used in each example and comparative example are as follows.

(Surface conditioner)
Polyether-modified polydimethylsiloxane having an acrylic group: BYK-UV3500 (produced by Big Chemie Japan, represented by the general formula (P) -1, Z ¹ and Z ² are acrylic groups, and R ^P1 and R ^P2 are A compound that is a polyethyleneoxy group or a polypropyleneoxy group.)
Polyester-modified polydimethylsiloxane having an acrylic group: BYK-UV3570 (manufactured by Big Chemie Japan, represented by the general formula (P) -2, Z ¹ and Z ² are all acrylic groups, and R ^P1 and R ^P2 are All compounds with a polyester structure.)
Polyether-modified polydimethylsiloxane having no photoreactivity: BYK-331 (by Big Chemie Japan)

As is clear from the above results, in Examples 1 and 2, the photocurable resin composition had good pad printability, and the silver layer had low volume resistivity and excellent conductivity.
On the other hand, in Comparative Example 1, the photocurable resin composition could not be pad-printed because no surface conditioner was used. Therefore, for reference, when the silver layer was formed by a coating method using a bar coater instead of the pad printing method, the volume resistivity was small and the conductivity was excellent.
In Comparative Example 2 using a polyether-modified polydimethylsiloxane not having a photoreactive group instead of a photoreactive modified polysiloxane, the pad printability of the photocurable resin composition was good, but silver The layer had a high volume resistivity and was poor in conductivity. This is because the polyether-modified polydimethylsiloxane having no photoreactive group does not react with the base resin or a partial polymer during the polymerization at the stage of curing the photocurable resin composition. It is presumed that after the curing of the photosensitive resin composition, it was released from the formed receiving layer and mixed into the silver layer.

  INDUSTRIAL APPLICABILITY The present invention can be used for various electronic devices including a silver layer on a base material such as an electromagnetic wave shield, a touch panel, and an antenna of a wireless communication device casing.

  DESCRIPTION OF SYMBOLS 1 ... Laminated body, 2 ... Base material, 2a ... One main surface of a base material, 2b ... The other main surface of a base material, 3 ... Receiving layer, 3a ... Receiving Layer surface, 4 ... silver layer

Claims (2)

A laminate in which a silver layer is provided on a substrate via a receiving layer,
The receiving layer is formed using a photocurable resin composition comprising a photocurable resin and a modified polysiloxane having a photoreactive group other than the photocurable resin. A laminate characterized by the following.   An electronic apparatus using the laminate according to claim 1, wherein the substrate is provided as a casing.

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