JP2016010954A - Laminate and circuit board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate which is excellent in joining strength between a wiring part and an electronic part under high-temperature, high-humidity conditions and a circuit board.SOLUTION: A laminate has a silver layer 12 on a substrate 11, and the silver layer 12 has a surface whose skewness of the roughness curve satisfies at least one of conditions (i) and (ii). (i) The change rate of the skewness is 35% or greater after the time lapse of 240 h under the conditions of the temperature of 85°C and the relative humidity of 85%. (ii) The change rate of the skewness is 40% or greater after the time lapse of 480 h under the conditions of the temperature of 85°C and the relative humidity of 85%.

Description

  The present invention relates to a laminate including a silver layer, and a circuit board on which electronic components are mounted on the laminate.

Circuit boards in which electronic parts such as external connection electrodes are bonded to wiring portions on a base material with a conductive adhesive or the like are mounted on a wide range of products, and an enormous amount is used.
Such a circuit board usually has a problem that the bonding force between the wiring part and the electronic component tends to be reduced under high temperature and high humidity conditions.
On the other hand, as a technique for improving the bonding force between the wiring portion and the electronic component, the surface of the bonding portion of the electronic component is covered with a metal such as silver, or the surface roughness of the bonding portion surface is 0.1 μm or more and 10 μm. A method of making the ratio less than the maximum is disclosed (see Patent Document 1).

  However, even the technique disclosed in Patent Document 1 has a problem in that sufficient bonding strength between the wiring portion and the electronic component may not be obtained under high temperature and high humidity conditions. In particular, in the circuit board in which the wiring portion is made of silver, the effect of the surface state of the silver wiring (silver layer) on the bonding force between the silver wiring and the electronic component has not been sufficiently studied. Development of a new laminate having a silver layer on a support suitable for application to a circuit board has been desired.

JP 2002-077655 A

  An object of the present invention is to provide a laminate including a silver layer capable of maintaining a high bonding force with an electronic component even under high temperature and high humidity conditions, and a circuit board on which the electronic component is mounted on the laminate. .

The present invention is a laminate comprising a silver layer on a substrate, and the silver layer having a surface satisfying at least one of the following conditions (i) and (ii) with a skewness of a roughness curve.
(I) After 240 hours have passed under the conditions of a temperature of 85 ° C. and a relative humidity of 85%, the skewness change rate is 35% or more.
(Ii) The rate of change in skewness is 40% or more after 480 hours have passed under the conditions of a temperature of 85 ° C. and a relative humidity of 85%.
Moreover, this invention is an electronic component through a conductive junction part on the surface where the skewness of the roughness curve among the silver layers of the laminate satisfies at least one of the conditions (i) and (ii). A circuit board on which is mounted is provided.

  The laminate of the present invention includes a silver layer that can maintain a high bonding strength with an electronic component even under high temperature and high humidity conditions. The electronic component can be mounted on the laminate to form a circuit board.

It is a schematic sectional drawing which shows an example of the laminated body which concerns on this invention. It is a schematic sectional drawing which shows an example of the laminated body provided with the contact | adherence layer based on this invention. It is a schematic sectional drawing for demonstrating an example of the manufacturing method of the laminated body which concerns on this invention. It is a schematic diagram for demonstrating the circuit board which concerns on this invention, and the lateral-pressing shear strength test in the Example.

  Preferred examples of the laminate and circuit board of the present invention will be described below. However, the present invention is not limited to these examples. For example, additions, omissions, substitutions, and other changes (amount, number, position, size, etc.) are possible without departing from the spirit of the present invention. It is.

<< Laminate >>
The laminate according to the present invention includes a silver layer on a substrate, and the silver layer has a surface satisfying at least one of the following conditions (i) and (ii) with a skewness of a roughness curve.
(I) After 240 hours have passed under the conditions of a temperature of 85 ° C. and a relative humidity of 85%, the skewness change rate is 35% or more.
(Ii) The rate of change in skewness is 40% or more after 480 hours have passed under the conditions of a temperature of 85 ° C. and a relative humidity of 85%.
The laminated body has a surface in which the silver layer has a surface in which the rate of change in skewness of a roughness curve after a predetermined time has passed in a predetermined range under the above-described high-temperature and high-humidity condition. A high bonding force between the silver layer and the electronic component through the part is maintained for a long time even under high temperature and high humidity conditions. Here, “bonding force” means a force for integrally bonding the silver layer and the electronic component. For example, if the silver layer and the electronic component are bonded using a conductive adhesive, The adhesive layer formed by curing the conductive adhesive corresponds to the force (adhesive force) for bonding the silver layer and the electronic component.
In the present specification, the surface of the silver layer satisfying at least one of the above conditions (i) and (ii) is the surface that forms a conductive junction with the electronic component of the silver layer.

FIG. 1 is a schematic cross-sectional view showing an example of a laminate according to the present invention.
The laminated body 1 shown here is provided with a silver layer 12 on a substrate 11, and the silver layer 12 is patterned into a predetermined shape on the substrate 11. The surface (one main surface) 12a of the silver layer 12 is a surface on which an electronic component is mounted via a conductive joint in a circuit board described later. Further, the back surface (the other main surface) 12 b of the silver layer 12 is a contact surface with the surface 11 a of the substrate 11.
In addition, in the laminated body 1, the silver layer 12 may be laminated | stacked on the whole surface 11a of the base material 11, for example.

  The laminated body according to the present invention is not limited to the one shown in FIG. 1, and a part of the structure may be appropriately changed within a range not impairing the effects of the present invention. For example, other layers other than the silver layer 12 may be provided on the base material 11, and the other layers may include those layers in order to improve the adhesion between the base material 11 and the silver layer 12. An adhesion layer provided between them can be exemplified.

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

The laminated body 2 shown here is provided with an adhesion layer 13 between the base material 11 and the silver layer 12, and is the same as the laminated body 1 except for this point.
The adhesion layer 13 is laminated on the entire surface 11 a of the substrate 11, and the silver layer 12 is laminated on a part of the surface 13 a of the adhesion layer 13. Here, although the adhesion layer 13 is laminated on the entire surface 11a of the substrate 11, the entire surface of the back surface 12b of the silver layer 12 is in contact with the surface 13a of the adhesion layer 13 in the laminate 2. It is preferable. For example, the adhesion layer 13 may be laminated not only on the entire surface 11a of the base material 11 but on a part thereof, and in that case, the adhesion layer 13 may be patterned.

<Base material>
Although the base material 11 can select arbitrary shapes according to the objective, It is preferable that it is plate shape, a film form, or a sheet form, it is preferable that thickness is 10-10000 micrometers, and it is 50-5000 micrometers. More preferred.

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

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

<Silver layer>
In the silver layer 12, the skewness of the roughness curve in the exposed surface of the part where the electronic component is mounted through at least the conductive joint (a predetermined part of the surface 12 a in FIGS. 1 and 2) What is necessary is just to be comprised so that at least one of i) and (ii) may be satisfy | filled. In FIGS. 1 and 2, the silver layer 12 is illustrated as a plate having a side surface that connects the front surface 12 a and the back surface 12 b, but without the side surface, The silver layer may have a shape having the surface 12a from the surface 11a or the surface 13a of the adhesion layer 13 via a curved surface or the like.

  The silver layer 12 is made of metallic silver or contains metallic silver as a main component. Here, “having metallic silver as a main component” means that the ratio of metallic silver is sufficiently high so that it can be regarded as being composed solely of metallic silver. For example, the ratio of metallic silver is 95% by mass or more. It is preferable that it is 97 mass% or more, and it is especially preferable that it is 99 mass% or more. The upper limit value of the ratio of metallic silver in the silver layer 12 is, for example, 100% by mass, 99.9% by mass, 99.8% by mass, 99.7% by mass, 99.6% by mass, 99.5% by mass, 99 4 mass%, 99.3% by mass, 99.2 mass% and 99.1 mass% can be selected.

  The silver layer 12 is preferably formed using a metal silver forming material to be described later. By using a metallic silver forming material instead of a plating method or the like, the silver layer 12 can be easily formed so that the skewness of the roughness curve of the surface 12a satisfies at least one of the above conditions (i) and (ii).

The skewness (Rsk) of the roughness curve represents the mean square of the roughness curve Z (x) at the reference length l made dimensionless by the cube of the root mean square height Rq. Specifically, the skewness (Rsk) of the roughness curve is obtained by the following formula (I). Skewness (Rsk) means the degree of skewness and represents the symmetry between the peak and valley when the average line is the center. That is, the peak and valley are symmetrical with respect to the average line when the skewness is 0, and when the skewness is greater than 0, they are biased downward with respect to the average line, and the skewness is less than 0. Is biased upward with respect to the average line.
Here, the roughness curve Z (x) is the same as the “surface roughness” based on JIS B0601: 2001 (ISO4287: 1997), that is, the roughness curve y = Z (x) in the arithmetic average roughness (Ra). is there.

（式中、Ｒｑは二乗平均平方根高さであり、ｌは二乗平均平方根高さＲｑの三乗によって無次元化した基準長さであり、Ｚ（ｘ）は粗さ曲線である。）

(In the formula, Rq is the root mean square height, l is a reference length made dimensionless by the cube of the root mean square height Rq, and Z (x) is a roughness curve.)

The condition that the silver layer satisfies the above condition (i) is that when a test is performed in which the silver layer is allowed to pass for 240 hours under conditions of a temperature of 85 ° C. and a relative humidity of 85%, the surface roughness curve is expressed by ) -1 is satisfied.
(Rsk ₂₄₀ −Rsk ₀ ) / Rsk ₀ × 100 ≧ 35 (i) −1
(Where Rsk ₀ is the skewness of the roughness curve before the test; Rsk ₂₄₀ is the skewness of the roughness curve after the test (after 240 hours)).

Similarly, the condition that the silver layer satisfies the above condition (ii) is that when the test is conducted for 480 hours at a temperature of 85 ° C. and a relative humidity of 85%, the surface roughness curve is as follows. It means satisfying the relationship of formula (ii) -1.
(Rsk ₄₈₀ −Rsk ₀ ) / Rsk ₀ × 100 ≧ 40 (ii) −1
(Where Rsk ₀ is the skewness of the roughness curve before the test; Rsk ₄₈₀ is the skewness of the roughness curve after the test (after 480 hours)).

In the present invention, preferable conditions of the conditions (i) and (ii) are shown below.
(I) After 240 hours, the rate of change is preferably 50% or more, more preferably 65% or more, further preferably 80% or more, and particularly preferably 95% or more. .
(Ii) After 480 hours, the rate of change is preferably 80% or more, more preferably 130% or more, further preferably 180% or more, and particularly preferably 230% or more. Most preferably, it is 280% or more.
The suitable values of the above conditions (i) and (ii) can be arbitrarily combined.

  In the present invention, satisfying at least one of the conditions (i) and (ii) means that when the silver layer is placed under a high temperature and high humidity condition of a temperature of 85 ° C. and a relative humidity of 85% for 240 hours or 480 hours, This means that the skewness of the surface roughness curve changes greatly from the initial value. This means that the surface state of the silver layer changes greatly. In order for the silver layer 12 to maintain a high bonding force with an electronic component even under high temperature and high humidity conditions, for example, the surface roughness of the silver layer 12 is set within a predetermined range, the surface of the silver layer 12 is It is not sufficient to set the rate of change of roughness within a predetermined range, and it is necessary to satisfy at least one of the conditions (i) and (ii). Here, “surface roughness” is based on JIS B0601: 2001 (ISO4287: 1997), means arithmetic average roughness (Ra), and is a reference length in the direction of the average line from the roughness curve. When only l is extracted, the X-axis is taken in the direction of the average line of the extracted portion, the Y-axis is taken in the direction of the vertical magnification, and the roughness curve is expressed by y = Z (x), the following formula (II) Is a value expressed in nanometer (nm) units.

  The skewness of the roughness curve on the surface of the silver layer 12 may satisfy at least one of the conditions (i) and (ii), but preferably satisfies both the conditions (i) and (ii).

The skewness of the roughness curve on the surface of the silver layer 12 is preferably 0.005 or more, preferably 0.01 or more, in the initial stage (that is, elapsed time 0 hours) before the silver layer 12 is aged under predetermined conditions. More preferably, it is preferably 0.5 or less.
The skewness of the roughness curve on the surface of the silver layer 12 is preferably 0.2 or more at a stage where the silver layer 12 has passed 240 hours under conditions of a temperature of 85 ° C. and a relative humidity of 85%, and is 0.4 or more. More preferably, it is preferably 8 or less.
The skewness of the roughness curve on the surface of the silver layer 12 is preferably 0.3 or more and 0.5 or more when the silver layer 12 has passed 480 hours under conditions of a temperature of 85 ° C. and a relative humidity of 85%. More preferably, it is preferably 15 or less.

The skewness of the roughness curve on the surface of the silver layer 12 can be obtained by measuring the surface shape of the silver layer 12 from above the surface. The surface to be measured at this time may be the above-described surface 12a of the silver layer 12 (a surface on which an electronic component is mounted via a conductive joint in a circuit board described later), or the silver layer 12 is cut. Alternatively, it may be a section that has been cut and newly exposed. When the silver layer 12 is cut, the cross section is exposed between two different surfaces (for example, between the front surface 12a and the back surface 12b of the silver layer 12). When the silver layer 12 is cut, the cross section is exposed in a partial region in the depth direction from the surface (for example, a partial region in the thickness direction of the silver layer 12 from the surface 12a of the silver layer 12). . The direction in which the silver layer 12 is cut or cut is not particularly limited. As a cross section of the silver layer 12, for example, as shown in FIG. 1, a cross section in a direction perpendicular to the surface 12a of the silver layer 12 or the surface 11a of the base material 11, the surface 12a of the silver layer 12 or the base material 11 Any of a cross section in a direction parallel to the surface 11a, a cross section of the silver layer 12 in a direction that forms an angle other than 0 ° and 90 ° with respect to the surface 12a of the silver layer 12 or the surface 11a of the substrate 11 Good. And the external shape of a cross section is not specifically limited, For example, a square may be sufficient as shown in FIG. 1, and the triangle seen when the corner | angular part of a rectangular parallelepiped may be cut | disconnected may be sufficient. The surface for measuring the shape of the silver layer 12 may be the surface of the silver layer 12 that is exposed when the laminate 1 or 2 is stored under conditions of a temperature of 85 ° C. and a relative humidity of 85%.
The surface shape of the silver layer 12 can be measured by a known method such as a method using a microscope such as a shape measuring laser microscope.

  The cross section of the silver layer 12 in the direction perpendicular to the surface 11a of the base material 11 is cut, for example, by cooling the silver layer 12 to an extremely low temperature using a refrigerant such as liquid nitrogen, It can be exposed by cutting the silver layer 12 using an apparatus for cutting the test piece. If a microtome is used, the cross section of the silver layer 12 can also be exposed by cutting.

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

  Although the thickness of the silver layer 12 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 12 is equal to or more than the lower limit value, the conductivity can be further improved, and the structure of the silver layer 12 can be more stably maintained. Moreover, the laminated body 1 can be made thinner by the thickness of the silver layer 12 being the said upper limit or less.

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

<Adhesion layer>
The material of the adhesion layer 13 may be appropriately adjusted according to the type of the base material 11 and is not particularly limited, but is preferably a variety of resins or those formed using a silane coupling agent.
Moreover, the material of the contact | adherence layer 13 may be only 1 type, may be 2 or more types, and when it is 2 or more types, the combination and ratio can be adjusted arbitrarily according to the objective.

  Especially, when the material of the contact | adherence layer 13 is various resin, what was formed using urethane acrylate resin is preferable, and what was formed by superposing | polymerizing urethane acrylate resin is more preferable.

  The urethane acrylate resin used for forming the adhesion layer 13 is preferably a urethane acrylate resin having a polycarbonate skeleton (hereinafter sometimes referred to as “polycarbonate skeleton-containing urethane acrylate resin”).

  Moreover, when the material of the adhesion layer 13 is formed using a silane coupling agent, the silane coupling agent is a compound represented by the following general formula (3) (hereinafter referred to as “compound (3)”. "Is sometimes abbreviated as").

（式中、Ｒ^１１は炭素数１〜５のアルキル基、アルコキシアルキル基又はアルキルカルボニル基であり；Ｒ^１２は炭素数１〜５のアルキル基又は炭素数６〜１２のアリール基であり；Ｒ^１３は炭素数１〜１０のアルキレン基であり；Ｒ^１４は炭素数１〜５のアルキレン基であり、前記アルキレン基中の１個以上のメチレン基はカルボニル基で置換されていてもよく；Ｚはアミノ基、メルカプト基又は炭素数６〜１２のアリール基であり；ｍ１は２又は３であり、複数個のＲ^１１は互いに同一でも異なっていてもよく；ｍ２及びｍ３はそれぞれ独立に０又は１であり、ただし、Ｚがアミノ基である場合には、ｍ２及びｍ３の少なくとも一方は１である。）

(Wherein R ¹¹ is an alkyl group having 1 to 5 carbon atoms, an alkoxyalkyl group or an alkylcarbonyl group; R ¹² is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms; R ¹³ is an alkylene group having 1 to 10 carbon atoms; R ¹⁴ is an alkylene group having 1 to 5 carbon atoms, and one or more methylene groups in the alkylene group may be substituted with a carbonyl group; Z Is an amino group, a mercapto group or an aryl group having 6 to 12 carbon atoms; m1 is 2 or 3, and a plurality of R ¹¹ may be the same or different from each other; m2 and m3 are each independently 0 or 1; provided that when Z is an amino group, at least one of m2 and m3 is 1.)

(Compound (3))
The compound (3) is represented by the general formula (3).
In the formula, R ¹¹ is an alkyl group having 1 to 5 carbon atoms, an alkoxyalkyl group, or an alkylcarbonyl group.
The alkyl group for R ¹¹ may be linear, branched or cyclic.
Examples of linear or branched alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and n-pentyl group. , Isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group and 2-methylbutyl group.
Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group.
The alkyl group for R ¹¹ is preferably linear or branched, and preferably has 1 to 3 carbon atoms.

Examples of the alkoxyalkyl group at R ^11, alkoxy group constituting it, a monovalent group in which the alkyl group as R ¹¹ is bonded to an oxygen atom, an alkylene group wherein the alkoxy group is attached Is a group formed by removing one hydrogen atom from the alkyl group as R ¹¹ . However, the total carbon number of the alkoxy group and the alkylene group (the carbon number of the alkoxyalkyl group) is 2 to 5.
The alkoxyalkyl group for R ¹¹ is preferably linear or branched, preferably has 3 or less carbon atoms, and more preferably is a methoxymethyl group or a 2-methoxyethyl group.

Examples of the alkyl group in R ^11, the alkyl group is a carbonyl group (-C (= O) -) as R ¹¹ 1 monovalent group formed by bonding to a carbon atom of may be exemplified. However, the alkyl group bonded to the carbon atom of the carbonyl group has 1 to 4 carbon atoms (the alkylcarbonyl group has 2 to 5 carbon atoms).
The alkylcarbonyl group in R ¹¹ is preferably linear or branched, preferably has 3 or less carbon atoms, and more preferably a methylcarbonyl group (acetyl group) or an ethylcarbonyl group. preferable.

In the formula, R ¹² is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms.
Examples of the alkyl group in R ^12, wherein can be exemplified those alkyl groups same as in R ^11, may be the mutually the same and R ^11, may be different.

The aryl group in R ¹² may be monocyclic or polycyclic, and includes a phenyl group, 1-naphthyl group, 2-naphthyl group, o-toluyl group, m-toluyl group, p-toluyl group, xylyl group (dimethyl group). Phenyl group) and the like. In addition, one or more hydrogen atoms of these aryl groups may be substituted with an alkyl group and / or an alkoxy group. Here, examples of the alkyl group in which a hydrogen atom is substituted include the same groups as the alkyl group in R ¹¹ , and examples of the alkoxy group in which a hydrogen atom is substituted include that the alkyl group in R ¹¹ is an oxygen atom. A monovalent group formed by bonding to can be exemplified. And when these alkyl groups and / or alkoxy groups are substituted, the aryl group has 12 or less carbon atoms including these alkyl groups and / or alkoxy groups.
The aryl group in R ¹² is preferably monocyclic, and more preferably a phenyl group.

In the formula, R ¹³ is an alkylene group having 1 to 10 carbon atoms, and in the present invention, the “alkylene group” includes linear, branched and cyclic divalent saturated hydrocarbon groups. .
Examples of the alkylene group for R ¹³ include a divalent group formed by removing one hydrogen atom from an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, and n-propyl. Group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, n-hexyl group, 2 -Methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl Group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethylpentyl group, 2,2,3- Trimethylbutyl group, n-octyl group, isooctyl group, nonyl group, decyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, isobornyl group , 1-adamantyl group, 2-adamantyl group and tricyclodecyl group.

The alkylene group for R ¹³ preferably has 1 to 7 carbon atoms, more preferably 1 to 5 carbon atoms, and specifically includes a methylene group, an ethylene group, a propylene group (methylethylene group). ), Trimethylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1,2-dimethylethylene group, 1,1-dimethylethylene group, ethylethylene group, pentamethylene group, 1-methyl Tetramethylene group, 2-methyltetramethylene group, 1,1-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, 1,3-dimethyltrimethylene group, 1-ethyltrimethylene group, 2-ethyltrimethylene group Group, 1-methyl-2-ethylethylene group, n-propylethylene group and the like.

In the formula, R ¹⁴ is an alkylene group having 1 to 5 carbon atoms, and among the alkylene groups in R ¹³ , the same as those having 1 to 5 carbon atoms, and preferably having 1 to 3 carbon atoms. .
In addition, the alkylene group in R ¹⁴ is a methylene group or is formed by connecting 2 to 5 methylene groups, and one of these methylene groups (—CH ₂ —) constituting the alkylene group. One or more may be substituted with a carbonyl group (—C (═O) —). The number of methylene groups substituted with a carbonyl group depends on the total number of methylene groups in the alkylene group and is not particularly limited. For example, R ¹⁴ may be composed of only a carbonyl group, One or more alkylene groups and one or more carbonyl groups may be mixed. In general, the number of carbonyl groups in R ¹⁴ is preferably 2 or less, and more preferably 1.

Wherein, Z is an amino group _(-NH 2), a mercapto group (-SH) or an aryl group having 6 to 12 carbon atoms.
Examples of the aryl group in Z, can be exemplified the same ones as the aryl group in R ^12, it may be the mutually the same and R ^12, may be different.

Wherein, m1 is 2 or 3, a plurality of R ¹¹ may be the same or different from each other.
M2 and m3 are each independently 0 or 1. However, when Z is an amino group, at least one of m2 and m3 is 1 (m2 and m3 are not 0).

As particularly preferred compound (3), R ¹¹ and R ¹² are alkyl groups having 1 to 3 carbon atoms, R ¹³ is an alkylene group having 1 to 5 carbon atoms, and R ¹⁴ is an alkylene group having 1 to 3 carbon atoms. Examples thereof include a group or a carbonyl group, and Z is an amino group, a mercapto group or a phenyl group. Such compounds (3) include N-2- (aminoethyl) -3-aminopropyltrimethoxysilane ((CH ₃ O) ₃ Si (CH ₂ ) ₃ NH (CH ₂ ) ₂ NH ₂ ), N -2- (aminoethyl) -3-aminopropylmethyldimethoxysilane ((CH ₃ O) ₂ Si (CH ₃ ) (CH ₂ ) ₃ NH (CH ₂ ) ₂ NH ₂ ), 3-ureidopropyltriethoxysilane ( _{(CH 3 CH 2 O) 3} Si (CH 2) 3 NHC (= O) NH 2), N- phenyl-3-aminopropyltrimethoxysilane _{((CH 3 O) 3 Si} (CH 2) 3 NHC 6 H _5), 3-mercaptopropyl trimethoxysilane _{((CH 3 O) 3 Si} (CH 2) 3 SH), 3- mercaptopropyl methyldimethoxysilane _((CH 3 O) _{Si (CH 3) (CH 2} ) 3 SH) can be exemplified.

  Compound (3) is a silane coupling agent, but a commercially available product may be used, or a compound synthesized by a known method may be used.

  The compound (3) used for forming the adhesion layer 13 may be only one kind or two or more kinds. When there are two or more kinds, the combination and ratio are not particularly limited.

  Although the thickness of the contact | adherence layer 13 can be set arbitrarily according to the objective, it is preferable that it is 0.5-10 micrometers, and it is more preferable that it is 0.5-4 micrometers. The adhesiveness of the base material 11 and the silver layer 12 improves more because the thickness of the contact | adherence layer 13 is more than the said lower limit. Moreover, the laminated body 2 can be made thinner by the thickness of the adhesion layer 13 being the upper limit or less.

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

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

[Step of forming a silver layer on a substrate]
In order to manufacture the laminated body 1, the silver layer 12 is formed on the surface (one main surface) 11a of the base material 11, as shown to Fig.3 (a) and FIG.3 (b).
The silver layer 12 is prepared, for example, by preparing a silver ink composition in which a material for forming metallic silver is blended, and adhering it to a desired location on the surface 11a of the substrate 11, and drying treatment or heating as necessary. It is preferably formed by appropriately selecting post-treatment such as (baking) treatment. The heat treatment may be performed also as a drying treatment.
Further, the silver ink composition is adhered to a predetermined portion or the entire surface of the surface 11a of the substrate 11, and a silver layer is obtained by appropriately selecting post-treatment such as drying treatment or heating (firing) treatment as necessary. After forming (a silver layer before patterning, not shown), the silver layer 12 can be formed by patterning the silver layer into a desired shape by a known method such as etching.
The silver ink composition is preferably in a liquid form, and preferably has a metallic silver forming material dissolved or uniformly dispersed therein.

<Metallic silver forming material>
The metal silver forming material may be any material that has silver atoms (silver elements) and generates metal silver by structural change such as decomposition, and examples thereof include silver salts, silver complexes, and organic silver compounds. 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. In particular, the metal silver forming material is preferably a silver salt or a silver complex.
Further, the material for forming metallic silver is preferably one that decomposes by heating to form metallic silver.
By using a metal silver forming material, metal silver is generated from the material, and a silver layer containing the metal silver is formed.
In the present invention, the metal silver forming material may be used singly or in combination of two or more. When two or more are used in combination, the combination and ratio can be arbitrarily adjusted. .

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

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

（式中、Ｒは１個以上の水素原子が置換基で置換されていてもよい炭素数１〜２０の脂肪族炭化水素基若しくはフェニル基、水酸基、アミノ基、又は一般式「Ｒ^１−ＣＹ_２−」、「ＣＹ_３−」、「Ｒ^１−ＣＨＹ−」、「Ｒ^２Ｏ−」、「Ｒ^５Ｒ^４Ｎ−」、「（Ｒ^３Ｏ）_２ＣＹ−」若しくは「Ｒ^６−Ｃ（＝Ｏ）−ＣＹ_２−」で表される基であり；
Ｙ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. “ _2- ”, “CY ₃ —”, “R ¹ —CHY—”, “R ² O—”, “R ⁵ R ⁴ N—”, “(R ³ O) ₂ CY—” or “R ⁶ —C”. A group represented by (= O) —CY ₂ —;
Y is each independently a fluorine atom, chlorine atom, bromine atom or hydrogen atom; R ¹ is an aliphatic hydrocarbon group or phenyl group having 1 to 19 carbon atoms; R ² is an aliphatic group having 1 to 20 carbon atoms R ³ is an aliphatic hydrocarbon group having 1 to 16 carbon atoms; R ⁴ and R ⁵ are each independently an aliphatic hydrocarbon group having 1 to 18 carbon atoms; R ⁶ is carbon An aliphatic hydrocarbon group, a hydroxyl group or a group represented by the formula "AgO-" of formula 1-19;
X 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- A phthaloyl-3-aminopropyl group, a 2-ethoxyvinyl group, or a 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個以上の前記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 ₂ ” in which one or more hydrogen atoms may be substituted with a substituent. - "," CY ₃ - "," ^R 1 -CHY - "," ^{R 2} O - "," ^R 5 ^{R 4} N -, "" ^(R _{3 O)} 2 CY- "or" ^R 6 -C ( ═O) —CY ₂ — ”.

  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 in which the aliphatic hydrocarbon group is bonded to an oxygen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group (—OH), a cyano group (—C≡N), a phenoxy group (—O— C ₆ H ₅ ) and the like can be exemplified, and the number and position of substituents are not particularly limited. 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 in R each independently represents a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom. In the general formulas “R ¹ —CY ₂ —”, “CY ₃ —” and “R ⁶ —C (═O) —CY ₂ —”, a plurality of Y may be the same or different from each other. Good.

R ¹ in R is an aliphatic hydrocarbon group having 1 to 19 carbon atoms or a phenyl group (C ₆ H ₅ —), and the aliphatic hydrocarbon group in R ¹ has 1 to 19 carbon atoms. 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.

Among these, R is preferably a linear or branched alkyl group, a group represented by the general formula “R ⁶ —C (═O) —CY ₂ —”, a hydroxyl group, or a phenyl group. . 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 independently represents 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 benzyl. A 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 the general formula “R ⁷ It is a group represented by “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 include those similar to the aliphatic hydrocarbon group in R.

Examples of the halogen atom in X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In the phenyl group and benzyl group in X, 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 and 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 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a thienyl group (C ₄ H ₃ S—), or a phenyl group or diphenyl in which one or more hydrogen atoms may be substituted with a substituent. group (biphenyl _{group, C 6 H 5 -C 6 H} 4 -) it 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, the bonding position of these with an adjacent group or atom (oxygen atom, sulfur atom, carbonyl group, carbonyloxy group) in X is not particularly limited. For example, the thienyl group may be a 2-thienyl group or a 3-thienyl group.

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

Among these, X 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) —”. It is preferable that at least one X is a hydrogen atom.

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

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

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

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

(Silver carboxylate (4))
The 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.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In the silver ink composition, the compounding amount of the nitrogen-containing compound is preferably 0.2 to 15 mol, and more preferably 0.3 to 5 mol, per mol of the carboxylate silver.
By defining the compounding amount of the nitrogen-containing compound as described above, the silver ink composition is further improved in stability and the quality of the silver layer (metallic silver) is further improved. Furthermore, the conductive layer can be formed more stably without performing heat treatment at a high temperature.

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

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

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

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

The alkoxy group having 20 or less carbon atoms in R ²¹ has 1 to 20 carbon atoms, and examples thereof include monovalent groups 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).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  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 compounding of the reducing agent is high, since this compound is in the same state as at the time of heat treatment of the silver ink composition described later, the decomposition promoting action of the silver carboxylate by the reducing agent, It is speculated that the formation of metallic silver may be initiated in at least part of the silver carboxylate. Such a silver ink composition containing metallic silver may be able to form a silver layer by performing post-treatment under milder conditions than the silver ink composition not containing metallic silver at the time of forming the silver layer. In addition, even when the amount of the reducing agent is sufficiently large, a silver layer may be formed by performing post-treatment under the same mild conditions. In this way, by adopting conditions that promote the decomposition of the silver carboxylate, the silver layer can be formed by post-treatment, by heat treatment at a lower temperature, or only by drying at room temperature without performing heat treatment. Sometimes it 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.

  In this invention, it is preferable to mix | blend reducing agent, and it exists in the tendency which can further reduce the surface roughness of a silver layer by suppressing the fluctuation | variation of dripping speed.

  In the present invention, it is also preferable to produce a silver ink composition by supplying carbon dioxide to a mixture containing the metallic silver forming material, alcohol and nitrogen-containing compound. In this case, a method similar to the above can be adopted as a method for supplying carbon dioxide.

  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.

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

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

  When the silver ink composition 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 60-370 degreeC, and it is more preferable that it is 70-280 degreeC. The heating time may be adjusted according to the heating temperature, but is usually preferably 1 minute to 24 hours, and more preferably 1 minute to 12 hours. The β-ketocarboxylate (1) is decomposed at a low temperature without using a reducing agent or the like known in the art, unlike a metal silver forming material such as silver oxide. Reflecting such decomposition temperature, the silver ink composition can form metallic silver at an extremely lower temperature than the conventional one as described above.

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

  In the present specification, “humidification” means that the humidity is artificially increased unless otherwise specified, and preferably the relative humidity is 5% or more. At the time of heat treatment, since the humidity in the treatment environment becomes extremely low due to the high treatment temperature, it can be said that the relative humidity of 5% is clearly artificially increased.

  The relative humidity when the heat treatment of the silver ink composition is performed under humidified conditions is preferably 10% or more, more preferably 30% or more, further preferably 50% or more, and 70%. It is particularly preferable that the ratio be 90% or more, most preferably 90% or more, or 100%. And you may perform the heat processing under humidification conditions by spraying the high pressure steam heated to 100 degreeC or more.

The heat treatment of the silver ink composition may be performed in two stages. For example, in the first stage heat treatment, there is exemplified a method in which the silver ink composition is mainly dried rather than the formation of metal silver, and the formation of metal silver is completed in the second stage heat treatment.
In the first-stage heat treatment, the heating temperature may be appropriately adjusted according to the type of compounding component of the silver ink composition, but is preferably 60 to 110 ° C, more preferably 70 to 90 ° C. preferable. Moreover, what is necessary is just to adjust a heating time according to heating temperature, Usually, it is preferable that it is 5 second-12 hours, and it is more preferable that it is 30 second-2 hours.
In the second stage heat treatment, the heating temperature may be appropriately adjusted according to the type of compounding component of the silver ink composition so that metallic silver is satisfactorily formed, but it should be 60 to 280 ° C. Preferably, it is 70-260 degreeC. Moreover, what is necessary is just to adjust a heating time according to heating temperature, Usually, it is preferable that it is 1 minute-12 hours, and it is more preferable that it is 1 minute-10 hours.

Among them, the heat treatment of the silver ink composition is mainly the drying of the silver ink composition, not the formation of metallic silver as described above, under the non-humidifying condition in the heat treatment of the first step, and the second step. It is particularly preferable to perform the heat treatment in a two-stage method in which the formation of metallic silver is performed to the end as described above under humidified conditions.
In the present specification, “non-humidification” means that the above “humidification” is not performed, that is, the humidity is not artificially increased, and preferably the relative humidity is less than 5%. .

In the particularly preferred method described above, the heating temperature during the heat treatment under the first non-humidifying condition is preferably 60 to 110 ° C, more preferably 70 to 90 ° C. The heating time is preferably 5 seconds to 1 hour, more preferably 30 seconds to 30 minutes, and particularly preferably 30 seconds to 10 minutes.
In the particularly preferable method described above, the heating temperature during the heat treatment under the second humidifying condition is preferably 60 to 130 ° C, and more preferably 70 to 110 ° C. The heating time is preferably 1 minute to 2 hours, more preferably 1 minute to 1 hour, and particularly preferably 1 minute to 30 minutes.

  When the silver ink composition is used, the silver layer 12 is a layer made of a conductor formed by the post-treatment of the silver ink composition, and contains metal silver as a main component.

  When the laminate according to the present invention is a substrate in which an adhesion layer is provided between the substrate and the silver layer (for example, the laminate 2 shown in FIG. 2), the laminate includes, for example, an adhesion layer on the substrate. It can manufacture with the manufacturing method which has the process to form and the process of forming a silver layer on an adhesion layer.

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

  The material for forming the adhesion layer in the composition for the adhesion layer (hereinafter sometimes abbreviated as “adhesion layer forming material”) may be only one kind, two or more kinds, or two or more kinds. The combination and ratio can be adjusted arbitrarily.

  When the adhesion layer forming material is a resin forming material (monomer or base resin), it is preferably a urethane acrylate resin as described above, and more preferably a polycarbonate skeleton-containing urethane acrylate resin.

When the adhesion layer forming material is a resin forming material, the composition for the adhesion layer preferably includes a resin forming material, an initiator (polymerization initiator), and a solvent.
The initiator may be appropriately selected from known ones according to the type of resin forming material, and is not particularly limited.
The solvent may be any solvent that does not inhibit the polymerization reaction, and may be appropriately selected from known solvents such as cyclohexanone, 1,2-dimethoxyethane (dimethyl cellosolve), propylene glycol monomethyl ether acetate, and the like. The said solvent may be used individually by 1 type, may use 2 or more types together, and is a case where 2 or more types are used together, The combination and ratio can be adjusted arbitrarily.

  When the adhesion layer forming material is a silane coupling agent, the compound (3) is preferably used as described above.

When the adhesion layer forming material is a silane coupling agent, the adhesion layer composition preferably includes a silane coupling agent and a solvent.
The solvent is not particularly limited as long as the silane coupling agent is not significantly deteriorated, and preferable examples include alcohols having 2 or more carbon atoms such as ethanol and 2-propanol (isopropyl alcohol). The said solvent may be used individually by 1 type, may use 2 or more types together, and is a case where 2 or more types are used together, The combination and ratio can be adjusted arbitrarily.

The composition for the adhesion layer contains the resin forming material and, if necessary, components other than the resin forming material (in the case of using the resin forming material as the adhesion layer forming material, an initiator, a solvent, etc.). It is obtained by blending.
The blending method and blending conditions of each component can be the same as in the case of the silver ink composition except that the blending components are different.

For example, when the composition for the adhesion layer is formed by blending the resin forming material, the initiator, and the solvent, the ratio of the blended amount of the resin forming material to the total amount of the blending components is 25 to 75 masses. %, Preferably 35 to 65% by mass.
Moreover, in the composition for the adhesion layer, the blending amount of the initiator is preferably 0.01 to 0.1 times by mass with respect to the blending amount of the resin forming material, and is 0.02 to 0.08 times by mass. It is more preferable that
Moreover, in the composition for contact | adherence layers, it is preferable that the compounding quantity of a solvent is 0.1-3 mass times with respect to the compounding quantity of the resin formation material, and is 0.5-1.5 mass times. Is more preferable.

  On the other hand, when using a composition comprising a silane coupling agent and a solvent as the adhesion layer composition, the ratio of the amount of the silane coupling agent to the total amount of the ingredients is 1 to 50% by mass. Preferably, it is 3-30 mass%. By being more than a lower limit, an adhesion layer can be formed more efficiently, and by being below an upper limit, the handleability of the composition for adhesion layers improves more.

The composition for the adhesion layer using the resin forming material may be formed by blending other components other than the resin forming material, the initiator, and the solvent.
Similarly, the composition for the adhesion layer using the silane coupling agent may be a mixture of other components other than the silane coupling agent and the solvent.
Even when any of the resin forming material and the silane coupling agent is used, the other components in the adhesive layer composition can be arbitrarily selected according to the purpose, and are not particularly limited. And the said other component 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.
Regardless of whether the resin forming material or the silane coupling agent is used, the ratio of the blended amount of the other components to the total amount of the blended components in the composition for the adhesion layer is preferably 10% by mass or less. More preferably, it is 5 mass% or less.

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

  In the step of forming the adhesion layer on the substrate, the amount of the adhesion layer composition to be adhered to a desired location on the substrate 11 or the blending amount of the adhesion layer forming material in the adhesion layer composition is adjusted. By doing so, the thickness of the adhesion layer 13 can be adjusted.

  What is necessary is just to select the said post-processing at the time of adhesion layer formation suitably according to the kind of composition for adhesion layers. For example, when the adhesion layer forming material is a resin forming material, ultraviolet irradiation treatment or heat treatment may be performed, and when the adhesion layer forming material is a silane coupling agent, heat treatment may be performed. .

[Step of forming a silver layer on the adhesive layer]
After the step of forming the adhesion layer on the base material, for example, instead of the base material in which the adhesion layer is not formed, such as the base material 11 shown in FIGS. Except for using the base material on which the layer is formed, in the same manner as the step of forming the silver layer on the base material described with reference to FIGS. 3 (a) and 3 (b), A silver layer can be formed.

<< Circuit board >>
In the circuit board according to the present invention, on the surface of the silver layer of the laminate, the skewness of the roughness curve satisfies at least one of the conditions (i) and (ii), via a conductive junction. Electronic parts are mounted, and the silver layer of the laminate is used as a wiring part.
The circuit board is made of the same laminate as the conventional one, except that the surface roughness curve has a skewness satisfying at least one of the conditions (i) and (ii) as a silver layer. Can be configured.

For example, examples of the conductive joint include a hardened conductive adhesive and a solder-made one, but a hardened conductive adhesive is preferable. As the conductive adhesive, a known adhesive such as an ultraviolet curable adhesive can be used as appropriate.
Moreover, as said electronic component, arbitrary things can be selected according to the use of a circuit board.

  The circuit board can maintain a high bonding force between the silver layer and the electronic component even under a high temperature and high humidity condition by using the laminate. This is mainly because, under high temperature and high humidity conditions, at least the interface between the bonding layer (conductive bonding portion) and the silver layer, preferably the interface between the bonding layer (conductive bonding portion) and the silver layer, and the bonding layer (conductive) This is because the interface breakage is suppressed at both the interface between the bonding portion) and the electronic component.

For example, when a test is performed in which the silver layer is allowed to elapse for 480 hours at a temperature of 85 ° C. and a relative humidity of 85%, the rate of change in bonding force between the silver layer and the electronic component is preferably −50% or more. -20% or more is more preferable. This means that it is preferable to satisfy the relationship of the following formula (iii) -1, and it is more preferable to satisfy the relationship of the following formula (iii) -2.
(F ₄₈₀ −F ₀ ) / F ₀ × 100 ≧ −50 (...) (iii) -1
(F ₄₈₀ −F ₀ ) / F ₀ × 100 ≧ −20 (...) (iii) -2
(Where F ₀ is the bonding force between the silver layer and the electronic component before the test; F ₄₈₀ is the bonding force between the silver layer and the electronic component after the test (after 480 hours have elapsed).)

  Here, as the “bonding force”, for example, in accordance with JEITA ET-7409-102, a surface mounted component is observed when a lateral pressing shear strength test is performed. Shear force can be used.

  Since the circuit board can stably mount electronic components even under high temperature and high humidity conditions, it is possible to maintain stable performance over a long period of time.

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

[Example 1]
<Manufacture of laminate and circuit board>
(Manufacture of silver ink composition)
By adding silver 2-methylacetoacetate to 2-ethylhexylamine (0.4 times molar amount with respect to silver 2-methylacetoacetate described later) and stirring for 15 minutes so that the liquid temperature becomes 50 ° C. or less A liquid product was obtained. To this liquid, formic acid (0.8-fold molar amount with respect to silver 2-methylacetoacetate) was added dropwise over 30 minutes so that the temperature of the reaction solution was 50 ° C. or lower. After completion of the formic acid addition, the reaction solution was further stirred at 25 ° C. for 1.5 hours to obtain a silver ink composition (I-2). Table 1 shows the mixing ratio of each component. In Table 1, “nitrogen-containing compound (molar ratio)” means the compounding amount (number of moles) of nitrogen-containing compound per mol of silver carboxylate ([number of moles of nitrogen-containing compound] / [silver carboxylate] Number of moles]). Similarly, the “reducing agent (molar ratio)” is the reductant compounding amount (mole number) per mol of silver carboxylate compound ([reducing agent mole number] / [silver carboxylate mole number]). means.

(Manufacture of adhesive layer composition)
Ultraviolet curable polycarbonate skeleton-containing urethane acrylate resin (“Nippon Gosei Co., Ltd.“ UV3310B ”, viscosity: 40000-70000 (60 ° C.) (mPa · s), functional group number: 2, so as to have the blending amounts shown in Table 2) Weight average molecular weight: 5000, recommended UV irradiation amount: 800 (mJ / cm ² )), cyclohexanone (manufactured by Wako Pure Chemical Industries, Ltd.), and photoinitiator (“Irgacure 127” manufactured by BASF) were added, and room temperature (25 ° C. ) For 10 minutes to prepare an adhesive layer composition. In addition, the compounding quantity currently displayed by the mass% unit in Table 2 means the ratio of each compounding component with respect to the total amount of a compounding component.

(Manufacture of laminates)
Using a bar coater (# 01), the adhesive layer composition obtained above was applied onto one main surface (surface) of a substrate (thickness 2 mm) made of polycarbonate (PC) / ABS resin alloy. Then, after drying in an oven at 80 ° C. for 5 minutes, the coating film dried using an ozone-less high-pressure mercury lamp is irradiated with ultraviolet rays at a dose of 100 mJ / cm ² and adhered to the substrate surface. Layers (thickness 3-4 μm) were formed.

  Next, after applying the silver ink composition obtained above on the adhesion layer by a screen printing method, this is heated (baked) in an oven at 80 ° C. for 2 hours to form a silver layer as a conductive layer. (Thickness 1 μm) was formed on the surface of the adhesion layer to obtain a laminate.

(Manufacture of circuit boards)
A circuit board having the structure shown in FIG. 4 was manufactured by the following procedure.
That is, a conductive adhesive (“QMI516IE” manufactured by Henkel Co., Ltd.) 0.07 mg was applied to a predetermined portion on the surface of the silver layer of the laminate, and 0Ω1608 chip (the surface of the terminal portion at both ends was gold-plated) as an electronic component. A terminal portion was brought into contact with the conductive adhesive, and the conductive adhesive was cured under the standard curing conditions to fix the chip, thereby forming the conductive adhesive on the silver layer of the laminate. A circuit board on which the chip was mounted via a bonding layer was obtained. A plurality of such circuit boards were manufactured and subjected to the following evaluation. Table 3 shows the characteristics of the conductive adhesive used.

<Evaluation of circuit board>
(Calculation of change rate of skewness)
The circuit board obtained above is stored at a temperature of 85 ° C. and a relative humidity of 85%. The circuit board is stored before the start of storage, 240 hours, 480 hours and 720 hours after the start of storage. The skewness (Rsk) of the roughness curve on the surface of the silver layer was calculated, and the change rate of the skewness after storage for a predetermined time relative to the start of storage was calculated. The results are shown in Table 4. The skewness of the roughness curve was calculated by the following method. That is, using a shape measurement laser microscope ("VK-X100" manufactured by Keyence Corporation), the shape of the exposed surface of the silver layer where the bonding layer is not formed is measured from above the exposed surface ( Measurement mode: surface shape, measurement size: 2048 × 1536, measurement quality: high accuracy), correction of substrate tilt, high-pass filter (cut-off value λ _C : 0.08 mm) in the obtained cross-sectional curve Was applied to obtain a roughness curve. Then, the skewness (Rsk) of the roughness curve was calculated from the profile of the obtained roughness curve in a measurement range of 50 × 50 μm.

(Evaluation of bonding strength)
According to the following procedure, a transverse press shear strength test was performed as shown in FIG. 4 in accordance with JEITA ET-7409-102. 4A and 4B are schematic diagrams for explaining the circuit board according to the present invention used in the test and the lateral pressing shear strength test. FIG. 4A is a plan view and FIG. 4B is a side view.
That is, the circuit board 30 before the start of storage and after storage for a predetermined time is used, and among the chips 14 of the circuit board 30 (the chips), the pressing jig 9 is applied to the side surface of the main body portion 14c between the terminal portions 14a and 14b at both ends. The tip of the was brought into contact. At this time, the height (shear height) h of the lower surface 9a of the pressing jig 9 from the surface 12a of the silver layer 12 was set to 0.1 mm. Then, the shear rate of 0. 0 is parallel to the surface of the silver layer 12 and perpendicular to the longitudinal direction of the main body portion 14c of the chip 14 (direction connecting the terminal portions 14a and 14b). By pushing the pushing jig 9 at 5 mm / min, a shearing force was applied to the chip 14, and the shearing force (N) when the chip 14 was peeled from the laminate 3 was defined as the bonding force. The results are shown in Table 4. In FIG. 4, reference numeral 15 denotes a bonding (adhesion) layer formed by curing the conductive adhesive, which corresponds to the above-described conductive bonding portion.

[Example 2, Comparative Examples 1-2]
<Manufacture of laminate and circuit board, and evaluation of circuit board>
As shown in Table 4, a laminate and a circuit board were produced in the same manner as in Example 1 except that at least one of the laminate and the chip was changed, and the circuit board was evaluated. The results are shown in Table 4.
In addition, the chip | tip used in Example 2 is a chip | tip used in Example 1, and the terminal part surface of both ends replaced with gold plating, and was tin-plated.
The comparative laminate used in Comparative Examples 1 and 2 is obtained by forming a 1 μm thick silver plating layer on the surface of a SUS304 base material having a thickness of 100 μm.

[Examples 3-4, Comparative Examples 3-4]
<Manufacture of laminate and circuit board, and evaluation of circuit board>
In the same manner as Examples 1-2 and Comparative Examples 1-2, except that “CA-110” manufactured by AGF shown in Table 3 was used as the conductive adhesive instead of “QMI516IE” manufactured by Henkel. A laminate and a circuit board were manufactured, and the circuit board was evaluated. The results are shown in Table 5.
The comparative laminate used in Comparative Examples 3 and 4 in Table 5 is the same as that used in Comparative Examples 1 and 2.

[Examples 5-6, Comparative Examples 5-6]
<Manufacture of laminate and circuit board, and evaluation of circuit board>
In the same manner as Examples 1-2 and Comparative Examples 1-2, except that “CA-100” manufactured by AGF shown in Table 3 was used as the conductive adhesive instead of “QMI516IE” manufactured by Henkel. A laminate and a circuit board were manufactured, and the circuit board was evaluated. The results are shown in Table 6.
The comparative laminates used in Comparative Examples 5 and 6 in Table 6 are the same as those used in Comparative Examples 1 and 2.

  As is clear from the above results, in the laminates of Examples 1 to 4, the skewness of the roughness curve on the surface of the silver layer satisfies both the conditions (i) and (ii), and is long under high temperature and high humidity conditions. Even when stored for a long time, a high bonding (adhesion) force between the silver layer and the electronic component was maintained. In these examples, when the peeling site of the chip on the circuit board after the measurement of the shearing force (bonding force) was observed, in any example, the chip was peeled off before and after the storage regardless of the conductive adhesion. It was confirmed that it was caused by cohesive failure of the bonding (adhesion) layer formed by curing the agent. That is, in these circuit boards, no interface breakdown occurred at any of the interface between the bonding layer and the silver layer and the interface between the bonding layer and the electronic component.

  On the other hand, in the laminates of Comparative Examples 1 to 6, the skewness of the roughness curve on the surface of the silver layer does not satisfy both conditions (i) and (ii), and is stored under high temperature and high humidity conditions. The bonding strength between the silver layer and the electronic component decreased. As in the case of the above example, when the peeling site of the chip on the circuit board after the measurement of the shearing force (bonding force) was observed, in any of the comparative examples, the chip was peeled off before the start of storage. As in the case of, it was caused by cohesive failure of the bonding (adhesion) layer, but after storage, it was confirmed that it was caused by interface failure at the interface between the bonding layer and the silver layer. However, even after storage, no interface breakdown occurred at the interface between the bonding layer and the electronic component.

  When the rate of change in surface roughness (arithmetic mean roughness (Ra)) is calculated instead of the rate of change in skewness (Rsk) of the roughness curve of the silver layer surface, the above examples and comparative examples There was no clear difference.

  The calculated value and rate of change of the skewness of the roughness curve shown in the above results are for the exposed surface of the silver layer surface where the bonding layer is not formed, but the surface where the bonding layer is formed (bonding layer) As a result of confirming the calculated value and the rate of change of the skewness, the value of the skewed surface was the same as the exposed surface, and the surface of the silver layer showed the same tendency with respect to the skewness of the roughness curve regardless of the presence or absence of exposure.

As described above, it was confirmed that the rate of change in skewness of the roughness curve on the surface of the silver layer had an effect on the bonding force between the silver layer and the conductive bonding portion.
According to the present invention, the silver layer has a high temperature and high humidity regardless of the type of the bonding layer (conductive bonding portion) and regardless of the type of plating (bonding portion of the electronic component) on the surface of the terminal portion of the chip. It was confirmed that high bonding strength with electronic components could be maintained even under conditions.

[Example 7]
<Manufacture of laminate and circuit board, and evaluation of circuit board>
(Manufacture of silver ink composition)
2-methylacetoacetate silver, 2-ethylhexylamine (2.25-fold molar amount with respect to 2-methylacetoacetate silver), 3,5-dimethyl-1-hexyn-3-ol (Surfinol 61 manufactured by Air Products Japan Co., Ltd.) ”) (0.1-fold molar amount with respect to silver 2-methylacetoacetate), and the mixture was stirred at room temperature (25 ° C.) for 60 minutes to obtain a silver ink composition (I-3). Table 7 shows the blending ratio of each component. In Table 7, “nitrogen-containing compound (molar ratio)” means the compounding amount (number of moles) of nitrogen-containing compound per mol of silver carboxylate ([number of moles of nitrogen-containing compound] / [silver carboxylate] Number of moles]). “Alcohol (molar ratio)” also means the blending amount (number of moles) of alcohol per mole of silver carboxylate ([number of moles of alcohol] / [number of moles of silver carboxylate]).

(Manufacture of adhesive layer composition)
N-2- (aminoethyl) -3-aminopropyltrimethoxysilane ((CH ₃ O) ₃ Si (CH ₂ ) ₃ NH (CH ₂ ) ₂ NH ₂ as compound (3), “KBM603” manufactured by Shin-Etsu Silicone Co., Ltd. ), 2-propanol is blended so that the ratio of the blending amount to the total amount of the blending components is 20% by mass and 80% by mass, respectively, and stirred at room temperature (25 ° C.) for 60 minutes, whereby the composition for the adhesion layer I got a thing.

(Manufacture of laminates and circuit boards, and evaluation of circuit boards)
On the base material (thickness 0.25 mm) made of polyethylene naphthalate (PEN), the composition for the adhesion layer obtained above is applied using an applicator, and heat-treated at 120 ° C. for 10 minutes using an oven. By doing so, the adhesion layer (thickness 0.5-1 micrometer) was formed on the base material.
Thereafter, a silver layer (thickness: 1 μm) was formed on the surface of the adhesion layer by the same method as in Example 1 to produce a laminate and a circuit board, and the circuit board was evaluated. The results are shown in Table 8.

[Example 8]
<Manufacture of laminate and circuit board, and evaluation of circuit board>
In the same manner as in Example 7, an adhesion layer (thickness of 0.5 to 1 μm) was formed on a polyethylene naphthalate base material (thickness of 0.25 mm).
Next, after applying a silver ink composition (II-1) (“TEC-IJ-010” manufactured by Inktec, silver concentration of 15% by mass) in which a silver complex is blended on the adhesion layer by a screen printing method, This was heated (baked) in an oven at 150 ° C. for 1 hour to form a silver layer (thickness: 1 μm) as a conductive layer on the surface of the adhesion layer to obtain a laminate.
Next, using this laminate, a circuit board was produced and evaluated in the same manner as in Example 1. The results are shown in Table 8.

[Comparative Example 7]
<Manufacture of laminate and circuit board, and evaluation of circuit board>
In the same manner as in Example 1, an adhesion layer (thickness 3 to 4 μm) was formed on the surface of a base material (thickness 2 mm) made of polycarbonate / ABS resin alloy.
Next, a silver ink composition (II-2) obtained by blending a silver complex and silver particles on the adhesion layer by screen printing (“TEC-PA-010” manufactured by Inktec, a silver concentration of 55% by mass, binder-free) Use) is heated (baked) in an oven at 80 ° C. for 2 hours to form a silver layer (thickness 1 μm) as a conductive layer on the surface of the adhesion layer, Obtained.
Next, using this laminate, a circuit board was produced and evaluated in the same manner as in Example 1. The results are shown in Table 8.

[Comparative Example 8]
<Manufacture of laminate and circuit board, and evaluation of circuit board>
In the same manner as in Example 1, an adhesion layer (thickness 3 to 4 μm) was formed on the surface of a base material (thickness 2 mm) made of polycarbonate / ABS resin alloy.
Next, a silver ink composition (II-3) in which silver particles are blended on the adhesion layer by a screen printing method (“RA RS 056” manufactured by Toyochem Co., Ltd., silver concentration 66% by mass, synthetic resin content 1 to 10) (Mass%) is applied and heated (baked) in an oven at 80 ° C. for 2 hours to form a silver layer (thickness: 1 μm) as a conductive layer on the surface of the adhesion layer. Got.
Next, using this laminate, a circuit board was produced and evaluated in the same manner as in Example 1. The results are shown in Table 8.

[Comparative Example 9]
<Evaluation of silver plate>
For the silver plate having a thickness of 0.1 mm, the skewness of the roughness curve on the surface of the silver layer (silver plate) and the rate of change thereof were calculated in the same manner as in Example 1. The results are shown in Table 8.

As is clear from the above results, in the laminates of Examples 7 to 8, the skewness of the roughness curve on the surface of the silver layer satisfies both the conditions (i) and (ii), and is long under high temperature and high humidity conditions. Even when stored for a long time, a high bonding (adhesion) force between the silver layer and the electronic component was maintained. In these examples, when the peeling site of the chip on the circuit board after the measurement of the shearing force (bonding force) was observed, in any example, the chip was peeled off before and after the storage regardless of the conductive adhesion. It was confirmed that it was caused by cohesive failure of the bonding (adhesion) layer formed by curing the agent. That is, in these circuit boards, no interface breakdown occurred at any of the interface between the bonding layer and the silver layer and the interface between the bonding layer and the electronic component.
On the other hand, as for the laminated body of Comparative Examples 7-8, and the silver plate in Comparative Example 9, the skewness of the roughness curve on the surface of the silver layer did not satisfy both the conditions (i) and (ii).

  The calculated value and rate of change of the skewness of the roughness curve shown in the above results are for the exposed surface of the silver layer surface where the bonding layer is not formed, but the surface where the bonding layer is formed (bonding layer) As a result of confirming the calculated value of the skewness and the rate of change, the surface of the silver layer surface was the same value as the exposed surface, and the silver layer surface showed the same tendency with respect to the skewness of the roughness curve regardless of the presence or absence of exposure. .

[Examples 9 to 10]
<Manufacture of laminate and circuit board, and evaluation of circuit board>
A laminated body and a circuit board were produced in the same manner as in Examples 7 to 8 except that “CA-110” manufactured by AGF was used instead of “QMI516IE” manufactured by Henkel as the conductive adhesive, The substrate was evaluated. The results are shown in Table 9.

  The laminated bodies of Examples 9 to 10 are the same as the laminated bodies of Examples 7 to 8, and as described above, the skewness of the roughness curve on the surface of the silver layer has the conditions (i) and (ii). Is satisfied together. As is clear from the above results, the circuit boards of Examples 9 to 10 maintained a high bonding (adhesion) force between the silver layer and the electronic component even when stored for a long time under high temperature and high humidity conditions. . In these examples, when the peeling site of the chip on the circuit board after the measurement of the shearing force (bonding force) was observed, in any example, the chip was peeled off before and after the storage regardless of the conductive adhesion. It was confirmed that it was caused by cohesive failure of the bonding (adhesion) layer formed by curing the agent. That is, in these circuit boards, no interface breakdown occurred at any of the interface between the bonding layer and the silver layer and the interface between the bonding layer and the electronic component.

<Evaluation of laminate>
The laminated body of Example 1, the laminated bodies of Comparative Examples 7 and 8, and the silver plate in Comparative Example 9 were further evaluated by the following methods.
That is, about the laminated body of Example 1, and the laminated body of Comparative Examples 7 and 8, it cooled using liquid nitrogen and fractured | ruptured, and the cross section similar to what is shown in FIG. 1 was exposed. Moreover, about the silver plate in the comparative example 9, the cross section was exposed by cut | disconnecting using a microtome.
Subsequently, the laminate (broken laminate) or the silver plate (broken silver plate) having this cross section is left standing and stored under the same conditions as in Example 1 (temperature 85 ° C. and relative humidity 85%). Calculate the skewness (Rsk) of the roughness curve of the cross-section of the silver layer (ie, the exposed surface under conditions of temperature 85 ° C. and relative humidity 85%) before starting and after 240 hours and 480 hours from the start of storage. Then, the change rate of the skewness after the storage for a predetermined time before the storage start was calculated. The results are shown in Table 10. The skewness of the roughness curve was calculated by the following method. That is, the shape of the cross section of the silver layer was measured using a shape measurement laser microscope (“VK-X100” manufactured by Keyence Corporation), and a high-pass filter (cutoff value λ _C : 0. 08mm) was applied to obtain a roughness curve. And the skewness (Rsk) of the roughness curve was calculated from the profile of the obtained roughness curve.

As described above, the laminated body of Example 1 maintains a high bonding (adhesion) force between the silver layer and the electronic component even when stored for a long time under high temperature and high humidity conditions. As is clear from the above results, in the laminated body of Example 1, the skewness of the roughness curve of the cross section of the silver layer satisfies both the conditions (i) and (ii), and the conductive joint is interposed. The skewness of the roughness curve and the rate of change thereof showed the same tendency between the electronic component mounting surface and the cross section. That is, the rate of change in skewness of the roughness curve of the silver layer cross section satisfies at least one of the conditions (i) and (ii), so that the silver layer has a high bonding strength with electronic components even under high temperature and high humidity conditions. We were able to confirm that it could be maintained.
On the other hand, as for the laminated body of Comparative Examples 7-8 and the silver plate in Comparative Example 9, the skewness of the roughness curve on the surface of the silver layer did not satisfy both conditions (i) and (ii).

  The present invention can be used for a circuit board having silver wiring and electronic components on a base material.

1, 2, 3 Laminated body 11 Base material 11a Surface of base material 12 Silver layer 12a Surface of silver layer 12b Back surface of silver layer 13 Adhesion layer 13a Surface of adhesion layer 14 Chip (electronic component)
14a, 14b Chip terminal portion 14c Chip body portion 15 Bonding layer (adhesive layer)
30 Circuit board

Claims (2)

A laminate comprising a silver layer on a substrate, the silver layer having a surface satisfying at least one of the following conditions (i) and (ii) with a skewness of a roughness curve.
(I) After 240 hours have passed under the conditions of a temperature of 85 ° C. and a relative humidity of 85%, the skewness change rate is 35% or more.
(Ii) The rate of change in skewness is 40% or more after 480 hours have passed under the conditions of a temperature of 85 ° C. and a relative humidity of 85%.   On the surface where the skewness of the roughness curve among the silver layers of the laminate according to claim 1 satisfies at least one of the conditions (i) and (ii), an electronic component is interposed via a conductive joint. A circuit board characterized by being mounted.

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