JP6346486B2 - Laminate, data transmitter / receiver, communication device, and transparent conductive film - Google Patents

Description

  The present invention relates to a laminate in which a conductive layer is provided on a base material via a receiving layer, and a data transmission / reception body, a communication device, and a transparent conductive film using the laminate.

  Metallic silver is widely used as a recording material and printing plate material, and as a highly conductive material because of its excellent conductivity. When metallic silver is applied to such applications, there is a technique in which a silver ink composition containing a metallic silver forming material is prepared, this composition is adhered onto a substrate, and heated (baked). Adopted. By this method, a laminate in which metallic silver (conductor) is formed on a substrate is obtained, and this conductor is used as the recording material, printing plate material, or highly conductive material. And as a forming material of metallic silver at this time, silver carboxylate such as β-ketocarboxylate silver (see Patent Document 1) is known. It can be formed and can form metallic silver of better quality than silver ink compositions that have been widely used in the past, so it is extremely useful.

  On the other hand, in order to improve the adhesion strength between the printed layer formed using the ink composition and the base material, a method of forming a receiving layer on the base material and forming the printed layer on the receiving layer is employed. Sometimes. As the receiving layer to which the ink composition is attached in this manner, for example, those containing a polyvinyl acetal resin (see Patent Document 2) and those containing latex and polyvinyl alcohol (see Patent Document 3) are known.

JP 2009-114232 A JP-A-8-118786 JP 2010-283194 A

  Even when a silver layer (conductive layer) is formed on a substrate using the silver ink composition, it is desired to improve the adhesion strength between the conductive layer and the substrate by providing a receiving layer. However, when the conductive layer is formed on the receiving layer described in Patent Documents 2 and 3 using the silver ink composition as described above, for example, the adhesion performance between the conductive layer and the substrate, and the conductive layer There is a problem in that it is impossible to achieve both crack resistance performance that suppresses the generation of cracks, and the development of a new receiving layer suitable for the use of the silver ink composition has been desired.

  The present invention has been made in view of the above circumstances, and even if a conductive layer is provided on a substrate via a receiving layer, and the conductive layer is formed using a silver ink composition, An object of the present invention is to provide a laminate capable of achieving both adhesion performance between a layer and a substrate and crack resistance performance in a conductive layer, and a data transmission / reception body, a communication device and a transparent conductive film using the laminate. To do.

To solve the above problem,
The present invention is a laminate in which a conductive layer is provided on a substrate via a receptor layer, and the receptor layer is represented by the following formulas (i) -1, (i) -2, and (i) -3. The polyvinyl acetal resin (A) having a structural unit and a glass transition temperature (Tg) of less than 70 ° C. are represented by the following formulas (i) -1, (i) -2, and (i) -3. The base material which has a structural unit and is formed by mixing a polyvinyl acetal resin (B) having a Tg of 80 ° C. or more, and the conductive layer is based on JIS K 5600-5-6 In the adhesion test of the conductive layer, a laminate is provided that is classified into category 0 or category 1.

（式中、Ｒ^２１は水素原子又は炭素数１〜５のアルキル基である。）

(In the formula, R ²¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

In the present invention, the polyvinyl acetal resin (A) is preferably mixed in an amount of 0.2 parts by mass or more and less than 5 parts by mass with respect to 1 part by mass of the polyvinyl acetal resin (A).
The present invention also provides a data transmitter / receiver using the laminate and including the conductive layer as an antenna.
Moreover, this invention provides the communication apparatus characterized by using the said laminated body and having provided the said base material as a housing | casing.
Moreover, this invention provides the transparent conductive film characterized by using the said laminated body and having the said conductive layer as an ultra fine wiring or an ultra-thin wiring.

  According to the present invention, even if a conductive layer is provided on a substrate via a receiving layer, and the conductive layer is formed using a silver ink composition, the adhesion performance between the conductive layer and the substrate is improved. Provided are a laminate capable of achieving both excellent and crack resistance performance, and a data transmitter / receiver, a communication device and a transparent conductive film using the laminate.

It is a schematic sectional drawing which illustrates the laminated body of this invention.

<< Laminate >>
The laminate of the present invention is a laminate in which a conductive layer is provided on a substrate via a receptor layer, and the receptor layer has the following formulas (i) -1, (i) -2, and (i): -3, a polyvinyl acetal resin (A) having a glass transition temperature (Tg) of less than 70 ° C, and the following formulas (i) -1, (i) -2, and (i) -3 It is formed by mixing a polyvinyl acetal resin (B) having a structural unit represented by Tg of 80 ° C. or higher,
The conductive layer is characterized by being classified as Class 0 or Class 1 in an adhesion test between the substrate and the conductive layer in accordance with JIS K 5600-5-6.

（式中、Ｒ^２１は水素原子又は炭素数１〜５のアルキル基である。）

(In the formula, R ²¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)

In the laminate, the receiving layer can improve the adhesion strength between the conductive layer and the base material, and can achieve both the crack resistance performance of the conductive layer. That is, the receiving layer and the conductive layer, and the receiving layer and the base material each have high adhesion strength, and the conductive layer provided via the receiving layer is remarkably suppressed from peeling from the base material. In addition, the receiving layer can stably maintain high adhesion strength between the conductive layer and the substrate. In addition to this, it is possible to achieve both the crack resistance performance of the conductive layer.
Thus, the adhesive strength between the conductive layer and the substrate is high, and the compatibility with the crack resistance of the conductive layer is due to the use of a specific polyvinyl acetal resin as the compound that forms the receptor layer.

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

<Base material>
The base material 2 can select arbitrary shapes according to the objective, for example, it is preferable that it is a film form or a sheet form, it is preferable that thickness is 0.5-5000 micrometers, and it is 0.5-2000 micrometers. It is more preferable. By being more than a lower limit, the structure of a receiving layer can be hold | maintained more stably, and the handling property at the time of formation of a receiving layer or a conductive layer becomes more favorable by being below an upper limit.

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

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

<Receptive layer>
The receiving layer 3 is formed using a polyvinyl acetal resin.
The shape of the receiving layer 3 when the laminate 1 is viewed in plan so that the main surface of the substrate 2 (surface on which the receiving layer 3 is formed) is looked down from above can be arbitrarily set according to the purpose, What is necessary is just to set in consideration of the shape of the conductive layer 4 described later. For example, the receiving layer 3 may be provided on the entire surface of the base material 2, or the receiving layer 3 may be provided on only a part of the surface of the base material 2. May be patterned.

  The thickness of the receiving layer 3 is preferably 0.001 to 20 μm, and more preferably 0.002 to 5 μm. By being more than a lower limit, the adhesive strength of the conductive layer 4 improves more, and by being below an upper limit, the structure of a receiving layer can be hold | maintained more stably.

[Polyvinyl acetal resin]
The polyvinyl acetal resin is a polyvinyl acetal (polyvinyl acetal resin) having the structural units (i) -1, (i) -2, and (i) -3, and has a glass transition temperature (Tg) of less than 70 ° C. Resin (A) and polyvinyl acetal resin (B) whose Tg is 80 degreeC or more are mixed. In the polyvinyl acetal resin, the arrangement order of the structural units (i) -1, (i) -2, and (i) -3 is not particularly limited.

^{Wherein, R 21} is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
The alkyl group in R ²¹ may be linear, branched or cyclic, and is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert group -Butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group can be exemplified, linear or branched It is preferable that it is a shape.

  The polyvinyl acetal resin is formed by mixing a polyvinyl acetal resin (A) having a glass transition temperature (Tg) of less than 70 ° C. and a polyvinyl acetal resin (B) having a Tg of 80 ° C. or more. As described above, by using a resin in which resins having different Tg are mixed, the adhesion strength between the conductive layer 4 and the base material 2 can be further improved, and the crack resistance performance of the conductive layer can be made compatible. .

<Polyvinyl acetal resin (A)>
The polyvinyl acetal resin (A) (hereinafter sometimes referred to as “resin (A)”) has a Tg of less than 70 ° C. In the present invention, the Tg of the resin (A) is preferably 68 ° C. or less, and more preferably 66 ° C. or less.
Moreover, although the lower limit of Tg of resin (A) changes with uses of the laminated body 1, it is preferable that it is 50 degreeC and it is more preferable that it is 60 degreeC. By using the thing of such a range, the adhesiveness to the base material of the receiving layer 3 improves more with respect to the temperature change in the use environment of the laminated body 1. FIG.

<Polyvinyl acetal resin (B)>
The polyvinyl acetal resin (B) (hereinafter sometimes referred to as “resin (B)”) has a Tg of 80 ° C. or higher. In the present invention, the Tg of the resin (B) is preferably 82 ° C. or higher, and more preferably 84 ° C. or higher.
Moreover, although the upper limit of Tg of resin (B) changes with uses of the laminated body 1, it is preferable that it is 100 degreeC and it is more preferable that it is 90 degreeC. By using the thing of such a range, the stability of the receiving layer 3 improves more with respect to the temperature change in the use environment of the laminated body 1. FIG.

The resin (A) and the resin (B) preferably have a Tg difference of 15 ° C. or higher, and more preferably 20 ° C. or higher.
By setting it as such a range, it is thought that it can contribute to coexistence with the improvement of the adhesiveness of the receiving layer 3 to the base material, and the crack resistance performance of a conductive layer.

The molecular weight of the polyvinyl acetal resin is preferably 53000 or more, more preferably 54000 or more, further preferably 55000 or more, particularly preferably 58000 or more, and most preferably 62000 or more. . By setting it as such a range, the outstanding effect by which deterioration of the receiving layer 3 is suppressed is acquired.
The upper limit of the molecular weight of the polyvinyl acetal resin is not particularly limited, but is preferably 200,000 because the effects of the present invention can be sufficiently obtained and the receiving layer 3 can be formed more easily.
Here, "molecular weight" is a theoretical value calculated using the molecular weight of the monomer, assuming that all the monomers used for the synthesis of the polyvinyl acetal resin have reacted to form a polyvinyl acetal resin. When the polyvinyl acetal resin has only the structural units (i) -1, (i) -2, and (i) -3, the monomer may be one that derives the structural unit (i) -1, structural unit (i ) -2 and those that induce structural unit (i) -3 need only be considered.

  As the structural unit (i) -1 possessed by the polyvinyl acetal resin, only one type or two or more types may be used, and when there are two or more types, the combination and ratio thereof are not particularly limited.

The laminate of the present invention is characterized in that the receiving layer 3 is formed by mixing two types of resins (resin (A) and resin (B)) having different Tg. By using two types of resins having different Tg for the receiving layer 3, it is possible to achieve both the adhesion performance between the base material 2 and the conductive layer 4 and the crack resistance performance of the conductive layer. The reason is guessed as follows.
Usually, by increasing the Tg of the resin, the rigidity of the skeleton is increased, and the dimensional stability and the like can be improved. On the other hand, if the Tg of the resin is low, flexibility can be secured.
According to the present invention, the resin (A) having a low Tg and flexibility so that it has excellent adhesion to the base material and the conductive layer, and the resin structure having a high Tg and a high rigidity make the structure of the resin rigid. By forming the receiving layer by mixing the resin (B) capable of forming a conductive layer, the adhesion performance to the base material and the conductive layer is ensured, and the followability to the conductive layer is also provided. It is thought that a balance can be achieved.

  In the present invention, the mixing ratio of the resin (A) and the resin (B) is preferably such that the resin (A) is mixed in an amount of 1 part by mass and the resin (B) is mixed in an amount of 0.2 parts by mass or more and less than 5 parts by mass. More preferably, 0.2 part by mass or more and less than 4 parts by mass of resin (B) is added to 1 part by mass of resin (A), and resin (B) is added to 1 part by mass of resin (A). It is particularly preferable to mix 0.2 parts by mass or more and less than 3 parts by mass. By setting the mixing ratio in the above range, the balance between the resin (A) and the resin (B) is optimal in order to achieve both the adhesion performance between the base material 2 and the conductive layer 4 and the crack resistance performance of the conductive layer. Can be.

In the polyvinyl acetal resin, the ratio of the amount of the structural unit (i) -2 (the number of moles of the structural unit (i) -2) to the total amount of the repeating units constituting the polyvinyl acetal resin (the total number of moles of the repeating unit) is 12 moles. % Or less, more preferably 10 mol% or less, and particularly preferably 8 mol% or less. And the said ratio should just be larger than 0, it is preferable that it is 0.5 mol% or more, it is more preferable that it is 0.75 mol% or more, and it is especially preferable that it is 1 mol% or more.
The polyvinyl acetal resin has a ratio of the amount of the structural unit (i) -3 (the number of moles of the structural unit (i) -3) to the total amount of the repeating units (the total number of moles of the repeating unit) constituting the polyvinyl acetal resin is 0. It is larger, preferably 5 to 50 mol%, more preferably 10 to 45 mol%, and particularly preferably 15 to 40 mol%.
In addition, the polyvinyl acetal resin has a ratio of the amount of the structural unit (i) -1 (the number of moles of the structural unit (i) -1) to the total amount of the repeating units (the total number of moles of the repeating unit) constituting the polyvinyl acetal resin is 0. It is larger, preferably 45 to 90 mol%, more preferably 50 to 85 mol%, and particularly preferably 55 to 80 mol%.

  The polyvinyl acetal resin may have other structural units other than the structural units (i) -1, (i) -2, and (i) -3 within a range that does not impair the effects of the present invention. The ratio of the amount of the other structural unit (number of moles of the other structural unit) to the total amount of repeating units (total number of moles of the repeating unit) constituting the polyvinyl acetal resin may be 5 mol% or less. Preferably, it is 3 mol% or less, more preferably 1 mol% or less. The polyvinyl acetal resin preferably has only the structural units (i) -1, (i) -2, and (i) -3.

  The polyvinyl acetal resin is obtained by polymerizing the structural units (i) -1, (i) -2 and (i) -3, and, if necessary, the monomer for deriving the other structural units by a known method. It is done. The polymerization temperature and polymerization time are not particularly limited, and may be set as appropriate according to the polymerization method and the type of monomer used. After the polymerization reaction, the polyvinyl acetal resin may be taken out by a known method, and may be purified as necessary. Moreover, you may use a commercial item as polyvinyl acetal resin.

  Each of the polyvinyl acetal resins (A) and (B) used for forming the receiving layer 3 may be one kind or two kinds or more, and in the case of two kinds or more, the combination and ratio are not particularly limited.

<Conductive layer>
The conductive layer 4 is preferably formed using a metal silver forming material.
The shape of the conductive layer 4 when the laminate 1 is viewed in plan so that the main surface of the substrate 2 (the surface on which the receiving layer 3 is formed) is looked down from above can be arbitrarily set according to the purpose. For example, the conductive layer 4 may be provided on the entire surface of the receiving layer 3, or the conductive layer 4 may be provided on only a part of the surface of the receiving layer 3, and the conductive layer 4 is patterned. It may be.

  Although the thickness of the conductive layer 4 can be arbitrarily set according to the purpose, it is preferably 0.01 to 10 μm, and more preferably 0.05 to 2 μm. By being more than a lower limit, the effect by having provided the conductive layer 4 becomes higher, and the structure of the laminated body 1 can be hold | maintained more stably by being below an upper limit.

The metallic silver forming material is decomposed by heating or the like to form metallic silver.
In the present invention, the metal silver forming material may be used alone or in combination of two or more. When using 2 or more types together, the combination and ratio can be adjusted arbitrarily.

[Silver carboxylate]
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個以上の該メチレン基はカルボニル基で置換されていてもよい。）

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

(Silver β-ketocarboxylate (1))
The β-ketocarboxylate silver (1) is represented by the general formula (1).
In the formula, R represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a phenyl group, a hydroxyl group, an amino group, or a general formula “R ¹ -CY 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 formed by bonding the aliphatic hydrocarbon group to an oxygen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group (—OH), a cyano group (—C≡N), a phenoxy group (—O— C ₆ H ₅ ) and the like can be exemplified, and the number and position of substituents are not particularly limited. When the number of substituents is plural, the plural substituents may be the same as or different from each other.
Examples of the aliphatic hydrocarbon group that is a substituent include the same aliphatic hydrocarbon groups as those described above for R except that the number of carbon atoms is 1 to 16.

Y 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, or a benzyl group, and at least one X is preferably a hydrogen atom.

The silver β-ketocarboxylate (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), 2- ethylacetoacetate silver _{(CH 3 -C (= O)} -CH (CH 2 CH 3) -C (= O) -OAg), propionylacetate silver _{(CH 3 CH 2 -C (=} O) -CH 2 -C (= O) -OAg), 2-n- Buchiruaseto silver acetate _{(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), benzoyl acetate silver _{(C 6 H 5 -C (=} O) -CH 2 -C (= O) -OAg), Pibaroiruaseto silver acetate ((C _{H 3) 3 C-C (} = O) -CH 2 -C (= O) -CH 2 -C (= O) -OAg), isobutyryl acetoacetate silver _{((CH 3) 2 CH-} C (= O) —CH ₂ —C (═O) —CH ₂ —C (═O) —OAg), or silver acetonedicarboxylate (AgO—C (═O) —CH ₂ —C (═O) —CH ₂ — C (= O) -OAg) is preferred.

  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.

  The laminated body of the present invention is not limited to that 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, in addition to the base material, the receiving layer, and the conductive layer, other layers may be formed. In addition, here, the main surface of the base material is shown in which the receiving layer and the conductive layer are provided on only one surface, but both surfaces of the main surface (the one surface and the opposite side to the one surface) And the other side of the substrate) may be provided with a receiving layer and a conductive layer.

<< Manufacturing Method of Laminate >>
The laminate of the present invention can be produced in the same manner as the known laminate except that a polyvinyl acetal resin is used for forming the receiving layer and the metal silver forming material is used for forming the conductive layer.
As a preferable method for producing the laminate, a step of forming the receptor layer on the base material using a polyvinyl acetal resin (hereinafter sometimes abbreviated as “receptor layer forming step”), and the receptor layer There can be exemplified a production method characterized by comprising a step of forming the conductive layer using the metal silver forming material (hereinafter sometimes abbreviated as “conductive layer forming step”).

<Receptive layer formation process>
In the receiving layer forming step, the receiving layer (receiving layer 3) is formed on the base material (base material 2) using a polyvinyl acetal resin.
The receptor layer can be formed, for example, by preparing a composition for forming a receptor layer in which a polyvinyl acetal resin is blended, attaching the composition to a substrate, and performing a heat treatment.

  Examples of the receiving layer forming composition include a liquid composition in which a polyvinyl acetal resin and a solvent are blended.

The solvent used for the preparation of the composition for forming a receiving layer is not particularly limited as long as the polyvinyl acetal resin is not significantly deteriorated, and preferable examples include those having 2 or more carbon atoms such as ethanol and 2-propanol (isopropyl alcohol). Alcohol can be illustrated.
The said solvent 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.

  In the composition for forming the receiving layer, the ratio (concentration) of the blended amount of the polyvinyl acetal resin in the total amount of the blended components is preferably 0.3 to 50% by weight, and 0.7 to 30% by weight. Is more preferable. By being more than a lower limit, a receiving layer can be formed more efficiently, and by being below an upper limit, the handleability of the said composition improves more.

The composition for forming the receiving layer may be one in which other components are blended in addition to the polyvinyl acetal resin and the solvent.
The other components can be arbitrarily selected according to the purpose and are not particularly limited.
In the composition for forming a receiving layer, the ratio of the blended amount of the other components to the total amount of the blended components is preferably 10% by mass or less, and more preferably 5% by mass or less.
One of these other components 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.

  All of the components in the composition for forming the receiving layer may be dissolved, or some or all of the components may not be dissolved, but the components that are not dissolved are preferably uniformly dispersed. .

The composition for receiving layer formation is obtained by mix | blending components other than polyvinyl acetal resin and polyvinyl acetal resin.
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 it is preferably 5 to 85 ° C.
Further, the blending time (mixing time) may be appropriately adjusted according to the type of blending component and the temperature at the blending, but is preferably 2 to 15 hours, for example.

The liquid receptive layer forming composition can be deposited on the substrate by a known method such as a printing method, a coating method, or a dipping method.
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 receiving layer forming step, the thickness of the receiving layer can be adjusted by adjusting the amount of the receiving layer forming composition to be adhered to the substrate or the blending amount of the polyvinyl acetal resin in the receiving layer forming composition.

  The conditions for the heat treatment of the composition for forming a receiving layer deposited on the substrate may be adjusted as appropriate according to the type of ingredients of the composition. For example, the removal (drying) of the solvent proceeds smoothly. It is preferable to adjust to. Usually, it is preferable that heating temperature is 50-180 degreeC, and it is more preferable that it is 70-160 degreeC. Although what is necessary is just to adjust a heating time according to heating temperature, Usually, it is preferable that it is 3 to 60 minutes, and it is more preferable that it is 5 to 40 minutes.

In the receiving layer forming step, the substrate may be heat-treated (annealed) before the receiving layer forming composition is adhered. By heat-treating the base material, shrinkage of the base material is suppressed and dimensional stability is improved when the silver ink composition is heat-treated (baked) in the conductive layer forming step described later.
The conditions for the heat treatment of the base material before adhering the composition for forming the receiving layer may be appropriately adjusted according to the type of the base material, and are not particularly limited, but the heat treatment is performed at 60 to 200 ° C. for 10 to 60 minutes. Preferably, the conditions may be the same as the conditions for the heating (firing) treatment of the silver ink composition in the conductive layer forming step.

<Conductive layer formation process>
Next, in the conductive layer forming step, a conductive layer is formed on the receiving layer using the metal silver forming material.
The conductive layer is prepared by preparing a silver ink composition in which a metallic silver forming material is blended, and depositing it on the receiving layer, followed by solidification by appropriately selecting a post-treatment such as a drying treatment or a heating (firing) treatment. Can be formed. The heat treatment may be performed also as a drying treatment.
As the silver ink composition, a liquid one is preferable, and one in which a metallic silver forming material is uniformly dispersed is preferable.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The amine compound is n-propylamine, n-butylamine, n-hexylamine, n-octylamine, n-dodecylamine, n-octadecylamine, sec-butylamine, tert-butylamine, 3-aminopentane, 3-methyl. Butylamine, 2-aminooctane, 2-ethylhexylamine, 2-phenylethylamine, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, N-methyl-n-hexylamine, diisobutylamine, N-methylbenzylamine Di (2-ethylhexyl) amine, 1,2-dimethyl-n-propylamine, N, N-dimethyl-n-octadecylamine or N, N-dimethylcyclohexylamine is preferred.
In addition, since the components in the silver ink composition (second mixture) are more uniformly dispersed and the quality is stabilized at the time of supplying carbon dioxide, which will be described later, the amine compound has a branched alkyl group. Those are preferred.

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

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

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

In the silver ink composition, the compounding amount of the nitrogen-containing compound is preferably 0.4 to 15 mol, and more preferably 0.8 to 5 mol, per mol of the silver carboxylate.
By defining the blending amount of the nitrogen-containing compound as described above, the silver ink composition is further improved in stability and the quality of the conductive layer 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, metallic silver (conductor) having sufficient conductivity can be formed even by heat treatment at a low temperature.
The reducing agent is one or more reductions 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)”). It is preferable that the compound be a reactive compound (hereinafter simply abbreviated as “reducing compound”).
HC (= O) -R ²¹ (5)
(In the formula, R ²¹ represents an alkyl group having 20 or less carbon atoms, an alkoxy group, an N, N-dialkylamino group, a hydroxyl group, or an amino group.)

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

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

The alkoxy group having 20 or less carbon atoms in R ²¹ has 1 to 20 carbon atoms, and examples thereof include monovalent groups 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 conductive layer more easily and more stably.

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

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

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

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

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

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

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

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

  In the silver ink composition, the amount of acetylene alcohol (2) is preferably 0.03 to 0.7 mol per mol of the metal silver forming material, and preferably 0.05 to 0.3 mol. It is more preferable that 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 can be arbitrarily selected according to the purpose, and are not particularly limited. Preferred examples include solvents other than alcohols, and can be arbitrarily selected according to the type and amount of compounding components.
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.
One of these other components 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.

  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 30 ° C.
The blending time (mixing time) is not particularly limited as long as each blending component does not deteriorate, but it is preferably 5 to 120 minutes.

[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 further to the second mixture, It is preferable to produce a silver ink composition by blending the reducing agent. 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. (according to an ultrasonic viscometer) of 5 Pa · s or more, it is preferable to supply 100 L or more of carbon dioxide gas. It is more preferable to supply the above. In addition, although the viscosity at 20-25 degreeC of a silver ink composition was demonstrated here, the temperature at the time of use of a silver ink composition is not limited to 20-25 degreeC, It can select arbitrarily.

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

  The temperature of the first mixture at the time of supplying carbon dioxide gas is preferably 5 to 70 ° C, more preferably 7 to 60 ° C, and particularly preferably 10 to 50 ° C. By setting it to the lower limit or higher, carbon dioxide can be supplied more efficiently, and by setting it to the upper limit or lower, 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. (according to an ultrasonic viscometer) Is preferably 3 Pa · s or more. 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.

The second mixture is further mixed with the reducing agent 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.

  Although the temperature at the time of the compounding of the reducing compound is not particularly limited as long as each compounding component does not deteriorate, it 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) ] / [Metal silver forming material, nitrogen-containing compound, reducing agent, alcohol, and other components (mass)] × 100) is preferably 10% by mass or less, more preferably 5% by mass or less. Preferably, even if 0 mass, that is, no other component is blended, the silver ink composition exhibits its effect sufficiently.

  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 forms a conductive layer (conductor) by performing post-treatment under milder conditions than the silver ink composition not containing metallic silver during the formation of the conductive layer. There are things you can do. In addition, even when the amount of the reducing agent is sufficiently large, the conductive layer may be formed by performing post-treatment under the same mild conditions. In this way, by adopting conditions that promote the decomposition of the silver carboxylate, the conductive 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 conductive layer by suppressing the fluctuation | variation of dripping speed.

  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. It is preferable that (by an ultrasonic viscometer) is 1 Pa · s or more.

  The silver ink composition may be deposited on the receiving layer in the same manner as the receiving layer forming composition.

  In the conductive layer forming step, the thickness of the conductive layer can be adjusted by adjusting the amount of the silver ink composition to be adhered to the receiving layer or the blending amount of the metal silver forming material in the silver ink composition.

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

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

  The method for heat treatment of the silver ink composition is not particularly limited, and for example, 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 and pressure reduction.

  When the heat treatment of the silver ink composition is performed under humidified conditions, it is preferably performed in an atmosphere with a relative humidity of 10% or more, more preferably in an atmosphere with a relative humidity of 60% or more, and a relative humidity of 80%. It is particularly preferable to perform in the above atmosphere, and may be performed by spraying high-pressure steam heated to 100 ° C. or higher. By conducting heat treatment under humidifying conditions in this manner, a conductive layer having a low resistance value (excellent conductivity) can be formed in a short time.

The heat treatment of the silver ink composition may be performed in two stages. For example, in the first stage heat treatment, a method of mainly drying the silver ink composition rather than forming the conductive layer, and forming the conductive layer to the end in the second stage heat treatment can be exemplified.
In the first-stage heat treatment, the heating temperature may be appropriately adjusted according to the type of the composition component of the ink composition, but is preferably 50 to 110 ° C, more preferably 70 to 90 ° C. . Moreover, what is necessary is just to adjust a heating time according to heating temperature, Usually, it is preferable that it is 0.2 to 12 hours, and it is more preferable that it is 0.4 to 5 hours.
In the second-stage heat treatment, the heating temperature may be appropriately adjusted according to the type of compounding components of the ink composition so that the conductive layer is formed satisfactorily, but is preferably 60 to 350 ° C. 70 to 180 ° C. is more preferable. 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.

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

In the laminate of the present invention, since the receiving layer is formed using a polyvinyl acetal resin, the adhesion strength between the receiving layer and the substrate is high, and the conductive layer is formed using a silver ink composition. Even if it is a thing, the adhesive strength of a receiving layer and a conductive layer is high, ie, the adhesive strength of a conductive layer and a base material is high, and peeling from the base material of a conductive layer is suppressed notably. And the laminated body of this invention satisfy | fills classification 0 or 1 in the adhesiveness test of a base material and a conductive layer based on JISK5600-5-6. And since a receiving layer suppresses deterioration, the high adhesive strength of a conductive layer and a base material can be maintained stably.
The conductive layer can be widely used as a recording material, a printing plate material, a highly conductive material, and the like.

<< Data Transmitter / Transmitter, Communication Equipment, and Transparent Conductive Film >>
The data transmission / reception body of the present invention is characterized in that the laminate is used and the conductive layer is provided as an antenna, and the configuration is the same as that of a known data reception / transmission body except that the lamination is used. be able to. For example, in the laminate 1 shown in FIG. 1, an IC chip electrically connected to the conductive layer 4 is provided on the base material 2 or the receiving layer 3 to form an antenna portion, whereby a non-contact type data receiving / transmitting body is obtained. Can be configured.
Further, the communication device of the present invention is characterized in that the laminate is used and the base is provided as a casing, the laminate is used as an antenna portion, and the casing is configured by the base in the laminate. Except for this, the configuration can be the same as that of a known communication device. For example, a mobile phone can be configured by combining a voice input unit, a voice output unit, an operation switch, a display unit, and the like in addition to the laminate.
The transparent conductive film of the present invention is characterized in that the laminate is used, the conductive layer is provided as ultrafine wiring or ultrathin wiring, and the conductive layer is provided as ultrafine wiring or ultrathin wiring. It can be set as the structure similar to a well-known transparent conductive film. For example, in addition to the laminate, a touch panel or an optical display can be configured by combining with a transparent substrate or the like.
The line width of the ultrafine wiring is preferably 1 μm to 20 μm, more preferably 1.3 μm to 15 μm, and even more preferably 1.5 μm to 13 μm.
In addition, the cross-sectional shape of the ultrafine wiring is preferably a semi-elliptical shape in which approximately half the region in the minor axis direction of the ellipse is cut off.
On the other hand, the ultrathin wiring specifically has a thickness of preferably 5 nm to 10 μm, more preferably 7 nm to 5 μm, and even more preferably 10 nm to 1 μm.
The cross-sectional shape of the ultrathin wiring is the same as the cross-sectional shape of the ultrathin wiring.
In the transparent conductive film of the present invention, the conductive layer only needs to satisfy at least one of the line width and thickness as described above.
If the line width or thickness is as described above, it is difficult to visually recognize the presence of the conductive layer, so that it can function as a transparent conductive film.
The data transmission / reception body, communication device, and transparent conductive film of the present invention can be further reduced in weight and thickness as compared with the prior art. In addition, the conductive layer can be formed at a low temperature, and since a wide range of materials such as a base material can be selected, the degree of freedom in design can be dramatically improved and a more rational structure can be obtained. .

  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.

<Manufacture of laminates>
[Example 1]
(Manufacture of silver ink composition)
Under ice-cooling, silver 2-methylacetoacetate (210.0 g) was added to 2-ethylhexylamine (290.3 g, 2.4-fold mol based on the silver 2-methylacetoacetate below) so as to keep the temperature at 25 ° C. or lower. The solution was obtained by stirring for 30 minutes after the end of the addition. Furthermore, after stirring for 1 hour as it is, carbon dioxide gas was supplied to the obtained yellow transparent reaction liquid (first mixture) at a flow rate of 900 mL / min for 7 hours while stirring at 20 ° C. A mixture (second mixture) in which the liquid was thickened was obtained. The viscosity of this mixture was measured by the following method and found to be 15 Pa · s.
Next, formic acid (0.83 mol per mol of silver 2-methylacetoacetate) was added to the resulting mixture (30.0 g) under ice cooling so that the temperature of the reaction solution was 50 ° C. or lower. By stirring at 25 ° C. for 1.5 hours, a silver ink composition was obtained.

(Measurement method of viscosity)
With respect to the measurement object (5 g), in an environment at a temperature of 23 ° C., a sensor (vibrating body) of an ultrasonic viscometer (“VISCOMATE VM-10A-MH” manufactured by CBC) was inserted to measure the viscosity.

(Manufacture of composition for forming receiving layer)
As the polyvinyl acetal resin, the ratio of the blended amount of the resin 1 in which the resin A and the resin B in Table 1 below are mixed so that A: B = 1: 1 is based on the total amount of the blended components ([polyvinyl acetal The amount of resin blended (mass) / [total blended amount of polyvinyl acetal resin and ethanol (mass)] × 100) was added to ethanol so as to be 10 mass%, and dissolved by stirring at 20 to 70 ° C. for 12 hours. Thus, an ethanol solution was obtained as a composition for forming a receiving layer. In Table ^{1, R 21} represents an ^{R 21} in formula (i) -1.

(Measurement method of Tg)
It was measured by differential scanning calorimetry (DSC). That is, using the following apparatus, the sample (about 10 g) was heated from 20 ° C. to 150 ° C. at a rate of temperature increase of 10 ° C./min to remove moisture, and then from 150 ° C. to 20 ° C. at a rate of temperature decrease of 10 ° C./min. Then, the temperature was raised again from 20 ° C. to 150 ° C. at a rate of temperature rise of 10 ° C./min. During this period, the temperature at which the sample phase transitioned and the specific heat was changed was determined as Tg.
Measuring device: differential thermal analyzer (“DSC6200R” manufactured by SII)
Container: Made of aluminum Reference: Alumina

(Manufacture of laminates)
The obtained ethanol solution was applied onto a polycarbonate substrate (thickness 1.5 mm) using a bar coater (bar No. 010), and heat treated at 80 ° C. for 30 minutes using an oven. A receiving layer was formed on the material. At this time, the coating amount of the ethanol solution on the base material was 7 to 10 g / m ² .
Next, a printing pattern is formed on the receiving layer with the silver ink composition obtained above by a screen printing method, and the conductive layer (heated) is heated on the receiving layer by heat treatment at 80 ° C. for 1 hour using an oven. The pattern of (processed material) was formed, and the laminated body was obtained. At this time, the coating amount of the silver ink composition on the receiving layer was 5 to 30 g / m ² .

<Evaluation of laminate>
<Adhesion strength between conductive layer and substrate>
About the obtained laminated body, based on JISK5600-5-6, the adhesive strength of a conductive layer and a base material was evaluated. That is, after cutting the cross-cut from the surface side in two directions orthogonal to the conductive layer so that 25 areas having the same area are formed, and pasting the tape on the surface of the conductive layer after the cross-cut, Remove this tape and check the number x of the 25 areas where peeling of the conductive layer from the substrate (receptive layer) is not observed. evaluated. The results are shown in Table 3. In Table 3, “x / 25” means that no peeling of the conductive layer from the base material was observed in x out of 25 regions.
A: The conductive layer does not peel at all, and the adhesion strength is extremely high. (Class 0)
○: A part of the conductive layer was peeled off, but there was no practical problem and the adhesion strength was high. (Category 1)
(Triangle | delta): A part of conductive layer peels, there exists a problem practically, and adhesive strength is low. (Category 2-4)
X: The conductive layer of an equivalent area peels and is not worthy of evaluation of adhesion strength (Category 5).
<Crack of laminate>
About the obtained laminated body, the presence or absence of the crack of a conductive layer was evaluated visually. The results are shown in Table 3.
In Table 3, “◯” indicates that there was no crack by visual observation and the volume resistivity was 30 μΩ · cm, and “×” indicates that there was a crack by visual observation and no conduction occurred.
The volume resistivity was measured by the following method.
(Measurement of volume resistivity)
For the obtained conductive pattern, the line resistance value R (Ω), the cross-sectional area A (cm ² ), and the line length L (cm) were measured, and the volume resistivity ρ was calculated by the equation “ρ = R × A / L”. (Ω · cm) was calculated. The wire resistance value R is measured using a digital multimeter ("PC5000a" manufactured by Sanwa Denki Keiki Co., Ltd.), and the cross-sectional area A is measured using a shape measurement laser microscope ("VK-X100" manufactured by Keyence Corporation). did. The results are shown in Table 3.

<Manufacture and evaluation of laminate>
[Examples 2 to 4, Comparative Examples 1 to 5]
As a polyvinyl acetal resin, a laminate was produced in the same manner as in Example 1 except that the resins 2 to 9 obtained by mixing the resins A to C shown in Table 1 at a weight ratio shown in Table 2 were used. evaluated. The results are shown in Table 3.

As is clear from the above results, the laminates of Examples 1 to 4 have high adhesion strength between the conductive layer and the substrate, and satisfy the classification 0 in the adhesion test according to JIS K 5600-5-6. It was. Furthermore, in addition to being excellent in adhesion, the laminates of Examples 1 to 4 also had excellent crack resistance performance of the conductive layer. That is, the laminates of Examples 1 to 4 were able to achieve both the adhesion performance between the conductive layer and the substrate and the crack resistance performance of the conductive layer.
On the other hand, the laminated bodies of Comparative Examples 1 to 5 could not achieve both the adhesion performance between the conductive layer and the base material and the crack resistance performance of the conductive layer.

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

  DESCRIPTION OF SYMBOLS 1 ... Laminated body, 2 ... Base material, 3 ... Receiving layer, 4 ... Conductive layer

Claims (4)

A laminate in which a conductive layer is provided on a substrate via a receiving layer,
The said receiving layer has the structural unit represented by following formula (i) -1, (i) -2, and (i) -3, and the glass transition temperature (Tg) is less than 70 degreeC polyvinyl acetal resin ( A) and a polyvinyl acetal resin (B) having structural units represented by the following formulas (i) -1, (i) -2, and (i) -3 and having a Tg of 80 ° C. or higher are mixed. Formed,
The conductive layer, in compliance with JIS K 5600-5-6, in an adhesion test of the base material and the conductive layer, classification 0 or classification 1 der is, the polyvinyl acetal resin (A) to 1 part by weight On the other hand, the polyvinyl acetal resin (B) is mixed in an amount of 0.2 parts by mass or more and less than 5 parts by mass .

(In the formula, R ²¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) A data receiving / transmitting body comprising the laminate according to claim 1 , wherein the conductive layer is provided as an antenna. A communication device using the laminate according to claim 1 , wherein the base material is provided as a casing. A transparent conductive film comprising the laminate according to claim 1 , wherein the conductive layer is provided as an ultrafine wiring having a line width of 1 μm to 20 μm or an ultrathin wiring having a thickness of 5 nm to 10 μm .

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