JP6008676B2 - LAMINATE, METHOD FOR PRODUCING LAMINATE, AND COMMUNICATION DEVICE - 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, a manufacturing method thereof, and a communication device 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. In general, when metallic silver is applied to such applications, a silver ink composition containing metallic silver or a material for forming the metallic silver is prepared, and the composition is deposited on a substrate, and deposited as necessary. A method of heating (firing) the composition thus formed is employed. As a material for forming metallic silver, silver oxide has been widely used so far. 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.

  On the other hand, as a silver ink composition for forming such a conductor, a composition containing silver β-ketocarboxylate has been disclosed in recent years (see Patent Document 1). Such a silver ink composition can form a conductor having better quality than silver ink compositions that have been widely used so far, and unlike a silver ink composition containing silver oxide, a reducing agent is used. Since the conductor can be formed quickly even at a low temperature, it is extremely useful.

International Publication No. 2007/004437

  However, for a silver layer (conductive layer) formed from a conventional silver ink composition containing silver β-ketocarboxylate, further improvement in adhesion strength with the substrate is desired.

  The present invention has been made in view of the above circumstances, and a laminated body in which a conductive layer having high adhesion strength to the base material is provided on the base material, a method for manufacturing the same, and a communication device using the laminated body It is an issue to provide.

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 formed using a compound represented by the following general formula (3). The conductive layer is formed using β-ketocarboxylate silver represented by the following general formula (1), and adheres to the base material and the conductive layer in accordance with JIS K 5600-5-6. Provided is a laminate characterized by satisfying classification 0 or 1 in the test.

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

（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 ^２ Ｏ−」、「Ｒ ^５ Ｒ ^４ Ｎ−」、「（Ｒ ^３ Ｏ） _２ ＣＹ−」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 ^７ Ｏ−」、「Ｒ ^７ Ｓ−」、「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。）

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

  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 is a manufacturing method of the laminated body by which the electrically conductive layer was provided through the receiving layer on the base material, Comprising: On the said base material, using the compound represented by following General formula (3) A laminate comprising: a step of forming the receiving layer; and a step of forming the conductive layer on the receiving layer using silver β-ketocarboxylate represented by the following general formula (1) : A manufacturing method is provided.

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

（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 ^２ Ｏ−」、「Ｒ ^５ Ｒ ^４ Ｎ−」、「（Ｒ ^３ Ｏ） _２ ＣＹ−」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 ^７ Ｏ−」、「Ｒ ^７ Ｓ−」、「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。）

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

  The manufacturing method of the laminated body of this invention may have the process of carrying out the plasma process of the surface which forms the said receiving layer of the said base | substrate further before the process of forming the said receiving layer.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body by which the conductive layer with high adhesive strength with this base material was provided on the base material, its manufacturing method, and the communication apparatus using this laminated body are provided.

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

<Laminated body>
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 is a compound represented by the following general formula (3) (hereinafter referred to as “compound ( 3) ", which is abbreviated as"), and satisfies the classification 0 or 1 in the adhesion test of the base material and conductive layer in accordance with JIS K 5600-5-6. It is characterized by.

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

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

  In the laminate, the receiving layer improves the adhesion strength between the conductive layer and the substrate. 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. Thus, the adhesive strength between the conductive layer and the substrate is high because the specific compound (3) is used as the compound forming 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 substrate 2 is preferably in the form of a film or a sheet, the thickness is preferably 12 to 5000 μm, and more preferably 12 to 2000 μm. 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.
Moreover, the base material 2 may consist of 2 or more types of materials, such as a glass epoxy resin.

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 the compound (3).
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.

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

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

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

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

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

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

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

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

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

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

As particularly preferred compound (3), R ¹¹ and R ¹² are alkyl groups having 1 to 3 carbon atoms, R ¹³ is an alkylene group having 1 to 5 carbon atoms, and R ¹⁴ is an alkylene group having 1 to 3 carbon atoms. Examples thereof include a group or a carbonyl group, and Z is an amino group, a mercapto group or a phenyl group.

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

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

[Conductive layer]
The conductive layer 4 is preferably formed using silver carboxylate having a group represented by the formula “—COOAg”.
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 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.

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

The silver carboxylate is 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「−ＣＯＯＡｇ」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 “—COOAg”, and when the aliphatic hydrocarbon group has a methylene group, The above methylene group 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. Among these β-ketocarboxylates (1), among those represented by the general formula (1), the remaining raw materials and impurities in the heat-treated product (conductor, metallic silver) formed by the heating (firing) treatment The concentration of can be further reduced. 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.

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

(Silver carboxylate (4))
The carboxylate silver (4) is represented by the general formula (4). In the formula, R ⁸ is represented by an aliphatic hydrocarbon group having 1 to 19 carbon atoms, a carboxy group (—COOH) or the formula “—COOAg”. Group.
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.

  Similarly to silver β-ketocarboxylate (1), silver carboxylate (4) has a higher concentration of the remaining raw materials and impurities in the heat-treated product (conductor, metal silver) formed by the heating (firing) treatment. Can be reduced.

  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.

<Method for producing laminate>
The laminate of the present invention can be produced by the same method as that of a known laminate except that the compound (3) is used for forming the receptor layer and the silver carboxylate is used for forming the conductive layer.
As a preferable method for producing the laminate, a step of forming the receptor layer on the substrate using the compound (3) (hereinafter sometimes abbreviated as “receptor layer forming step”), and the receptor A production method characterized by having a step of forming the conductive layer using the silver carboxylate (hereinafter sometimes abbreviated as “conductive layer forming step”) on the layer is exemplified.

[Receptive layer forming step]
In the receiving layer forming step, the receiving layer (receiving layer 3) is formed on the base material (base material 2) using the compound (3).
The receptor layer can be formed, for example, by preparing a composition for forming a receptor layer in which the compound (3) is blended, attaching the composition to a substrate, and performing heat treatment.

  Examples of the composition for forming a receiving layer include a liquid composition in which the compound (3) 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 compound (3) is not significantly deteriorated. Preferred examples include those having 2 or more carbon atoms such as ethanol and 2-propanol (isopropyl alcohol). The 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 a receiving layer, the ratio (concentration) of the compound (3) in the total amount of the compounding components is preferably 0.3 to 50% by mass, and 0.7 to 30% by mass. It 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 compound (3) 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 forming a receiving layer is obtained by blending a component other than the compound (3) and the compound (3).
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.
Moreover, what is necessary is just to adjust a mixing | blending time (mixing time) suitably according to the kind of mixing | blending component, and the temperature at the time of mixing | blending, For example, it is preferable that it is 0.5 to 15 hours.

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, offset printing, dip printing, ink jet printing, dispenser printing, 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 amount of compound (3) 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 reaction of the compound (3) and the removal of the solvent (Drying) is preferably adjusted so as to proceed smoothly. Usually, it is preferable that heating temperature is 50-180 degreeC, and it is more preferable that it is 80-160 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 30 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.

  In the present invention, the surface of the substrate on which the receiving layer is to be formed may be subjected to plasma treatment before the receiving layer forming composition is adhered. That is, the manufacturing method further includes a step of plasma-treating the surface of the base material on which the receiving layer is formed (hereinafter sometimes abbreviated as “plasma treatment step”) before the receiving layer forming step. May be. By conducting the plasma treatment on the substrate, in the conductive layer forming step described later, bleeding of the silver ink composition on the receiving layer is suppressed, and the conductor (metal silver) formed by the heating (firing) treatment is Occurrence of a portion (hereinafter abbreviated as “beard-like bleeding portion”) generated by extending in a whisker shape from the surface is suppressed, or the length of the portion is shortened.

  In the plasma treatment step, plasma treatment may be performed by a known method. For example, in the case of atmospheric pressure plasma treatment, the treatment may be performed under conditions such as a voltage of 290 to 300 W and an air velocity of 1.0 to 5.0 m / min.

[Conductive layer forming step]
Next, in the conductive layer forming step, a conductive layer is formed on the receiving layer using the silver carboxylate.
The conductive layer can be formed by preparing a silver ink composition containing silver carboxylate, adhering it to the receiving layer, and subjecting it to a heat treatment.
As the silver ink composition, a liquid one is preferable, and one in which the silver carboxylate is uniformly dispersed is preferable.

  In the silver ink composition, the silver content in the silver carboxylate 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.

(Amine compound, ammonium salt)
The silver ink composition preferably contains an amine compound and / or an ammonium salt in addition to the silver carboxylate. The amine compound and / or ammonium salt preferably has 2 to 25 carbon atoms.

  The amine compound having 2 to 25 carbon atoms may be any of primary amine, secondary amine and tertiary amine. Moreover, C2-C25 ammonium salt is a quaternary ammonium salt of this carbon number. The amine compound and ammonium salt may be either chain or cyclic. Further, the number of nitrogen atoms forming the amine or ammonium salt 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.

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 preferable tetraalkylammonium halides include dodecyltrimethylammonium bromide and tetradodecylammonium bromide.

Up to this point, mainly chain amines and ammonium salts have been described. In the amine compound and ammonium salt, the nitrogen atom forming the amine or ammonium salt is part of the ring skeleton (heterocyclic skeleton). Such a heterocyclic compound may be used. That is, the amine compound may be a cyclic amine, and the ammonium salt may be a cyclic ammonium salt. The ring (ring containing a nitrogen atom forming an amine or ammonium salt) skeleton at this time may be either monocyclic or polycyclic, and the number of ring members (number of atoms constituting the ring skeleton) is not particularly limited, Either an aliphatic ring or an aromatic ring may be used.
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” refers to a nitrogen atom forming an amine or ammonium salt 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 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 the present invention, only an amine compound may be used, or only an ammonium salt may be used, and an amine compound and an ammonium salt may be used in combination, but it is preferable to use only an amine compound.

  Any of the amine compounds and ammonium salts may be used alone, or two or more of them 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 total compounding amount of the amine compound and the ammonium salt is preferably 1 to 10 mol, and more preferably 1.5 to 7 mol, per mol of the carboxylate silver. By being more than a lower limit, stability of a silver ink composition improves more, and the quality of an electroconductive layer improves more by being below an upper limit.

(alcohol)
The silver ink composition may be further blended with alcohol in addition to the silver carboxylate.
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.)

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 blending amount of acetylene alcohol (2) is preferably 0.03 to 0.7 mole, and 0.05 to 0.3 mole per mole of the above-mentioned silver carboxylate. It is more preferable. By being more than a lower limit, stability of a silver ink composition improves more, and the quality of an electroconductive layer improves more by being below an upper limit.

  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 silver carboxylate, amine compound and / or ammonium salt, and alcohol.
The other components can be arbitrarily selected according to the purpose and are not particularly limited.
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 the silver carboxylate and components other than the silver carboxylate.
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 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 silver carboxylate in the silver ink composition.

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

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

In the laminate of the present invention, since the receiving layer is formed using the compound (3), the adhesive strength between the conductive layer and the substrate of the receiving layer is high, that is, the adhesive strength between the conductive layer and the substrate is high. It is high and the peeling of the conductive layer from the substrate is remarkably suppressed. Specifically, the laminate of the present invention satisfies classification 0 or 1 in the adhesion test of the base material and the conductive layer based on JIS K 5600-5-6.
The conductive layer can be widely used as a recording material, a printing plate material, a highly conductive material, and the like.

For example, in “JP 2009-49275 A”, a silver layer is formed by forming a receiving layer with a silane coupling agent on a glass epoxy resin base material, and metallic silver colloidal fine particles are blended on the receiving layer. The specific example of the laminated body which formed the conductive layer using the ink composition is described. And as said silane coupling agent, the laminated body using the following silane coupling agent (i), (ii), (iii) or (iv) is described, and any laminated body is a conductive layer, It is described that the adhesion strength with the substrate was high.
N-2- (aminoethyl) -3-aminopropyltrimethoxysilane ((CH ₃ O) ₃ Si (CH ₂ ) ₃ NH (CH ₂ ) ₂ NH ₂ ) (i)
3-mercaptopropyltrimethoxysilane ((CH ₃ O) ₃ Si (CH ₂ ) ₃ SH) (ii)
3-Glycidoxypropyltrimethoxysilane ((CH ₃ O) ₃ Si (CH ₂ ) ₃ OCH ₂ CH (O) CH ₂ ) (iii)
Vinyltrimethoxysilane ((CH ₃ O) ₃ SiCH═CH ₂ ) (iv)
Here, the silane coupling agents (i), (ii), (iii) and (iv) were used in Example 1, Example 5, Comparative Example 2 and Comparative Example 5 described later in this specification, respectively. Is the same. As will be described later, in the laminates of Examples 1 and 5, the adhesion strength between the conductive layer and the substrate was high, but in the laminates of Comparative Examples 2 and 5, the adhesion strength between the conductive layer and the substrate was high. Improvements are not recognized. That is, when the silane coupling agents (iii) and (iv) are used, results different from the results disclosed in “JP 2009-49275 A” are obtained. This is because the type of silver ink composition to be deposited on the receiving layer is different during the production of the laminate, and the conductive layer is formed when the metal silver colloidal fine particles are used and when the silver carboxylate is used. It is presumed that the process is different. Thus, the conductive layer (heat-treated product) in the laminate of the present invention has a unique configuration, unlike a conductive layer (heat-treated product) formed from a conventional metal silver or metal silver forming material. It is estimated that

<Communication equipment>
The communication device according to 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. Other than that, 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 communication device of the present invention has high stability of the antenna portion and excellent durability.

  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)
Silver 2-methylacetoacetate (100 parts by mass), 2-ethylhexylamine (300 parts by mass), and 3,5-dimethyl-1-hexyn-3-ol ("Surfinol 61" manufactured by Air Products Japan) (4 parts by mass) Part) and the mixture was stirred at 25 ° C. or lower for 60 minutes to obtain a silver ink composition.

(Manufacture of laminates)
A base material (thickness: 100 μm) made of polyethylene terephthalate was heat-treated at 150 ° C. for 30 minutes.
Next, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane ((CH ₃ O) ₃ Si (CH ₂ ) ₃ NH (CH ₂ ) is formed on the substrate as a receiving layer forming composition. ₂ NH ₂ , an isopropyl alcohol solution (concentration 5% by mass) of compound (3) was applied by a spin coater and heat-treated at 120 ° C. for 10 minutes to form a receiving layer on the substrate. At this time, the coating amount of the isopropyl alcohol solution on the base material was 0.2 to 1.3 g / m ² .
Next, the silver ink composition obtained above was applied onto the receptor layer with a spin coater, and heat treated at 150 ° C. for 30 minutes to form a conductive layer on the receptor layer to obtain a laminate. At this time, the coating amount of the silver ink composition on the receiving layer was 6.0 to 9.6 g / m ² .

<Evaluation of laminate>
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, The tape was peeled off, and the number of areas where peeling of the conductive layer from the base material (receiving layer) was observed among the 25 areas. And according to the following reference | standard, the adhesive strength of a conductive layer and a base material was evaluated. The results are shown in Table 1.
A: The conductive layer does not peel at all, and the adhesion strength is extremely high. (Classification 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 off, and is not worthy of evaluation of adhesion strength (Class 5).

<Manufacture and evaluation of laminate>
[Example 2]
As compound (3), instead of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane ((CH ₃ O) ₂ Si A laminate was produced and evaluated in the same manner as in Example 1 except that (CH ₃ ) (CH ₂ ) ₃ NH (CH ₂ ) ₂ NH ₂ ) was used. The results are shown in Table 1.

[Example 3]
As compound (3), instead of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane ((CH ₃ CH ₂ O) ₃ Si (CH ₂ ) ₃ NHC ( = O) A laminate was produced and evaluated in the same manner as in Example 1 except that NH ₂ ) was used. The results are shown in Table 1.

[Example 4]
As the compound (3), N-2-in place of (aminoethyl) -3-aminopropyltrimethoxysilane, N- phenyl-3-aminopropyltrimethoxysilane _{((CH 3 O) 3 Si} (CH 2) 3 A laminate was produced and evaluated in the same manner as in Example 1 except that NHC ₆ H ₅ ) was used. The results are shown in Table 1.

[Example 5]
As the compound (3), 3-mercaptopropyltrimethoxysilane ((CH ₃ O) ₃ Si (CH ₂ ) ₃ SH) is used instead of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane. A laminate was produced and evaluated in the same manner as in Example 1 except that it was not. The results are shown in Table 1.

[Example 6]
As a compound (3), instead of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane ((CH ₃ O) ₂ Si (CH ₃ ) (CH ₂ ) ₃ A laminate was produced and evaluated in the same manner as in Example 1 except that (SH) was used. The results are shown in Table 1.

[Comparative Example 1]
Example 1 except that methyltrimethoxysilane ((CH ₃ O) ₃ SiCH ₃ ) was used as the compound (3) instead of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane. A laminate was produced and evaluated in the same manner as described above. The results are shown in Table 1.

[Comparative Example 2]
As compound (3), instead of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane ((CH ₃ O) ₃ Si (CH ₂ ) ₃ OCH ₂ A laminate was produced and evaluated in the same manner as in Example 1 except that (CH (O) CH ₂ ) was used. The results are shown in Table 1.

[Comparative Example 3]
As compound (3), instead of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane ((CH ₃ O) ₃ Si (CH ₂ ) ₃ OC (= A laminate was produced and evaluated in the same manner as in Example 1 except that O) C (CH ₃ ) ═CH ₂ ) was used. The results are shown in Table 1.

[Comparative Example 4]
As compound (3), instead of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane ((CH ₃ O) ₃ Si (CH ₂ ) ₃ NH ₂ ) was used. A laminate was produced and evaluated in the same manner as in Example 1 except that it was used. The results are shown in Table 1.

[Comparative Example 5]
Implemented except that instead of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, vinyltrimethoxysilane ((CH ₃ O) ₃ SiCH═CH ₂ ) was used as compound (3). A laminate was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 6]
As compound (3), instead of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane ((CH ₃ O) ₃ Si (CH ₂ ) ₃ OC (= A laminate was produced and evaluated in the same manner as in Example 1 except that O) CH = CH ₂ ) was used. The results are shown in Table 1.

[Comparative Example 7]
As compound (3), instead of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane ((CH ₃ O) ₃ Si (CH ₂ ) _A laminate was produced and evaluated in the same manner as in Example 1 except that ₂ CF ₃ ) was used. The results are shown in Table 1.

[Comparative Example 8]
As compound (3), instead of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane ((CH ₃ CH ₂ O) ₃ Si (CH ₂ ) ₃ N = A laminate was produced and evaluated in the same manner as in Example 1 except that C = O) was used. The results are shown in Table 1.

[Comparative Example 9]
As compound (3), instead of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine ((CH ₃ CH ₂ O) ₃ Si (CH ₂ ) ₃ N═C (CH ₃ ) (CH ₂ ) ₃ CH ₃ ) was used, and the laminate was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.

  As is clear from the above results, the laminates of Examples 1 to 6 were superior to the laminates of Comparative Examples 1 to 9 in adhesion strength between the conductive layer and the substrate.

<Manufacture of laminates>
[Example 7]
(Manufacture of silver ink composition)
Silver 2-methylacetoacetate (100 parts by mass), 2-ethylhexylamine (300 parts by mass), and 3,5-dimethyl-1-hexyn-3-ol ("Surfinol 61" manufactured by Air Products Japan) (4 parts by mass) Part) and the mixture was stirred at 25 ° C. or lower for 60 minutes to obtain a silver ink composition.

(Manufacture of laminates)
A base material (thickness: 100 μm) made of polyethylene terephthalate was heat-treated at 150 ° C. for 30 minutes.
Next, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane ((CH ₃ O) ₃ Si (CH ₂ ) ₃ NH (CH ₂ ) is formed on the substrate as a receiving layer forming composition. ₂ NH ₂ , an isopropyl alcohol solution (concentration 5% by mass) of compound (3) was applied by a spin coater and heat-treated at 120 ° C. for 10 minutes to form a receiving layer on the substrate. At this time, the coating amount of the isopropyl alcohol solution on the base material was 0.2 to 1.3 g / m ² .
Next, the silver ink composition obtained above was applied onto the receptor layer with a spin coater, and heat-treated at 150 ° C. for 1 hour to form a conductive layer on the receptor layer to obtain a laminate. At this time, the coating amount of the silver ink composition on the receiving layer was 6.0 to 9.6 g / m ² .

<Evaluation of laminate>
About the obtained laminated body, the adhesive strength of a conductive layer and a base material was evaluated by the same method as Example 1. The results are shown in Table 2.

<Manufacture and evaluation of laminate>
[Example 8]
As shown in Table 2, a laminate was produced and evaluated in the same manner as in Example 7, except that the concentration of the isopropyl alcohol solution of compound (3) was changed to 10% by mass instead of 5% by mass. . The results are shown in Table 2.

[Example 9]
As shown in Table 2, a laminate was produced and evaluated in the same manner as in Example 7, except that the concentration of the isopropyl alcohol solution of compound (3) was changed to 20% by mass instead of 5% by mass. . The results are shown in Table 2.

[Example 10]
As shown in Table 2, laminates were produced and evaluated in the same manner as in Example 7 except that the temperature of the heat treatment of the silver ink composition was changed to 120 ° C. instead of 150 ° C. The results are shown in Table 2.

[Example 11]
As shown in Table 2, laminates were produced and evaluated in the same manner as in Example 8 except that the temperature of the heat treatment of the silver ink composition was changed to 120 ° C. instead of 150 ° C. The results are shown in Table 2.

[Example 12]
As shown in Table 2, a laminate was produced and evaluated in the same manner as in Example 9 except that the temperature of the heat treatment of the silver ink composition was changed to 120 ° C. instead of 150 ° C. The results are shown in Table 2.

[Example 13]
As shown in Table 2, the laminate was prepared in the same manner as in Example 7 except that the heat treatment of the silver ink composition was performed at 80 ° C. for 7 hours instead of being performed at 150 ° C. for 1 hour. Manufactured and evaluated. The results are shown in Table 2.

[Example 14]
As shown in Table 2, the laminate was prepared in the same manner as in Example 8 except that the heat treatment of the silver ink composition was performed at 80 ° C. for 7 hours instead of being performed at 150 ° C. for 1 hour. Manufactured and evaluated. The results are shown in Table 2.

[Example 15]
As shown in Table 2, the laminate was prepared in the same manner as in Example 9, except that the heat treatment of the silver ink composition was performed at 80 ° C. for 7 hours instead of being performed at 150 ° C. for 1 hour. Manufactured and evaluated. The results are shown in Table 2.

  As is clear from the above results, the laminates of Examples 7 to 15 differ in the concentration of the isopropyl alcohol solution of compound (3) and the heat treatment conditions of the silver ink composition. Excellent adhesion strength with the substrate.

<Manufacture of laminates>
[Example 16]
(Manufacture of silver ink composition)
Silver 2-methylacetoacetate (100 parts by mass), 2-ethylhexylamine (300 parts by mass), and 3,5-dimethyl-1-hexyn-3-ol ("Surfinol 61" manufactured by Air Products Japan) (4 parts by mass) Part) and the mixture was stirred at 25 ° C. or lower for 60 minutes to obtain a silver ink composition.

(Manufacture of composition for forming receiving layer)
N-2- (aminoethyl) -3-aminopropyltriethoxysilane ((CH ₃ CH ₂ O) ₃ Si (CH ₂ ) ₃ NH (CH ₂ ) ₂ NH ₂ , “KBM-603” manufactured by Shin-Etsu Chemical Co., Ltd. Compound (3)) and isopropyl alcohol were mixed and stirred at room temperature (25 ° C.) for 1 hour, whereby N-2- (aminoethyl) -3-aminopropyltriethoxy was obtained as a receiving layer forming composition. An isopropyl alcohol solution of silane (concentration 5% by mass) was obtained.

(Manufacture of laminates)
Using a table-top gravure printing machine (K303 Multi-Coater) and a copper gravure printing plate, the obtained composition for forming a receiving layer was used as a base material made of polyethylene terephthalate (“Q-83” manufactured by Teijin DuPont, thickness 75 μm). ) Coated on top. And the receiving layer was formed on the base material by heat-processing the coated base material at 120 degreeC for 10 minute (s).
Next, a predetermined pattern was printed on the receiving layer with the silver ink composition obtained above using an inkjet printer (“KM-512L” manufactured by Konica Minolta). At this time, printing was performed under conditions of 360 dpi, 42 pL × 1 dpd. And the electrically conductive layer was formed on the receiving layer by heat-processing the printed base material at 270 degreeC for 100 second by IR drying furnace, and also for 150 minutes at 150 degreeC by hot-air oven, and the laminated body was obtained.

<Evaluation of laminate>
About the obtained laminated body, the adhesive strength of a conductive layer and a base material was evaluated by the same method as Example 1. The results are shown in Table 3.
Moreover, about the obtained laminated body, while measuring the thickness of a receiving layer using a laser microscope (Keyence Corporation "VK-X100"), it is electrically conductive using a microscope (Keyence Corporation "VHX-600"). The layer pattern (wiring pattern) was observed, the length of the whisker-like bleeding part was measured, and evaluated according to the following criteria. The results are shown in Table 3.
A: The length of the whisker-like bleeding site is less than 10 μm.
○: The length of the whisker-like bleeding site is 10 μm or more and less than 150 μm.
X: The length of the whisker-like bleeding part is 150 μm or more.

<Manufacture and evaluation of laminate>
[Examples 17 to 24]
As shown in Table 3, Example 16 and Example 16 except that at least one of the concentration of the isopropyl alcohol solution of N-2- (aminoethyl) -3-aminopropyltriethoxysilane and the thickness of the receiving layer was changed. The laminated body was manufactured and evaluated by the same method. The results are shown in Table 3.

[Comparative Example 10]
As shown in Table 3, the receptor layer-forming composition was not coated on the substrate (that is, a predetermined pattern was printed directly on the substrate with the silver ink composition), and the receptor layer was formed on the substrate. A laminate was manufactured and evaluated in the same manner as in Example 16 except that it was not formed. The results are shown in Table 3.

[Example 25]
As shown in Table 4, the receiving layer forming surface of the substrate was subjected to atmospheric pressure plasma treatment under the condition of 300 W using an atmospheric pressure plasma generation device (“YAP500” manufactured by YAMATO Material), and then the surface of the plasma treatment surface A laminate was produced and evaluated in the same manner as in Example 16 except that the composition for forming a receiving layer was applied to the laminate. The results are shown in Table 4.

[Examples 26 to 33]
As shown in Table 4, the receiving layer forming surface of the substrate was subjected to atmospheric pressure plasma treatment under the condition of 300 W using an atmospheric pressure plasma generation device (“YAP500” manufactured by YAMATO Material), and then the surface of the plasma treatment surface A laminate was produced and evaluated in the same manner as in Examples 17 to 31 except that the composition for forming a receiving layer was applied to the laminate. The results are shown in Table 4.

As is clear from the above results, the laminates of Examples 16 to 33 are different in the concentration of the isopropyl alcohol solution of compound (3) and the thickness of the receiving layer. The thickness of the receiving layer was 0.2 μm or more, and the adhesion strength between the conductive layer and the substrate was excellent. Further, from the comparison between Examples 16 to 24 and Examples 25 to 33, when the thickness of the receiving layer is substantially the same, the laminate in which the receiving layer forming surface of the substrate is plasma-treated is more plasma. The length of the whisker-like bleeding part in the pattern of the conductive layer was generally shorter than that of the untreated laminate. This is presumably because bleeding was suppressed during pattern printing of the silver ink composition. Regardless of the presence or absence of the plasma treatment, the length of the whisker-like bleeding portion tended to be shorter as the receiving layer was thicker, and this was particularly noticeable when the plasma treatment was not performed. When the plasma treatment is not performed, it is considered that whisker-like bleeding can be almost completely suppressed when the thickness of the receiving layer is approximately 0.5 μm or more. On the other hand, when the plasma treatment is performed, the effect of the plasma treatment tends to increase as the receiving layer becomes thinner, particularly when the thickness of the receiving layer is 0.4 μm or less, particularly 0.3 to 0.4 μm. The effect of the plasma treatment was more noticeable.
On the other hand, the laminate of Comparative Example 10 had a low adhesion strength between the conductive layer and the substrate because no receptor layer was formed.

  The present invention can be used as a product or member provided with a conductive layer as a recording material, a printing plate material, a highly conductive material, or the like.

  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 receiving layer is formed using a compound represented by the following general formula (3),
The conductive layer is formed using silver β-ketocarboxylate represented by the following general formula (1),
The laminated body characterized by satisfy | filling classification 0 or 1 in the adhesiveness test of the said base material and electroconductive layer based on JISK5600-5-6.

(Wherein R ¹¹ is an alkyl group having 1 to 5 carbon atoms, an alkoxyalkyl group or an alkylcarbonyl group; R ¹² is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms; R ¹³ is an alkylene group having 1 to 10 carbon atoms; R ¹⁴ is an alkylene group having 1 to 5 carbon atoms, and one or more methylene groups in the alkylene group may be substituted with a carbonyl group; Z Is an amino group, a mercapto group or an aryl group having 6 to 12 carbon atoms; m1 is 2 or 3, and a plurality of R ¹¹ may be the same or different from each other; m2 and m3 are each independently 0 or 1; provided that when Z is an amino group, at least m2 is 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 ” 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. )   A communication device using the laminate according to claim 1, wherein the base material is provided as a casing. A method for producing a laminate in which a conductive layer is provided on a substrate via a receiving layer,
Forming the receptor layer on the substrate using a compound represented by the following general formula (3);
Forming the conductive layer on the receptor layer using β-ketocarboxylate represented by the following general formula (1) ;
The manufacturing method of the laminated body characterized by having.

(Wherein R ¹¹ is an alkyl group having 1 to 5 carbon atoms, an alkoxyalkyl group or an alkylcarbonyl group; R ¹² is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms; R ¹³ is an alkylene group having 1 to 10 carbon atoms; R ¹⁴ is an alkylene group having 1 to 5 carbon atoms, and one or more methylene groups in the alkylene group may be substituted with a carbonyl group; Z Is an amino group, a mercapto group or an aryl group having 6 to 12 carbon atoms; m1 is 2 or 3, and a plurality of R ¹¹ may be the same or different from each other; m2 and m3 are each independently 0 or 1; provided that when Z is an amino group, at least m2 is 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 ” 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. )   The method for producing a laminate according to claim 3, further comprising a step of performing a plasma treatment on a surface of the base material on which the receiving layer is formed before the step of forming the receiving layer.

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