TW201305290A - Condensate of amino-bearing silane coupling agent with metal alkoxide compound, material for laminate base comprising same as main component, laminate base and elecroconductive member, and processes for manufacturing same - Google Patents

Condensate of amino-bearing silane coupling agent with metal alkoxide compound, material for laminate base comprising same as main component, laminate base and elecroconductive member, and processes for manufacturing same Download PDF

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TW201305290A
TW201305290A TW101116482A TW101116482A TW201305290A TW 201305290 A TW201305290 A TW 201305290A TW 101116482 A TW101116482 A TW 101116482A TW 101116482 A TW101116482 A TW 101116482A TW 201305290 A TW201305290 A TW 201305290A
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condensate
group
coupling agent
substrate
metal
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Koji Iura
Akihiro Matsubayashi
Kenji Fukunaga
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Ube Nitto Kasei Co
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/389—Improvement of the adhesion between the insulating substrate and the metal by the use of a coupling agent, e.g. silane
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/54—Nitrogen-containing linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/58—Metal-containing linkages
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0703—Plating
    • H05K2203/0709—Catalytic ink or adhesive for electroless plating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
    • H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Silicon Polymers (AREA)

Abstract

Provided are: a condensate which can enhance the tight adhesion between a substrate and an electroconductive pattern formed using an electrocoductive ink, particularly, an ink or paste that contains metal nanoparticles; and a process for manufacturing the same. This condensate is a condensate which is obtained by hydrolytic condensation of an amino-bearing silane coupling agent with a metal alkoxide compound represented by general formula (I) and which comprises M-O repeating units as the main skeleton. R1 nM(OR2)m-n (I) In general formula (I), R1 is a nonhydrolyzable group; R2 is C1-6 alkyl; M is at least one metal selected from the group consisting of Si, Ti, Al, Zr, Li, Na, Ca, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La, Nd and In; m represents the valence of M and is 3 or 4; when m is 4, n is an integer of 0 to 2, while when m is 3, n is an integer of 0 to 1; and in a case where multiple R1 moieties are present, the R1 moieties may be the same or different from each other, while in a case wherein multiple OR2 moieties are present, the OR2 moieties may be the same or different from each other.

Description

帶胺基之矽烷偶合劑與金屬烷氧化物之縮合物、以其為主成分之積層基板用材料、積層基板及導電性構件、以及該等之製造方法 Condensate of an amine group-containing decane coupling agent and a metal alkoxide, a material for a laminated substrate mainly comprising the same, a laminated substrate, a conductive member, and the like

本發明係關於一種帶胺基之矽烷偶合劑與金屬烷氧化物(metal alkoxides)之縮合物、以其為主成分之積層基板用材料、積層基板及導電性構件、以及該等之製造方法。 The present invention relates to a condensate of an amine group-containing decane coupling agent and metal alkoxides, a material for a laminated substrate mainly comprising the same, a laminated substrate, a conductive member, and the like.

近年來，使用含有金屬奈米粒子之油墨或糊劑的可印刷電子受到關注。 In recent years, printable electrons using inks or pastes containing metal nanoparticles have attracted attention.

關於藉由印刷之導電性圖案之製造，先前係使用適合高黏度糊劑之印刷方法使包含銀粉、樹脂黏合劑及有機溶劑之高黏度導電性樹脂糊劑圖案化。然而，由於銀粉之尺寸較大而導致細線之印刷困難等，因此近年來盛行使含有金屬奈米粒子之油墨或糊劑圖案化之研究。再者，由於金屬奈米粒子係由分散劑所被覆，故而若僅進行塗佈、乾燥，則所形成之圖案不具有導電性，為了表現導電性而使分散劑昇華並使金屬奈米粒子彼此融合，因此需要200℃左右之燒結。進而，由於乾燥步驟中去除分散劑，故而金屬奈米粒子於乾燥後之燒結狀態下幾乎僅成為金屬成分，難以獲得與基材之密合性。 Regarding the production of a conductive pattern by printing, a high-viscosity conductive resin paste containing silver powder, a resin binder, and an organic solvent has been previously patterned by a printing method suitable for a high-viscosity paste. However, in recent years, studies on patterning of inks or pastes containing metal nanoparticles have been carried out because of the large size of silver powder, which makes printing of fine lines difficult. Further, since the metal nanoparticles are coated with a dispersing agent, the pattern formed does not have conductivity when applied and dried only, and the dispersing agent is sublimated in order to express conductivity, and the metal nanoparticles are mutually in contact with each other. Fusion, so sintering at around 200 °C is required. Further, since the dispersing agent is removed in the drying step, the metal nanoparticles are almost only a metal component in a sintered state after drying, and it is difficult to obtain adhesion to the substrate.

作為用於印刷之導電性圖案形成用基材，先前，不僅使用玻璃類或陶瓷類，亦使用聚對苯二甲酸乙二酯膜、聚萘二甲酸乙二酯膜、聚醯亞胺膜、聚碳酸酯膜等具有柔軟性且可彎折之各種膜。但，難以應對圖案之微細化。 As a substrate for forming a conductive pattern for printing, conventionally, not only glass or ceramics but also polyethylene terephthalate film, polyethylene naphthalate film, polyimine film, and A variety of films which are flexible and bendable, such as a polycarbonate film. However, it is difficult to cope with the miniaturization of the pattern.

因此，亦揭示有對上述基材實施加工而成之基材。例如於專利文獻1中揭示有如下導電性圖案形成用基材：該基材係預先於金屬超微粒子層之下側設置由無機氧化物微粒子所構成之凝集促進層，於塗佈金屬超微粒子溶液時，溶劑選擇性地主要向下層之由無機氧化物微粒子所形成之細孔浸透，藉此可促進金屬超微粒子之凝集。 Therefore, a substrate obtained by processing the above substrate is also disclosed. For example, Patent Document 1 discloses a substrate for forming a conductive pattern in which an aggregation promoting layer composed of inorganic oxide fine particles is provided on a lower side of a metal ultrafine particle layer, and a metal ultrafine particle solution is applied. At this time, the solvent is selectively soaked mainly by the pores formed by the inorganic oxide fine particles in the lower layer, whereby the aggregation of the metal ultrafine particles can be promoted.

專利文獻1：日本特開2003-229653號公報 Patent Document 1: Japanese Patent Laid-Open Publication No. 2003-229653

然而，關於該等具有多孔質層之基材，存在如下問題：於鍍敷等濕式製程中，處理液進入多孔質中，對電路特性造成不良影響，或於使用以銀為主成分之油墨之情形時促進導電時之遷移，及所形成之導電性圖案對於多孔質層之密合性較弱，故而導電性圖案因摩擦等而簡單地剝離或斷線等。 However, the base material having such a porous layer has a problem that the treatment liquid enters the porous state in a wet process such as plating, which adversely affects circuit characteristics, or uses an ink containing silver as a main component. In the case of promoting the migration at the time of conduction and the adhesion of the formed conductive pattern to the porous layer, the conductive pattern is simply peeled off or broken due to friction or the like.

本發明係鑒於上述問題而成立者，目的在於提供一種使用導電性油墨、其中尤其是含有金屬奈米粒子之油墨或糊劑而形成之導電性圖案對於基材的密合性較高，抑制金屬之遷移，且可獲得優異之導電性之積層基板及導電性構件，並提供用以獲得該等的帶胺基之矽烷偶合劑與金屬烷氧化物之縮合物，及以其為主成分之積層基板用材料，以及該等之製造方法。 The present invention has been made in view of the above problems, and an object thereof is to provide a conductive pattern formed using a conductive ink, particularly an ink or a paste containing metal nanoparticles, which has high adhesion to a substrate and inhibits metal. a laminate substrate and a conductive member which are excellent in conductivity, and a condensate for obtaining an amine group-containing decane coupling agent and a metal alkoxide, and a laminate mainly comprising the same A material for a substrate, and a method of manufacturing the same.

為了達成上述目的，本發明者等人反覆進行潛心研究，結果發現，將使帶胺基之矽烷偶合劑與金屬烷氧化物 進行水解-縮合反應而成之以M-O之重複單位為主骨架之縮合物作為積層基板用材料而積層於基材表面所成之導電性構件係使用導電性油墨、其中尤其是含有金屬奈米粒子之油墨或糊劑而形成之導電性圖案對於基材的密合性較高，抑制金屬之遷移，且可獲得優異之導電性，從而完成本發明。 In order to achieve the above object, the inventors of the present invention have repeatedly conducted intensive studies, and as a result, have found that an amine group-containing decane coupling agent and a metal alkoxide are used. A conductive material obtained by laminating a condensate of a repeating unit of MO and having a repeating unit of MO as a material for a laminated substrate, which is formed on a surface of a substrate, is made of a conductive ink, and particularly contains metal nanoparticles. The conductive pattern formed by the ink or the paste has high adhesion to the substrate, inhibits migration of the metal, and can obtain excellent conductivity, thereby completing the present invention.

即，本發明係關於一種縮合物，其係使帶胺基之矽烷偶合劑與通式(I)所示之金屬烷氧化物進行水解-縮合反應而成之以M-O之重複單位作為主骨架者。 That is, the present invention relates to a condensate obtained by subjecting an amine group-containing decane coupling agent to a metal alkoxide represented by the formula (I) to carry out a hydrolysis-condensation reaction with a repeating unit of MO as a main skeleton. .

R1 nM(OR2)m-n (I) R 1 n M(OR 2 ) mn (I)

(式中，R1為非水解性基，R2為碳數1~6之烷基，M表示選自Si、Ti、Al、Zr、Li、Na、Ca、Sr、Ba、Zn、B、Ga、Y、Ge、Pb、P、Sb、V、Ta、W、La、Nd、In之金屬原子群中之至少1種金屬原子，m為金屬原子M之價數且為3或4，於m為4之情形時，n為0~2之整數，於m為3之情形時，n為0~1之整數，於存在複數個R1之情形時，各R1彼此可相同亦可不同，於存在複數個OR2之情形時，各OR2彼此可相同亦可不同)。 (wherein R 1 is a non-hydrolyzable group, R 2 is an alkyl group having 1 to 6 carbon atoms, and M represents a group selected from the group consisting of Si, Ti, Al, Zr, Li, Na, Ca, Sr, Ba, Zn, B, At least one metal atom of a metal atom group of Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La, Nd, In, m is a valence of the metal atom M and is 3 or 4, When m is 4, n is an integer of 0 to 2. When m is 3, n is an integer of 0 to 1. When there are a plurality of R 1 , each R 1 may be the same or different. In the case where there are a plurality of OR 2s , each OR 2 may be the same or different from each other).

又，本發明係關於一種積層基板用材料，係以上述縮合物作為主成分。 Moreover, the present invention relates to a material for a laminated substrate, which comprises the above condensate as a main component.

進而，本發明係關於一種上述積層基板用材料積層於基材表面所成之積層基板、及關於一種導電性構件，其係於積層基板之積層有積層基板用材料之面，印刷或塗佈含有金屬奈米粒子之導電性材料而形成有導電性圖案。 Furthermore, the present invention relates to a laminated substrate formed by laminating a material for a laminated substrate on a surface of a substrate, and a conductive member which is laminated on a surface of a laminated substrate and which is coated or coated. A conductive pattern is formed by the conductive material of the metal nanoparticles.

又，本發明係關於一種縮合物之製造方法，具備以下步驟：使帶胺基之矽烷偶合劑於溶劑中進行縮合反應而獲得反應液之第1步驟；及使通式(I)所示之金屬烷氧化物與上述第1步驟中所獲得之反應液混合以進行縮合反應之第2步驟。 Further, the present invention relates to a method for producing a condensate, comprising the steps of: subjecting an amine group-containing decane coupling agent to a condensation reaction in a solvent to obtain a reaction liquid; and subjecting the compound (I) The metal alkoxide is mixed with the reaction liquid obtained in the above first step to carry out the second step of the condensation reaction.

R1 nM(OR2)m-n (I) R 1 n M(OR 2 ) mn (I)

(式中，R1為非水解性基，R2為碳數1~6之烷基，M表示選自Si、Ti、Al、Zr、Li、Na、Ca、Sr、Ba、Zn、B、Ga、Y、Ge、Pb、P、Sb、V、Ta、W、La、Nd、In之金屬原子群中之至少1種金屬原子，m為金屬原子M之價數且為3或4，於m為4之情形時，n為0~2之整數，於m為3之情形時，n為0~1之整數，於存在複數個R1之情形時，各R1彼此可相同亦可不同，於存在複數個OR2之情形時，各OR2彼此可相同亦可不同)。 (wherein R 1 is a non-hydrolyzable group, R 2 is an alkyl group having 1 to 6 carbon atoms, and M represents a group selected from the group consisting of Si, Ti, Al, Zr, Li, Na, Ca, Sr, Ba, Zn, B, At least one metal atom of a metal atom group of Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La, Nd, In, m is a valence of the metal atom M and is 3 or 4, When m is 4, n is an integer of 0 to 2. When m is 3, n is an integer of 0 to 1. When there are a plurality of R 1 , each R 1 may be the same or different. In the case where there are a plurality of OR 2s , each OR 2 may be the same or different from each other).

進而，本發明係關於一種積層基板之製造方法，其係藉由將上述縮合物塗佈於基材表面而獲得於基材積層有縮合物之積層基板；及一種導電性構件之製造方法，其係於上述積層基板之積層有積層基板用材料之面印刷或塗佈含有金屬奈米粒子之導電性材料後，進行燒成而形成導電性圖案。 Furthermore, the present invention relates to a method for producing a laminated substrate obtained by applying the condensate to a surface of a substrate to obtain a laminated substrate having a condensate deposited on a substrate, and a method for producing a conductive member. A conductive material containing metal nanoparticles is printed or applied on the surface of the laminated substrate with the material for the laminated substrate, and then fired to form a conductive pattern.

如上所述，根據本發明可提供：使用導電性油墨、其中尤其是含有金屬奈米粒子之油墨或糊劑而形成之導電性圖案對於基材的密合性較高，抑制金屬之遷移，且可獲得優異之導電性之積層基板及導電性構件，用以獲得該等的 帶胺基之矽烷偶合劑與金屬烷氧化物之縮合物，及以其為主成分之積層基板用材料，以及該等之製造方法。 As described above, according to the present invention, it is provided that a conductive pattern formed using a conductive ink, particularly an ink or a paste containing metal nanoparticles, has high adhesion to a substrate and inhibits metal migration, and A laminate substrate and a conductive member having excellent conductivity can be obtained for obtaining such A condensate of an amine-containing decane coupling agent and a metal alkoxide, and a material for a laminate substrate containing the same as a main component, and a method for producing the same.

以下，詳細說明本發明。 Hereinafter, the present invention will be described in detail.

(縮合物及其製造方法) (condensate and its manufacturing method) (帶胺基之矽烷偶合劑) (Alkane-based decane coupling agent)

關於本發明之縮合物，由於帶胺基之矽烷偶合劑可經由胺基與金屬形成配位鍵，故而若將含有該矽烷偶合劑之層固定於基材，則可使含有金屬奈米粒子之油墨或糊劑經由燒成而使金屬奈米粒子融合而形成之導電性圖案與基材之間的密合性大幅度提高。 In the condensate of the present invention, since the amine group-containing decane coupling agent can form a coordinate bond with the metal via the amine group, if the layer containing the decane coupling agent is fixed to the substrate, the metal nanoparticle can be contained. The adhesion between the conductive pattern formed by fusing the metal nanoparticles by firing the ink or the paste and the substrate is greatly improved.

作為帶胺基之矽烷偶合劑，並無特別限定，例如可列舉如下者：N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷 The decane coupling agent having an amine group is not particularly limited, and examples thereof include N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane.

N-(2-胺基乙基)-3-胺基丙基甲基二乙氧基矽烷 N-(2-Aminoethyl)-3-aminopropylmethyldiethoxydecane

N-(2-胺基乙基)-3-胺基丙基甲基二丙氧基矽烷 N-(2-Aminoethyl)-3-aminopropylmethyldipropoxydecane

N-(2-胺基乙基)-3-胺基丙基甲基二異丙氧基矽烷 N-(2-Aminoethyl)-3-aminopropylmethyldiisopropoxydecane

N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷 N-(2-Aminoethyl)-3-aminopropyltrimethoxydecane

N-(2-胺基乙基)-3-胺基丙基三乙氧基矽烷 N-(2-Aminoethyl)-3-aminopropyltriethoxydecane

N-(2-胺基乙基)-3-胺基丙基三丙氧基矽烷 N-(2-Aminoethyl)-3-aminopropyltripropoxydecane

N-(2-胺基乙基)-3-胺基丙基三異丙氧基矽烷 N-(2-Aminoethyl)-3-aminopropyltriisopropoxydecane

N-(2-胺基乙基)-3-胺基異丁基二甲基甲氧基矽烷 N-(2-Aminoethyl)-3-aminoisobutyldimethylmethoxydecane

N-(2-胺基乙基)-3-胺基異丁基甲基二甲氧基矽烷 N-(2-Aminoethyl)-3-aminoisobutylmethyldimethoxydecane

N-(2-胺基乙基)-11-胺基十一烷基三甲氧基矽烷 N-(2-Aminoethyl)-11-aminoundecyltrimethoxydecane

N-(2-胺基乙基)-3-胺基丙基矽烷三醇 N-(2-Aminoethyl)-3-aminopropyl decane triol

3-胺基丙基三甲氧基矽烷 3-aminopropyltrimethoxydecane

3-胺基丙基三乙氧基矽烷 3-aminopropyltriethoxydecane

3-三乙氧基矽基-N-(1,3-二甲基-亞丁基)丙胺 3-triethoxyindolyl-N-(1,3-dimethyl-butylene)propylamine

N-苯基-3-胺基丙基三甲氧基矽烷 N-phenyl-3-aminopropyltrimethoxydecane

N,N-雙[3-(三甲氧基矽基)丙基]乙二胺 N,N-bis[3-(trimethoxyindolyl)propyl]ethylenediamine

(胺基乙基胺基乙基)苯基三甲氧基矽烷 (aminoethylaminoethyl)phenyltrimethoxydecane

(胺基乙基胺基乙基)苯基三乙氧基矽烷 (aminoethylaminoethyl)phenyltriethoxydecane

(胺基乙基胺基乙基)苯基三丙氧基矽烷 (aminoethylaminoethyl)phenyltripropoxydecane

(胺基乙基胺基乙基)苯基三異丙氧基矽烷 (aminoethylaminoethyl)phenyltriisopropoxydecane

(胺基乙基胺基甲基)苯基三甲氧基矽烷 (aminoethylaminomethyl)phenyltrimethoxydecane

(胺基乙基胺基甲基)苯基三乙氧基矽烷 (aminoethylaminomethyl)phenyltriethoxydecane

(胺基乙基胺基甲基)苯基三丙氧基矽烷 (aminoethylaminomethyl)phenyltripropoxydecane

(胺基乙基胺基甲基)苯基三異丙氧基矽烷 (aminoethylaminomethyl)phenyltriisopropoxydecane

N-(乙烯基苄基)-2-胺基乙基-3-胺基丙基三甲氧基矽烷 N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxydecane

N-(乙烯基苄基)-2-胺基乙基-3-胺基丙基甲基二甲氧基矽烷 N-(vinylbenzyl)-2-aminoethyl-3-aminopropylmethyldimethoxydecane

N-β-(N-乙烯基苄胺基乙基)-N-γ-(N-乙烯基苄基)-γ-胺基丙基三甲氧基矽烷 N-β-(N-vinylbenzylaminoethyl)-N-γ-(N-vinylbenzyl)-γ-aminopropyltrimethoxydecane

N-β-(N-二(乙烯基苄基)胺基乙基)-γ-胺基丙基三甲氧基矽烷 N-β-(N-bis(vinylbenzyl)aminoethyl)-γ-aminopropyltrimethoxydecane

N-β-(N-二(乙烯基苄基)胺基乙基)-N-γ-(N-乙烯基苄基)-γ-胺基丙基三甲氧基矽烷 N-β-(N-bis(vinylbenzyl)aminoethyl)-N-γ-(N-vinylbenzyl)-γ-aminopropyltrimethoxydecane

甲基苄胺基乙基胺基丙基三甲氧基矽烷 Methylbenzylaminoethylaminopropyltrimethoxydecane

二甲基苄胺基乙基胺基丙基三甲氧基矽烷 Dimethylbenzylaminoethylaminopropyltrimethoxydecane

苄胺基乙基胺基丙基三甲氧基矽烷 Benzylaminoethylaminopropyltrimethoxydecane

苄胺基乙基胺基丙基三乙氧基矽烷 Benzylaminoethylaminopropyltriethoxydecane

3-脲基丙基三乙氧基矽烷 3-ureidopropyltriethoxydecane

3-(N-苯基)胺基丙基三甲氧基矽烷 3-(N-phenyl)aminopropyltrimethoxydecane

N,N-雙[3-(三甲氧基矽基)丙基]乙二胺 N,N-bis[3-(trimethoxyindolyl)propyl]ethylenediamine

(胺基乙基胺基乙基)苯乙基三甲氧基矽烷 (aminoethylaminoethyl)phenethyltrimethoxydecane

(胺基乙基胺基乙基)苯乙基三乙氧基矽烷 (aminoethylaminoethyl)phenethyltriethoxydecane

(胺基乙基胺基乙基)苯乙基三丙氧基矽烷 (aminoethylaminoethyl)phenethyltripropoxydecane

(胺基乙基胺基乙基)苯乙基三異丙氧基矽烷 (aminoethylaminoethyl)phenethyltriisopropoxydecane

(胺基乙基胺基甲基)苯乙基三甲氧基矽烷 (aminoethylaminomethyl) phenethyltrimethoxydecane

(胺基乙基胺基甲基)苯乙基三乙氧基矽烷 (aminoethylaminomethyl)phenethyltriethoxydecane

(胺基乙基胺基甲基)苯乙基三丙氧基矽烷 (aminoethylaminomethyl)phenethyltripropoxydecane

(胺基乙基胺基甲基)苯乙基三異丙氧基矽烷 (aminoethylaminomethyl)phenethyltriisopropoxydecane

N-[2-[3-(三甲氧基矽基)丙基胺基]乙基]乙二胺 N-[2-[3-(trimethoxyindolyl)propylamino]ethyl]ethylenediamine

N-[2-[3-(三乙氧基矽基)丙基胺基]乙基]乙二胺 N-[2-[3-(triethoxyindolyl)propylamino]ethyl]ethylenediamine

N-[2-[3-(三丙氧基矽基)丙基胺基]乙基]乙二胺 N-[2-[3-(tripropoxydecyl)propylamino]ethyl]ethylenediamine

N-[2-[3-(三異丙氧基矽基)丙基胺基]乙基]乙二胺。 N-[2-[3-(Triisopropoxydecyl)propylamino]ethyl]ethylenediamine.

該等帶胺基之矽烷偶合劑可單獨使用1種，亦可組合使用2種以上。又，亦可將帶胺基之矽烷偶合劑與不帶胺基之矽烷偶合劑組合使用。 These amine-containing decane coupling agents may be used alone or in combination of two or more. Further, an amine group-containing decane coupling agent may be used in combination with a decane coupling agent having no amine group.

又，關於本發明之縮合物，於考慮例如於聚醯亞胺膜等有機基材以高溫燒結含有金屬奈米粒子之油墨或糊劑而 形成導電性圖案之情況時，耐熱性較為重要。因此，成為縮合物之原料之矽烷偶合劑較有效的是使用耐熱性較高之矽烷偶合劑。即，對於矽烷偶合劑之縮合物，大多情況下要求，不會於印刷下述導電性材料後之高溫處理中引起熱分解或昇華等而保持膜之形態並且不使其功能(耐熱性、與基材或導電性構件之接著性等)降低。 Further, the condensate of the present invention is considered to sinter an ink or paste containing metal nanoparticles at a high temperature on an organic substrate such as a polyimide film. When a conductive pattern is formed, heat resistance is important. Therefore, a decane coupling agent which is a raw material of a condensate is effective in using a decane coupling agent which is high in heat resistance. In other words, in many cases, it is required that the condensate of the decane coupling agent does not cause thermal decomposition or sublimation during high-temperature treatment after printing the following conductive material, and the form of the film is maintained and does not function (heat resistance, and The adhesion of the substrate or the conductive member, etc.) is lowered.

根據該觀點，於上述所列舉之矽烷偶合劑中，就耐熱性高而言較佳為(胺基乙基胺基甲基)苯基三甲氧基矽烷。又，就廉價之方面而言較佳為N-(2-胺基乙基)3-胺基丙基三甲氧基矽烷。若綜合考慮對聚醯亞胺膜等有機基材、燒結導電性材料而成之導電性圖案的接著性、進而耐熱性高，則較佳為(胺基乙基胺基甲基)苯基三甲氧基矽烷。又，就對導電性圖案之接著性之觀點而言，該矽烷偶合劑之胺基數較佳為2以上、例如2或3。此種於分子內帶有兩個以上胺基之矽烷偶合劑中，例如亦可較佳地使用(胺基乙基胺基甲基)苯乙基三甲氧基矽烷及N-[2-[3-(三甲氧基矽基)丙基胺基]乙基]乙二胺。其中，就密合性之觀點而言尤佳為(胺基乙基胺基甲基)苯乙基三甲氧基矽烷。 From this point of view, among the above-described decane coupling agents, (aminoethylaminomethyl)phenyltrimethoxydecane is preferred because of its high heat resistance. Further, in terms of inexpensiveness, N-(2-aminoethyl) 3-aminopropyltrimethoxydecane is preferred. When considering the adhesion to a conductive pattern such as an organic substrate such as a polyimide film or a sintered conductive material, and further having high heat resistance, it is preferably (aminoethylaminomethyl)phenyl trimethyl. Oxydecane. Further, from the viewpoint of the adhesion of the conductive pattern, the number of amine groups of the decane coupling agent is preferably 2 or more, for example 2 or 3. In the decane coupling agent having two or more amine groups in the molecule, for example, (aminoethylaminomethyl)phenethyltrimethoxydecane and N-[2-[3 -(Trimethoxydecyl)propylamino]ethyl]ethylenediamine. Among them, (aminoethylaminomethyl)phenethyltrimethoxydecane is particularly preferable from the viewpoint of adhesion.

帶胺基之矽烷偶合劑較佳為選自由(胺基乙基胺基甲基)苯基三甲氧基矽烷、(胺基乙基胺基甲基)苯乙基三甲氧基矽烷及N-[2-[3-(三甲氧基矽基)丙基胺基]乙基]乙二胺所組成之群之1種以上。 The amine-containing decane coupling agent is preferably selected from the group consisting of (aminoethylaminomethyl)phenyltrimethoxydecane, (aminoethylaminomethyl)phenethyltrimethoxydecane, and N-[ One or more groups consisting of 2-[3-(trimethoxyindenyl)propylamino]ethyl]ethylenediamine.

關於本發明之縮合物中之帶胺基之矽烷偶合劑的濃度，並無特別限制，較佳為40~99質量%，更佳為60~98 質量%，尤佳為80~95質量%。 The concentration of the amine group-containing decane coupling agent in the condensate of the present invention is not particularly limited, but is preferably 40 to 99% by mass, more preferably 60 to 98. The mass% is particularly preferably 80 to 95% by mass.

(金屬烷氧化物) (metal alkoxide)

本發明之縮合物所使用之金屬烷氧化物由下述通式(I)表示。 The metal alkoxide used in the condensate of the present invention is represented by the following formula (I).

R1 nM(OR2)m-n (I) R 1 n M(OR 2 ) mn (I)

於上述通式(I)中，M表示選自Si、Ti、Al、Zr、Li、Na、Ca、Sr、Ba、Zn、B、Ga、Y、Ge、Pb、P、Sb、V、Ta、W、La、Nd、In之金屬原子群中之至少1種金屬原子。 In the above formula (I), M represents a group selected from the group consisting of Si, Ti, Al, Zr, Li, Na, Ca, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta. At least one metal atom of the metal atom group of W, La, Nd, or In.

通常由於獲得及合成較容易，故M較佳為Si、Ti、Al、Zr，尤佳為Ti。 M is usually Si, Ti, Al, Zr, and particularly preferably Ti, because it is easy to obtain and synthesize.

於上述通式(I)中，R1表示非水解性基，例如碳數1~20之烷基，具有(甲基)丙烯醯氧基、胺基或環氧基之碳數1~20之烷基或烯基，碳數2~20之烯基，碳數6~20之芳基，或碳數7~20之芳烷基。 In the above formula (I), R 1 represents a non-hydrolyzable group, for example, an alkyl group having 1 to 20 carbon atoms, and has a carbon number of 1 to 20 of (meth)acryloxy group, an amine group or an epoxy group. An alkyl group or an alkenyl group, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.

此處，作為碳數1~20之烷基，較佳為碳數1~10者，又，該烷基可為直鏈狀、分枝狀、環狀之任一種。除此以外，亦可列舉含有羥基、硫醇、咪唑等取代基之官能基。作為碳數1~20之烷基之例，可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、戊基、己基、辛基、環戊基、環己基等。 Here, the alkyl group having 1 to 20 carbon atoms is preferably a carbon number of 1 to 10, and the alkyl group may be any of a linear chain, a branched chain, and a cyclic group. Other than this, a functional group containing a substituent such as a hydroxyl group, a thiol or an imidazole may also be mentioned. Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, second butyl group, tert-butyl group, and pentyl group. Hexyl, octyl, cyclopentyl, cyclohexyl and the like.

作為具有(甲基)丙烯醯氧基、胺基或環氧基之碳數1~20之烷基，較佳為具有上述取代基之碳數1~10之烷基，又，該烷基可為直鏈狀、分枝狀、環狀之任一種。作為該具有取代基之烷基之例，可列舉：γ-丙烯醯氧基丙基、γ- 甲基丙烯醯氧基丙基、γ-胺基丙基、3-(2-胺基乙基胺基)丙基、3-苯基胺基丙基、γ-環氧丙氧基丙基、3,4-環氧基環己基等。 The alkyl group having 1 to 20 carbon atoms having a (meth) acryloxy group, an amine group or an epoxy group is preferably an alkyl group having 1 to 10 carbon atoms having the above substituent, and the alkyl group may be It is any of a linear chain, a branching shape, and a ring shape. Examples of the alkyl group having a substituent include γ-acryloxypropyl group and γ-. Methyl propylene methoxypropyl, γ-aminopropyl, 3-(2-aminoethylamino)propyl, 3-phenylaminopropyl, γ-glycidoxypropyl, 3,4-epoxycyclohexyl and the like.

作為碳數2~20之烯基，較佳為碳數2~10之烯基，又，該烯基可為直鏈狀、分枝狀、環狀之任一種。作為該烯基之例，可列舉：乙烯基、烯丙基、丁烯基、己烯基、辛烯基等。 The alkenyl group having 2 to 20 carbon atoms is preferably an alkenyl group having 2 to 10 carbon atoms, and the alkenyl group may be linear, branched or cyclic. Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a hexenyl group, and an octenyl group.

作為碳數6~20之芳基，較佳為碳數6~10之芳基，例如可列舉：苯基、甲苯基、二甲苯基、萘基等。 The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

作為碳數7~20之芳烷基，較佳為碳數7~10之芳烷基，例如可列舉：苄基、苯乙基、苯丙基、萘甲基等。 The aralkyl group having 7 to 20 carbon atoms is preferably an aralkyl group having 7 to 10 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a phenylpropyl group, and a naphthylmethyl group.

另一方面，R2為碳數1~6之烷基，可為直鏈狀、分枝狀、環狀之任一種，作為其例，可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、戊基、己基、環戊基、環己基等。 On the other hand, R 2 is an alkyl group having 1 to 6 carbon atoms, and may be any of a linear chain, a branched chain, and a cyclic chain. Examples thereof include methyl group, ethyl group, n-propyl group, and hetero ring. Propyl, n-butyl, isobutyl, t-butyl, tert-butyl, pentyl, hexyl, cyclopentyl, cyclohexyl and the like.

又，於上述通式(I)所示之金屬烷氧化物中，m為金屬原子M之價數且為3或4，於m為4之情形時，n為0~2之整數，於m為3之情形時，n為0~1之整數。於存在複數個R1之情形時，各R1彼此可相同亦可不同，又，於存在複數個OR2之情形時，各OR2彼此可相同亦可不同。 Further, in the metal alkoxide represented by the above formula (I), m is a valence of the metal atom M and is 3 or 4. When m is 4, n is an integer of 0 to 2, and m is In the case of 3, n is an integer from 0 to 1. In the case where a plurality of R 1 are present, each R 1 may be the same or different from each other, and in the case where a plurality of OR 2 are present, each OR 2 may be the same or different from each other.

於上述通式(I)所示之金屬烷氧化物中，作為M為4價之Ti、Si、Zr，且m為4，n為0~3之整數之情形時的烷氧化物之例，可列舉：四甲氧基鈦、四乙氧基鈦、四-正丙氧基鈦、四異丙氧基鈦(四異丙氧化鈦)、四-正丁氧基 鈦、四異丁氧基鈦、四-第二丁氧基鈦、四-第三丁氧基鈦、甲基三甲氧基鈦、甲基三乙氧基鈦、甲基三丙氧基鈦、甲基三異丙氧基鈦、乙基三甲氧基鈦、乙基三乙氧基鈦、丙基三乙氧基鈦、丁基三甲氧基鈦、苯基三甲氧基鈦、苯基三乙氧基鈦、乙烯基三甲氧基鈦、乙烯基三乙氧基鈦、γ-環氧丙氧基丙基三甲氧基鈦、γ-丙烯醯氧基丙基三甲氧基鈦、γ-甲基丙烯醯氧基丙基三甲氧基鈦、二甲基二甲氧基鈦、甲基苯基二甲氧基鈦等，及將上述化合物中之鈦置換為矽烷或鋯之化合物。其中，可較佳地使用四異丙氧化鈦。 In the metal alkoxide represented by the above formula (I), an example of the alkoxide in the case where M is tetravalent Ti, Si, and Zr, and m is 4, and n is an integer of 0 to 3, Examples thereof include titanium tetramethoxy, titanium tetraethoxide, titanium tetra-n-propoxyoxide, titanium tetraisopropoxide (titanium tetraisopropoxide), and tetra-n-butoxy group. Titanium, titanium tetraisobutoxide, titanium tetra-butoxide, titanium tetra-butoxybutoxide, titanium trimethoxytitanium, methyltriethoxytitanium, methyltripropoxytitanium, Methyl triisopropoxytitanium, ethyl trimethoxytitanium, ethyltriethoxytitanium, propyltriethoxytitanium, butyltrimethoxytitanium, phenyltrimethoxytitanium, phenyltriethyl Titanium oxide, vinyl trimethoxy titanium, vinyl triethoxy titanium, γ-glycidoxypropyltrimethoxy titanium, γ-acryloxypropyltrimethoxytitanium, γ-methyl A acryloxypropyltrimethoxytitanium, a dimethyldimethoxytitanium, a methylphenyldimethoxytitanium or the like, and a compound obtained by replacing titanium in the above compound with decane or zirconium. Among them, titanium tetraisopropoxide can be preferably used.

又，於上述通式(I)所示之金屬烷氧化物中，作為於M為3價之鋁，且m為3，n為0~1之整數之情形時的烷氧化物之例，可列舉：三甲氧基鋁、三乙氧基鋁、三-正丙氧基鋁、三異丙氧基鋁、三-正丁氧基鋁、三異丁氧基鋁、三-第二丁氧基鋁、三-第三丁氧基鋁、甲基二甲氧基鋁、甲基二乙氧基鋁、甲基二丙氧基鋁、乙基二甲氧基鋁、乙基二乙氧基鋁、丙基二乙氧基鋁等。 Further, in the metal alkoxide represented by the above formula (I), an example of the alkoxide in the case where M is trivalent aluminum and m is 3 and n is an integer of 0 to 1 may be used. Listed: trimethoxy aluminum, triethoxy aluminum, tri-n-propoxy aluminum, triisopropoxy aluminum, tri-n-butoxy aluminum, triisobutoxy aluminum, tri-second butoxy Aluminum, tri-t-butoxy aluminum, methyl dimethoxy aluminum, methyl diethoxy aluminum, methyl dipropoxy aluminum, ethyl dimethoxy aluminum, ethyl diethoxy aluminum , propyl diethoxy aluminum, and the like.

該等金屬烷氧化物可單獨使用1種，亦可組合使用2種以上。 These metal alkoxides may be used alone or in combination of two or more.

於本發明之縮合物中，於上述矽烷偶合劑與上述金屬烷氧化物之比例於為質量%之比例之情形時，較佳為80：20~95：5。 In the condensate of the present invention, in the case where the ratio of the above decane coupling agent to the metal alkoxide is in a ratio of mass%, it is preferably 80:20 to 95:5.

(縮合物之製作) (production of condensate)

於本發明中，利用溶膠-凝膠反應使上述帶胺基之矽烷偶合劑與金屬烷氧化物進行水解-縮合反應而製作以M-O (M與上述相同，以下相同)之重複單位作為主骨架之縮合物。本發明之縮合物之製造方法具備：使帶胺基之矽烷偶合劑例如於水等溶劑中進行縮合反應而獲得反應液之第1步驟；使通式(I)所示之金屬烷氧化物與上述第1步驟中所獲得之反應液混合而進行縮合反應之第2步驟。 In the present invention, the above-described amine-based decane coupling agent is subjected to a hydrolysis-condensation reaction with a metal alkoxide by a sol-gel reaction to produce M-O. The repeating unit (M is the same as above, the same below) is used as a condensate of the main skeleton. The method for producing a condensate of the present invention comprises: a first step of obtaining a reaction liquid by subjecting an amine group-containing decane coupling agent to a condensation reaction in a solvent such as water; and a metal alkoxide represented by the formula (I) The reaction liquid obtained in the above first step is mixed to carry out the second step of the condensation reaction.

於上述第1步驟及第2步驟中之縮合反應中，作為溶劑，例如可使用醇系、賽路蘇系、酮系、醚系、二醇醚系等之極性溶劑，就相溶性之觀點而言較佳為二醇醚系，尤佳為乙二醇單-第三丁醚。縮合反應可藉由如下方式進行：於上述溶劑中，針對帶胺基之矽烷偶合劑或烷氧化物，使用水、或水與鹽酸、硫酸、硝酸等酸、或作為固體酸之陽離子交換樹脂，於通常為0~70℃、較佳為20~60℃之溫度下進行水解處理，於使用固體酸之情形時，於將其去除後，進而視需要蒸餾去除或添加溶劑。藉由上述反應，可獲得以M-O之重複單位作為主骨架之縮合物。 In the condensation reaction in the first step and the second step, as the solvent, for example, a polar solvent such as an alcohol system, a celecoxib system, a ketone system, an ether system or a glycol ether system can be used, from the viewpoint of compatibility. It is preferably a glycol ether system, and particularly preferably ethylene glycol mono-tert-butyl ether. The condensation reaction can be carried out by using water, or water with an acid such as hydrochloric acid, sulfuric acid, nitric acid or a cation exchange resin as a solid acid, in the above solvent, for the amine-containing decane coupling agent or alkoxide. The hydrolysis treatment is carried out at a temperature of usually 0 to 70 ° C, preferably 20 to 60 ° C. When a solid acid is used, it is removed, and then a solvent is optionally removed or added as needed. By the above reaction, a condensate having a repeating unit of M-O as a main skeleton can be obtained.

上述以M-O之重複單位作為主骨架之縮合物殘留有帶胺基之矽烷偶合劑之胺基、或藉由通式(I)中的OR2之水解而產生之OH基，因此對聚醯亞胺膜、或遮罩材、接合片等有機物、或者金屬等無機物之接著性亦優異。 The condensate in which the repeating unit of MO is used as the main skeleton remains an amine group of an amine group-containing decane coupling agent or an OH group produced by hydrolysis of OR 2 in the general formula (I), and thus An amine film, an organic substance such as a masking material or a bonding sheet, or an inorganic substance such as a metal is also excellent in adhesion.

本發明之縮合物之製造方法較佳為進而具備於上述第1步驟中所獲得之反應液中添加三硫醇(triazinethiol)衍生物之第3步驟。藉此，使用導入有三硫醇衍生物之縮合物的導電性構件可進一步提高密著強度。此處，所謂「將三硫醇衍生物導入縮合物中」，主要係指使三硫醇衍 生物僅包含於縮合物中之形態，但此處之所謂導入亦包含三硫醇衍生物與縮合物進行化學反應或形成配位鍵之形態。 The method for producing a condensate of the present invention preferably further comprises adding three to the reaction liquid obtained in the first step. The third step of the triazinethiol derivative. By using this, there are three imported The conductive member of the condensate of the thiol derivative can further increase the adhesion strength. Here, the so-called "will be three Mercaptan derivatives are introduced into the condensate," The thiol derivative is only included in the form of the condensate, but the so-called introduction here also includes three A form in which a thiol derivative chemically reacts with a condensate or forms a coordinate bond.

該第3步驟較佳為於第2步驟後進行，即，於利用溶膠-凝膠反應使帶胺基之矽烷偶合劑與金屬烷氧化物進行水解-縮合反應而獲得的以M-O之重複單位作為主骨架之縮合物中，添加三硫醇衍生物而進行反應。又，第3步驟亦可與第2步驟同時進行，即，同時添加帶胺基之矽烷偶合劑、金屬烷氧化物及三硫醇衍生物而進行反應。進而，第3步驟亦可於第2步驟前進行，即，於帶胺基之矽烷偶合劑中添加三硫醇衍生物並進行反應後，添加金屬烷氧化物而進行反應。進而，第3步驟亦可與第1步驟同時進行，即，於帶胺基之矽烷偶合劑進行縮合反應前添加三硫醇衍生物而進行反應。 The third step is preferably carried out after the second step, that is, a repeating unit of MO obtained by performing a hydrolysis-condensation reaction of an amine group-containing decane coupling agent and a metal alkoxide by a sol-gel reaction. In the condensate of the main skeleton, add three The reaction is carried out by a thiol derivative. Moreover, the third step can also be carried out simultaneously with the second step, that is, simultaneously adding an amine group-containing decane coupling agent, a metal alkoxide and three The reaction is carried out by a thiol derivative. Further, the third step may be carried out before the second step, that is, adding three to the amine-containing decane coupling agent After the thiol derivative is reacted, a metal alkoxide is added to carry out a reaction. Further, the third step may be carried out simultaneously with the first step, that is, adding three before the condensation reaction of the amine-containing decane coupling agent The reaction is carried out by a thiol derivative.

作為三硫醇衍生物，例如可列舉：下述通式(II)及/或通式(III)及/或通式(IV)所示之化合物。 As three Examples of the thiol derivative include compounds represented by the following formula (II) and/or formula (III) and/or formula (IV).

於上述通式(II)、(III)、(IV)中，R表示-SR3、-OR3、-NHR3或NR3R4等。R3及R4分別獨立表示氫原子或碳數1~18之烷基、苯基、芳烷基、烯基、環烷基、不飽和烷基、氟化烷基、氟化苯基、氟化芳烷基或氟化不飽和烷基，R3與R4亦可由另一端連接而形成環。又，X1、X2分別獨立表示選自氫原子、丙二酸衍生物、琥珀酸衍生物、琥珀酸甲酯衍生物、丙酸衍生物、酮衍生物、碸衍生物、硝基衍生物及乙醯基衍生物中之殘基，但不存在X1、X2兩者均為氫原子之情況。 In the above formulae (II), (III), (IV), R represents -SR 3 , -OR 3 , -NHR 3 or NR 3 R 4 or the like. R 3 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, a phenyl group, an aralkyl group, an alkenyl group, a cycloalkyl group, an unsaturated alkyl group, a fluorinated alkyl group, a fluorinated phenyl group, or a fluorine group. An aralkyl group or a fluorinated unsaturated alkyl group, and R 3 and R 4 may be bonded to each other to form a ring. Further, X 1 and X 2 each independently represent a hydrogen atom, a malonic acid derivative, a succinic acid derivative, a methyl succinate derivative, a propionic acid derivative, a ketone derivative, an anthracene derivative, and a nitro derivative. And a residue in the acetamino derivative, but there is no case where both X 1 and X 2 are hydrogen atoms.

於該等三硫醇衍生物中，就與各種金屬烷氧化物縮合物之相溶性、尤其是對於高濃度之金屬烷氧化物縮合物之相溶性而言，較佳為分子量較小之通式(II)所表示的三 環之至少兩個碳經硫醇基(-SH)取代之三硫醇衍生物。其中，尤佳為三環之全部的碳經硫取代之情形，尤佳為全部經硫醇基(-SH)取代之2,4,6-巰基-三。於此情形時，由於分子量最小，故而可使自低濃度至高濃度之各種金屬烷氧化物縮合物的金屬與硫醇之配位有效且均勻地進行。此種三硫醇化合物可作為工業製品而相對容易地獲得，就材料成本之觀點而言亦極其有效。 In these three Among the thiol derivatives, the compatibility with various metal alkoxide condensates, especially for a high concentration of metal alkoxide condensates, is preferably a formula (II) having a small molecular weight. Indicated three At least two carbons of the ring are replaced by a thiol group (-SH) Mercaptan derivative. Among them, especially good for three In the case where all of the carbon of the ring is substituted by sulfur, it is particularly preferred that all of the thiol group (-SH) is substituted with 2,4,6-mercapto-three. . In this case, since the molecular weight is the smallest, the coordination of the metal of the metal alkoxide condensate from a low concentration to a high concentration with the mercaptan can be efficiently and uniformly performed. Such three Thiol compounds are relatively easy to obtain as industrial products and are extremely effective from the viewpoint of material cost.

該等三硫醇衍生物可單獨使用或混合使用2種以上。三硫醇衍生物相對於帶胺基之矽烷偶合劑、金屬烷氧化物及三硫醇衍生物之(固形物成分或有效成分)合計量的比例較佳為0.05~10質量%。 The three The thiol derivatives may be used alone or in combination of two or more. three a thiol derivative relative to an amine group-containing decane coupling agent, a metal alkoxide, and three The ratio of the total amount of the thiol derivative (solid content or active ingredient) is preferably from 0.05 to 10% by mass.

於本發明之縮合物之製造方法中，可進而具備混合填料之第4步驟。藉此，可於縮合物之膜表面構築凹凸結構，可防止印刷時之導電性材料之滲洇。其結果，可實現細線圖案之印刷。填料之1次粒徑較佳為30~1500 nm之範圍。此處，1次粒徑可藉由稀釋填料分散液並利用掃描式電子顯微鏡進行觀察，根據電子顯微鏡圖像計算粒子之平均粒徑而獲得。於1次粒徑小於30 nm之情形時，對導電性材料印刷時之印刷性的效果較小。又，於1次粒徑大於1500 nm之情形時，粒子容易於製作溶液時沈澱，使均勻膜之製膜稍微變難。 In the method for producing a condensate of the present invention, the fourth step of mixing the filler may be further provided. Thereby, the uneven structure can be formed on the film surface of the condensate, and the penetration of the conductive material at the time of printing can be prevented. As a result, printing of a thin line pattern can be achieved. The primary particle diameter of the filler is preferably in the range of 30 to 1500 nm. Here, the primary particle diameter can be obtained by diluting the filler dispersion and observing it with a scanning electron microscope, and calculating the average particle diameter of the particles from the electron microscope image. When the primary particle diameter is less than 30 nm, the effect on the printability at the time of printing of the conductive material is small. Further, in the case where the primary particle diameter is larger than 1500 nm, the particles are easily precipitated when the solution is formed, and the film formation of the uniform film is slightly difficult.

作為填料，可使用無機填料或有機填料之任一種。作為無機填料，例如可列舉：二氧化矽、二氧化矽微粒子、膠體二氧化矽、氧化鋁、膠體氧化鋁、膠體氧化鈦、氧化 鋯溶膠、矽酸鈣、沸石、高嶺石、多水高嶺土、白雲母、滑石、碳酸鈣、硫酸鈣、水鋁土等。其中，可較佳地使用膠體二氧化矽。作為二氧化矽之具體例，例如可列舉：LEVASIL系列(H.C.Starck股份有限公司製造)，甲醇二氧化矽溶膠、IPA-ST、MEK-ST、NBA-ST、XBA-ST、DMAC-ST、ST-UP、ST-OUP、ST-20、ST-40、ST-C、ST-N、ST-O、ST-50、ST-OL、MP-2040(以上，由日產化學工業股份有限公司製造)，Quartron PL系列(扶桑化學股份有限公司製造)，OSCAL系列(日揮觸媒化成股份有限公司製造)，Hipresica(宇部日東化成股份有限公司製造)等。其中，就填料對上述縮合物之溶液之分散性的觀點而言，可最佳地使用Hipresica。又，作為有機填料，可列舉聚醯亞胺粒子等。 As the filler, any of an inorganic filler or an organic filler can be used. Examples of the inorganic filler include cerium oxide, cerium oxide microparticles, colloidal cerium oxide, aluminum oxide, colloidal alumina, colloidal titanium oxide, and oxidation. Zirconium sol, calcium citrate, zeolite, kaolinite, halloysite, muscovite, talc, calcium carbonate, calcium sulfate, bauxite, and the like. Among them, colloidal cerium oxide can be preferably used. Specific examples of the cerium oxide include LEVASIL series (manufactured by HC Starck Co., Ltd.), methanol cerium oxide sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, and ST. -UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, MP-2040 (above, manufactured by Nissan Chemical Industry Co., Ltd.) , Quartron PL series (manufactured by Fuso Chemical Co., Ltd.), OSCAL series (made by Risei Chemicals Co., Ltd.), Hipresica (manufactured by Ube Nitto Chemical Co., Ltd.), etc. Among them, Hipresica can be optimally used from the viewpoint of the dispersibility of the filler to the solution of the above condensate. Further, examples of the organic filler include polyamidene particles and the like.

關於填料相對於帶胺基之矽烷偶合劑之比例，較佳為填料為10~80質量%之範圍，更佳為20~70質量%，進而較佳為30~70質量%。關於填料相對於帶胺基之矽烷偶合劑與金屬烷氧化物之比例，較佳為填料為10~70質量%之範圍，更佳為20~70質量%，進而較佳為30~60質量%。 The ratio of the filler to the decane coupling agent having an amine group is preferably in the range of 10 to 80% by mass, more preferably 20 to 70% by mass, still more preferably 30 to 70% by mass. With respect to the ratio of the filler to the amine-containing decane coupling agent and the metal alkoxide, the filler is preferably in the range of 10 to 70% by mass, more preferably 20 to 70% by mass, still more preferably 30 to 60% by mass. .

於添加之填料之比例小於上述比例之情形時，有時對導電性材料印刷時之印刷性的效果無法充分滿足。又，於添加之填料之比例大於上述比例之情形時，有時於積層基板上獲得之縮合物之溶膠-凝膠膜成為多孔結構，使電特性稍微下降。進而，於濕式步驟中液體會殘留於多孔質之膜表面。 When the ratio of the filler to be added is less than the above ratio, the effect of the printability at the time of printing the conductive material may not be sufficiently satisfied. Further, when the ratio of the filler to be added is larger than the above ratio, the sol-gel film of the condensate obtained on the laminated substrate may have a porous structure, and the electrical characteristics may be slightly lowered. Further, the liquid remains on the surface of the porous film in the wet step.

又，使用填料之縮合物的膜表面之表面被覆率較佳為10~100%之範圍，更佳為30~100%，進而較佳為50~100%。藉此，可實現下述導電性構件之印刷線之細線化。此處，所謂表面被覆率，係指填料相對於縮合物之膜之表面整體的佔有率。表面被覆率之測定方法係利用光學顯微鏡觀察將縮合物塗佈於聚醯亞胺膜等基材之塗膜表面，對於觀察到之圖像，利用圖像處理軟體以粒子部分成為黑色之方式二值化為白色與黑色，求得填料部分之面積佔有率(%)。關於表面被覆率之具體測定方法，於實施例部分加以敍述。雖然關於使用填料之縮合物之膜表面的表面被覆率實現導電性構件之印刷線之細線化的理由未必明確，但可認為係藉由使用填料粒子而於縮合物之塗膜表面形成凹凸結構，該凹凸結構防止印刷之銀糊劑等油墨之滲洇者。其中，考慮濕式製程或導電時之遷移而將不成為多孔質之情況為條件。 Further, the surface coverage of the film surface using the condensate of the filler is preferably in the range of 10 to 100%, more preferably 30 to 100%, still more preferably 50 to 100%. Thereby, the thinning of the printing line of the following conductive member can be achieved. Here, the surface coverage ratio means the occupancy ratio of the filler to the entire surface of the film of the condensate. The method of measuring the surface coverage rate is to observe the surface of the coating film of the substrate such as a polyimide film by an optical microscope, and to observe the image, the image processing software is used to make the particle portion black. The value is white and black, and the area occupancy (%) of the filler portion is obtained. The specific measurement method of the surface coverage rate is described in the examples. Although the reason why the surface coverage of the film surface using the condensate of the filler achieves the thinning of the printed wiring of the conductive member is not necessarily clear, it is considered that the uneven structure is formed on the surface of the coating film of the condensate by using the filler particles. The uneven structure prevents infiltration of ink such as printed silver paste. Among them, it is considered that the wet process or the migration during conduction is not required to be porous.

於本發明之縮合物之製造方法中，第4步驟較佳為於第2步驟之後進行，即，於利用溶膠-凝膠反應使帶胺基之矽烷偶合劑與金屬烷氧化物進行水解-縮合反應而獲得的以M-O之重複單位作為主骨架之縮合物中混合填料。又，第4步驟亦可與第2步驟同時進行，即，同時混合帶胺基之矽烷偶合劑、金屬烷氧化物及填料而進行反應。進而，第4步驟亦可與第1步驟同時進行，即，於帶胺基之矽烷偶合劑進行縮合反應前混合填料而進行反應。 In the method for producing a condensate of the present invention, the fourth step is preferably carried out after the second step, that is, the hydrolysis-condensation of the amine-containing decane coupling agent with the metal alkoxide by a sol-gel reaction The condensate obtained by the reaction and having the repeating unit of MO as a main skeleton is a mixed filler. Further, the fourth step may be carried out simultaneously with the second step, that is, the reaction is carried out by simultaneously mixing an amine group-containing decane coupling agent, a metal alkoxide, and a filler. Further, the fourth step may be carried out simultaneously with the first step, that is, the mixture is mixed and the reaction is carried out before the condensation reaction of the amine group-containing decane coupling agent.

關於使填料混合之形態，可省略添加三硫醇衍生物 而進行反應之第3步驟。又，關於使填料混合之形態，亦可省略添加金屬烷氧化物而進行反應之第2步驟。即，亦可由帶胺基之矽烷偶合劑與填料獲得縮合物。 Regarding the form in which the filler is mixed, the addition of three may be omitted. The third step of the reaction is carried out by a thiol derivative. Further, in the form of mixing the filler, the second step of adding the metal alkoxide to carry out the reaction may be omitted. That is, a condensate can also be obtained from an amine group-containing decane coupling agent and a filler.

又，對於本發明之縮合物之製造方法中供給三硫醇衍生物及填料之方法進行說明。於本發明中，第4步驟亦可於第2及第3步驟之後進行，即，於使上述縮合物與三硫醇衍生物反應而成者中添加填料。又，第3步驟亦可於第2及第4步驟之後進行，即，於混合上述縮合物與填料而成者中添加三硫醇衍生物。進而，第3及第4步驟亦可於第2步驟之後同時進行，即，於上述縮合物中同時添加三硫醇衍生物及填料。又，第2、第3及第4步驟亦可同時進行，即，同時混合帶胺基之矽烷偶合劑、金屬烷氧化物、三硫醇衍生物及填料而進行反應。 Further, in the method for producing a condensate of the present invention, three are supplied A method of a thiol derivative and a filler will be described. In the present invention, the fourth step may also be performed after the second and third steps, that is, to make the condensate and the third A filler is added to the thiol derivative reaction. Further, the third step may be performed after the second and fourth steps, that is, adding three in the case of mixing the condensate and the filler. Mercaptan derivative. Further, the third and fourth steps may be simultaneously performed after the second step, that is, three additions are simultaneously added to the condensate Mercaptan derivatives and fillers. Further, the second, third and fourth steps can also be carried out simultaneously, that is, simultaneously mixing an amine group-containing decane coupling agent, a metal alkoxide, and three The thiol derivative and the filler are reacted.

(積層基板用材料) (Material for laminated substrate)

本發明之縮合物可較佳地用作積層基板用材料。利用上述製造方法所製造之縮合物可藉由上述水解-縮合反應而獲得以特定濃度含有以M-O之重複單位作為主骨架之縮合物的塗敷液之狀態，因此於使用本發明之縮合物作為積層基板用材料之情形時，較佳為以塗敷液之狀態塗佈於基材表面。又，塗敷液亦可於獲得上述縮合物後調整為特定濃度。關於該塗敷液中之上述縮合物之濃度，只要為可於基材表面塗敷之濃度，則並無特別限制，通常為0.05~35質量%，較佳為0.1~20質量%，更佳為0.2~10質量%。若縮合物之濃度超過35質量%，則液體之穩定性下降，即，有 時液體變得容易凝膠化而使保存時間(適用期)變短。又，若縮合物之濃度未達0.05質量%，則有時無法獲得充分之效果。 The condensate of the present invention can be preferably used as a material for a laminate substrate. The condensate produced by the above-described production method can obtain a coating liquid containing a condensate containing a repeating unit of MO as a main skeleton at a specific concentration by the above hydrolysis-condensation reaction, and thus the condensate of the present invention is used as In the case of a material for a laminated substrate, it is preferably applied to the surface of the substrate in the state of a coating liquid. Further, the coating liquid may be adjusted to a specific concentration after obtaining the above condensate. The concentration of the condensate in the coating liquid is not particularly limited as long as it can be applied to the surface of the substrate, and is usually 0.05 to 35% by mass, preferably 0.1 to 20% by mass, more preferably It is 0.2 to 10% by mass. If the concentration of the condensate exceeds 35% by mass, the stability of the liquid decreases, that is, When the liquid becomes easy to gel, the storage time (pot life) becomes short. Further, when the concentration of the condensate is less than 0.05% by mass, a sufficient effect may not be obtained.

本發明之積層基板用材料係以上述方式製造，並以本發明之縮合物為主成分。所謂主成分，例如係指積層基板用材料中之縮合物為50質量%以上。 The material for a laminated substrate of the present invention is produced in the above manner, and the condensate of the present invention is mainly composed. The main component is, for example, 50% by mass or more of the condensate in the material for a laminated substrate.

關於本發明之積層基板用材料，由於可藉由使用上述帶胺基之矽烷偶合劑而大幅度提高導電性圖案與基材之密合性，因此非常有用。雖然其原因未必明確，但推測為帶胺基之矽烷偶合劑經由胺基與金屬形成配位鍵。又，上述金屬烷氧化物可使積層於基材表面之該層不產生裂痕而以一定厚度均勻地積層，因此較為有效。 The material for a laminated substrate of the present invention is very useful because it can greatly improve the adhesion between the conductive pattern and the substrate by using the above-described amine-containing decane coupling agent. Although the reason is not necessarily clear, it is presumed that the amine group-containing decane coupling agent forms a coordinate bond with the metal via the amine group. Further, the metal alkoxide is effective in that the layer deposited on the surface of the substrate is not uniformly cracked and is uniformly deposited to a certain thickness.

於本發明之積層基板用材料中，若可使三硫醇衍生物於上述塗敷液中固定化，則更佳。於使用含有對聚醯亞胺膜等有機基材、燒結導電油墨而成之導電性圖案具有接著性的金屬烷氧化物縮合物，與三硫醇衍生物之塗敷液作為塗敷液之情形時，與單獨使用金屬烷氧化物縮合物之塗敷液之情形相比，可獲得密著強度提高之效果，且具有減少金屬烷氧化物縮合物之使用量之效果。除了成本以外，其對降低塗敷步驟中之塗敷不均等加工上的故障亦極為有效。 In the material for a laminated substrate of the present invention, if three It is more preferable that the thiol derivative is immobilized in the above coating liquid. A metal alkoxide condensate having an adhesion to a conductive pattern formed by sintering an organic substrate such as a polyimide film or a conductive ink, and three When the coating liquid of the thiol derivative is used as the coating liquid, the effect of improving the adhesion strength can be obtained as compared with the case of using the coating liquid of the metal alkoxide condensate alone, and the metal alkoxide is reduced. The effect of the amount of condensate used. In addition to the cost, it is also extremely effective in reducing the processing failure in the coating unevenness in the coating step.

該等三硫醇衍生物可單獨使用或混合使用2種以上。三硫醇衍生物係以用以改善金屬與有機基材之密合性之充分之量使用。本發明所使用之三硫醇衍生物之調 配量相對於塗敷液總量，較佳為0.0001~0.3質量%，更佳為以0.0005~0.25質量%之比例使用，進而較佳為0.001~0.2質量%。若為多於0.3質量%之量，則有金屬與有機基材之密著力降低之傾向。雖然其原因未必明確，但推測為三硫醇衍生物由於溶解性較低，故根據溶劑組成而析出等。另一方面，若為少於0.0001質量%之量，則與未使用三硫醇衍生物之情形相比，有無法充分改善接著力之虞。 The three The thiol derivatives may be used alone or in combination of two or more. three The thiol derivative is used in an amount sufficient to improve the adhesion between the metal and the organic substrate. The three used in the present invention The amount of the thiol derivative to be added is preferably 0.0001 to 0.3% by mass, more preferably 0.0005 to 0.25 mass%, still more preferably 0.001 to 0.2 mass%, based on the total amount of the coating liquid. If it is more than 0.3% by mass, the adhesion between the metal and the organic substrate tends to decrease. Although the reason may not be clear, it is presumed to be three. Since the thiol derivative has low solubility, it is precipitated depending on the solvent composition. On the other hand, if it is less than 0.0001% by mass, then with three unused In contrast to the case of the thiol derivative, there is a possibility that the adhesion force cannot be sufficiently improved.

於上述中，雖然對使帶胺基之矽烷偶合劑與金屬烷氧化物進行水解-縮合反應而成之以M-O之重複單位作為主骨架之縮合物進行了敍述，但未使用金屬烷氧化物而僅使用帶胺基之矽烷偶合劑的縮合物亦可提高導電性圖案對基材之密合性。 In the above, a condensate in which a repeating unit of MO is used as a main skeleton by subjecting an amine group-containing decane coupling agent to a metal alkoxide to undergo a hydrolysis-condensation reaction is described, but a metal alkoxide is not used. The use of only a condensate of an amine-containing decane coupling agent can also improve the adhesion of the conductive pattern to the substrate.

作為此種帶胺基之矽烷偶合劑之例，就可期待與金屬之密合性之官能基數較多之方面而言，可較佳地使用上述矽烷偶合劑。 As an example of such an amine group-containing decane coupling agent, the above-described decane coupling agent can be preferably used in terms of a large number of functional groups which are expected to have adhesion to a metal.

進而，其中就高耐熱性而言，可更佳地使用(胺基乙基胺基甲基)苯基三甲氧基矽烷，又，就廉價之方面而言，可更佳地使用N-(2-胺基乙基)3-胺基丙基三甲氧基矽烷。若綜合考慮對聚醯亞胺膜等有機基材、燒結導電性材料而成之導電性圖案之接著性、進而耐熱性高，則較佳為(胺基乙基胺基甲基)苯基三甲氧基矽烷。 Further, among them, (aminoethylaminomethyl)phenyltrimethoxydecane can be more preferably used in terms of high heat resistance, and N-(2) can be more preferably used in terms of inexpensiveness. -Aminoethyl)3-aminopropyltrimethoxydecane. When considering the adhesion to a conductive pattern such as an organic substrate such as a polyimide film or a sintered conductive material, and further having high heat resistance, it is preferably (aminoethylaminomethyl)phenyltrimethyl. Oxydecane.

又，矽烷偶合劑之胺基之數就剝離強度之觀點而言，較佳為2以上。作為此種具有兩個胺基之矽烷偶合劑，較佳為上述所列舉之(胺基乙基胺基甲基)苯基三甲氧基矽烷 或N-(2-胺基乙基)3-胺基丙基三甲氧基矽烷。於使用該等矽烷偶合劑之情形時，可於不使用金屬烷氧化物之情況下，進一步提高導電性圖案對基材之密合性。進而，就對導電性圖案之接著性之觀點而言，該矽烷偶合劑之胺基之數較佳為2以上、例如2或3。此種於分子內帶有兩個以上胺基之矽烷偶合劑中，例如亦可較佳地使用(胺基乙基胺基甲基)苯乙基三甲氧基矽烷及N-[2-[3-(三甲氧基矽基)丙基胺基]乙基]乙二胺。其中，就密合性之觀點而言，尤佳為(胺基乙基胺基甲基)苯乙基三甲氧基矽烷。於使用該等矽烷偶合劑之情形時，亦可於不使用金屬烷氧化物之情況下，進一步提高導電性圖案對基材之密合性。 Further, the number of the amine groups of the decane coupling agent is preferably 2 or more from the viewpoint of the peel strength. As such a decane coupling agent having two amine groups, the above-exemplified (aminoethylaminomethyl)phenyltrimethoxydecane is preferred. Or N-(2-aminoethyl) 3-aminopropyltrimethoxydecane. When such a decane coupling agent is used, the adhesion of the conductive pattern to the substrate can be further improved without using a metal alkoxide. Further, from the viewpoint of the adhesion of the conductive pattern, the number of the amine groups of the decane coupling agent is preferably 2 or more, for example 2 or 3. In the decane coupling agent having two or more amine groups in the molecule, for example, (aminoethylaminomethyl)phenethyltrimethoxydecane and N-[2-[3 -(Trimethoxydecyl)propylamino]ethyl]ethylenediamine. Among them, (aminoethylaminomethyl)phenethyltrimethoxydecane is particularly preferable from the viewpoint of adhesion. When such a decane coupling agent is used, the adhesion of the conductive pattern to the substrate can be further improved without using a metal alkoxide.

帶胺基之矽烷偶合劑較佳為選自由(胺基乙基胺基甲基)苯基三甲氧基矽烷、(胺基乙基胺基甲基)苯乙基三甲氧基矽烷及N-[2-[3-(三甲氧基矽基)丙基胺基]乙基]乙二胺所組成之群之1種以上者。 The amine-containing decane coupling agent is preferably selected from the group consisting of (aminoethylaminomethyl)phenyltrimethoxydecane, (aminoethylaminomethyl)phenethyltrimethoxydecane, and N-[ One or more of the group consisting of 2-[3-(trimethoxyindenyl)propylamino]ethyl]ethylenediamine.

(積層基板及其製造方法) (Laminated substrate and method of manufacturing the same)

本發明之特徵在於，其係將上述積層基板用材料積層於基材表面之積層基板。本發明之積層基板可藉由將上述塗敷液塗敷於基材表面而獲得。 The present invention is characterized in that the laminated substrate material is laminated on a laminated substrate on the surface of the substrate. The laminated substrate of the present invention can be obtained by applying the above coating liquid to the surface of a substrate.

作為可於本發明之積層基板中使用之基材，並無特別限定，於不阻礙發明效果之範圍內，可使用有機基材及無機基材之任一種。作為有機基材，可列舉：由聚乙烯、聚丙烯等聚烯烴系樹脂、聚氯乙烯、氯乙烯共聚物等氯乙烯系樹脂、環氧樹脂、聚芳酯、聚碸、聚醚碸、聚醯亞胺、 氟樹脂、苯氧樹脂、三乙醯纖維素、聚對苯二甲酸乙二酯、聚醯亞胺、聚苯硫醚、聚萘二甲酸乙二酯、聚碳酸酯、聚甲基丙烯酸甲酯等丙烯酸系樹脂、賽璐凡、尼龍、聚苯乙烯系樹脂、ABS(acrylonitrile-butadiene-styrene，丙烯腈-丁二烯-苯乙烯)樹脂等各種樹脂類所構成之膜等。又，作為無機基材，可列舉：石英玻璃、無鹼玻璃、結晶化透明玻璃、Pyrex(註冊商標)等各種玻璃等。作為基材，除了上述以外，亦可列舉紙、不織布、布、各種金屬、各種陶瓷等。又，可根據用途而適當組合該等基材，例如可使用將銅箔與聚醯亞胺積層而成之可撓性印刷基板材料、或將紙與聚烯烴樹脂積層而成之聚烯烴樹脂被覆紙。進而，使用該等樹脂等並成型為立體形狀之物體亦可用作支持體。 The substrate to be used in the laminated substrate of the present invention is not particularly limited, and any of an organic substrate and an inorganic substrate can be used as long as the effects of the invention are not impaired. Examples of the organic substrate include a polyolefin resin such as polyethylene or polypropylene, a vinyl chloride resin such as polyvinyl chloride or a vinyl chloride copolymer, an epoxy resin, a polyarylate, a polyfluorene, a polyether, and a poly Yttrium, Fluororesin, phenoxy resin, triacetyl cellulose, polyethylene terephthalate, polyimide, polyphenylene sulfide, polyethylene naphthalate, polycarbonate, polymethyl methacrylate A film made of various resins such as an acrylic resin, a ceramide resin, a nylon, a polystyrene resin, or an ABS (acrylonitrile-butadiene-styrene) resin. In addition, examples of the inorganic substrate include quartz glass, alkali-free glass, crystallized transparent glass, and various glasses such as Pyrex (registered trademark). Examples of the substrate include paper, non-woven fabric, cloth, various metals, various ceramics, and the like. Moreover, these base materials can be suitably combined according to the use, and for example, a flexible printed circuit board material obtained by laminating a copper foil and polyimide, or a polyolefin resin laminated with a paper and a polyolefin resin can be used. paper. Further, an object formed into a three-dimensional shape using such a resin or the like can also be used as a support.

該等之中，尤其就於燒結含有金屬奈米粒子之油墨或糊劑時，可藉由高溫處理而實現低電阻之觀點，耐熱性、尺寸穩定性及機械特性等觀點而言，較佳為聚醯亞胺膜。 Among these, in particular, when sintering an ink or a paste containing metal nanoparticles, it is preferable to achieve low resistance by high-temperature treatment, heat resistance, dimensional stability, and mechanical properties. Polyimine film.

作為此種聚醯亞胺膜，較佳為玻璃轉移溫度(Tg)為200℃以上者，更佳為250℃以上者，尤佳為300℃以上者。上述Tg可根據固體黏彈性圖譜中之tan δ之峰值溫度或損失彈性模數E"之峰值溫度而較佳地獲得。 As such a polyimide film, the glass transition temperature (Tg) is preferably 200 ° C or higher, more preferably 250 ° C or higher, and particularly preferably 300 ° C or higher. The above Tg can be preferably obtained from the peak temperature of tan δ or the peak temperature of the loss elastic modulus E" in the solid viscoelastic spectrum.

此種聚醯亞胺膜可使用芳香族聚醯亞胺膜。 An aromatic polyimide film can be used for such a polyimide film.

聚醯亞胺膜可由構成聚醯亞胺膜之酸酐成分與二胺成分獲得。作為酸酐成分，可列舉含有3,3',4,4'-聯苯四甲酸二酐、均苯四甲酸二酐等作為主成分者，但並不限定於該等。又，作為二胺成分，可列舉含有對伸苯基二胺 (paraphenylenediamin)、4,4-二胺基二苯醚等作為主成分者，但並不限定於該等。作為聚醯亞胺膜之具體例，例如可列舉：商品名為「Upilex(S或R)」(註冊商標，宇部興產股份有限公司製造)者、商品名為「Kapton」(註冊商標，Toray Dupont公司製造)者、商品名為「Apical」(註冊商標，Kaneka公司製造)者等聚醯亞胺膜等。 The polyimide film can be obtained from an acid anhydride component and a diamine component constituting the polyimide film. Examples of the acid anhydride component include 3,3', 4,4'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, and the like as a main component, but are not limited thereto. Further, examples of the diamine component include p-phenylenediamine (paraphenylenediamin), 4,4-diaminodiphenyl ether or the like as a main component, but is not limited thereto. Specific examples of the polyimine film include, for example, "Upilex (S or R)" (registered trademark, manufactured by Ube Industries, Ltd.), and the product name is "Kapton" (registered trademark, Toray). A polyimine film such as those manufactured by Dupont Co., Ltd., whose product name is "Apical" (registered trademark, manufactured by Kaneka Co., Ltd.).

於使用塑膠膜作為基材之情形時，基材之厚度並無特別限制，可根據用途而適當選擇，通常為1~300 μm左右，較佳為2~200 μm，進而更佳為3~150 μm。於小於1 μm之情形時，有操作性變差之傾向，若為300 μm以上，則有變得剛直而使操作性降低，重量增加，進而成本提高之傾向。 When a plastic film is used as the substrate, the thickness of the substrate is not particularly limited and may be appropriately selected depending on the application, and is usually about 1 to 300 μm, preferably 2 to 200 μm, and more preferably 3 to 150. Mm. When it is less than 1 μm, the workability tends to be inferior. When the thickness is 300 μm or more, the workability is reduced, the workability is lowered, the weight is increased, and the cost tends to increase.

對於上述基材，為了改善與配置於其表面之含有使金屬烷氧化物進行水解-縮合反應而成之以M-O之重複單位作為主骨架之縮合物的塗敷液之潤濕性，或為了提高與塗敷液之有效成分之密合性，可視需要對該表面實施電暈處理、電漿處理、鉻酸處理(濕式)、火焰處理、熱風處理、臭氧-紫外線照射處理、鹼處理、噴砂處理、溶劑處理或底塗處理。該等表面處理法可根據基材之種類而適當選擇，通常，就效果及操作性等方面而言，可較佳地使用電暈處理、電漿處理、鹼處理。 In order to improve the wettability of the coating liquid which is a condensate containing a repeating unit of MO as a main skeleton in which a metal alkoxide is subjected to a hydrolysis-condensation reaction disposed on the surface thereof, or in order to improve Adhesion to the active ingredient of the coating liquid, the surface may be subjected to corona treatment, plasma treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone-ultraviolet irradiation treatment, alkali treatment, sand blasting Treatment, solvent treatment or primer treatment. These surface treatment methods can be appropriately selected depending on the type of the substrate, and in general, corona treatment, plasma treatment, and alkali treatment can be preferably used in terms of effects and workability.

作為將上述塗敷液塗敷於基材表面之方法，並無特別限制，可藉由先前公知之方法，例如旋塗法、噴塗法、棒塗法、刀塗法、輥塗法、刮塗法、模塗法、凹版印刷塗佈 法等進行塗敷，於成膜後，進行自然乾燥或加熱乾燥，藉此可形成所期望之層。加熱乾燥之情形時之加熱溫度例如較佳為100~300℃，更佳為120~250℃，進而較佳為150~200℃。於加熱溫度未達100℃之情形時，有時需要較長之乾燥時間。又，於加熱溫度超過300℃之情形時，有時於連續製造裝置方面使成本增加。關於加熱時間，例如較佳為60~3600秒，更佳為75~1800秒，進而更佳為90~180秒。於乾燥時間短於60秒之情形時，存在乾燥不充分之情況，於長於3600秒之情形時，存在製造耗費時間而使成本增加之情況。由自然乾燥或加熱乾燥後之縮合物所獲得之層的厚度通常為0.01~3 μm左右，較佳為0.02~1 μm，更佳為0.05~0.5 μm。若層之厚度為0.01 μm以下，則無法獲得充分之效果，若為3 μm以上，則存在於塗膜上形成缺陷之可能性。 The method of applying the above coating liquid to the surface of the substrate is not particularly limited, and may be a conventionally known method such as spin coating, spray coating, bar coating, knife coating, roll coating, and blade coating. Method, die coating, gravure coating The film is applied by a method or the like, and after film formation, natural drying or heat drying is performed, whereby a desired layer can be formed. The heating temperature in the case of heat drying is, for example, preferably from 100 to 300 ° C, more preferably from 120 to 250 ° C, still more preferably from 150 to 200 ° C. When the heating temperature is less than 100 ° C, a long drying time is sometimes required. Moreover, when the heating temperature exceeds 300 ° C, the cost may increase in terms of continuous production equipment. The heating time is, for example, preferably 60 to 3600 seconds, more preferably 75 to 1800 seconds, and still more preferably 90 to 180 seconds. When the drying time is shorter than 60 seconds, there is a case where the drying is insufficient, and when it is longer than 3600 seconds, there is a case where the manufacturing takes time and the cost increases. The thickness of the layer obtained by natural drying or heating and drying of the condensate is usually about 0.01 to 3 μm, preferably 0.02 to 1 μm, more preferably 0.05 to 0.5 μm. When the thickness of the layer is 0.01 μm or less, a sufficient effect cannot be obtained, and if it is 3 μm or more, there is a possibility that defects are formed on the coating film.

(導電性構件及其製造方法) (Electrically conductive member and method of manufacturing the same)

關於作為本發明之電子零件之導電性構件所使用的含有金屬奈米粒子之導電性材料，可廣泛使用公知或市售之含有為形成導電性圖案而供給之金屬奈米粒子的膠體、油墨或糊劑。例如可列舉：MITSUBOSHI BELTING製造之銀糊劑MDot-SLP/H、Harima化成製造之NPS typeHP、大研化學製造之CA-2503-4。其中，就與縮合物之膜(溶膠-凝膠膜)之密合性而言，可較佳地使用MITSUBOSHI BELTING製造之銀糊劑MDot-SLP/H。金屬奈米粒子之金屬可較佳地使用銀或銅。 As the conductive material containing the metal nanoparticles used as the conductive member of the electronic component of the present invention, a known or commercially available colloid or ink containing the metal nanoparticles supplied to form the conductive pattern can be widely used. Paste. For example, the silver paste MDot-SLP/H manufactured by MITSUBOSHI BELTING, the NPS type HP manufactured by Harima Chemical Co., Ltd., and CA-2503-4 manufactured by Dayan Chemical Co., Ltd. are mentioned. Among them, in terms of adhesion to a film of a condensate (sol-gel film), a silver paste MDot-SLP/H manufactured by MITSUBOSHI BELTING can be preferably used. The metal of the metal nanoparticle can preferably use silver or copper.

含有金屬奈米粒子之油墨或糊劑於燒成後之膜厚並無特別限定，通常為0.1~30 μm，較佳為0.3~20 μm，更佳為0.5~15 μm。於含有金屬奈米粒子之油墨或糊劑於燒成後之膜厚薄於0.1 μm之情形時，有時無法充分獲得作為配線材料之性能。又，於燒成後之膜厚厚於30 μm厚之情形時，有時會產生裂痕。 The film thickness of the ink or paste containing the metal nanoparticles is not particularly limited, and is usually 0.1 to 30 μm, preferably 0.3 to 20 μm, more preferably 0.5 to 15 μm. When the thickness of the ink or paste containing the metal nanoparticles is less than 0.1 μm after firing, the performance as a wiring material may not be sufficiently obtained. Further, when the film thickness after firing is thicker than 30 μm, cracks may occur.

於本發明中，含有金屬奈米粒子之油墨或糊劑可藉由各種印刷方法或塗佈方式而形成圖案。例如，可使用能夠進行線狀塗佈之分注器印刷方法形成任意之線狀圖案，可使用熱量(thermal)、壓電、微型泵、靜電等各種方式之油墨噴射印刷方法形成任意之線狀或面狀圖案，可使用凸版印刷方法、軟板印刷方法、平版印刷方法、凹版印刷方法、凹版印刷方法、反轉套版印刷方法(Reverse off-set printing)、片式絲網印刷方法、滾網印刷方法等公知之各種印刷方法形成任意之圖案。又，亦可使用凹版輥方式、槽模(slot die)塗佈方式、旋塗方式等公知之各種塗佈方式，於積層基板之整面或一部分連續之面形成圖案，亦可使用間隔塗敷模塗機等於積層基板之整面或一部分斷續之面形成圖案，或者亦可使用浸漬塗佈方法(亦稱作浸塗方式(dip method))，使含有金屬奈米粒子之油墨或糊劑附著於積層基板整體。作為更佳之印刷方法，可列舉：油墨噴射印刷方法、軟板印刷方法、凹版印刷方法、反轉套版印刷方法、片式絲網印刷方法、滾網印刷方法。 In the present invention, the ink or paste containing the metal nanoparticles can be patterned by various printing methods or coating methods. For example, any linear pattern can be formed using a dispenser printing method capable of linear coating, and any linear pattern can be formed by various methods such as thermal, piezoelectric, micropump, and static electricity. Or a planar pattern, which may use a relief printing method, a flexographic printing method, a lithography method, a gravure printing method, a gravure printing method, a reverse off-set printing method, a chip screen printing method, and a roll pattern. Various printing methods such as a web printing method form an arbitrary pattern. Further, it is also possible to form a pattern on the entire surface or a part of the continuous surface of the laminated substrate by using various known coating methods such as a gravure roll method, a slot die coating method, and a spin coating method, and it is also possible to use a spacer coating. The die coater is formed by patterning the entire surface or a part of the intermittent surface of the laminated substrate, or may be an ink or paste containing metal nanoparticles by using a dip coating method (also referred to as a dip method). Adhered to the entire laminated substrate. As a more preferable printing method, an ink jet printing method, a soft-plate printing method, a gravure printing method, a reverse offset printing method, a sheet type screen printing method, and a roll screen printing method are mentioned.

藉由該等方法而圖案化之含有金屬奈米粒子之油墨或 糊劑可利用加熱進行燒成而形成導電性圖案。作為此時之燒成條件，雖然因使用之基材而有所限定，但為了優異之導電性及藉由進行燒結而增強圖案之強度，越高溫越好。尤其是於使用聚醯亞胺作為基材之情形時，較佳為於150~550℃下進行燒成，鑒於更優異之導電性之實現以及生產性，更佳為於200~300℃下進行燒成。 An ink containing metal nanoparticles coated by such methods or The paste can be fired by heating to form a conductive pattern. The firing conditions at this time are limited by the substrate to be used, but the higher the temperature, the better the conductivity and the strength of the pattern by sintering. In particular, when polyimide is used as the substrate, it is preferably calcined at 150 to 550 ° C, and more preferably at 200 to 300 ° C in view of more excellent conductivity and productivity. Burnt.

此處，表示使用含有金屬奈米粒子之油墨或糊劑作為導電層之情形。對於形成於基材之導電圖案，可進而藉由濕式鍍敷製程而進行金屬鍍敷。藉此，可進一步提高導電性構件之導電率。此時，使用之金屬只要為可進行濕式鍍敷者，則無任何限制，例如通常可使用眾所周知之無電鍍鎳製程。進而，可僅進行無電電鍍，亦可藉由電解鍍敷進而形成與由無電電鍍所形成之金屬不同之金屬作為電解鍍敷之電極層。 Here, the case where an ink or a paste containing metal nanoparticles is used as the conductive layer is shown. For the conductive pattern formed on the substrate, metal plating can be further performed by a wet plating process. Thereby, the electrical conductivity of the electroconductive member can be further improved. In this case, the metal to be used is not limited as long as it can be wet-plated. For example, a well-known electroless nickel plating process can be usually used. Further, electroless plating may be performed only, and a metal different from the metal formed by electroless plating may be formed as an electrode layer for electrolytic plating by electrolytic plating.

本發明之導電性構件由於使用本發明之積層基板，故而導電性圖案對基材的密合性較高，抑制金屬之遷移，且可獲得優異之導電性。尤其是，於使用含有三硫醇衍生物之塗敷液之情形時，可抑制導電時之離子遷移，故而較為有效。推測其原因在於，三硫醇衍生物之官能基捕獲游離之金屬離子。 Since the conductive member of the present invention uses the laminated substrate of the present invention, the conductivity of the conductive pattern to the substrate is high, the migration of the metal is suppressed, and excellent conductivity can be obtained. Especially, the use contains three In the case of a coating liquid of a thiol derivative, ion migration during conduction can be suppressed, which is effective. Presumably the reason is that three The functional group of the thiol derivative captures free metal ions.

進而，作為導入之三硫醇衍生物之另一個作用，可列舉導電性圖案對基材之密合性較高。其原因在於，基於藉由使上述燒成過程中之無機氧化物之結構產生變化而促進矽烷偶合劑之胺基的表面露出等之效果，使與作為油墨 或糊劑所含有之金屬奈米粒子彼此融合而形成之金屬被膜即導電性圖案之間的密合性進一步提高，抑制由摩擦或黏著性物質之脫失所引起之剝離。 Further, as the introduction three Another effect of the thiol derivative is that the conductivity pattern has high adhesion to the substrate. The reason for this is to promote the effect of exposing the surface of the amine group of the decane coupling agent by changing the structure of the inorganic oxide during the baking process, and to form the metal nanoparticles contained in the ink or the paste. The adhesion between the conductive films formed by the fusion of the metal films, which are formed by fusion, is further improved, and the peeling caused by the friction or the removal of the adhesive substance is suppressed.

本發明之導電性構件係藉由於積層有本發明之帶胺基之矽烷偶合劑與金屬烷氧化物之縮合物的積層基板上印刷或塗佈含有金屬奈米粒子之油墨或糊劑而獲得。該導電性構件可用作貼合於電漿顯示面板、飛機用液晶面板、汽車導航系統用液晶面板等各種平板顯示面板上而使用之透明電磁波遮罩。又，亦可用作RFID(Radio Frequency Identification，射頻識別)、無線LAN(Local Area Network，區域網絡)、利用電磁感應之供電、電磁波吸收等所使用之各種天線。進而，可用以製造各種平板顯示面板所使用之匯流電極或定址電極，或併用半導體油墨、電阻油墨或介電質油墨且反覆進行多次印刷而製作之電子電路等。 The electroconductive member of the present invention is obtained by printing or coating an ink or paste containing metal nanoparticles on a laminated substrate in which a condensate of an amine group-containing decane coupling agent of the present invention and a metal alkoxide is laminated. The conductive member can be used as a transparent electromagnetic wave mask used for bonding to various flat panel display panels such as a plasma display panel, an aircraft liquid crystal panel, and a liquid crystal panel for a car navigation system. Moreover, it can also be used as various antennas used for RFID (Radio Frequency Identification), wireless LAN (Local Area Network), power supply by electromagnetic induction, electromagnetic wave absorption, and the like. Further, it is possible to manufacture an electronic circuit or the like which is formed by using a bus electrode or an address electrode used in various flat panel display panels, or a semiconductor ink, a resistive ink or a dielectric ink, and repeatedly printing a plurality of times.

以下，藉由實施例更詳細地說明本發明，但本發明之內容並不限定於實施例。 Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples.

實施例 Example <導電性構件之密合性評價1：剝離強度> <Adhesion Evaluation of Conductive Member 1: Peel Strength>

以下，表示用以評價與銀糊劑之密合性之工序。 Hereinafter, the step for evaluating the adhesion to the silver paste will be described.

首先，對於下述實施例及比較例中所製作之導電性構件(長度為20 mm)，將切割成5 mm寬之雙面膠(日東電工製造之多用途用雙面接著膠帶No.5015)貼附於銀糊劑側，使用具備旋轉筒型支持器之拉伸試驗機(SHIMADZU製造之EZ Test/CE)並將雙面膠固定於旋轉筒之筒表面， 以夾頭挾持聚醯亞胺膜並沿90°之方向以500 mm/min之速度撕下(剝離)，藉此測定密著強度。 First, the conductive member (length: 20 mm) produced in the following examples and comparative examples was cut into a double-sided tape of 5 mm width (multi-purpose double-sided adhesive tape No. 5015 manufactured by Nitto Denko) Attached to the side of the silver paste, using a tensile tester (SEM Test/CE manufactured by SHIMADZU) equipped with a rotating cylinder type holder and fixing the double-sided tape to the surface of the drum of the rotating drum. The adhesion strength was measured by holding the polyimide film with a chuck and tearing (peeling) at a speed of 500 mm/min in the direction of 90°.

<導電性構件之密著強度評價方法2：柵格剝離> <Method for evaluating adhesion strength of conductive members 2: Grid peeling>

於印刷、燒成含有銀奈米粒子之油墨的導電構件表面，以1 mm間隔形成縱橫成直角之各11條切口，於黏貼黏著性膠帶(Nichiban股份有限公司製造之「Sellotape(註冊商標)」)後將其剝離，根據網目之剝離程度進行評價。作為剝離之表記方法，係設為剝離面積0%=10分，未達5%=8分，5%~未達15%=6分，15%~未達35%=4分，35%~未達65%=2分，65%以上=0分。 For the surface of a conductive member which is printed and fired with an ink containing silver nanoparticles, 11 slits are formed at right angles and at right angles at intervals of 1 mm to adhere the adhesive tape ("Sellotape (registered trademark)" manufactured by Nichiban Co., Ltd. After that, it was peeled off and evaluated according to the degree of peeling of the mesh. As a method of exfoliation, it is set as the peeling area 0% = 10 points, less than 5% = 8 points, 5% ~ less than 15% = 6 points, 15% ~ less than 35% = 4 points, 35% ~ Less than 65% = 2 points, more than 65% = 0 points.

<導電性構件之導電性之評價方法> <Method for Evaluating Conductivity of Conductive Member>

使用電阻率計Loresta GP(Mitsubishi Chemical Analytech公司製造)，藉由四端子法並將測定電壓設為10 V而測定導電率。 Conductivity was measured by a four-terminal method using a resistivity meter Loresta GP (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) and the measurement voltage was set to 10 V.

<塗敷液製備方法> <Method for preparing coating liquid> (實施例1) (Example 1)

首先，將作為帶胺基之矽烷偶合劑之(胺基乙基胺基甲基)苯基三甲氧基矽烷10.0 g溶解於乙二醇單-第三丁醚50.0 g中。於其中滴加水0.9 g，於60℃下進行1小時縮合反應，製備縮合物1溶液。其次，將作為金屬烷氧化物之四異丙氧化鈦1.9 g溶解於乙二醇單-第三丁醚160.5 g中。於其中滴加縮合物1溶液37.8 g，於30℃下進行4小時縮合反應，製備縮合物2溶液。繼而，藉由對所獲得之縮合物2溶液15.1 g與乙二醇單-第三丁醚4.9 g進行混合製備而製作實施 例1之塗敷液1。 First, 10.0 g of (aminoethylaminomethyl)phenyltrimethoxydecane as an amine group-containing decane coupling agent was dissolved in 50.0 g of ethylene glycol mono-tert-butyl ether. 0.9 g of water was added dropwise thereto, and a condensation reaction was carried out at 60 ° C for 1 hour to prepare a condensate 1 solution. Next, 1.9 g of tetraisopropoxide as a metal alkoxide was dissolved in 160.5 g of ethylene glycol mono-tert-butyl ether. 37.8 g of a condensate 1 solution was added dropwise thereto, and a condensation reaction was carried out at 30 ° C for 4 hours to prepare a condensate 2 solution. Then, it was prepared by mixing and preparing 15.1 g of the obtained condensate 2 solution and 4.9 g of ethylene glycol mono-tert-butyl ether. Coating liquid 1 of Example 1.

(實施例2) (Example 2)

以與實施例1相同之方式製備縮合物2溶液，將該縮合物2溶液14.8 g與乙二醇單-第三丁醚4.8 g混合，進而，添加0.4 g之溶液1，該溶液1係作為三硫醇衍生物之2,4,6-巰基-S-三1.6 g溶解於乙二醇單-第三丁醚78.6 g中而獲得者，並進行製備，藉此製作實施例2之塗敷液2。實施例2中之三硫醇衍生物相對於帶胺基之矽烷偶合劑、金屬烷氧化物及三硫醇衍生物之(固形物成分或有效成分)合計量的比例為2.0質量%。 A condensate 2 solution was prepared in the same manner as in Example 1, and 14.8 g of the condensate 2 solution was mixed with 4.8 g of ethylene glycol mono-tert-butyl ether, and further, 0.4 g of the solution 1 was added, and the solution 1 was used as three 2,4,6-mercapto-S-III of a thiol derivative 1.6 g of a solution obtained by dissolving in ethylene glycol mono-tert-butyl ether 78.6 g was prepared, and thereby the coating liquid 2 of Example 2 was produced. The third of the second embodiment a thiol derivative relative to an amine group-containing decane coupling agent, a metal alkoxide, and three The ratio of the total amount of the thiol derivative (solid content or active ingredient) was 2.0% by mass.

(實施例3) (Example 3)

以與實施例1相同之方式製備縮合物2溶液，將該縮合物2溶液14.9 g與乙二醇單-第三丁醚4.8 g混合，進而，添加0.3 g之溶液1並進行製備，藉此製作實施例3之塗敷液3。實施例3中之三硫醇衍生物相對於帶胺基之矽烷偶合劑、金屬烷氧化物及三硫醇衍生物之(固形物成分或有效成分)合計量的比例為1.5質量%。 A condensate 2 solution was prepared in the same manner as in Example 1, and 14.9 g of the condensate 2 solution was mixed with 4.8 g of ethylene glycol mono-tert-butyl ether, and further, 0.3 g of the solution 1 was added and prepared. The coating liquid 3 of Example 3 was produced. The third of the third embodiment a thiol derivative relative to an amine group-containing decane coupling agent, a metal alkoxide, and three The ratio of the total amount of the thiol derivative (solid content or active ingredient) was 1.5% by mass.

(比較例1) (Comparative Example 1)

於將四異丙氧化鈦10.1 g溶解於乙二醇單-第三丁醚19.9 g中而成之液體中，一面攪拌一面緩緩滴加60質量%之硝酸1.7 g、水0.6 g及乙二醇單-第三丁醚7.8 g之混合溶液，其後於30℃下攪拌4小時而獲得反應溶液。藉由於該液體中混合乙二醇單-第三丁醚102.2 g並進行攪拌而獲得比較例1之塗敷液4。 Into a liquid obtained by dissolving 10.1 g of titanium tetraisopropoxide in 19.9 g of ethylene glycol mono-tert-butyl ether, slowly adding 60% by mass of nitric acid 1.7 g, water 0.6 g and ethylene two while stirring. A mixed solution of 7.8 g of alcohol mono-tert-butyl ether was stirred at 30 ° C for 4 hours to obtain a reaction solution. The coating liquid 4 of Comparative Example 1 was obtained by mixing 102.2 g of ethylene glycol mono-tert-butyl ether in the liquid and stirring.

(比較例2) (Comparative Example 2)

藉由於比較例1所獲得之塗敷液4(9.8 g)中混合實施例2所使用之溶液1(0.2 g)而獲得比較例2之塗敷液5。 The coating liquid 5 of Comparative Example 2 was obtained by mixing the solution 1 (0.2 g) used in Example 2 with the coating liquid 4 (9.8 g) obtained in Comparative Example 1.

(比較例3) (Comparative Example 3)

將作為不帶胺基之矽烷偶合劑之甲基三甲氧基矽烷71.0 g、四乙氧基矽烷52.0 g、異丙醇97.1 g、0.1 N之硝酸9.6 g及水82.7 g依序混合，進行24小時水解縮合反應。 71.0 g of methyltrimethoxydecane, 52.0 g of tetraethoxydecane, 97.1 g of isopropanol, 9.6 g of nitric acid of 0.1 N, and 82.7 g of water were sequentially mixed as a decane coupling agent without an amine group. Hour hydrolysis condensation reaction.

藉由利用甲基異丁基酮1586.1 g及丙二醇單甲醚909.2 g之混合溶劑稀釋所獲得之反應液而獲得比較例3之塗敷液6。 The coating liquid 6 of Comparative Example 3 was obtained by diluting the obtained reaction liquid with a mixed solvent of methyl isobutyl ketone 1586.1 g and propylene glycol monomethyl ether 909.2 g.

(比較例4) (Comparative Example 4)

藉由於比較例2所獲得之塗敷液5(9.8 g)中混合實施例2所使用之溶液1(0.2 g)而獲得比較例4之塗敷液7。 The coating liquid 7 of Comparative Example 4 was obtained by mixing the solution 1 (0.2 g) used in Example 2 with the coating liquid 5 (9.8 g) obtained in Comparative Example 2.

(實施例7) (Example 7) 縮合物1溶液之製備 Preparation of condensate 1 solution

藉由將實施例1所獲得之縮合物1溶液(4.8 g)與乙二醇單-第三丁醚(25.3 g)混合並進行製備而製作實施例7之塗敷液8。 The coating liquid 8 of Example 7 was produced by mixing and preparing a condensate 1 solution (4.8 g) obtained in Example 1 and ethylene glycol mono-tert-butyl ether (25.3 g).

(實施例8) (Example 8) 縮合物3溶液之製備 Preparation of condensate 3 solution

將N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷(18.3 g)溶解於乙二醇單-第三丁醚(79.4 g)中。於其中滴加水(2.2 g)，於60℃下進行1小時縮合反應，製備縮合物3溶液。其次，將縮合物3溶液(4.8 g)與乙二醇單-第三丁醚(25.3 g)混合並進行製備，藉此製作實施例8之塗敷液9。 N-(2-Aminoethyl)-3-aminopropyltrimethoxydecane (18.3 g) was dissolved in ethylene glycol mono-tert-butyl ether (79.4 g). Water (2.2 g) was added dropwise thereto, and a condensation reaction was carried out at 60 ° C for 1 hour to prepare a condensate 3 solution. Next, the condensate 3 solution (4.8 g) and ethylene glycol mono-tert-butyl ether (25.3 g) The mixture was prepared and prepared, whereby the coating liquid 9 of Example 8 was produced.

(實施例11) (Example 11)

將(胺基乙基胺基乙基)苯乙基三甲氧基矽烷(5.8 g)溶解於乙二醇單-第三丁醚(28.7 g)中。於其中滴加水(0.5 g)，於60℃下進行1小時縮合反應，製備縮合物4溶液。其次，將四異丙氧化鈦(0.6 g)溶解於乙二醇單-第三丁醚(48.1 g)中。於其中滴加縮合物4溶液(11.3 g)，於30℃下進行4小時縮合反應，製備縮合物5溶液。進而，將縮合液5溶液(60.0 g)與乙二醇單-第三丁醚(19.5 g)混合並進行製備，藉此製作實施例11之塗敷液10。 (Aminoethylaminoethyl)phenethyltrimethoxydecane (5.8 g) was dissolved in ethylene glycol mono-tert-butyl ether (28.7 g). Water (0.5 g) was added dropwise thereto, and a condensation reaction was carried out at 60 ° C for 1 hour to prepare a condensate 4 solution. Next, tetraisopropoxide (0.6 g) was dissolved in ethylene glycol mono-tert-butyl ether (48.1 g). A condensate 4 solution (11.3 g) was added dropwise thereto, and a condensation reaction was carried out at 30 ° C for 4 hours to prepare a condensate 5 solution. Further, a solution of the condensation liquid 5 (60.0 g) and ethylene glycol mono-tert-butyl ether (19.5 g) were mixed and prepared, whereby the coating liquid 10 of Example 11 was produced.

(實施例12) (Embodiment 12)

將N-[2-[3-(三甲氧基矽基)丙基胺基]乙基]乙二胺(7.7 g)溶解於乙二醇單-第三丁醚(36.6 g)中。於其中滴加水(0.8 g)，於60℃下進行1小時縮合反應，製備縮合物6溶液。其次，將縮合物6溶液(4.8 g)與乙二醇單-第三丁醚(25.3 g)混合並進行製備，藉此製作實施例12之塗敷液11。 N-[2-[3-(Trimethoxymethyl)propylamino]ethyl]ethylenediamine (7.7 g) was dissolved in ethylene glycol mono-tert-butyl ether (36.6 g). Water (0.8 g) was added dropwise thereto, and a condensation reaction was carried out at 60 ° C for 1 hour to prepare a condensate 6 solution. Next, a condensate 6 solution (4.8 g) was mixed with ethylene glycol mono-tert-butyl ether (25.3 g) and prepared, whereby the coating liquid 11 of Example 12 was produced.

(實施例13) (Example 13)

將四異丙氧化鈦(0.6 g)溶解於乙二醇單-第三丁醚(48.1 g)中。於其中滴加縮合物6溶液(11.3 g)，於30℃下進行4小時縮合反應，製備縮合物7溶液。進而，將縮合液7溶液(22.6 g)與乙二醇單-第三丁醚(7.4 g)混合並進行製備，藉此製作實施例13之塗敷液12。 Tetraisopropoxide (0.6 g) was dissolved in ethylene glycol mono-tert-butyl ether (48.1 g). A condensate 6 solution (11.3 g) was added dropwise thereto, and a condensation reaction was carried out at 30 ° C for 4 hours to prepare a condensate 7 solution. Further, a solution of the condensation liquid 7 (22.6 g) and ethylene glycol mono-tert-butyl ether (7.4 g) were mixed and prepared, whereby the coating liquid 12 of Example 13 was produced.

<塗敷液成膜方法及銀糊劑印刷方法> <Coating liquid film forming method and silver paste printing method> (實施例4) (Example 4)

利用邁耶棒(松尾產業，No.1弦線形2密耳(76.2 μm)，濕膜厚6 μm)將實施例1之塗敷液1塗佈於聚醯亞胺膜(宇部興產股份有限公司製造之Upilex SGA，厚度35 μm)之單面，利用烘箱以200℃乾燥90秒鐘。其次，藉由絲網印刷對塗佈有塗敷液1之聚醯亞胺膜的兩個面中之塗佈有塗敷液1之面印刷MITSUBOSHI BELTING製造之銀糊劑MDot-SLP/H後，於送風烘箱中以250℃燒成30分鐘，藉此製作印刷有銀糊劑之導電性構件。此時，燒成後之糊劑厚度為10 μm。將藉由「導電性構件之密著強度之評價1」的密合性評價結果示於表1。 The coating liquid 1 of Example 1 was applied to a polyimide film using a Meyer rod (Songtail Industry, No. 1 string linear 2 mil (76.2 μm), wet film thickness 6 μm) (Ube Hiroshi Co., Ltd.) The company's Upilex SGA, 35 μm thick single side, was dried in an oven at 200 ° C for 90 seconds. Next, the silver paste MDot-SLP/H manufactured by MITSUBOSHI BELTING was printed on the surface of the two surfaces coated with the coating liquid 1 coated with the coating liquid 1 by screen printing. It was baked at 250 ° C for 30 minutes in a blowing oven to prepare a conductive member printed with a silver paste. At this time, the thickness of the paste after firing was 10 μm. The results of the adhesion evaluation by "Evaluation 1 of the adhesion strength of a conductive member" are shown in Table 1.

(實施例5) (Example 5)

使用實施例2之塗敷液2，以與實施例4同樣之方法形成塗膜，製作印刷有銀糊劑之導電性構件。此時，燒成後之糊劑厚度為10 μm。將評價結果示於表1。 Using the coating liquid 2 of Example 2, a coating film was formed in the same manner as in Example 4 to prepare a conductive member on which a silver paste was printed. At this time, the thickness of the paste after firing was 10 μm. The evaluation results are shown in Table 1.

(實施例6) (Example 6)

使用實施例3之塗敷液3，以與實施例4同樣之方法形成塗膜，製作印刷有銀糊劑之導電性構件。此時，燒成後之糊劑厚度為10 μm。將評價結果示於表1。 Using the coating liquid 3 of Example 3, a coating film was formed in the same manner as in Example 4 to prepare a conductive member on which a silver paste was printed. At this time, the thickness of the paste after firing was 10 μm. The evaluation results are shown in Table 1.

(比較例5) (Comparative Example 5)

使用比較例1之塗敷液4，以與實施例4同樣之方法形成塗膜，製作印刷有銀糊劑之導電性構件。此時，燒成後之糊劑厚度為10 μm。將評價結果示於表1。 Using the coating liquid 4 of Comparative Example 1, a coating film was formed in the same manner as in Example 4 to prepare a conductive member on which a silver paste was printed. At this time, the thickness of the paste after firing was 10 μm. The evaluation results are shown in Table 1.

(比較例6) (Comparative Example 6)

使用比較例2之塗敷液5，以與實施例4同樣之方法形成塗膜，製作印刷有銀糊劑之導電性構件。此時，燒成後之糊劑厚度為10 μm。將評價結果示於表1。 Using the coating liquid 5 of Comparative Example 2, a coating film was formed in the same manner as in Example 4 to prepare a conductive member on which a silver paste was printed. At this time, the thickness of the paste after firing was 10 μm. The evaluation results are shown in Table 1.

(比較例7) (Comparative Example 7)

使用比較例3之塗敷液6，以與實施例4同樣之方法形成塗膜，製作印刷有銀糊劑之導電性構件。此時，燒成後之糊劑厚度為10 μm。將評價結果示於表1。 Using the coating liquid 6 of Comparative Example 3, a coating film was formed in the same manner as in Example 4 to prepare a conductive member on which a silver paste was printed. At this time, the thickness of the paste after firing was 10 μm. The evaluation results are shown in Table 1.

(比較例8) (Comparative Example 8)

使用比較例4之塗敷液7，以與實施例4同樣之方法形成塗膜，製作印刷有銀糊劑之導電性構件。此時，燒成後之糊劑厚度為10 μm。將評價結果示於表1。 Using the coating liquid 7 of Comparative Example 4, a coating film was formed in the same manner as in Example 4 to prepare a conductive member on which a silver paste was printed. At this time, the thickness of the paste after firing was 10 μm. The evaluation results are shown in Table 1.

(比較例9) (Comparative Example 9)

將未塗佈塗敷液之聚醯亞胺膜(宇部興產股份有限公司製造之Upilex SGA，厚度35 μm)作為基材，以與實施例4同樣之方法印刷銀糊劑，製作印刷有銀糊劑之導電性構件。此時，燒成後之糊劑厚度為10 μm。將評價結果示於表1。 A silver paste was printed in the same manner as in Example 4, using a polyimide film (Upilex SGA manufactured by Ube Industries, Ltd., thickness: 35 μm) which was not coated with a coating liquid as a substrate, and silver was printed thereon. A conductive member of a paste. At this time, the thickness of the paste after firing was 10 μm. The evaluation results are shown in Table 1.

又，關於藉由柵格剝離之密合性之評價結果，分數為4分。 Further, regarding the evaluation result of the adhesion by the grid peeling, the score was 4 points.

(實施例9) (Example 9)

使用實施例7之塗敷液8，以與實施例4同樣之方法形成塗膜，製作印刷有銀糊劑之導電性構件。此時，燒成後之糊劑厚度為10 μm。將評價結果示於表1。 Using the coating liquid 8 of Example 7, a coating film was formed in the same manner as in Example 4 to prepare a conductive member on which a silver paste was printed. At this time, the thickness of the paste after firing was 10 μm. The evaluation results are shown in Table 1.

(實施例10) (Embodiment 10)

使用實施例8之塗敷液9，以與實施例4同樣之方法形成塗膜，製作印刷有銀糊劑之導電性構件。此時，燒成後之糊劑厚度為10 μm。將評價結果示於表1。又，導電率為4.5 Ω˙cm，顯示出較高之導電率。根據該結果，顯示藉由本方法製作之導電性構件兼具優異之密合性與導電性。 Using the coating liquid 9 of Example 8, a coating film was formed in the same manner as in Example 4 to prepare a conductive member on which a silver paste was printed. At this time, the thickness of the paste after firing was 10 μm. The evaluation results are shown in Table 1. Also, the conductivity is 4.5 Ω ̇cm, which shows a high electrical conductivity. From the results, it was revealed that the conductive member produced by the method has excellent adhesion and conductivity.

(實施例14) (Example 14)

使用實施例11之塗敷液10，以與實施例4同樣之方法形成塗膜，而製作印刷有銀糊劑之導電性構件。此時，燒成後之糊劑厚度為10 μm。形成之圖案未剝離，其剝離強度為1.07 N/mm。又，關於藉由柵格剝離之密合性之評價，形成之圖案未剝離，其分數為10分。進而，導電率為4.5 Ω˙cm，顯示出較高之導電率。根據該結果，顯示出藉由本方法製作之導電性構件兼具優異之密合性與導電性。 Using the coating liquid 10 of Example 11, a coating film was formed in the same manner as in Example 4 to prepare a conductive member printed with a silver paste. At this time, the thickness of the paste after firing was 10 μm. The formed pattern was not peeled off, and the peel strength was 1.07 N/mm. Further, regarding the adhesion by the grid peeling, the formed pattern was not peeled off, and the score was 10 minutes. Further, the electric conductivity was 4.5 Ω ̇cm, which showed a high electrical conductivity. From the results, it was revealed that the conductive member produced by the method has excellent adhesion and conductivity.

(實施例15) (Example 15)

使用實施例12之塗敷液11，以與實施例4同樣之方法形成塗膜，製作印刷有銀糊劑之導電性構件。此時，燒成後之糊劑厚度為10 μm。形成之圖案未剝離，其剝離強度為1.12 N/mm。又，導電率為4.5 Ω˙cm，顯示出較高之導電率。根據該結果，顯示藉由本方法製作之導電性構件兼具優異之密合性與導電性。 Using the coating liquid 11 of Example 12, a coating film was formed in the same manner as in Example 4 to prepare a conductive member on which a silver paste was printed. At this time, the thickness of the paste after firing was 10 μm. The formed pattern was not peeled off and its peel strength was 1.12 N/mm. Also, the conductivity is 4.5 Ω ̇cm, which shows a high electrical conductivity. From the results, it was revealed that the conductive member produced by the method has excellent adhesion and conductivity.

(實施例16) (Embodiment 16)

使用實施例13之塗敷液12，以與實施例4同樣之方法形成塗膜，製作印刷有銀糊劑之導電性構件。此時，燒成 後之糊劑厚度為10 μm。形成之圖案未剝離，其剝離強度為1.09 N/mm。又，導電率為4.5 Ω˙cm，顯示出較高之導電率。根據該結果，顯示藉由本方法製作之導電性構件兼具優異之密合性與導電性。 Using the coating liquid 12 of Example 13, a coating film was formed in the same manner as in Example 4 to prepare a conductive member on which a silver paste was printed. At this time, firing The paste thickness afterwards was 10 μm. The formed pattern was not peeled off, and the peel strength was 1.09 N/mm. Also, the conductivity is 4.5 Ω ̇cm, which shows a high electrical conductivity. From the results, it was revealed that the conductive member produced by the method has excellent adhesion and conductivity.

(實施例17) (Example 17)

除了將作為基材之聚醯亞胺膜自宇部興產股份有限公司製造之厚度35 μm之Upilex SGA變更為Toray Dupont股份有限公司製造之厚度25 μm之Kapton EN以外，以與實施例14相同之方法製作導電性構件。此時，燒成後之糊劑厚度為10 μm。關於藉由柵格剝離之密合性之評價，形成之圖案未剝離，其分數為10分。又，導電率為4.5 Ω˙cm。 The same procedure as in Example 14 was carried out except that the polyimine film as the substrate was changed from the 35 μm Upilex SGA manufactured by Ube Industries Co., Ltd. to the Kapton EN having a thickness of 25 μm manufactured by Toray Dupont Co., Ltd. Method A conductive member is produced. At this time, the thickness of the paste after firing was 10 μm. Regarding the evaluation of the adhesion by the grid peeling, the formed pattern was not peeled off, and the score was 10 minutes. Also, the electrical conductivity is 4.5 Ω ̇cm.

(參考例1) (Reference example 1)

除了將聚醯亞胺膜自宇部興產股份有限公司之厚度35 μm之Upilex SGA變更為Toray Dupont股份有限公司製造之厚度25 μm之Kapton EN以外，以與比較例9相同之方法製作印刷有銀糊劑之導電性構件。此時，燒成後之糊劑厚度為10 μm。關於藉由柵格剝離之密合性之評價結果，形成之圖案全部剝離，其分數為0分。 Silver was printed in the same manner as in Comparative Example 9 except that the Polyimide film was changed from Upilex SGA having a thickness of 35 μm from Ube Industries Co., Ltd. to Kapton EN having a thickness of 25 μm manufactured by Toray Dupont Co., Ltd. A conductive member of a paste. At this time, the thickness of the paste after firing was 10 μm. Regarding the evaluation results of the adhesion by the grid peeling, the formed patterns were all peeled off, and the score was 0 minutes.

如上所述，使用帶胺基之矽烷偶合劑之情形(實施例4、9、10、14、15、16)與使用不帶胺基之矽烷偶合劑之情形(比較例5、7)相比，導電性構件之密著強度較大。 As described above, the case of using an amine group-containing decane coupling agent (Examples 4, 9, 10, 14, 15, 16) was compared with the case of using a decane coupling agent without an amine group (Comparative Examples 5 and 7). The conductive member has a high adhesion strength.

又，使用進而利用三硫醇製作之縮合物的導電性構件之密著強度(實施例5、6)與未使用三硫醇之情形(實施例4)相比，導電性構件之密著強度更大。 Also, use and use three The adhesion strength of the conductive member of the condensate produced by the thiol (Examples 5 and 6) and the unused three In the case of the mercaptan (Example 4), the adhesion strength of the electroconductive member is larger.

(絕緣可靠性試驗) (Insulation reliability test)

於對以實施例10、14~17之方法製作之印刷有銀糊劑之導電性構件層壓遮罩層後，於85℃、85%RH之環境下施加52 V之偏壓電壓1000小時而進行絕緣可靠性試驗。作為判定標準，於絕緣電阻值成為未達1 M Ω時，判斷為產生故障。其後利用光學顯微鏡進行樹枝狀結晶之觀察。其結 果，確認各個導電構件於1000小時內均未產生樹枝狀結晶，不會產生故障。 After laminating the conductive layer on the conductive member printed with the silver paste prepared by the method of Examples 10 and 14 to 17, a bias voltage of 52 V was applied for 1000 hours at 85 ° C and 85% RH. Conduct insulation reliability test. As a criterion, when the insulation resistance value is less than 1 M Ω, it is determined that a failure has occurred. Thereafter, observation of dendritic crystals was carried out using an optical microscope. Its knot As a result, it was confirmed that each of the conductive members did not generate dendrites within 1000 hours, and no malfunction occurred.

(無電電鍍之評價) (Evaluation of electroless plating)

對印刷有以實施例5之方法製作之銀糊劑的導電性構件進行無電鍍鎳處理。利用場發射型掃描電子顯微鏡(FE-SEM，Field Emission Scanning Electron Microscopy)觀察所獲得之樣本之截面結構，將結果示於圖1。進而，對樣本中之鎳元素之分佈進行調查，將結果示於圖2。根據圖1及圖2，可確認於印刷之銀層上形成有厚度約為100 nm之鎳層，顯示可對形成於基材之導電圖案應用濕式鍍敷製程。 The electroconductive member on which the silver paste produced by the method of Example 5 was printed was subjected to electroless nickel plating treatment. The cross-sectional structure of the obtained sample was observed by a field emission scanning electron microscope (FE-SEM, Field Emission Scanning Electron Microscopy), and the results are shown in Fig. 1. Further, the distribution of the nickel element in the sample was investigated, and the results are shown in Fig. 2. According to Fig. 1 and Fig. 2, it was confirmed that a nickel layer having a thickness of about 100 nm was formed on the printed silver layer, and it was shown that a wet plating process can be applied to the conductive pattern formed on the substrate.

其次，對使用有填料之縮合物、積層基板及導電性構件之製造進行說明。 Next, the production of a condensate using a filler, a laminated substrate, and a conductive member will be described.

<添加有填料之塗敷液之製備方法> <Preparation method of coating liquid to which filler is added> (實施例18~實施例37) (Examples 18 to 37)

使用乙二醇單-第三丁醚作為溶劑，以固形物成分濃度成為2質量%之方式，按照表2所示比例依序添加實施例11所製作之塗敷液10及二氧化矽粒子漿料(宇部日東化成股份有限公司製造之「Hipresica」)，而製備作為縮合物溶液之實施例18~實施例37各自之塗敷液18~37。二氧化矽粒子漿料之二氧化矽粒子係使用表2所示之平均粒徑不同之5種(0.08 μm、0.15 μm、0.35 μm、0.68 μm、1.05 μm)。 The coating liquid 10 and the cerium oxide particle slurry prepared in Example 11 were sequentially added in the proportions shown in Table 2, using ethylene glycol mono-tertiary dibutyl ether as a solvent and a solid content concentration of 2% by mass. The coating liquids 18 to 37 of each of Examples 18 to 37 which are condensate solutions were prepared as "Hipresica" manufactured by Ube Nitto Chemical Co., Ltd.). The cerium oxide particles of the cerium oxide particle slurry were used in five types (0.08 μm, 0.15 μm, 0.35 μm, 0.68 μm, 1.05 μm) having different average particle diameters as shown in Table 2.

<添加有填料之塗敷液之成膜方法及銀糊劑印刷方法> <Film Forming Method of Filling Coating Liquid and Silver Paste Printing Method> (實施例38至57) (Examples 38 to 57)

分別使用實施例18至37所製作之塗敷液18至37，利用自動棒式塗佈機(松尾產業製造之K Control-Coater(電動塗佈機)，濕膜厚5~14 μm)塗佈於聚醯亞胺膜(宇部興產股份有限公司製造之Upilex SGA，厚度35 μm)之單面，於烘箱中以200℃乾燥90秒鐘。其次，藉由絲網印 刷對聚醯亞胺膜之兩個面中之塗佈有塗敷液之面印刷MITSUBOSHI BELTING製造之銀糊劑MDot-SLP/H而形成150 μm間距(絲網版之設計為線：45 μm/空間：105 μm)之梳型圖案電極後，使用送風烘箱以250℃乾燥30分鐘，藉此製作印刷有銀糊劑之導電性構件。 Each of the coating liquids 18 to 37 prepared in Examples 18 to 37 was coated with an automatic bar coater (K Control-Coater (electric coater) manufactured by Matsuo Industries, wet film thickness: 5 to 14 μm). One side of a polyimide film (Upilex SGA manufactured by Ube Industries, Ltd., thickness 35 μm) was dried in an oven at 200 ° C for 90 seconds. Second, by screen printing The silver paste MDot-SLP/H manufactured by MITSUBOSHI BELTING was printed on the coated surface of the two sides of the polyimide film to form a 150 μm pitch (the screen design was a line: 45 μm). / The space: 105 μm) of the comb-shaped pattern electrode was dried at 250 ° C for 30 minutes using a blown oven to prepare a conductive member printed with a silver paste.

(印刷性之評價) (evaluation of printability)

所獲得之導電性構件之印刷細線化率可根據下述式而算出：(印刷細線化率)(%)=(塗佈有塗敷液之膜之線寬)×100/(未塗佈塗敷液之膜之線寬)。式中，(塗佈有塗敷液之膜之線寬)係利用光學顯微鏡(尼康股份有限公司製造之ECLIPCE LV100)觀察20處之所獲得之導電性構件之銀油墨圖案之線寬(μm)，並根據其平均值而算出。又，式中之(未塗佈塗敷液之膜之線寬)係另外藉由除了未使用塗敷液以外與實施例38相同之方法，於聚醯亞胺膜上印刷銀糊劑而製作導電性構件，並藉由相同之方法而算出線寬。將其結果示於表3。此處，印刷細線化率小於100%者可製作線寬較細之電路，可提高積體密度，因此判斷為印刷性良好。 The printing thinning ratio of the obtained conductive member can be calculated according to the following formula: (printing thinning ratio) (%) = (line width of film coated with coating liquid) × 100 / (uncoated coating) The line width of the film of the dressing). In the formula, the line width (μm) of the silver ink pattern of the conductive member obtained at 20 places was observed by an optical microscope (ECLIPCE LV100 manufactured by Nikon Co., Ltd.). And calculated based on the average value. Further, in the formula (the line width of the film to which the coating liquid was not applied), a silver paste was printed on the polyimide film in the same manner as in Example 38 except that the coating liquid was not used. The conductive member was calculated and the line width was calculated by the same method. The results are shown in Table 3. Here, when the printing thinning ratio is less than 100%, a circuit having a thin line width can be produced, and the density of the integrated body can be improved. Therefore, it is judged that the printability is good.

(表面被覆率之評價) (Evaluation of surface coverage rate)

對於實施例38至57，使用光學顯微鏡(尼康股份有限公司製造之ECLIPCE LV100)求得所獲得之導電性構件之表面被膜率(%)。即，利用光學顯微鏡觀察印刷銀糊劑前之於聚醯亞胺膜上積層有縮合物之塗膜的積層基板之表面，對於該圖像，利用圖像處理軟體「ImageJ」以粒子部分 成為黑色之方式調整亮度或對比度而二值化為白色與黑色，藉由以黑色之面積、即粒子存在部分之面積除以總面積而表示為百分比。將其作為粒子之部分之表面被膜率(%)。將其結果示於表3。此處，表面被覆率較小之情形表示表面之凹凸相對較少。 For Examples 38 to 57, the surface coating ratio (%) of the obtained electroconductive member was determined using an optical microscope (ECLIPCE LV100 manufactured by Nikon Co., Ltd.). That is, the surface of the laminated substrate on which the coating film having the condensed product was laminated on the polyimide film before the printing of the silver paste was observed with an optical microscope, and the image processing software "ImageJ" was used as the particle portion for the image. In the form of black, the brightness or contrast is adjusted to be binarized to white and black, and is expressed as a percentage by dividing the area of black, that is, the area of the portion where the particles are present, by the total area. The surface film ratio (%) which is a part of the particles. The results are shown in Table 3. Here, the case where the surface coverage is small indicates that the unevenness of the surface is relatively small.

根據表3中所獲得之結果，製作整理印刷細線化率與表面被覆率之關係之圖表，將其示於圖3。大體上可確認，於表面被覆率較大之情形時，有可實現印刷線之細線化之傾向。 Based on the results obtained in Table 3, a graph showing the relationship between the finishing line thinning ratio and the surface coverage ratio is shown in Fig. 3. In general, it has been confirmed that when the surface coverage is large, there is a tendency that the printed line can be thinned.

[產業上之可利用性] [Industrial availability]

使用本發明之帶胺基之矽烷偶合劑與金屬烷氧化物的縮合物而製膜之積層基板可提供一種導電性構件，其係對使用含有金屬奈米粒子之油墨或糊劑而形成之導電性圖案之密合性較高，抑制金屬之遷移，且可獲得優異之導電性。 The laminated substrate formed by using the condensate of the amine-containing decane coupling agent of the present invention and the metal alkoxide can provide a conductive member which is electrically conductive by using an ink or paste containing metal nanoparticles. The adhesion of the pattern is high, the migration of the metal is suppressed, and excellent conductivity is obtained.

圖1係實施例5中，對印刷有銀糊劑之導電性構件進行無電鍍鎳處理之樣本的截面結構之照片。 Fig. 1 is a photograph showing a cross-sectional structure of a sample subjected to electroless nickel treatment on a conductive member printed with a silver paste in Example 5.

圖2係實施例5中，對印刷有銀糊劑之導電性構件進行無電鍍鎳處理之樣本的鎳元素之分佈之調查結果。 Fig. 2 is a result of investigation of the distribution of nickel elements in a sample subjected to electroless nickel treatment on a conductive member printed with a silver paste in Example 5.

圖3係對實施例38至57之印刷細線化率與表面被覆率之關係進行整理而成之圖表。 Fig. 3 is a graph showing the relationship between the printing thinning ratio and the surface coverage ratio of Examples 38 to 57.

Claims (16)

一種縮合物，其係使帶胺基之矽烷偶合劑與通式(I)所示之金屬烷氧化物進行水解-縮合反應而成之以M-O之重複單位作為主骨架者；R1 nM(OR2)m-n (I)(式中，R1為非水解性基，R2為碳數1~6之烷基，M表示選自Si、Ti、Al、Zr、Li、Na、Ca、Sr、Ba、Zn、B、Ga、Y、Ge、Pb、P、Sb、V、Ta、W、La、Nd、In之金屬原子群中之至少1種金屬原子，m為金屬原子M之價數且為3或4，於m為4之情形時，n為0~2之整數，於m為3之情形時，n為0~1之整數，於存在複數個R1之情形時，各R1彼此可相同亦可不同，於存在複數個OR2之情形時，各OR2彼此可相同亦可不同)。 A condensate obtained by subjecting an amine group-containing decane coupling agent to a metal alkoxide represented by the formula (I) to carry out a hydrolysis-condensation reaction with a repeating unit of MO as a main skeleton; R 1 n M ( OR 2 ) mn (I) (wherein R 1 is a non-hydrolyzable group, R 2 is an alkyl group having 1 to 6 carbon atoms, and M represents a selected from the group consisting of Si, Ti, Al, Zr, Li, Na, Ca, Sr At least one metal atom of a metal atom group of Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La, Nd, In, and m is a valence of the metal atom M and is 3 or 4, in m of the case 4, the n-represents an integer of 0 to 2, the time in the m of the case 3, the n-represents an integer of 0 to 1, in the presence of a plurality of R case of 1, each R 1 may be the same or different from each other, and in the case where a plurality of OR 2 are present, each OR 2 may be the same or different from each other). 如申請專利範圍第1項之縮合物，其中，上述帶胺基之矽烷偶合劑與上述金屬烷氧化物之比例為80質量%：20質量%~95質量%：5質量%。 The condensate of the first aspect of the invention, wherein the ratio of the amine group-containing decane coupling agent to the metal alkoxide is 80% by mass: 20% by mass to 95% by mass: 5% by mass. 如申請專利範圍第1項或第2項之縮合物，其中，上述帶胺基之矽烷偶合劑係選自由(胺基乙基胺基甲基)苯基三甲氧基矽烷、(胺基乙基胺基甲基)苯乙基三甲氧基矽烷及N-[2-[3-(三甲氧基矽基)丙基胺基]乙基]乙二胺所組成之群中之1種以上。 The condensate of claim 1 or 2, wherein the amine group-containing decane coupling agent is selected from the group consisting of (aminoethylaminomethyl)phenyltrimethoxynonane, (aminoethyl) One or more of the group consisting of aminomethyl)phenethyltrimethoxydecane and N-[2-[3-(trimethoxyindenyl)propylamino]ethyl]ethylenediamine. 如申請專利範圍第1項或第2項之縮合物，其中，上述金屬烷氧化物之M為Ti。 The condensate of claim 1 or 2, wherein M of the metal alkoxide is Ti. 如申請專利範圍第1項或第2項之縮合物，其中，上 述縮合物進而導入有三硫醇衍生物，三硫醇衍生物相對於帶胺基之矽烷偶合劑與金屬烷氧化物及三硫醇衍生物之(固形物成分或有效成分)合計量之比例為0.05~10質量%。 The condensate of claim 1 or 2, wherein the condensate is further introduced into three Thiol derivative, three a thiol derivative relative to an amine group-containing decane coupling agent and a metal alkoxide and three The ratio of the total amount of the thiol derivative (solid content or active ingredient) is 0.05 to 10% by mass. 如申請專利範圍第1項或第2項之縮合物，其中，上述縮合物進而包含填料。 The condensate of claim 1 or 2, wherein the condensate further comprises a filler. 一種積層基板用材料，係以申請專利範圍第1項至第6項中任一項之縮合物作為主成分者。 A material for a laminated substrate, which is a condensate of any one of claims 1 to 6 as a main component. 一種積層基板，係於基材表面積層有申請專利範圍第7項之積層基板用材料。 A laminated substrate is a material for a laminated substrate having a surface area of a substrate of the seventh application of the patent application. 如申請專利範圍第8項之積層基板，其中，上述基材為聚醯亞胺膜，上述聚醯亞胺膜之厚度為1~150 μm之範圍。 The laminated substrate according to claim 8, wherein the substrate is a polyimide film, and the polyimide film has a thickness of 1 to 150 μm. 一種導電性構件，係於申請專利範圍第8項或第9項之積層基板之積層有積層基板用材料之面印刷或塗佈導電性材料而形成有導電性圖案。 A conductive member is formed by printing or coating a conductive material on a surface of a laminated substrate for a laminated substrate of the eighth or ninth aspect of the patent application, and forming a conductive pattern. 如申請專利範圍第10項之導電性構件，其中，上述導電性材料含有金屬奈米粒子，並且上述金屬奈米粒子之金屬為銀或銅。 The conductive member according to claim 10, wherein the conductive material contains metal nanoparticles, and the metal of the metal nanoparticles is silver or copper. 一種縮合物之製造方法，具備以下步驟：使帶胺基之矽烷偶合劑於溶劑中進行縮合反應而獲得反應液之第1步驟；及使通式(I)所示之金屬烷氧化物與上述第1步驟中所獲得之反應液混合以進行縮合反應之第2步驟； R1 nM(OR2)m-n (I)(式中，R1為非水解性基，R2為碳數1~6之烷基，M表示選自Si、Ti、Al、Zr、Li、Na、Ca、Sr、Ba、Zn、B、Ga、Y、Ge、Pb、P、Sb、V、Ta、W、La、Nd、In之金屬原子群中之至少1種金屬原子，m為金屬原子M之價數且為3或4，於m為4之情形時，n為0~2之整數，於m為3之情形時，n為0~1之整數，於存在複數個R1之情形時，各R1彼此可相同亦可不同，於存在複數個OR2之情形時，各OR2彼此可相同亦可不同)。 A method for producing a condensate, comprising the steps of: subjecting an amine group-containing decane coupling agent to a condensation reaction in a solvent to obtain a reaction liquid; and subjecting the metal alkoxide represented by the formula (I) to the above The reaction liquid obtained in the first step is mixed to carry out the second step of the condensation reaction; R 1 n M(OR 2 ) mn (I) (wherein R 1 is a non-hydrolyzable group, and R 2 is a carbon number 1~ 6 alkyl, M is selected from the group consisting of Si, Ti, Al, Zr, Li, Na, Ca, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La At least one metal atom of the metal atom group of Nd or In, m is a valence of the metal atom M and is 3 or 4. When m is 4, n is an integer of 0 to 2, and m is 3 In the case of the case, n is an integer of 0 to 1. When there are a plurality of R 1 , each R 1 may be the same or different, and in the case where there are a plurality of OR 2 , each OR 2 may be the same. different). 如申請專利範圍第12項之縮合物之製造方法，進而具備於上述第2步驟所獲得之縮合物中添加三硫醇衍生物之第3步驟。 The method for producing a condensate according to claim 12, further comprising adding three to the condensate obtained in the second step The third step of the thiol derivative. 如申請專利範圍第12項或第13項之縮合物之製造方法，進而具備於上述第2步驟所獲得之縮合物中混合填料之第4步驟。 The method for producing a condensate according to claim 12 or 13, further comprising the fourth step of mixing the filler in the condensate obtained in the second step. 一種積層基板之製造方法，係藉由將申請專利範圍第1項至第6項中任一項之縮合物塗佈於基材表面而獲得於基材積層有縮合物之積層基板。 A method of producing a laminated substrate by applying a condensate according to any one of the first to sixth aspects of the invention to a surface of a substrate to obtain a laminated substrate having a condensate deposited on a substrate. 一種導電性構件之製造方法，係於申請專利範圍第8項或第9項之積層基板之積層有積層基板用材料之面印刷或塗佈導電性材料後，進行燒成而形成導電性圖案。 A method for producing a conductive member is a method in which a conductive material is printed or coated on a surface of a laminated substrate for a laminated substrate of the eighth or ninth aspect of the patent application, and then fired to form a conductive pattern.
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