WO2012165081A1 - 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

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 C_1-6 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

Condensate of amino group-containing silane coupling agent and metal alkoxide compound, laminated substrate material comprising the same, laminated substrate and conductive member, and methods for producing them

The present invention relates to a condensate of a silane coupling agent having an amino group and a metal alkoxide compound, a laminated substrate material containing the same as a main component, a laminated substrate and a conductive member, and methods for producing them.

In recent years, printable electronics using ink or paste containing metal nanoparticles has attracted attention.

Regarding the production of a conductive pattern by printing, conventionally, a high-viscosity conductive resin paste containing silver powder, a resin binder, and an organic solvent has been patterned using a printing method suitable for the high-viscosity paste. However, in recent years, attempts to pattern inks or pastes containing metal nanoparticles have been actively performed because of the difficulty in printing fine lines due to the large size of silver powder. In addition, since the metal nanoparticles are coated with a dispersant, the pattern formed by simply applying and drying does not have electrical conductivity. In order to fuse them, sintering at about 200 ° C. is required. Furthermore, since the dispersing agent is removed from the metal nanoparticles in the drying step, the metal nanoparticles are almost only a metal component in the sintered state after drying, and it is difficult to obtain adhesion with the base material.

Conventionally, not only glass and ceramics but also various flexible and foldable films such as polyethylene terephthalate film, polyethylene naphthalate film, polyimide film, polycarbonate film, etc. have been used as substrates for forming conductive patterns used in printing. Is done. However, it is difficult to cope with pattern miniaturization.
Then, the base material which processed the said base material is also disclosed. For example, in Patent Document 1, an aggregation promoting layer made of inorganic oxide fine particles is previously provided on the lower side of a metal ultrafine particle layer, and when a metal ultrafine particle solution is applied, fine particles formed by the lower inorganic oxide fine particles are formed. A substrate for forming a conductive pattern is disclosed that can promote aggregation of ultrafine metal particles mainly by selectively permeating a solvent into the pores.

JP 2003-229653 A

However, in the base material having these porous layers, in a wet process such as plating, the treatment liquid enters the porous layer and adversely affects the circuit characteristics, or when an ink containing silver as a main component is used. Has a problem in that migration during conduction is promoted, and adhesion of the formed conductive pattern to the porous layer is weak, so that the conductive pattern can be easily peeled off or disconnected due to rubbing or the like.

The present invention has been made in view of the problems as described above, and has an adhesive property to a base material of a conductive pattern formed using a conductive ink, particularly an ink or paste containing metal nanoparticles. Highly laminated substrate and conductive member that suppress metal migration and provide excellent conductivity, condensate of amino group-containing silane coupling agent and metal alkoxide compound to obtain them, and main component thereof An object of the present invention is to provide a laminated substrate material and a method for producing them.

In order to achieve the above object, the present inventors have conducted intensive research, and as a result, the MO repeating unit obtained by hydrolysis-condensation reaction between a silane coupling agent having an amino group and a metal alkoxide compound. A conductive member obtained by laminating a condensate having a main skeleton on a substrate surface as a laminated substrate material is based on a conductive pattern formed using a conductive ink, particularly an ink or paste containing metal nanoparticles. The present inventors have found that adhesion to a material is high, metal migration is suppressed, and excellent conductivity is obtained, and the present invention has been achieved.

That is, the present invention provides a condensation having as a main skeleton a MO repeating unit obtained by subjecting a silane coupling agent having an amino group to a metal alkoxide compound represented by the general formula (I) to a hydrolysis-condensation reaction. Related to things.

The present invention also relates to a laminated substrate material containing the condensate as a main component.

Furthermore, the present invention prints the conductive material containing metal nanoparticles on the surface of the multilayer substrate on which the multilayer substrate material is laminated on the surface of the base material and the multilayer substrate. The present invention relates to a conductive member that is applied to form a conductive pattern.

The present invention also provides a first step of obtaining a reaction solution by subjecting a silane coupling agent having an amino group to a condensation reaction in a solvent, a metal alkoxide compound represented by the general formula (I), and the first step. It is related with the manufacturing method of the condensate provided with the 2nd process of mixing and reacting the obtained reaction liquid.

Furthermore, the present invention provides a method for producing a laminated substrate in which a condensate is laminated on a base material by applying the condensate on the surface of the base material, and a laminated substrate material for the laminated substrate is laminated. It is related with the manufacturing method of the electroconductive member which prints after apply | coating or apply | coats the electroconductive material containing a metal nanoparticle to the surface, and forms and forms an electroconductive pattern.

As described above, according to the present invention, the conductive ink, in particular, the conductive pattern formed using the ink or paste containing metal nanoparticles is highly adhesive to the base material, and metal migration is suppressed. , And a laminate substrate and a conductive member capable of obtaining excellent conductivity, a condensate of a silane coupling agent having an amino group and a metal alkoxide compound for obtaining them, and a laminate substrate material comprising the same as a main component, and A manufacturing method thereof can be provided.

In Example 5, it is a photograph of the cross-sectional structure of the sample which performed the electroless nickel plating process with respect to the electroconductive member in which the silver paste was printed. In Example 5, it is the result of having investigated the distribution of the nickel element of the sample which performed the electroless nickel plating process with respect to the electroconductive member on which the silver paste was printed. In Examples 38-57, it is the graph which put together the relationship between a printing thinning rate and a surface coverage.

Hereinafter, the present invention will be described in detail.

(Condensate and production method thereof)
(Silane coupling agent having amino group)
In the condensate according to the present invention, since the silane coupling agent having an amino group can form a coordinate bond with a metal via the amino group, when the layer containing the silane coupling agent is fixed to a substrate, The adhesion between the conductive pattern formed by fusing the ink or paste containing metal nanoparticles through the firing of the metal nanoparticles and the substrate can be greatly improved.

It does not specifically limit as a silane coupling agent which has an amino group, For example, the following are mentioned.
N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldipropoxysilane N- (2-aminoethyl) -3-aminopropylmethyldiisopropoxysilane N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropyltriethoxysilane N- (2-aminoethyl) -3-aminopropyltripropoxysilane N- (2-aminoethyl) -3-aminopropyltriisopropoxysilane N- (2-aminoethyl) -3-aminoisobutyldimethylmethoxysilane N -(2-Aminoethyl) -3-aminoisobutylmethyldimethoxysilane N (2-aminoethyl) -11-aminoundecyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylsilanetriol 3-aminopropyltrimethoxysilane 3-aminopropyltriethoxysilane 3-triethoxysilyl- N- (1,3-Dimethyl-butylidene) propylamine N-phenyl-3-aminopropyltrimethoxysilane N, N-bis [3- (trimethoxysilyl) propyl] ethylenediamine (aminoethylaminoethyl) phenyltrimethoxysilane (Aminoethylaminoethyl) phenyltriethoxysilane (aminoethylaminoethyl) phenyltripropoxysilane (aminoethylaminoethyl) phenyltriisopropoxysilane (aminoethylaminomethyl) phenyltrimethoxysilane ( Minoethylaminomethyl) phenyltriethoxysilane (aminoethylaminomethyl) phenyltripropoxysilane (aminoethylaminomethyl) phenyltriisopropoxysilane N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane N -(Vinylbenzyl) -2-aminoethyl-3-aminopropylmethyldimethoxylane N-β- (N-vinylbenzylaminoethyl) -N-γ- (N-vinylbenzyl) -γ-aminopropyltrimethoxysilane N -Β- (N-di (vinylbenzyl) aminoethyl) -γ-aminopropyltrimethoxysilane N-β- (N-di (vinylbenzyl) aminoethyl) -N-γ- (N-vinylbenzyl) -γ -Aminopropyltrimethoxysilanemethylbenzylaminoethylamino Propyltrimethoxysilane dimethylbenzylaminoethylaminopropyltrimethoxysilane benzylaminoethylaminopropyltrimethoxysilane benzylaminoethylaminopropyltriethoxysilane 3-ureidopropyltriethoxysilane 3- (N-phenyl) aminopropyltrimethoxysilane N, N-bis [3- (trimethoxysilyl) propyl] ethylenediamine (aminoethylaminoethyl) phenethyltrimethoxysilane (aminoethylaminoethyl) phenethyltriethoxysilane (aminoethylaminoethyl) phenethyltripropoxysilane (aminoethylaminoethyl) Phenethyl triisopropoxysilane (aminoethylaminomethyl) phenethyl trimethoxysilane (aminoethylaminomethyl) Netyltriethoxysilane (aminoethylaminomethyl) phenethyltripropoxysilane (aminoethylaminomethyl) phenethyltriisopropoxysilane N- [2- [3- (trimethoxysilyl) propylamino] ethyl] ethylenediamine N- [2- [3- (Triethoxysilyl) propylamino] ethyl] ethylenediamine N- [2- [3- (tripropoxysilyl) propylamino] ethyl] ethylenediamine N- [2- [3- (triisopropoxysilyl) propylamino] Ethyl] ethylenediamine

These silane coupling agents having an amino group may be used alone or in combination of two or more. Moreover, you may use combining the silane coupling agent which has an amino group, and the silane coupling agent which does not have an amino group.
In addition, the condensate according to the present invention has heat resistance when considering the formation of a conductive pattern by sintering an ink or paste containing metal nanoparticles on an organic substrate such as a polyimide film at a high temperature. is important. Therefore, it is effective to use a silane coupling agent having high heat resistance as the silane coupling agent as a raw material of the condensate. That is, the condensate of the silane coupling agent does not undergo thermal decomposition or sublimation during high-temperature treatment after printing a conductive material described later, and maintains its film form and its function (heat resistance, basicity, etc.). In many cases, it is required that the adhesiveness to a material or a conductive member does not deteriorate.
From this viewpoint, among the silane coupling agents mentioned above, (aminoethylaminomethyl) phenyltrimethoxysilane is preferable because of its high heat resistance. Further, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane is preferable because of its low cost. Considering the overall adhesion to organic substrates such as polyimide films and conductive patterns obtained by sintering conductive materials, and the high heat resistance, (aminoethylaminomethyl) phenyltrimethoxysilane preferable. In addition, from the viewpoint of adhesion to the conductive pattern, the number of amino groups of the silane coupling agent is preferably 2 or more, for example, 2 or 3. Among such silane coupling agents having two or more amino groups in the molecule, for example, (aminoethylaminomethyl) phenethyltrimethoxysilane and N- [2- [3- (trimethoxysilyl) propylamino] Ethyl] ethylenediamine is also preferably used. Among these, (aminoethylaminomethyl) phenethyltrimethoxysilane is particularly preferable from the viewpoint of adhesion.
Silane coupling agents having an amino group include (aminoethylaminomethyl) phenyltrimethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane and N- [2- [3- (trimethoxysilyl) propylamino] ethyl]. It is preferable that it is 1 or more types selected from the group which consists of ethylenediamine.

The concentration of the silane coupling agent containing an amino group in the condensate according to the present invention is not particularly limited, but is preferably 40 to 99% by mass, more preferably 60 to 98% by mass, and particularly preferably 80 to 95%. % By mass.

(Metal alkoxide)
The metal alkoxide compound used for the condensate according to the present invention is represented by the following general formula (I).

In the general formula (I), M is Si, Ti, Al, Zr, Li, Na, Ca, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W. And at least one metal atom selected from the group of metal atoms of La, Nd, and In.

M is preferably Si, Ti, Al, Zr, and particularly preferably Ti because it is generally easy to obtain and synthesize.

In the above general formula (I), R ¹ represents a non-hydrolyzable group, for example, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, a (meth) acryloyloxy group, an amino group or an epoxy group. And 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.

Here, the alkyl group having 1 to 20 carbon atoms is preferably one having 1 to 10 carbon atoms, and the alkyl group may be linear, branched or cyclic. In addition to this, functional groups containing substituents such as hydroxyl groups, thiols, and imidazoles can 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, sec-butyl group, tert-butyl group, pentyl group, hexyl group Octyl group, cyclopentyl group, cyclohexyl group and the like.
As the alkyl group having 1 to 20 carbon atoms having a (meth) acryloyloxy group, amino group or epoxy group, an alkyl group having 1 to 10 carbon atoms having the above substituent is preferable, and this alkyl group is linear, It may be either branched or annular. Examples of the alkyl group having this substituent include γ-acryloyloxypropyl group, γ-methacryloyloxypropyl group, γ-aminopropyl group, 3- (2-aminoethylamino) propyl group, 3-feraminopropyl group. , Γ-glycidoxypropyl group, 3,4-epoxycyclohexyl group and the like.
The alkenyl group having 2 to 20 carbon atoms is preferably an alkenyl group having 2 to 10 carbon atoms, and this alkenyl group may be linear, branched or cyclic. Examples of the alkenyl group include vinyl group, allyl group, butenyl group, hexenyl group, octenyl group and the like.
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.
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.

On the other hand, R ² is an alkyl group having 1 to 6 carbon atoms, which may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, Examples include isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl group and the like.

In the metal alkoxide compound represented by the general formula (I), m is the valence of the metal atom M and is 3 or 4, n is an integer of 0 to 2 when m is 4, m When is 3, it is an integer from 0 to 1. When R ¹ are a plurality, each R ¹ may be the same as each other or different, and if the OR ² there are a plurality, each OR ² may be the same with each other, or different Also good.

Examples of the alkoxide compound in the case where M is tetravalent Ti, Si, Zr, m is 4, and n is an integer of 0 to 3 in the metal alkoxide compound represented by the above general formula (I) Are tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium (titanium tetraisopropoxide), tetra-n-butoxy titanium, tetraisobutoxy titanium, tetra-sec-butoxy titanium, tetra- tert-butoxy titanium, methyl trimethoxy titanium, methyl triethoxy titanium, methyl tripropoxy titanium, methyl triisopropoxy titanium, ethyl trimethoxy titanium, ethyl triethoxy titanium, propyl triethoxy titanium, butyl trimethoxy titanium, phenyl trimethoxy titanium , Enyltriethoxytitanium, vinyltrimethoxytitanium, vinyltriethoxytitanium, γ-glycidoxypropyltrimethoxytitanium, γ-acryloyloxypropyltrimethoxytitanium, γ-methacryloyloxypropyltrimethoxytitanium, dimethyldimethoxytitanium, methylphenyldimethoxy Examples include titanium and the like, and compounds in which titanium in the above compound is replaced with silane or zirconium. Of these, titanium tetraisopropoxide is preferably used.

Examples of the alkoxide compound in the case where the metal alkoxide compound represented by the general formula (I) is trivalent aluminum, m is 3, and n is an integer of 0 to 1, Trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, triisopropoxyaluminum, tri-n-butoxyaluminum, triisobutoxyaluminum, tri-sec-butoxyaluminum, tri-tert-butoxyaluminum, methyldimethoxyaluminum, Examples thereof include methyldiethoxyaluminum, methyldipropoxyaluminum, ethyldimethoxyaluminum, ethyldiethoxyaluminum, and propyldiethoxyaluminum.

These metal alkoxide compounds may be used alone or in combination of two or more.

In the condensate according to the present invention, the ratio between the silane coupling agent and the metal alkoxide compound is preferably 80:20 to 95: 5 in the case of mass%.

(Preparation of condensate)
In the present invention, the silane coupling agent having an amino group and a metal alkoxide compound are subjected to hydrolysis-condensation reaction by a sol-gel reaction to repeat MO (M is the same as described above; hereinafter the same). A condensate having the main skeleton as a unit is prepared. The method for producing a condensate according to the present invention is represented by a first step of obtaining a reaction solution by subjecting a silane coupling agent having an amino group to a condensation reaction in a solvent such as water, and the general formula (I). A second step of mixing and reacting the metal alkoxide compound and the reaction solution obtained in the first step.

In the condensation reaction in the first step and the second step, examples of the solvent include polar solvents such as alcohol-based, cellosolve-based, ketone-based, ether-based, glycol ether-based, preferably glycol ether-based from the viewpoint of compatibility. Preferably, ethylene glycol mono-t-butyl ether is used. In the condensation reaction, a silane coupling agent or alkoxide compound having an amino group is used in the above solvent, and water or an acid such as hydrochloric acid, sulfuric acid or nitric acid, or a cation exchange resin as a solid acid, usually at 0 to 70 ° C. Preferably, the hydrolysis treatment is carried out at a temperature of 20 to 60 ° C., and when a solid acid is used, the solid acid is removed, and then the solvent is distilled off or added as desired. By the above reaction, a condensate having a repeating unit of MO as the main skeleton can be obtained.

In the condensate having the MO repeating unit as the main skeleton, the amino group of the silane coupling agent having an amino group and the OH group generated by hydrolysis of OR ² in the general formula (I) remain. It also has excellent adhesion to organic materials such as polyimide films, cover materials and bonding sheets, and inorganic materials such as metals.

The method for producing a condensate according to the present invention preferably further includes a third step of adding a triazine thiol derivative to the reaction solution obtained in the first step. Thereby, the electroconductive member using the condensate in which the triazine thiol derivative is introduced can further increase the adhesion strength. Here, “triazine thiol derivative is introduced into the condensate” mainly means a form in which the triazine thiol derivative is simply contained in the condensate. However, the triazine thiol derivative chemically reacts with the condensate or is distributed. Forms that form coordinate bonds are also included in the introduction referred to here.

In the third step, the MO repeating unit obtained by hydrolysis-condensation reaction of the silane coupling agent having an amino group and the metal alkoxide compound by sol-gel reaction after the second step is used as the main skeleton. It is preferable to add a triazine thiol derivative to the condensate to be reacted. In the third step, the silane coupling agent having an amino group, the metal alkoxide compound, and the triazine thiol derivative may be added and reacted simultaneously with the second step. Further, in the third step, the metal alkoxide compound may be added and reacted before the second step, that is, after the triazine thiol derivative is added and reacted with the silane coupling agent having an amino group. Furthermore, in the third step, a triazine thiol derivative may be added and reacted simultaneously with the first step, that is, before the silane coupling agent having an amino group undergoes a condensation reaction.

Examples of the triazine thiol derivative include compounds represented by the following general formula (II) and / or general formula (III) and / or general formula (IV).

In the general formulas (II), (III), and (IV), R represents —SR ³ , —OR ³ , —NHR ³ , NR ³ R ⁴ , or the like. R ³ and R ⁴ are each independently a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, phenyl group, aralkyl group, alkenyl group, cycloalkyl group, unsaturated alkyl group, fluorinated alkyl group, fluorinated phenyl group Represents a fluorinated aralkyl group or a fluorinated unsaturated alkyl group, and R ³ and R ⁴ may be connected at the other end to form a ring. X ¹ and X ² each independently represent a residue selected from a hydrogen atom, a malonic acid derivative, a succinic acid derivative, a methyl succinic acid derivative, a propionic acid derivative, a ketone derivative, a sulfone derivative, a nitro derivative, and an acetyl derivative. However, neither X ¹ nor X ² is a hydrogen atom.

Among these triazine thiol derivatives, at least 2 of the triazine ring represented by the general formula (II) having a small molecular weight in compatibility with various metal alkoxide condensates, particularly compatibility with high concentration metal alkoxide condensates. Triazine thiol derivatives in which two carbons are substituted with a thiol group (—SH) are preferred. Among them, the case where all the carbons of the triazine ring are substituted with sulfur is particularly preferable, and 2,4,6-trimercapto-triazine in which all the carbons are substituted with a thiol group (—SH) is particularly preferable. In this case, since the molecular weight is the smallest, the coordination between the metal and the thiol of various metal alkoxide condensates from a low concentration to a high concentration is performed efficiently and uniformly. Such a triazine thiol compound is relatively easily available as an industrial product and is extremely effective in terms of material cost.

These triazine thiol derivatives can be used alone or in admixture of two or more. The ratio of the triazine thiol derivative silane coupling agent having an amino group, the metal alkoxide compound, and the triazine thiol derivative to the total amount (solid content or active ingredient) is preferably 0.05 to 10% by mass.

The method for producing a condensate according to the present invention may further include a fourth step of mixing a filler. Thereby, an uneven structure can be constructed on the film surface of the condensate, and bleeding of the conductive material during printing can be prevented. As a result, a fine line pattern can be printed. The filler preferably has a primary particle size in the range of 30 to 1500 nm. Here, the primary particle size can be obtained by calculating the average particle size of the particles from an electron microscope image obtained by diluting the filler dispersion and observing with a scanning electron microscope. When the primary particle size is smaller than 30 nm, the effect on the printability during printing of the conductive material is small. Moreover, when the primary particle diameter is larger than 1500 nm, the particles are likely to settle when a solution is prepared, and it becomes somewhat difficult to form a uniform film.

As the filler, either an inorganic filler or an organic filler can be used. Examples of the inorganic filler include silica, silica fine particles, colloidal silica, alumina, colloidal alumina, colloidal titania, zirconia sol, calcium silicate, zeolite, kaolinite, halloysite, muscovite, talc, calcium carbonate, calcium sulfate, boehmite and the like. be able to. Of these, colloidal silica is preferably used. Specific examples of silica include LEVASIL series (manufactured by HC Starck Co., Ltd.), methanol silica sol, 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 (manufactured by Nissan Chemical Industries, Ltd.), Quatron PL series (Fuso Chemical Co., Ltd.), OSCAL series (manufactured by JGC Catalysts & Chemicals Co., Ltd.), and high plesica (manufactured by Ube Nitto Kasei Co., Ltd.). Among these, from the viewpoint of dispersibility of the filler in the above-mentioned condensate solution, high plesica is most preferably used. Moreover, a polyimide particle etc. are mentioned as an organic filler.

The ratio of the filler to the silane coupling agent having an amino group is preferably in the range of 10 to 80% by mass of filler, more preferably 20 to 70% by mass, and further preferably 30 to 70% by mass. The ratio of the filler to the silane coupling agent having an amino group and the metal alkoxide compound is preferably in the range of 10 to 70% by mass of filler, more preferably 20 to 70% by mass, and even more preferably 30 to 60% by mass. preferable.
When the ratio of the filler to be added is smaller than the above ratio, there may be a case where a sufficient effect cannot be expected on the printability when printing the conductive material. 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 has a porous structure, and the electrical characteristics may be slightly deteriorated. Furthermore, there is a possibility that the liquid stays on the porous membrane surface in the wet process.

Further, the surface coverage of the surface of the condensate film using the filler is preferably in the range of 10 to 100%, more preferably 30 to 100%, and even more preferably 50 to 100%. Thereby, the thinning of the printing line of the electroconductive member mentioned later is realizable. Here, the surface coverage refers to the exclusive rate of the filler with respect to the entire surface of the condensate film. The method for measuring the surface coverage is that an image obtained by observing the surface of the coating film obtained by coating the condensate on a substrate such as a polyimide film with an optical microscope is white and the particle portion is black with image processing software. It is determined by binarizing to black and determining the occupied area ratio (%) of the filler portion. A specific method for measuring the surface coverage will be described in the Examples section.
Although the reason why the surface coverage of the surface of the condensate film using the filler realizes thinning of the printing line of the conductive member is not necessarily clear, by using filler particles, the uneven structure is It is thought that ink bleeding such as silver paste formed on the surface of the coating film and printed with this uneven structure is stopped. However, in consideration of the wet process and migration during conduction, the condition is that it does not become porous.

In the method for producing a condensate according to the present invention, the fourth step was obtained after the second step, that is, a hydrolysis-condensation reaction of a silane coupling agent having an amino group and a metal alkoxide compound by a sol-gel reaction. It is preferable to mix a filler with a condensate having a repeating unit of MO as a main skeleton. In the fourth step, the silane coupling agent having an amino group, the metal alkoxide compound, and the filler may be mixed and reacted simultaneously with the second step. Furthermore, in the fourth step, the filler may be mixed and reacted simultaneously with the first step, that is, before the silane coupling agent having an amino group undergoes a condensation reaction.
About the form with which a filler is mixed, the 3rd process made to react by adding a triazine thiol derivative can be abbreviate | omitted. Moreover, about the form which mixes a filler, the 2nd process made to react by adding a metal alkoxide compound can also be abbreviate | omitted. That is, a condensate can also be obtained from a silane coupling agent having an amino group and a filler.

In the method for producing a condensate according to the present invention, a method for supplying a triazine thiol derivative and a filler will be described. In the present invention, in the fourth step, a filler may be added after the second and third steps, that is, in the reaction of the condensate with the triazine thiol derivative. In the third step, the triazine thiol derivative may be added to the mixture of the condensate and the filler after the second and fourth steps. Further, in the third and fourth steps, the triazine thiol derivative and the filler may be added to the condensate at the same time after the second step. Further, the second, third, and fourth steps may be simultaneously performed, that is, a silane coupling agent having an amino group, a metal alkoxide compound, a triazine thiol derivative, and a filler may be mixed and reacted at the same time.

(Laminated substrate material)
The condensate according to the present invention can be suitably used as a laminated substrate material. The condensate produced by the above production method can be obtained in the form of a coating liquid containing a condensate having a repeating unit of MO as a main skeleton at a predetermined concentration by the hydrolysis-condensation reaction. When using the condensate which concerns on invention as a laminated substrate material, it is preferable to apply | coat to the base-material surface in the state of a coating liquid. Further, the coating liquid can be adjusted to a predetermined concentration after obtaining the condensate. The concentration of the condensate in the coating solution is not particularly limited as long as it is a concentration that can be applied to the surface of the substrate, but is usually 0.05 to 35% by mass, preferably 0.1 to 20% by mass. %, More preferably 0.2 to 10% by mass. When the concentration of the condensate exceeds 35% by mass, the stability of the liquid is lowered, that is, the liquid is easily gelled, and the storage period (pot life) may be deteriorated. Further, if the concentration of the condensate is less than 0.05% by mass, sufficient effects may not be obtained.
The laminated substrate material according to the present invention is produced as described above, and contains the condensate according to the present invention as a main component. A main component means 50 mass% or more of the condensate in the laminated substrate material, for example.

In the laminated substrate material according to the present invention, the adhesion between the conductive pattern and the substrate can be greatly improved by using the silane coupling agent having an amino group, which is very useful. Although this cause is not necessarily clear, it is estimated that the silane coupling agent which has an amino group forms the coordinate bond with the metal via the amino group. Moreover, the said metal alkoxide compound is effective in order that the said layer laminated | stacked on the base-material surface may be uniformly laminated | stacked by fixed thickness, without generating a crack.

In the multilayer substrate material according to the present invention, it is more preferable if the triazine thiol derivative can be immobilized in the coating solution. When using a coating solution containing a triazine thiol derivative together with an organic base material such as a polyimide film or a metal alkoxide condensate having adhesiveness to a conductive pattern formed by sintering conductive ink as a coating solution As compared with the case of the coating liquid containing only the metal alkoxide condensate, the effect of improving the adhesion strength is obtained, and the amount of the metal alkoxide condensate used can be reduced. This is extremely effective not only for reducing costs but also for reducing processing troubles such as coating spots in the coating process.

These triazine thiol derivatives can be used alone or in admixture of two or more. The triazine thiol derivative is used in an amount sufficient to improve the adhesion between the metal and the organic substrate. The blending amount of the triazine thiol derivative used in the present invention is preferably 0.0001 to 0.3% by mass, and preferably 0.0005 to 0.25% by mass with respect to the total amount of the coating solution. More preferably, the content is 0.001 to 0.2% by mass. When the amount is larger than 0.3% by mass, the adhesion between the metal and the organic substrate tends to be reduced. The reason for this is not necessarily clear, but it is presumed that the triazine thiol derivative has low solubility, and thus is precipitated depending on the solvent composition. On the other hand, when the amount is less than 0.0001% by mass, the adhesive force may not be sufficiently improved as compared with the case where the triazine thiol derivative is not used.

In the above description, the condensate having a main skeleton of a MO repeating unit obtained by hydrolysis-condensation reaction between a silane coupling agent having an amino group and a metal alkoxide compound has been described. It is also possible to increase the adhesion of the conductive pattern to the substrate even for the condensate using only the silane coupling agent having an amino group.

As an example of such a silane coupling agent having an amino group, since the number of functional groups that can be expected to adhere to a metal is large, the silane coupling agent described above can be preferably used.
Of these, (aminoethylaminomethyl) phenyltrimethoxysilane is more preferably used because of its high heat resistance, and N- (2-aminoethyl) 3-aminopropyltrimethoxysilane is more preferable because of its low cost. Considering the overall adhesion to organic substrates such as polyimide films and conductive patterns obtained by sintering conductive materials, and the high heat resistance, (aminoethylaminomethyl) phenyltrimethoxysilane preferable.
The number of amino groups in the silane coupling agent is preferably 2 or more from the viewpoint of peel strength. As such a silane coupling agent having two amino groups, (aminoethylaminomethyl) phenyltrimethoxysilane and N- (2-aminoethyl) 3-aminopropyltrimethoxysilane mentioned above are preferable. When these silane coupling agents are used, the adhesion of the conductive pattern to the substrate can be further increased without using a metal alkoxide compound. Furthermore, from the viewpoint of adhesiveness to the conductive pattern, the number of amino groups of the silane coupling agent is preferably 2 or more, for example, 2 or 3. Among such silane coupling agents having two or more amino groups in the molecule, for example, (aminoethylaminomethyl) phenethyltrimethoxysilane and N- [2- [3- (trimethoxysilyl) propylamino] Ethyl] ethylenediamine is also preferably used. Among these, (aminoethylaminomethyl) phenethyltrimethoxysilane is particularly preferable from the viewpoint of adhesion. Even when these silane coupling agents are used, the adhesion of the conductive pattern to the substrate can be further increased without using a metal alkoxide compound.
Silane coupling agents having an amino group include (aminoethylaminomethyl) phenyltrimethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane and N- [2- [3- (trimethoxysilyl) propylamino] ethyl]. It is preferable that it is 1 or more types selected from the group which consists of ethylenediamine.

(Laminated substrate and manufacturing method thereof)
The present invention is characterized in that the laminated substrate material is a laminated substrate laminated on the surface of a base material. The laminated substrate according to the present invention can be obtained by coating the coating liquid on the substrate surface.

In the laminated substrate according to the present invention, the base material to be used is not particularly limited, and any of an organic base material and an inorganic base material can be used as long as the effects of the invention are not impaired. Organic base materials include polyolefin resins such as polyethylene and polypropylene, vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers, epoxy resins, polyarylate, polysulfone, polyethersulfone, polyimide, fluororesin, and phenoxy. Examples include resins, triacetyl cellulose, polyethylene terephthalate, polyimide, polyphenylene sulfide, polyethylene naphthalate, polycarbonate, films made of various resins such as cellophane, nylon, polystyrene resin, ABS resin, etc. It is done. 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 in addition to the above. Moreover, these base materials can be combined suitably according to a use, for example, the flexible printed circuit board material which laminated | stacked copper foil and the polyimide, and the polyolefin resin coating paper which laminated | stacked paper and polyolefin resin can be used. Furthermore, an object molded into a three-dimensional shape using these resins or the like can also be used as a support.

Among these, in particular, when an ink or paste containing metal nanoparticles is sintered, a low resistance can be realized by processing at a high temperature, and a polyimide film is preferable from the viewpoint of heat resistance, dimensional stability, mechanical properties, and the like. .
Such a polyimide film preferably has a glass transition temperature (Tg) of 200 ° C. or higher, more preferably 250 ° C. or higher, and particularly preferably 300 ° C. or higher. The Tg can be suitably obtained from the peak temperature of tan δ or the peak temperature of the loss elastic modulus E ″ in the solid viscoelastic spectrum.
An aromatic polyimide film can be used as such a polyimide film.
A polyimide film can be obtained from the acid anhydride component and diamine component which comprise a polyimide film. Examples of the acid anhydride component include, but are not limited to, those containing 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride and the like as main components. Examples of the diamine component include, but are not limited to, those containing paraphenylenediamine, 4,4-diaminodiphenyl ether as a main component. Specific examples of the polyimide film include, for example, a trade name “Upilex (S or R)” (registered trademark, manufactured by Ube Industries), a trade name “Kapton” (registered trademark, manufactured by Toray DuPont), and a product. Examples thereof include polyimide films such as “Apical” (registered trademark, manufactured by Kaneka Corporation).

When a plastic film is used as the substrate, there is no particular limitation on the thickness of the substrate, and it is appropriately selected depending on the application, but it is usually about 1 to 300 μm, preferably 2 to 200 μm, and still more preferably. 3 to 150 μm. If it is thinner than 1 μm, the operability tends to be poor, and if it is 300 μm or more, it becomes rigid and the operability is lowered, the weight is increased, and the cost is further increased.

The above-mentioned base material is intended to improve wettability with a coating liquid containing a condensate having a main skeleton of a MO repeating unit obtained by subjecting a metal alkoxide compound formulated on the surface to hydrolysis-condensation reaction. Or, for the purpose of improving the adhesion with the active ingredient of the coating liquid, the surface is optionally subjected to corona treatment, plasma treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, Alkali treatment, sandblast treatment, solvent treatment, or primer treatment can be performed. These surface treatment methods are appropriately selected depending on the type of substrate, but generally, corona treatment, plasma treatment, and alkali treatment are preferably used from the viewpoints of effects and operability.

There is no particular limitation on the method for applying the coating liquid to the substrate surface, and conventionally known methods such as spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, A desired layer can be formed by coating by a die coating method, a gravure coating method, etc., forming a film, and then naturally drying or heat drying. The heating temperature in the case of heating and drying is, for example, preferably 100 to 300 ° C, more preferably 120 to 250 ° C, and further preferably 150 to 200 ° C. When the heating temperature is less than 100 ° C., a long drying time may be required. Moreover, when heating temperature exceeds 300 degreeC, it may become a cost increase on a continuous manufacturing apparatus. With respect to the heating time, for example, 60 to 3600 seconds are preferable, 75 to 1800 seconds are more preferable, and 90 to 180 seconds are even more preferable. When the drying time is shorter than 60 seconds, drying may be insufficient. When the drying time is longer than 3600 seconds, manufacturing may take time and cost may be increased. The thickness of the layer obtained from the condensate after natural drying or heat drying is usually about 0.01 to 3 μm, preferably 0.02 to 1 μm, more preferably 0.05 to 0.5 μm. If the thickness of the layer is 0.01 μm or less, sufficient effects cannot be obtained, and if it is 3 μm or more, defects may be formed in the coating film.

(Conductive member and manufacturing method thereof)
The conductive material containing the metal nanoparticles used for the conductive member as the electronic component according to the present invention includes a colloid and an ink containing metal nanoparticles provided to form a known or commercially available conductive pattern Or a paste can be used widely. Examples thereof include silver paste MDot-SLP / H made by Mitsuboshi Belting, NPS typeHP made by Harima Kasei, and CA-2503-4 made by Daiken Chemical. Among these, a silver paste MDot-SLP / H made by Mitsuboshi Belting is preferably used because of its adhesion to the condensate film (sol-gel film). Silver or copper is preferably used as the metal of the metal nanoparticles.

The film thickness of the ink or paste containing metal nanoparticles after firing is not particularly limited, but is usually 0.1 to 30 μm, preferably 0.3 to 20 μm, more preferably 0.5 to 15 μm. If the thickness of the ink or paste containing metal nanoparticles after baking is less than 0.1 μm, sufficient performance as a wiring material may not be obtained. Moreover, when the film thickness after baking is thicker than 30 micrometers, a crack may enter.

In the present invention, the ink or paste containing metal nanoparticles is formed with a pattern by various printing methods or coating methods. For example, arbitrary linear pattern formation using a dispenser printing method capable of performing linear application, arbitrary linear or planar shape using various types of inkjet printing methods such as thermal, piezo, micro pump, static electricity, etc. Pattern formation, letterpress printing method, flexographic printing method, planographic printing method, intaglio printing method, gravure printing method, reverse offset printing method, sheet-fed screen printing method, rotary screen printing method, etc. Can be formed. Also, using various known coating methods such as gravure roll method, slot die method, spin coating method, etc., forming a pattern as a continuous surface on the entire surface or a part of the laminated substrate, lamination using an intermittent coating die coater, etc. A pattern can be formed as an intermittent surface on the entire surface or part of the substrate, or an ink or paste containing metal nanoparticles can be attached to the entire laminated substrate by using a dip coating method (also referred to as a dip method). More preferable printing methods include an inkjet printing method, a flexographic printing method, a gravure printing method, a reverse offset printing method, a sheet-fed screen printing method, and a rotary screen printing method.

The ink or paste containing metal nanoparticles patterned by these methods can be fired to form a conductive pattern. The firing conditions at this time are considerably limited depending on the base material used, but the higher the temperature, the better because the pattern strength increases with the progress of excellent conductivity and sintering. In particular, when polyimide is used as a base material, it is preferably fired at 150 to 550 ° C., and more preferably fired at 200 to 300 ° C. in view of realizing higher conductivity and productivity.

Here, the case where ink or paste containing metal nanoparticles is used as the conductive layer is shown. Metal plating can be further performed on the conductive pattern formed on the substrate by a wet plating process. Thereby, the electrical conductivity of an electroconductive member can further be improved. In this case, the metal to be used is not limited as long as it is a metal that can be wet-plated. For example, a generally well-known electroless nickel plating process can be used. Furthermore, only electroless plating may be used, or a metal different from the metal formed by electroless plating may be further formed by electrolytic plating as an electrode layer for electrolytic plating.

Since the conductive member according to the present invention uses the laminated substrate according to the present invention, the adhesion of the conductive pattern to the base material is high, metal migration is suppressed, and excellent conductivity can be obtained. . In particular, when a coating solution containing a triazine thiol derivative is used, ion migration can be suppressed during conduction, which is effective. About this cause, it is estimated that the functional group of the triazine thiol derivative supplements the liberated metal ion.

Furthermore, another effect of the introduced triazine thiol derivative is that the adhesiveness of the conductive pattern to the substrate is high. The cause of this is that the metal nanoparticles contained in the ink or paste are exchanged through effects such as promoting the surface exposure of the amino group of the silane coupling agent by changing the structure of the inorganic oxide in the firing process. This is presumed to be due to the further improvement of the adhesion between the conductive pattern, which is a metal film formed by fusing, and suppressing peeling due to abrasion or desorption of the adhesive substance.

The conductive member according to the present invention is obtained by printing or applying an ink or paste containing metal nanoparticles on a laminated substrate in which a condensate of a silane coupling agent having an amino group according to the present invention and a metal alkoxide compound is laminated. can get. This conductive member is used as a transparent electromagnetic wave shield used by bonding to various flat display panels such as a plasma display panel, an aircraft liquid crystal panel, and a car navigation liquid crystal panel. It can also be used as various antennas used for RFID, wireless LAN, power feeding by electromagnetic induction, electromagnetic wave absorption, and the like. Furthermore, it can be used to manufacture bus circuits and address electrodes used in various flat display panels, or electronic circuits that are produced by repeatedly printing a large number of times using a combination of semiconductor ink, resistance ink, and dielectric ink. .

Hereinafter, the present invention will be described in detail with reference to examples, but the content of the present invention is not limited to the examples.

<Evaluation of Adhesiveness of Conductive Member 1: Peel Strength>
The procedure for evaluating the adhesion with the silver paste is shown below.
First, double-sided tape (Nitto Denko's multi-use double-sided adhesive tape No. 5015) cut to 5 mm width is pasted on the silver paste side to the conductive member (length 20 mm) prepared in the following examples and comparative examples. Using a tensile tester (EZ Test / CE made by SHIMADZU) equipped with a rotating drum type support, a double-sided tape was fixed to the drum surface of the rotating drum, a polyimide film was sandwiched between chucks, and a 90 mm direction at 500 mm / min. The adhesion strength was measured by peeling (peeling) at a speed.

<Evaluation method 2 of adhesion strength of conductive member: cross-cut peeling>
The surface of the conductive member printed and baked with ink containing silver nanoparticles is cut into 11 cuts that intersect each other at 1 mm intervals vertically and horizontally, and adhesive tape (“Cello Tape (registered trademark)” manufactured by Nichiban Co., Ltd.) is applied. After peeling, the degree of peeling was measured. As a notation method of peeling, peeling area 0% = 10 points, less than 5% = 8 points, 5% to less than 15% = 6 points, 15% to less than 35% = 4 points, 35% to less than 65% = 2 Points, 65% or more = 0 points.

<Method for evaluating conductivity of conductive member>
Using a resistivity meter Loresta GP (manufactured by Mitsubishi Chemical Analytech Co., Ltd.), the conductivity was measured by a four-terminal method with a measurement voltage of 10V.

<Coating solution adjustment method>
Example 1
First, 10.0 g of (aminoethylaminomethyl) phenyltrimethoxysilane as a silane coupling agent having an amino group was dissolved in 50.0 g of ethylene glycol mono-t-butyl ether. Here, 0.9 g of water was dropped, and a condensation reaction was performed at 60 ° C. for 1 hour to prepare a condensate 1 solution. Next, 1.9 g of titanium tetraisopropoxide as a metal alkoxide compound was dissolved in 160.5 g of ethylene glycol mono-t-butyl ether. Here, 37.8 g of the condensate 1 solution was dropped, and a condensation reaction was performed at 30 ° C. for 4 hours to prepare a condensate 2 solution. Subsequently, 15.1 g of the obtained condensate 2 solution was mixed with 4.9 g of ethylene glycol mono-t-butyl ether to prepare a coating liquid 1 according to Example 1.

(Example 2)
A condensate 2 solution was prepared in the same manner as in Example 1, 14.8 g of this condensate 2 solution and 4.8 g of ethylene glycol mono-t-butyl ether were mixed, and 2,4,6- Coating solution 2 according to Example 2 was prepared by adding 0.4 g of solution 1 obtained by dissolving 1.6 g of trimercapto-S-triazine in 78.6 g of ethylene glycol mono-t-butyl ether. Was made. The ratio of the triazine thiol derivative to the total amount (solid content or active ingredient) of the silane coupling agent having an amino group, the metal alkoxide compound, and the triazine thiol derivative in Example 2 was 2.0% by mass.

(Example 3)
A condensate 2 solution is prepared in the same manner as in Example 1, 14.9 g of this condensate 2 solution is mixed with 4.8 g of ethylene glycol mono-t-butyl ether, and 0.3 g of solution 1 is further added to prepare. Thereby, the coating liquid 3 which concerns on Example 3 was produced. The ratio of the triazine thiol derivative to the total amount (solid content or active ingredient) of the silane coupling agent having an amino group, the metal alkoxide compound, and the triazine thiol derivative in Example 3 was 1.5% by mass.

(Comparative Example 1)
Mixing a solution of 10.1 g of titanium tetraisopropoxide in 19.9 g of ethylene glycol mono-t-butyl ether with 1.7 g of 60% by weight nitric acid, 0.6 g of water and 7.8 g of ethylene glycol mono-t-butyl ether The solution was slowly added dropwise with stirring, and then stirred at 30 ° C. for 4 hours to obtain a reaction solution. The coating solution 4 according to Comparative Example 1 was obtained by mixing 102.2 g of ethylene glycol mono-t-butyl ether with the solution and stirring.

(Comparative Example 2)
The coating liquid 5 according to Comparative Example 2 was obtained by mixing the coating liquid 4 (9.8 g) obtained in Comparative Example 1 with the solution 1 (0.2 g) used in Example 2.

(Comparative Example 3)
As a silane coupling agent having no amino group, 71.0 g of methyltrimethoxysilane and 52.0 g of tetraethoxysilane, 97.1 g of isopropyl alcohol, 9.6 g of 0.1N nitric acid and 82.7 g of water were sequentially mixed. A time hydrolysis condensation reaction was performed.
The obtained reaction liquid was diluted with a mixed solvent of 1586.1 g of methyl isobutyl ketone and 909.2 g of propylene glycol monomethyl ether to obtain a coating liquid 6 according to Comparative Example 3.

(Comparative Example 4)
A coating liquid 7 according to 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.

(Example 7)
Preparation of condensate 1 solution The condensate 1 solution (4.8 g) obtained in Example 1 and ethylene glycol mono-t-butyl ether (25.3 g) were mixed to prepare a coating according to Example 7. A working liquid 8 was produced.

(Example 8)
Preparation of condensate 3 solution N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (18.3 g) was dissolved in ethylene glycol mono-t-butyl ether (79.4 g). Water (2.2 g) was added dropwise thereto, and a condensation reaction was performed at 60 ° C. for 1 hour to prepare a condensate 3 solution. Next, a condensate 3 solution (4.8 g) and ethylene glycol mono-t-butyl ether (25.3 g) were mixed to prepare a coating liquid 9 according to Example 8.

(Example 11)
(Aminoethylaminoethyl) phenethyltrimethoxysilane (5.8 g) was dissolved in ethylene glycol mono-t-butyl ether (28.7 g). Water (0.5 g) was added dropwise thereto, and a condensation reaction was performed at 60 ° C. for 1 hour to prepare a condensate 4 solution. Next, titanium tetraisopropoxide (0.6 g) was dissolved in ethylene glycol mono-t-butyl ether (48.1 g). The condensate 4 solution (11.3 g) was added dropwise thereto, and a condensation reaction was performed at 30 ° C. for 4 hours to prepare a condensate 5 solution. Furthermore, a coating liquid 10 according to Example 11 was prepared by mixing and preparing the condensate 5 solution (60.0 g) and ethylene glycol mono-t-butyl ether (19.5 g).

(Example 12)
N- [2- [3- (Trimethoxysilyl) propylamino] ethyl] ethylenediamine (7.7 g) was dissolved in ethylene glycol mono-t-butyl ether (36.6 g). Water (0.8g) was dripped here, and the condensation reaction was performed at 60 degreeC for 1 hour, and the condensate 6 solution was prepared. Next, the condensate 6 solution (4.8 g) and ethylene glycol mono-t-butyl ether (25.3 g) were mixed to prepare a coating liquid 11 according to Example 12.

(Example 13)
Titanium tetraisopropoxide (0.6 g) was dissolved in ethylene glycol mono-t-butyl ether (48.1 g). The condensate 6 solution (11.3 g) was added dropwise thereto, and a condensation reaction was performed at 30 ° C. for 4 hours to prepare a condensate 7 solution. Furthermore, the coating liquid 12 according to Example 13 was prepared by mixing and preparing the condensation liquid 7 solution (22.6 g) and ethylene glycol mono-t-butyl ether (7.4 g).

<Coating liquid film forming method and silver paste printing method>
Example 4
The coating solution 1 according to Example 1 is a Mayer bar (Matsuo Sangyo No. 1 wire linear 2 mil (76.2 μm), wet film thickness 6 μm), polyimide film (Ube Industries, Ltd. Upilex SGA, thickness 35 μm) ) And dried in an oven at 200 ° C. for 90 seconds. Next, a silver paste MDot-SLP / H made by Mitsuboshi Belting is printed by screen printing on the surface of the polyimide film to which the coating liquid 1 is applied, to the surface to which the coating liquid 1 is applied. Was baked at 250 ° C. for 30 minutes to produce a conductive member printed with a silver paste. At this time, the paste thickness after firing was 10 μm. Table 1 shows the results of evaluation of adhesion according to “Evaluation 1 of adhesion strength of conductive member”.

(Example 5)
Using the coating liquid 2 according to Example 2, a coating film was prepared in the same manner as in Example 4 to produce a conductive member on which a silver paste was printed. At this time, the paste thickness after firing was 10 μm. The evaluation results are shown in Table 1.

(Example 6)
Using the coating liquid 3 according to Example 3, a coating film was prepared in the same manner as in Example 4 to produce a conductive member on which a silver paste was printed. At this time, the paste thickness after firing was 10 μm. The evaluation results are shown in Table 1.

(Comparative Example 5)
A coating film was prepared by the same method as in Example 4 using the coating liquid 4 according to Comparative Example 1, and a conductive member on which a silver paste was printed was prepared. At this time, the paste thickness after firing was 10 μm. The evaluation results are shown in Table 1.

(Comparative Example 6)
A coating film was prepared by the same method as in Example 4 using the coating liquid 5 according to Comparative Example 2, and a conductive member on which a silver paste was printed was prepared. At this time, the paste thickness after firing was 10 μm. The evaluation results are shown in Table 1.

(Comparative Example 7)
A coating film was prepared by the same method as in Example 4 using the coating liquid 6 according to Comparative Example 3, and a conductive member on which a silver paste was printed was prepared. At this time, the paste thickness after firing was 10 μm. The evaluation results are shown in Table 1.

(Comparative Example 8)
A coating film was prepared in the same manner as in Example 4 using the coating liquid 7 according to Comparative Example 4, and a conductive member on which a silver paste was printed was prepared. At this time, the paste thickness after firing was 10 μm. The evaluation results are shown in Table 1.

(Comparative Example 9)
Using a polyimide film not coated with a coating solution (Upilex SGA, Ube Industries, Ltd. Upilex SGA, thickness 35 μm) as a base material, a silver paste was printed in the same manner as in Example 4, and the conductive material on which the silver paste was printed A member was prepared. At this time, the paste thickness after firing was 10 μm. The evaluation results are shown in Table 1. Moreover, about the evaluation result of the adhesiveness by grid peeling, the score was 4 points.

Example 9
A coating film was prepared in the same manner as in Example 4 using the coating liquid 8 according to Example 7, and a conductive member on which a silver paste was printed was prepared. At this time, the paste thickness after firing was 10 μm. The evaluation results are shown in Table 1.

(Example 10)
A coating film was prepared in the same manner as in Example 4 using the coating liquid 9 according to Example 8, and a conductive member on which a silver paste was printed was prepared. At this time, the paste thickness after firing was 10 μm. The evaluation results are shown in Table 1. The conductivity was 4.5 Ω · cm, indicating a high conductivity. From this result, it was shown that the electroconductive member produced by this method has both excellent adhesion and electroconductivity.

(Example 14)
A coating film was prepared by the same method as in Example 4 using the coating liquid 10 according to Example 11, and a conductive member on which a silver paste was printed was prepared. At this time, the paste thickness after firing was 10 μm. The formed pattern was not peeled off, and its peel strength was 1.07 N / mm. Moreover, about evaluation of adhesiveness by cross-cut peeling, the formed pattern did not peel and the score was 10 points. Furthermore, the conductivity was 4.5 Ω · cm, indicating a high conductivity. From this result, it was shown that the electroconductive member produced by this method has both excellent adhesion and electroconductivity.

(Example 15)
A coating film was prepared by the same method as in Example 4 using the coating liquid 11 according to Example 12, and a conductive member on which a silver paste was printed was prepared. At this time, the paste thickness after firing was 10 μm. The formed pattern was not peeled off, and the peel strength was 1.12 N / mm. The conductivity was 4.5 Ω · cm, indicating a high conductivity. From this result, it was shown that the electroconductive member produced by this method has both excellent adhesion and electroconductivity.

(Example 16)
Using the coating liquid 12 according to Example 13, a coating film was prepared in the same manner as in Example 4 to produce a conductive member on which a silver paste was printed. At this time, the paste thickness after firing was 10 μm. The formed pattern was not peeled off, and its peel strength was 1.09 N / mm. The conductivity was 4.5 Ω · cm, indicating a high conductivity. From this result, it was shown that the electroconductive member produced by this method has both excellent adhesion and electroconductivity.

(Example 17)
A conductive member was formed in the same manner as in Example 14 except that the polyimide film as the base material was changed from Upilex SGA manufactured by Ube Industries, Ltd. to 35 μm in thickness, to Kapton EN manufactured by Toray DuPont, Inc., and 25 μm in thickness. Produced. At this time, the paste thickness after firing was 10 μm. Regarding the evaluation of adhesion by cross-cut peeling, the formed pattern was not peeled, and the score was 10. The conductivity was 4.5 Ω · cm.

(Reference Example 1)
A conductive member on which a silver paste was printed in the same manner as in Comparative Example 9 except that the polyimide film was changed from Ube Industries, Ltd. Upilex SGA, thickness 35 μm to Toray DuPont Kapton EN, thickness 25 μm Produced. At this time, the paste thickness after firing was 10 μm. Regarding the evaluation results of adhesion by cross-cutting, all of the formed patterns were peeled off, and the score was 0 points.

From the above, when a silane coupling agent having an amino group is used (Examples 4, 9, 10, 14, 15, 16) and when a silane coupling agent having no amino group is used (Comparative Examples 5 and 7). Compared to the adhesion strength of the conductive member. Moreover, the adhesive strength (Examples 5 and 6) of the conductive member using the condensate prepared by further using triazine thiol is higher than that when the triazine thiol is not used (Example 4). Is even bigger.

(Insulation reliability test)
After laminating a coverlay on the conductive member printed with the silver paste produced by the methods of Examples 10 and 14 to 17, a bias voltage of 52 V was applied for 1000 hours in an environment of 85 ° C. and 85% RH. An insulation reliability test was conducted. As a criterion, it was determined that a failure occurred when the insulation resistance value was less than 1 MΩ. Thereafter, dendrite was observed with an optical microscope. As a result, it was confirmed that none of the conductive members generated dendrite for 1000 hours and failed.

(Evaluation of electroless plating)
The electroless nickel plating process was performed with respect to the electroconductive member on which the silver paste produced by the method of Example 5 was printed. FIG. 1 shows the result of observation of the cross-sectional structure of the obtained sample with a field emission scanning electron microscope (FE-SEM). Furthermore, the result of examining the distribution of the nickel element in the sample is shown in FIG. From FIG. 1 and FIG. 2, it is confirmed that the nickel layer is formed with a thickness of about 100 nm on the printed silver layer, and the wet plating process can be applied to the conductive pattern formed on the substrate. It was shown that there is.

Next, the production of the condensate using the filler, the laminated substrate and the conductive member will be described.

<Method of adjusting coating liquid with filler added>
(Examples 18 to 37)
Using ethylene glycol mono-t-butyl ether as a solvent, the coating liquid 10 and the silica particle slurry prepared in Example 11 so that the solid content concentration is 2% by mass (“HIPRESSICA” manufactured by Ube Nitto Kasei Co., Ltd.) Were added in the order shown in Table 2 to prepare coating solutions 18 to 37 according to Examples 18 to 37 as condensate solutions, respectively. As shown in Table 2, five types (0.08 μm, 0.15 μm, 0.35 μm, 0.68 μm, 1.05 μm) having different average particle diameters were used as the silica particles in the silica particle slurry.

<Film forming method and silver paste printing method of coating liquid with filler added>
(Examples 38 to 57)
Using the coating liquids 18 to 37 prepared in Examples 18 to 37, respectively, with an automatic bar coater (K control coater manufactured by Matsuo Sangyo Co., Ltd., wet film thickness 5 to 14 μm), a polyimide film (Upilex SGA manufactured by Ube Industries, Ltd.) , 35 μm thick), and dried in an oven at 200 ° C. for 90 seconds. Next, a screen paste is applied to the surface of the polyimide film on which the coating solution is applied, and a silver paste MDot-SLP / H made by Mitsuboshi Belting is 150 μm pitch (screen plate design: line: 45 μm / space: 105 μm) comb-shaped pattern electrodes were printed and then dried at 250 ° C. for 30 minutes using a blower oven to produce a conductive member printed with a silver paste.

(Evaluation of printability)
The printed thinning rate of the obtained conductive member is the formula (printing thinning rate) (%) = (line width of the film with the coating liquid) × 100 / (line of the film with no coating liquid applied) It was calculated according to (width). In the formula, (line width of the film coated with the coating liquid) is 20 points of the line width (μm) of the silver ink pattern of the obtained conductive member observed with an optical microscope (ECLIPCE LV100 manufactured by Nikon Corporation). And calculated from the average value. In the formula, (line width of the film not coated with the coating solution) is a silver paste printed on the polyimide film in the same manner as in Example 38 except that the coating solution is not used. A conductive member was prepared, and the line width was calculated by the same method. The results are shown in Table 3. Here, when the print thinning ratio is smaller than 100%, a circuit with a narrow line width can be manufactured and the integration density can be improved. Therefore, it is determined that the printability is good.

(Evaluation of surface coverage)
In Examples 38 to 57, the surface coating rate (%) of the obtained conductive member was determined using an optical microscope (ECLIPCE LV100 manufactured by Nikon Corporation). That is, the surface of the laminated substrate in which the coating film of the condensate is laminated on the polyimide film before the silver paste is printed is observed with an optical microscope, and the image is turned black with the image processing software “ImageJ”. In this way, the luminance and contrast were adjusted to binarize into white and black, and the black area, that is, the area of the part where the particles existed was divided by the total area to display a percentage. This was defined as the surface coverage (%) of the particle portion. The results are shown in Table 3. Here, when the surface coverage is small, it indicates that the surface unevenness is relatively small.

From the results obtained in Table 3, a graph summarizing the relationship between the print thinning rate and the surface coverage was created and is shown in FIG. When the surface coverage is generally high, it can be confirmed that there is a tendency to make the printing line thinner.

The laminated substrate formed using the condensate of a silane coupling agent having an amino group and a metal alkoxide compound according to the present invention has high adhesion to a conductive pattern formed using an ink or paste containing metal nanoparticles. In addition, it is possible to provide a conductive member that suppresses metal migration and provides excellent conductivity.

Claims (16)

1. A condensate having as a main skeleton a MO repeating unit obtained by subjecting a silane coupling agent having an amino group and a metal alkoxide compound represented by the general formula (I) to a hydrolysis-condensation reaction.
   

   
2. The condensate according to claim 1, wherein a ratio of the amino group-containing silane coupling agent and the metal alkoxide compound is 80% by mass: 20% by mass to 95% by mass: 5% by mass.
3. The amino group-containing silane coupling agent includes (aminoethylaminomethyl) phenyltrimethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane and N- [2- [3- (trimethoxysilyl) propylamino] ethyl. The condensate according to claim 1 or 2, which is one or more selected from the group consisting of ethylenediamine.
4. The condensate according to any one of claims 1 to 3, wherein M of the metal alkoxide compound is Ti.
5. The condensate is further introduced with a triazine thiol derivative,
   The ratio of the triazine thiol derivative to the total amount (solid content or active ingredient) of the silane coupling agent having an amino group, the metal alkoxide compound, and the triazine thiol derivative is 0.05 to 10% by mass. The condensate described.
6. The condensate according to any one of claims 1 to 5, wherein the condensate further contains a filler.
7. A laminated substrate material comprising the condensate according to any one of claims 1 to 6 as a main component.
8. A laminated substrate in which the laminated substrate material according to claim 7 is laminated on a substrate surface.
9. The laminated substrate according to claim 8, wherein the base material is a polyimide film, and the thickness of the polyimide film is in the range of 1 to 150 µm.
10. A conductive member in which a conductive pattern is formed by printing or applying a conductive material on the surface of the multilayer substrate according to claim 8 or 9 on which the multilayer substrate material is laminated.
11. The conductive member according to claim 10, wherein the conductive material includes metal nanoparticles, and the metal of the metal nanoparticles is silver or copper.
12. A first step of obtaining a reaction solution by subjecting a silane coupling agent having an amino group to a condensation reaction in a solvent, a metal alkoxide compound represented by the general formula (I), and a reaction solution obtained in the first step A method for producing a condensate comprising a second step of mixing and condensation reaction.
    

    
13. The method for producing a condensate according to claim 12, further comprising a third step of adding a triazine thiol derivative to the condensate obtained in the second step.
14. The method for producing a condensate according to claim 12 or 13, further comprising a fourth step of mixing a filler with the condensate obtained in the second step.
15. A method for producing a laminated substrate, wherein the condensate according to any one of claims 1 to 6 is applied to a substrate surface to obtain a laminated substrate in which the condensate is laminated on the substrate.
16. A method for producing a conductive member, wherein a conductive material is printed or applied on a surface of the multilayer substrate according to claim 8 or 9 that is laminated, and then fired to form a conductive pattern.

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