JP5772480B2 - Ink receiving film, laminated substrate using the same, and conductive member - Google Patents

Description

  The present invention relates to an ink receiving film, a laminated substrate using the same, and a conductive member.

  Conventionally, methods for forming a wiring pattern on a printed wiring board are roughly classified into a subtractive method, a semi-additive method, and an additive method. In any of the above methods, a photolithography technique is used. However, a method for forming a desired wiring pattern by forming a resist pattern by a photolithography technique requires time to create a photomask. In addition to the etching process for removing unnecessary portions of the wiring metal, a resist exposure and development process for forming a resist pattern is also required. Therefore, it takes time and cost to form the wiring pattern.

  Therefore, in recent years, a method of forming a wiring pattern of a printed wiring board by using a conductive fine particle dispersed ink drawing method has been proposed. This conductive fine particle-dispersed ink drawing method forms a wiring pattern by patterning a conductive fine particle material directly on a substrate according to a desired wiring pattern using an ink jet printing method. Since the conductive fine particle dispersed ink drawing method does not require a mask, the number of manufacturing steps is smaller than a conventional method in which a resist pattern is formed by a photolithography technique to form a desired wiring pattern. However, in order to draw the pattern of the fine particle material with high definition, it is necessary to prevent bleeding during printing of the conductive paste.

  In order to solve such a problem, for example, in Patent Document 1, when an aggregation promoting layer composed of inorganic oxide fine particles is provided in advance on a base material and a metal ultrafine particle solution is applied, A conductive pattern forming base material that can promote aggregation of ultrafine metal particles by mainly allowing a solvent to selectively penetrate into the formed pores is disclosed.

JP 2003-229653 A

  However, in the base material having a porous layer such as the aggregation promoting layer, in the wet process such as plating, the treatment liquid enters the porous layer and adversely affects the circuit characteristics. However, there is a problem that migration during conduction (a phenomenon in which a metal component moves) is promoted.

  This time, when the present inventors tried to form a wiring with a base material having a porous layer, when the wiring board was used under high temperature and high humidity, dendritic migration occurred around the electrode and short-circuited immediately after energization. I found out.

  The present invention has been made in view of the above problems, and uses an ink receiving film that can prevent migration during conduction and prevent bleeding during conductive paste printing, and the same. An object is to provide a laminated substrate and a conductive member.

  In order to achieve the above object, as a result of intensive studies, the present inventors laminated an ink receiving film having a specific acid content and specific surface area on a substrate, the main component being a condensate of a silane coupling agent. The conductive member thus found has been found to be capable of preventing migration during conduction and preventing bleeding during printing of the conductive paste.

That is, the present invention is an ink receiving film mainly composed of a condensate of a silane coupling agent, and the acid content of the ink receiving film is 0.6 ppm or less as NO ₃ ⁻ and the specific surface area is 30 cm ² / cm. ^The present invention relates to an ink receiving film characterized by being ² or less.

  Further, according to the present invention, a conductive pattern is formed by printing or applying a conductive material on a laminated substrate in which the ink receiving film is laminated on a substrate, and on the surface of the laminated substrate on which the ink receiving film is laminated. The present invention relates to a conductive member.

  As described above, according to the present invention, it is possible to provide an ink receiving film capable of preventing the occurrence of migration during conduction and preventing bleeding during printing of a conductive paste, a laminated substrate using the same, and a conductive member. I can do it.

It is a conceptual diagram showing the comb-shaped pattern electrode printed on the electroconductive member in Experimental example 1 and 2. FIG.

(Ink receiving film)
In the ink receiving film according to the present invention, the porosity of the ink receiving film and the amount of acid in the film are defined in consideration of the migration resistance of the conductive member described later. The porosity of the ink receiving film can be determined by measuring the specific surface area of the film.

The acid content of the ink receiving film according to the present invention is 0.6 ppm or less as NO ₃ ⁻ , preferably 0.5 ppm or less, more preferably more than 0.1 and 0.5 ppm, and particularly preferably. It is in the range of 0.2 to 0.5 ppm. Specifically, the acid content of the ink receiving film in the present invention is determined by a method of measuring the concentration of nitrate ions detected in the following method for determining the amount of nitrate ions using ion chromatography.

  First, a condensate of a silane coupling agent is applied to a polyimide film and dried by heating at 200 ° C. for 90 seconds. Next, the polyimide film coated product after heat drying is cut into a size of 12 cm in length and 10 cm in width. A sample having a size of 12 cm long × 10 cm wide is placed in 10 g of pure water and heated at 50 ° C. for 4 hours, and then the liquid is recovered. Next, the acid content of the ink receiving film can be measured by measuring the nitrate ion content of this solution by the direct IC method of ion chromatography (DX Nippon Co., Ltd., DX-120). When the concentration of the detected nitrate ion is larger than 0.6 ppm, it is difficult to obtain a good result of enduring 1000 hours under high temperature and high humidity conditions in the insulation reliability test of the pattern printed with the conductive paste.

The specific surface area of the ink receiving film according to the present invention is 30 cm ² / cm ² or less, preferably 15 cm ² / cm ² or less, more preferably more than 1 and in the range of 15 cm ² / cm ² , particularly preferably. Is in the range of 7 to 13 cm ² / cm ² . Here, the specific surface area of the ink receiving film is the surface area of the ink receiving film per unit substrate area and per unit ink receiving film height. When the value of the specific surface area to be measured is larger than 30 cm ² / cm ² , in the insulation reliability test of the pattern on which the conductive paste is printed, a good result of enduring 1000 hours under a high temperature and high humidity condition can be obtained. difficult.

  In the ink receiving film according to the present invention, from the examples described later, even if the amount of nitrate ions remaining in the film is low, if the receiving film is porous, good results are obtained in the insulation reliability test. It was shown that it is not possible. That is, in the insulation reliability test, in order to obtain a good result of enduring 1000 hours, the amount of nitrate ions remaining in the film is lowered, and at the same time, the specific surface area of the receiving film is lowered, that is, it approaches a nonporous structure. It is necessary.

(Condensate of silane coupling agent)
The ink receiving film according to the present invention contains a condensate of a silane coupling agent as a main component. In the said condensate, it does not specifically limit as an example of the silane coupling agent used as a raw material, For example, the compound represented by following General formula (1) and its condensation product can be illustrated.

Here, in said formula (1), W is a C1-C20 alkoxy group, a hydroxyl group, a C1-C20 acetoxy group, a halogen atom, a hydrogen atom, a C1-C20 oxime group, a phenoxy group. , A group selected from the group consisting of an aminoxy group and an amide group. R is a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 30 carbon atoms having an amino group. A functional group selected from the group consisting of: Note that the aryl group having 6 to 20 carbon atoms may be substituted with an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a halogen atom.
X is an integer of 1 to 4, y is an integer of 0 to 3, and x + y = 4. Further, when x is 2 or more, the plurality of Ws may be the same or different from each other, and when y is 2 or more, the plurality of Rs may be the same or different from each other.

  Examples of the compound represented by the formula (1) include tetraalkoxysilanes represented by tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, and tetra-n-butoxysilane; Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane N-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyl Ethoxysilane, allyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3- Trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxy Silane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Triethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meta ) Acryloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropyltriisopropoxysilane, 3-ureidopropyltrimethoxysilane , Trialkoxysilanes represented by 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxy Silane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyl Dimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n- Cyclohex Dialkoxysilanes represented by rudimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane; trimethylmethoxysilane, trimethylethoxysilane Representative monoalkoxysilanes; 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-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N, N-bis [3 -(Trimethoxysilyl) propyl] ethylenediamine, (aminoethylaminoethyl ) Phenethyltrimethoxysilane, (aminoethylaminoethyl) phenethyltriethoxysilane, (aminoethylaminoethyl) phenethyltripropoxysilane, (aminoethylaminoethyl) phenethyltriisopropoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane , (Aminoethylaminomethyl) phenethyltriethoxysilane, (aminoethylaminomethyl) phenethyltripropoxysilane, (aminoethylaminomethyl) phenethyltripropoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-amino Propyltrimethoxysilane, 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-aminopropyltrimethoxysilane, methylbenzylaminoethylaminopropyltrimethoxysilane, dimethylbenzylaminoethylaminopropyltrimethoxysilane, benzylaminoethylaminopropyltri Methoxysilane, benzylaminoethylaminopropyltriethoxysilane, or 3- (N-phenyl) aminopropyltrimethoxysilane, 2- [2- (3-trimethoxysilylpropylamino) ethylamino] ethylamine, 2- [2- (3-triethoxysilyl Ropiruamino) ethylamino] ethylamine, 2- [2- (3-triisopropoxysilyl propyl) ethylamino] ethylamine, silane coupling agents such as p- aminophenyl trimethoxysilane. These may be used alone or in combination of two or more.

  The ink receiving film according to the present invention does not undergo thermal decomposition or sublimation during a high-temperature treatment (250 ° C. or higher) such as baking of the ink in the subsequent process, and the function of the film is not deteriorated while maintaining the form of the film. Required. For this reason, the silane coupling agent used as the raw material of the condensate is required to have heat resistance when condensed. Therefore, it is effective to use a silane coupling agent according to the present invention having high heat resistance after condensation. Examples of such silane coupling agents include phenyltriethoxysilane and p-aminophenyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, ( Aminoethylaminomethyl) phenethyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 2- [2- (3-trimethoxysilylpropylamino) ethylamino] ethylamine, among which phenyltriethoxysilane and p-amino Phenyltrimethoxysilane is preferably used. These may be used individually by 1 type and may be used in combination of 2 or more type. 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. The silane coupling agent preferably has an amino group in consideration of adhesion to an organic substrate such as a polyimide film, a conductive pattern formed by sintering conductive ink, and high heat resistance.

  In the present invention, the silane coupling agent is hydrolyzed and condensed by a sol-gel reaction to produce a condensate having a repeating unit of Si-O as the main skeleton. In the ink receiving film according to the present invention, it is extremely important to reduce the amount of acid remaining in the ink receiving film. For this reason, when producing a condensate having a repeating unit of Si-O as a main skeleton by hydrolysis-condensation reaction of the silane coupling agent by sol-gel reaction, the system should be used so that no acid is used or remains in the film. A neutralizing method is preferably used.

  Moreover, in this invention, it is preferable to mix the reaction material obtained by the said sol-gel reaction, and the metal alkoxide compound represented by following General formula (2), and to carry out a condensation reaction (sol-gel reaction).

  In the general formula (2), M represents 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, particularly preferably Ti, because it is generally easy to obtain and synthesize.

In the general formula (2), R ¹ is a non-hydrolyzable group such as an alkyl group having 1 to 20 carbon atoms, a (meth) acryloyloxy group, an amino group, or an epoxy 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.

Here, as a C1-C20 alkyl group, a C1-C10 thing is preferable, and this 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, and hexyl group. Octyl group, cyclopentyl group, cyclohexyl group and the like.
As a C1-C20 alkyl group which has a (meth) acryloyloxy group, an amino group, or an epoxy group, the C1-C10 alkyl group which has the said substituent is preferable, and this alkyl group is linear , 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, and 3-phenylaminopropyl 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 the 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, and 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, and cyclohexyl group.

In the metal alkoxide compound represented by the general formula (2), m is the valence of the metal atom M and is 3 or 4, and n is an integer of 0 to 2 when m is 4, m When is 3, it is an integer of 0-1. 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 2 in the metal alkoxide compound represented by the general formula (2). Is tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetraisobutoxy titanium, tetra-sec-butoxy titanium, tetra-tert-butoxy titanium, methyltri Methoxy 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, phenyl triethoxy titanium, vinyl Rimethoxytitanium, vinyltriethoxytitanium, γ-glycidoxypropyltrimethoxytitanium, γ-acryloyloxypropyltrimethoxytitanium, γ-methacryloyloxypropyltrimethoxytitanium, dimethyldimethoxytitanium, methylphenyldimethoxytitanium, and the above compounds And compounds in which titanium in is replaced with silane or zirconium.

  In addition, in the metal alkoxide compound represented by the general formula (2), as an example of the alkoxide compound in the case where M 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 individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, in the said sol-gel reaction, it is preferable that the ratio of the said silane coupling agent and the said metal alkoxide compound is 80: 20-95: 5 in the case of the mass%. When the added amount of the metal alkoxide compound is larger than this range, the reactivity of the solution becomes high, so that the speed of the sol-gel reaction of the condensate-containing liquid increases, and the solution gels and finally becomes uniform. It is difficult to realize a film. On the other hand, when the addition amount of the metal alkoxide compound is less than this range, the reactivity of the silane coupling agent is low, so the molecular weight does not increase and the ink receiving film cannot be formed well.

(Filler)
The ink receiving film according to the present invention preferably contains a filler. The filler preferably has a primary particle size in the range of 30 to 1000 nm. Here, the primary particle diameter can be obtained by diluting the filler dispersion and calculating the average particle diameter of the particles from an electron microscope image observed with a scanning electron microscope. When the primary particle size is smaller than 30 nm, the effect on the printability at the time of printing the conductive paste is small, and when the primary particle size is larger than 1000 nm, the particles are likely to settle when the solution is prepared, and uniform. It becomes difficult to form a film.

  As these fillers, either inorganic fillers or organic fillers can be used. Examples of the inorganic filler include silica fine particles, colloidal silica, alumina, colloidal alumina, colloidal titanium, zirconium sol, calcium silicate, zeolite, kaolinite, halloysite, muscovite, talc, calcium carbonate, calcium sulfate, boehmite and the like. it can. Among these, colloidal silica is preferable, for example, 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 (above, manufactured by Nissan Chemical Industries, Ltd.), Quatron The PL series (manufactured by Fuso Chemical Co., Ltd.), the OSCAL series (manufactured by Catalytic Chemical Industry Co., Ltd.), and the high presica (manufactured by Ube Nitto Kasei Co., Ltd.) are preferably used. Among these, from the viewpoint of the dispersibility of the filler in the solution of the above-mentioned condensate, High Plessica (manufactured by Ube Nitto Kasei Co., Ltd.) is most preferably used. Moreover, a polyimide particle etc. are mentioned as an organic filler.

The ink receiving film according to the present invention has no or few pores on the surface of the ink receiving film. The ratio of the filler to the condensate of the silane coupling agent 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 condensate of the silane coupling agent and the metal alkoxide compound is preferably such that the filler is in the range of 10 to 70% by mass, 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, the filler may not be evenly spread on the substrate during film formation, and there may be a case where a sufficient effect cannot be expected on the printability during conductive paste printing. When the ratio of the filler to be added is larger than the above ratio, the specific surface area of the obtained ink receiving film has a porous structure exceeding 30 cm ² / cm ^2, which may adversely affect the electrical characteristics. Furthermore, there is a possibility that the liquid stays on the porous membrane surface in the wet process.

(Preparation of ink receiving film preparation solution)
In the present invention, the silane coupling agent and the metal alkoxide compound are subjected to a hydrolysis-condensation reaction by a sol-gel reaction to form a repeating unit of MO (M is the same as described above, hereinafter the same) as the main skeleton. After preparing the condensate to be mixed, it is mixed with a filler. The method for producing a condensate used in the ink receiving film according to the present invention includes a first step of adding water to a silane coupling agent to cause a condensation reaction, the metal alkoxide compound represented by the general formula (2), and the first step. A second step of mixing and condensing the reactant obtained in one step, and a third step of mixing the solution obtained in the second step with a filler solution. The second step using the metal alkoxide compound can be omitted. Below, the form containing a 2nd process is described.

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, the metal alkoxide compound is hydrolyzed with water at a temperature of usually 0 to 70 ° C., preferably 20 to 60 ° C., and the solvent is distilled off or added as required. Can be done. By the above reaction, a condensate having a main skeleton of the M-O repeating unit can be obtained. In general, in these condensation reactions, a method of adding an acidic compound as a catalyst is preferably used. However, when considering the migration resistance of the conductive member described later, it is extremely important to reduce the amount of acid remaining in the film. Therefore, when a silane coupling agent is hydrolyzed-condensed by a sol-gel reaction to produce a condensate having a repeating unit of Si-O as the main skeleton, no acid is used or the film remains after using an acid. In the present invention, a method of neutralizing the system and a method using a two-phase system are preferably used in the present invention. As a specific method not using an acid, for example, the reaction is allowed to proceed only by a heating operation without using a commonly used acid catalyst under the conditions for performing the condensation reaction. On the other hand, as a specific method of neutralizing the system so that it does not remain in the film after using an acid, for example, as in Preparation Example 1 described later, in a two-layer system of a hydrophobic solvent and water, There is a synthesis method in which an acid / alkali catalyst is put into a composition or water to cause the reaction to proceed at the interface so that no acid / alkali remains in the solvent or the composition. By producing by such an operation, a membrane having a NO ₃ ⁻ concentration of 0.6 ppm or less as measured by ion chromatography 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 (2) 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 mixing with the filler in the third step can be carried out by mixing the filler described above with the solution of the condensate having the main skeleton of the MO repeating unit obtained by the above reaction. . The filler can be mixed in a state where it is mixed in an appropriate solvent.

  The condensate produced by the above production method can be obtained in the state of a coating solution containing a condensate having a repeating unit of MO as a main skeleton at a predetermined concentration by the hydrolysis-condensation reaction. When the ink receiving film according to the invention is produced on a substrate, it is preferably applied to the substrate surface in the state of a coating liquid. Further, the coating liquid can be adjusted to a predetermined concentration after obtaining the condensate. About the density | concentration of the said condensate in the said coating liquid, what is necessary is just a density | concentration which can be applied to the substrate surface, and there is no restriction | limiting in particular, Usually 0.05-35 mass%, Preferably 0.1-20 mass% More preferably, it is 0.2-10 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. On the other hand, if the concentration of the condensate is less than 0.05% by mass, the condensation reaction does not proceed sufficiently and the molecular weight does not increase, so that it may be difficult to obtain a coating film having a sufficient film thickness.

(Laminated substrate and manufacturing method thereof)
The present invention is characterized in that the ink receiving film is a laminated substrate laminated on a substrate surface. The laminated substrate according to the present invention can be obtained by coating the above-mentioned coating solution on the substrate surface.

  In the laminated substrate according to the present invention, the base material used as the substrate is not particularly limited. Specific examples of the substrate 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, and fluororesin. , Phenoxy resin, triacetylcellulose, polyethylene terephthalate, polyimide, polyphenylene sulfide, polyethylene naphthalate, polycarbonate, films made of various resins such as cellophane, nylon, polystyrene resin, ABS resin, etc., Examples thereof include quartz glass, non-alkali glass, crystallized transparent glass, and various glasses such as Pyrex (registered trademark), paper, nonwoven fabric, cloth, various metals, and various ceramics. 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, a polyimide film is preferable from the viewpoints of being able to realize low resistance by treating at high temperature when sintering conductive ink or paste, heat resistance, dimensional stability, mechanical properties, and the like. As this polyimide film, the polyimide film in which the inorganic layer is formed in the surface is especially preferable from an adhesive viewpoint with the inorganic film to form into a film.

  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.

  As such a polyimide film, for example, an aromatic polyimide film can be used. 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 name “ Examples thereof include polyimide films such as “Apical” (registered trademark, manufactured by Kaneka Corporation).

  When a plastic film is used as the substrate, the thickness of the substrate is not particularly limited and is appropriately selected depending on the application, but is usually about 1 to 150 μm, preferably 2 to 120 μm, more preferably 3 ˜100 μm. When the thickness is less than 1 μm, the operability of the substrate may be deteriorated. When the thickness exceeds 150 μm, the substrate becomes rigid and the operability is lowered, the weight is increased, and the cost may be further increased.

  The substrate has the purpose of improving wettability with a coating liquid containing a condensate having a main skeleton of a repeating unit of MO formed 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 treated with 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 applied. 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.

  The method for applying the coating liquid onto the substrate surface is not particularly limited, and conventionally known methods such as spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, and die coating are known. A desired layer can be formed by coating by a method, a gravure coating method, etc., forming a film, and then naturally drying or heat drying. The thickness of the layer 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 less than 0.01 μm, the amount of filler is reduced, and it is difficult to form a sufficient uneven structure. Therefore, the effect of improving the printability may not be sufficiently obtained. Defects may be formed.

(Conductive member and manufacturing method thereof)
As the conductive material containing metal nanoparticles used in the conductive member according to the present invention, a conductive ink or paste provided for forming a known or commercially available conductive pattern can be widely used. For example, FA-323 (manufactured by Fujikura Kasei), silver paste MDot-SLP / H (manufactured by Mitsuboshi Belting), NPStypeHP (manufactured by Harima Kasei), CA-2503-4 (manufactured by Daiken Chemical). Silver or copper is preferably used as the metal of the metal nanoparticles.

  The film thickness after firing of the conductive ink 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, and if it is more than 30 μm, cracks may occur.

  In the present invention, the conductive ink or paste is patterned 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. In addition, various known coating methods such as a gravure roll method, a slot die method, a spin coating method, etc. are used to form a pattern as a continuous surface on the entire surface or a part of the laminated substrate for forming a conductive pattern. The pattern is formed as an intermittent surface on the entire surface or part of the conductive pattern forming base material using a film or the like, or a dip coating method (also referred to as a dip method) is used on the entire laminated substrate for forming the conductive pattern. An ink or paste containing metal nanoparticles can also be attached. 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 conductive ink or paste patterned by these methods can be baked by heating 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 preferable to perform baking at a temperature of 250 ° C. for 0.5 hours or more.

  As described above, various flats such as a plasma display panel, an aircraft liquid crystal panel, a car navigation liquid crystal panel, etc. can be obtained by printing or applying a conductive ink or paste containing metal (nanoparticles) to the laminated substrate according to the present invention. Transparent electromagnetic shield used for bonding to display panels, RFID, wireless LAN, power feeding by electromagnetic induction, various antennas used for electromagnetic wave absorption, bus electrodes and address electrodes used for various flat display panels, semiconductor ink, It is possible to provide a conductive member that is used for manufacturing an electronic circuit or the like that is produced by repeatedly printing a large number of times by using a resistance ink and a dielectric ink in combination.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the content of this invention is not restricted to an Example.

(Experimental example 1)
First, a method for preparing a coating liquid for obtaining an ink receiving film formed on a substrate will be described.

(Preparation example 1) Preparation of coating liquid 1 16.8 g of phenyltriethoxysilane (PhTES) and 8.2 g of diphenyldiethoxysilane (DPhDES) were placed in 71.9 g of diethyl ether and stirred at room temperature for several minutes. A mixed liquid of concentrated hydrochloric acid 20.0 g and water 80.0 g was added to the obtained solution, and the mixture was vigorously stirred at room temperature for 3 hours. To the aqueous phase separated by the separatory funnel, 50.0 g of diethyl ether was added, shaken vigorously, and allowed to stand to separate the aqueous phase and the organic phase. This operation was repeated twice in total. To the organic phase separated by this operation, 100 g of NaOH aqueous solution with pH = 13 was added, and the mixture was vigorously stirred at room temperature for 3 hours. Diethyl ether (50.0 g) was added to the aqueous phase separated by the separatory funnel, shaken vigorously, and then allowed to stand to separate the aqueous phase and the organic phase. This operation was repeated twice in total. Thereafter, the separated organic phase was slowly stirred at room temperature to remove some diethyl ether, transferred to a petri dish, and dried in an oven at 50 ° C. for 9 days to obtain a solid.
Thus, the obtained solid was melt | dissolved in methyl isobutyl ketone so that it might become 1.0 mass%, and the coating liquid 1 which concerns on the preparation example 1 was obtained.

(Comparative Preparation Example 1) Preparation of coating solution 2 In a solution prepared by dissolving 10.1 g of titanium tetraisopropoxide in 19.9 g of ethylene glycol mono-t-butyl ether, 1.7 g of 60% by mass nitric acid and 0.6 g of water A mixed solution of 7.8 g of ethylene glycol mono-t-butyl ether was slowly added dropwise with stirring, and then stirred at 30 ° C. for 4 hours to obtain a reaction solution 1. The coating liquid 2 which concerns on the comparative preparation example 1 was obtained by mixing and stirring 102.2g of ethylene glycol mono- t-butyl ether with the liquid.

(Comparative Preparation Example 2) Preparation of Coating Solution 3 20.0 g of Reaction Solution 1 obtained in Comparative Preparation Example 1, 34.3 g of ethylene glycol mono-t-butyl ether, 13.3 g of propylene glycol, 63.1 g of methyl isobutyl ketone Then, 9.3 g of a titania nanoparticle dispersion liquid having a concentration of 15 wt% was mixed and stirred to obtain a coating liquid 3 according to Comparative Preparation Example 2.

  Next, an ink receiving film forming process and a conductive material printing process will be described.

Example 1
The coating liquid 1 according to Preparation Example 1 is a Mayer bar (Matsuo Sangyo No. 1 wire linear 2 mil (76.2 μm), wet film thickness 6 μm), polyimide film (Ubex Corporation Upilex SGA, thickness 35 μm) And dried in an oven at 200 ° C. for 90 seconds. By screen printing onto the sample, as shown in FIG. 1, after printing comb-shaped pattern electrodes with a pitch of 400 μm (line: about 280 μm / space: about 120 μm) from FA-323 manufactured by Fujikura Kasei Co., Ltd., using a blower oven The conductive member on which the silver paste was printed was produced by drying at 150 ° C. for 10 minutes. At this time, the paste thickness after firing was approximately 5 μm. A cover lay (CVA-0525KA) manufactured by Arisawa Seisakusho was pressed on the conductive member at 180 ° C. and 2.9 MPa for 30 minutes in a vacuum and laminated.

(Comparative Example 1)
Instead of the coating liquid 1 according to Preparation Example 1, Uera Nitto Kasei's porous film-forming paint Hicertec IR-S600 (condensate of silane coupling agent) is used, and the Mayer bar is a Mayer bar (Matsuo Sangyo No. .2 wire linear 6 mil (152.4 μm), wet film thickness was changed to 12 μm, and the same operation as in Example 1 was performed to prepare a comb pattern electrode on a polyimide substrate laminated with a coverlay.

(Comparative Example 2)
Using the coating liquid 2 according to Comparative Preparation Example 1 instead of the coating liquid 1 according to Preparation Example 1, the same operation as in Example 1 was performed, and the comb pattern electrode on the polyimide substrate laminated with the coverlay was formed. Prepared.

(Comparative Example 3)
Using the coating liquid 3 according to Comparative Preparation Example 2 instead of the coating liquid 1 according to Preparation Example 1, the same operation as in Example 1 was performed, and the comb pattern electrode on the polyimide substrate laminated with the coverlay was formed. Prepared.

(Insulation reliability test)
Insulation was performed by applying a bias voltage of 52 V for 1000 hours in an environment of 85 ° C. and 85% Rh to a comb-shaped pattern electrode on a polyimide substrate laminated with a coverlay prepared by the method of Example 1 and Comparative Examples 1 to 3. A reliability test was performed. 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.

(Calculation of migration speed)
In the insulation reliability test, the value calculated by dividing the distance between wires by the short-circuit time was adopted for the level short-circuited within 1000 hours. Moreover, in the level which cleared the 1000-hour test, the value calculated by dividing the dendrite length of the sample after the test by 1000 hours was adopted. The results for each electrode are summarized in Table 1.
As a result, it was found that only the sample produced by the method of Example 1 can obtain a good performance of enduring 1000 hours in the insulation reliability test.

(Nitrate ion content: ion chromatography)
Coating solutions 1 to 3 prepared by the methods of Preparation Example 1 and Comparative Preparation Examples 1 and 2 and “Hi-Ceratech IR-S600” manufactured by Ube Nitto Kasei Co., Ltd. were each applied to a polyimide film, and 90 ° C. at 90 ° C. It was dried in an oven for 2 seconds. A sample having a surface area of 12 cm in length and 10 cm in width was placed in 10 g of pure water and heated at 50 ° C. for about 4 hours, and then the liquid was recovered. The amount of nitrate ion in this solution was measured by a direct IC method of ion chromatography (IC Nippon Daionex DX-120). The results are summarized in Table 1.

(Measurement method of specific surface area)
Coating solutions 1 to 3 prepared by the methods of Preparation Example 1 and Comparative Preparation Examples 1 and 2 and “Hi-Ceratech IR-S600” manufactured by Ube Nitto Kasei Co., Ltd. were each applied to a polyimide film, and 90 ° C. at 90 ° C. It was dried in an oven for 2 seconds. A sample having a surface area of 10 cm in length and 10 cm in width was measured using “micromeritics, FlowSorbll2300” manufactured by Shimadzu Corporation. Incidentally, 0.0051g / cm ² weight per unit area of the polyimide film having a thickness of 35 [mu] m, the density of the polyimide as 1.47 g / cm ^3, in terms of and specific surface area measurements and ^{(cm 2} / cm 2) did. The results are summarized in Table 1.

From the results shown in Table 1, it is necessary to reduce the amount of nitrate ions remaining in the film within a range of 0.6 ppm or less in order to obtain good results for durability of 1000 hours in the insulation reliability test. However, when the nitrate ion amounts of the samples of Example 1 and Comparative Example 1 were compared, it was found that there was no significant difference in the amounts. However, the specific surface area of the sample of Comparative Example 1 is very large compared to the other samples, and even if the amount of nitrate ions remaining in the membrane is low, if the sample is porous, the insulation reliability Tests have been shown to give poor results.
In other words, in order to obtain a satisfactory result of enduring 1000 hours in the insulation reliability test, the nitrate ion amount remaining in the film is reduced, and at the same time, the specific surface area of the sample is reduced, that is, it approaches a nonporous structure. It became clear that is necessary.

Thus, in order to obtain a good test result in the insulation reliability test, it seems necessary to realize a non-porous structure. However, when such a structure is used as an ink receiving layer, Conventionally, it has been predicted that printability (line / space width that can be printed without causing disconnection or bonding) will be poor when screen printing is performed with ink.
In contrast, in the present invention, an ink receiving layer having both printability and insulation reliability can be realized by reducing the amount of acid in the film and introducing particles into the formed film. Examples thereof will be described below.

(Experimental example 2)
First, a method for preparing a condensate solution used in a coating solution for obtaining an ink receiving film will be described below.

Preparation Example 2 Preparation of Condensate 1 Solution Aminophenethyltrimethoxysilane (manufactured by Gelest) (5.6 g) was dissolved in ethylene glycol mono-t-butyl ether (23.7 g). Water (0.7g) was dripped here, and the condensation reaction was performed at 60 degreeC for 1 hour, and the condensate 1 solution was prepared.

Preparation Example 3 Preparation of Condensate 2 Solution Titanium tetraisopropoxide (0.9 g) was dissolved in ethylene glycol mono-t-butyl ether (80.2 g). Condensate 1 (18.9 g) was added dropwise thereto, and a condensation reaction was performed at 30 ° C. for 4 hours to prepare a condensate 2 solution.

  As a method of obtaining a condensate using these sol-gel reactions, a method of adding an acid as a normal catalyst is widely known. However, in the case of Preparation Examples 2 and 3, in view of the results in Experimental Example 1, the acid is added. The condensate was prepared by a method not using.

  Next, a method for adjusting the filler introduced into the ink receiving film will be described. In this experimental example, silica particles were used as the filler. As silica particles, “HI-PRECICA” manufactured by Ube Nitto Kasei Co., Ltd. and “MP-2040” manufactured by Nissan Chemical Industries, Ltd. were used.

In addition, the average particle | grains and CV value of the filler were measured in accordance with the following method.
(Measurement of average particle size)
After diluting to 1% by mass with water, one drop was dropped on a sample stage for an electron microscope and dried to prepare a sample. The sample was observed at 50,000 times with a scanning electron microscope (JSM-6700F, manufactured by JEOL Ltd.).
The average particle diameter of the silica particles was calculated from the image obtained using the image processing software (Mac-View, manufactured by Mountec) from the electron microscope image. The results are shown in Table 2.

(Measurement of CV value)
After diluting to 1% by mass with water, one drop was dropped on a sample stage for an electron microscope and dried to prepare a sample. The sample was observed at 50,000 times with a scanning electron microscope (JSM-6700F, manufactured by JEOL Ltd.).
After calculating the average particle diameter and standard deviation of the silica particles from the image obtained using the image processing software (Mac-View, manufactured by Mountec) from the electron microscope image, the CV value was calculated by the following equation. The results are shown in Table 2.

  Next, a method for preparing a coating liquid for obtaining an ink receiving film formed on a polyimide substrate will be described.

(Adjustment Example 4) Preparation of coating liquids P-0 to P-9 Coating liquids P-0 to P-9 were prepared according to the following procedure. Specifically, ethylene glycol mono-t-butyl ether as a solvent is added in the amount shown in Table 2, and the kind and amount of condensate 2 solution and silica particle slurry shown in Table 2 (silica particles are Ube Nitto Kasei Corporation). “Hi-Pureshka” was used in this order to prepare coating solutions P-0 to P-9. For the silica particles, three types (0.08 μm, 0.35 μm, 0.68 μm) having different average particle diameters were used. Here, in Table 2, “binder” refers to the condensate of the condensate 2 solution.

(Adjustment example 5) Preparation of coating liquid Instead of “HI-PRECICA” manufactured by Ube Nitto Kasei Co., Ltd. as silica particles, “MP-2040” manufactured by Nissan Chemical Industries, Ltd. was used, and the above P-0 to P- A coating solution was prepared in the same manner as in Example 9. As a result, the solution showed a tendency to gel under any of the binder / particle ratio conditions described above. As a result, it has been clarified that “High Plesica” is superior as a slurry solution that can be applied to a polyimide film as silica particles.

  Next, an ink receiving film forming process and a conductive material printing process will be described.

(Examples 2 to 10)
The coating liquids P-1 to P-9 shown in Table 2 were prepared by using a Mayer bar (Matsuo Sangyo No. 1 wire linear 2 mil (76.2 μm), wet film thickness 6 μm) and a polyimide film (Ube Industries, Ltd.). Upilex SGA (thickness: 35 μm) and dried in an oven at 200 ° C. for 90 seconds. By screen printing on the sample, a silver paste MDot made by Mitsuboshi Belting is printed at 100 μm pitch (screen plate design: line: 30 μm / space: 70 μm) as shown in FIG. The conductive member which concerns on Examples 2-10 with which the silver paste was printed was produced by drying for 30 minutes at 250 degreeC.

(Evaluation of printability)
The line width (μm) of the silver ink pattern on the polyimide film obtained by the method described above was evaluated. A narrower line width can produce a finer circuit and can improve the integration density, so that it can be determined that the printability is good.

(Printability, ion chromatography, specific surface area)
Based on the same method as in Experimental Example 1, the printability and ion chromatography of the metal oxide film, which is an ink-receiving film prepared on a polyimide film using the coating liquids P-1 to P-9, the specific surface area The evaluation results are summarized in Table 3.

  In either case, the line width is in a range where there is no problem in printing. Furthermore, it was confirmed that the amount of nitrate ions remaining in these series of films was low, and the specific surface area of the samples was also low.

Claims (9)

An ink receiving film comprising a condensate of a silane coupling agent as a main component, wherein the ink receiving film has an acid content of 0.6 ppm or less as NO ₃ ⁻ and a specific surface area of 30 cm ² / cm ² or less. An ink receiving film.   2. The ink receiving film according to claim 1, wherein the ink receiving film contains a filler, the filler has a particle size of 30 to 1000 nm, and the filler concentration with respect to the condensate of the silane coupling agent is 10 to 60% by mass.   The ink receiving film according to claim 1, wherein the silane coupling agent has an amino group.   The ink receiving film according to claim 2, wherein the filler is a silica filler. 5. The ink receiving film according to claim 1, wherein the acid content of the ink receiving film is 0.5 ppm or less as NO ₃ ⁻ and the specific surface area is 15 cm ² / cm ² or less.   6. A laminated substrate, wherein the ink receiving film according to claim 1 is laminated on the substrate.   The laminated substrate according to claim 6, wherein the substrate is a polyimide film, and the thickness of the polyimide film is in the range of 1 to 150 μm.   8. A conductive member, wherein a conductive pattern is formed by printing or applying a conductive material on the surface of the laminated substrate on which the ink receiving film is laminated.   The conductive member according to claim 8, wherein the conductive material includes metal nanoparticles, and the metal of the metal nanoparticles is silver or copper.

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