JP2009027155A - Coating liquid for forming ink-accepting film, manufacturing method therefor, the ink-accepting film, laminated substrate and wiring material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide coating liquid for forming ink-accepting film, which is employed optimally upon manufacturing wiring material through processes for printing ink containing metal paste and metal nanoparticles on the substrate and calcining it. <P>SOLUTION: The coating liquid for forming the ink-accepting film contains aggregate particle containing substance (A), consisting of at least one kind of metal oxide and contains 25-100 mass% of aggregate particle formed by connecting not less than 2 pieces of primary grain, whose average grain size is within a range of 2-200 nm; metal oxide particle (B) consisting of at least one kind of metal oxide and whose average particle size of primary particle that consists of the aggregate particle, having an average grain size larger than the average grain size of the primary grains constituting the aggregate particle, and condensate (C), having repeating unit of M-O obtained by reacting a specified alcoxide compound through hydrolysis-condensation reaction as the principal skeleton thereof. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a coating liquid for forming an ink receiving film, a method for producing the same, an ink receiving film, a laminated substrate, and a wiring material.

  In recent years, the development of materials using metal nanoparticles and metal pastes has become active. In particular, using inks containing these, direct wiring via a receiving layer on a substrate by a printing method such as inkjet or screen. Attention has been focused on a technique for forming (see, for example, Patent Document 1). This technique is characterized by the fact that wiring can be formed without steps such as masking and etching, and that it is a relatively low temperature (about 160 to 250 ° C.) process. Is used as a transparent substrate or the like constituting the display unit.

The wiring material is required to have a high transparency and low cost, and the substrate of the wiring material is required to be lightweight and difficult to break. An organic film such as a polyethylene terephthalate (PET) film has been used as a wiring material substrate. In particular, when printing directly on a substrate using a wiring forming ink containing a metal paste or metal nanoparticles, it is one of the advantages that the wiring can be formed at a relatively low temperature. The higher the allowable range, the more advantageous in terms of wiring reliability, ink selectivity, etc. Therefore, an organic film having a relatively high heat resistance (heat resistant temperature of 160 ° C. or higher) is used as the wiring material substrate. The technical significance of using it is great.

  By the way, when a wiring paste ink containing metal paste or metal nanoparticles is printed directly on a substrate by an inkjet method or the like, a receiving layer ( Ink-receiving film) is provided (for example, see Patent Document 1). As the ink-receiving film, a bead shape in which a water-soluble resin binder such as polyvinyl alcohol and spherical colloidal silica particles are connected in a planar shape. The thing etc. which apply | coated and dried the coating liquid which consists of an aqueous dispersion containing colloidal silica are known (for example, refer patent document 2).

  Similarly to the substrate, the ink receiving film is required to have a heat resistance of at least 160 ° C. or more, preferably 200 ° C. or more. However, an ink receiving film using a conventional resin binder is accompanied by the occurrence of cracks, decomposition, or accompanying it. There was a problem that discoloration would occur.

In addition, in the conventional ink receiving film, the printability may not be sufficient due to the occurrence of bleeding at the time of printing, and the adhesion of the wiring printed on the ink receiving film surface may not be sufficient. Further improvement in quality has been demanded.
JP 2006-59883 A International Publication No. 00/15552 Pamphlet

Under such circumstances, the present invention is particularly susceptible to occurrence of cracks or yellowing when a wiring is directly formed with an ink containing a metal paste or the like on an ink receiving film formed on a substrate surface made of an organic film. Coating liquid for forming an ink receiving film capable of suppressing printing and improving printability and adhesion, a method for efficiently producing the same, and an ink receiving film formed on a substrate using the coating liquid An object of the present invention is to provide a laminated substrate having the ink receiving film and a wiring material in which wiring is formed on the ink receiving film.

  As a result of intensive studies to achieve the above object, the inventors of the present invention have developed a product obtained by subjecting a specific aggregate particle-containing material and metal oxide particles to a hydrolysis-condensation reaction of an alkoxide compound as a binder. To find out that the object can be achieved by a coating liquid containing a condensate having a repeating unit of O (M: silicon, titanium, zirconium, aluminum) as a main skeleton, and to complete the present invention based on this knowledge. It came.

That is, the present invention
(1) Aggregate particle-containing material comprising 25 to 100 mass% of aggregate particles composed of at least one metal oxide and having two or more primary particles having an average particle diameter in the range of 2 to 200 nm ( A) and
Metal oxide particles (B) comprising an oxide of at least one metal and having an average particle size larger than the average particle size of primary particles constituting the aggregate particles;
Formula (I)
R ¹ _n M (OR ² ) _m−n (I)
Wherein R ¹ is a non-hydrolyzable group, R ² is an alkyl group having 1 to 6 carbon atoms, M is a metal atom selected from silicon, titanium, zirconium and aluminum, and m is a metal atom The valence of M is 3 or 4, and n is an integer of 0 to 2 when m is 4, an integer of 0 to 1 when m is 3, and each R when there are a plurality of R ^{1 1} may be different even identical to each other, if the OR ² there are a plurality, each OR ² may be different even identical to each other.)
A condensate (C) having, as a main skeleton, a repeating unit of MO obtained by subjecting an alkoxide compound represented by the following hydrolysis-condensation reaction:
A coating liquid for forming an ink receiving film, comprising:
(2) The metal oxide constituting the aggregate particles in the aggregate particle-containing material (A) includes an oxide of at least one metal selected from silicon, titanium, zirconium and aluminum, The ink-receiving film-forming coating according to (1) above, wherein the metal oxide constituting the product particles (B) includes an oxide of at least one metal selected from silicon, titanium, zirconium and aluminum. Working fluid,
(3) The aggregate particle-containing material (A) includes monodispersed primary particles of an oxide of at least one metal selected from silicon, titanium, zirconium and aluminum, and the average particle size of the primary particles is 2 The ink-receiving film-forming coating solution according to (1) or (2), which is -200 nm,
(4) The ink receiving film-forming coating solution according to (3), wherein the average particle diameter of the primary particles contained in the aggregate particle-containing material (A) is in the range of 5 to 100 nm,
(5) The ratio of the content of the component (B) to the total amount of the component (A) and the component (B) is 5 to 90% by mass based on the solid content, and the components (A), (B) and ( C) The ratio of the total amount of the component (A) and the component (B) to the total amount of the component is 40 to 95% by mass on the basis of the solid content, as described in any one of the above (1) to (4). Coating liquid for forming an ink receiving film,
(6) In the method for producing the coating liquid for forming an ink receiving film described in any one of (1) to (5) above,
(A) a step of preparing a dispersion of the aggregate particle-containing material (A),
(B) a step of preparing a dispersion of metal oxide particles (B),
(C) a step of preparing a binder liquid containing a condensate (C) having a repeating unit of MO as a main skeleton, and (d) a dispersion of aggregate particle-containing material (A), metal oxide particles (B And a binder liquid containing a condensate (C) having a repeating unit of MO as a main skeleton, and a method for producing an ink-receiving film-forming coating liquid,
(7) An ink receiving film formed by applying the coating liquid according to any one of (1) to (5) above,
(8) A laminated substrate, wherein the ink receiving film according to (7) is formed on a substrate,
(9) The laminated substrate according to (8), wherein the substrate is an organic substrate,
(10) A wiring material formed by forming wiring on the surface of the ink receiving film on the multilayer substrate according to (8) or (9), and (11) wiring is screen printing, inkjet printing, The wiring material according to (10), which is formed by any one of flexographic printing, gravure printing, and printing by a dispenser,
Is to provide.

The ink receiving film obtained by using the coating liquid of the present invention is composed of the aggregate particles derived from component (A) and the metal oxide particles derived from component (B) using a specific inorganic condensate (C) as a binder. It is considered that the substrate is in a three-dimensionally mixed state with a certain thickness.
In the ink receiving film, the average particle diameter of the metal oxide particles derived from the component (B) is larger than that of the primary particles constituting the aggregate particles derived from the component (A). Aggregate particles derived from component (A) are thought to be able to form pores on the surface of the ink receiving film to improve ink absorbency (printing characteristics), and metal oxide particles derived from component (B) It is considered that unevenness is formed on the surface of the ink receiving film and the anchor effect on the wiring is exhibited to improve the adhesion of the wiring.
In addition, by using a binder composed of a specific inorganic condensate (C), generation of cracks, discoloration, and the like can be suppressed even if a wiring is printed on the ink receiving film and then baked.
Therefore, according to the present invention, when a wiring is directly formed with an ink containing a metal paste, metal nanoparticles, etc. on an ink receiving film formed on a substrate surface made of an organic film, generation of cracks or yellowing occurs. Thus, it is possible to provide a coating liquid for forming an ink receiving film capable of suppressing the above and improving printability and adhesion.
Further, according to the present invention, it is possible to provide a method for efficiently producing the coating liquid, and further, an ink receiving film formed on a substrate using the coating liquid, and the ink receiving film. A wiring material in which wiring is formed on the laminated substrate and the ink receiving film can be provided.

First, the ink-receiving film-forming coating liquid of the present invention (hereinafter sometimes referred to as the coating liquid of the present invention) will be described.

The coating liquid of the present invention is composed of at least one metal oxide and contains 25 to 100% by mass of aggregate particles in which two or more primary particles having an average particle diameter in the range of 2 to 200 nm are combined. Aggregated particle-containing material (A),
Metal oxide particles (B) comprising an oxide of at least one metal and having an average particle size larger than the average particle size of primary particles constituting the aggregate particles;
Formula (I)
R ¹ _n M (OR ² ) _m−n (I)
Wherein R ¹ is a non-hydrolyzable group, R ² is an alkyl group having 1 to 6 carbon atoms, M is a metal atom selected from silicon, titanium, zirconium and aluminum, and m is a metal atom The valence of M is 3 or 4, and n is an integer of 0 to 2 when m is 4, an integer of 0 to 1 when m is 3, and each R when there are a plurality of R ^{1 1} may be different even identical to each other, if the OR ² there are a plurality, each OR ² may be different even identical to each other.)
A condensate (C) having, as a main skeleton, a repeating unit of MO obtained by subjecting an alkoxide compound represented by the following hydrolysis-condensation reaction:
It is characterized by including.

  In the coating liquid of the present invention, the aggregate particle-containing material (A) is composed of at least one metal oxide, and two or more primary particles having an average particle diameter in the range of 2 to 200 nm are bonded. The aggregated particles are contained in an amount of 25 to 100% by mass.

  (A) The oxide of the metal forming the aggregate particles in the aggregate particle-containing material is at least one selected from silicon, titanium, zirconium and aluminum from the viewpoint of stability, price, availability, etc. An oxide is mentioned, These may be used individually by 1 type and may be used in combination of 2 or more type. Antistatic properties can be simultaneously imparted using a tin-based oxide having conductivity such as antimony-tin-based oxide, indium-tin-based oxide, titanium oxide / tin-antimony oxide.

  The average particle diameter of the primary particles constituting the aggregate particles in the component (A) aggregate particle-containing material is 2 to 200 nm, preferably 5 to 100 nm, more preferably 10 to 80 nm, and still more preferably 10 to 30 nm. . In the present specification, the average particle diameter means an average value of particle diameters measured by a scanning electron microscope (SEM) unless otherwise specified. When the average particle diameter of the primary particles constituting the aggregate particles exceeds 200 nm, the pore diameter of the aggregate particles formed by these particles becomes too large, and the metal particles and metal nanoparticles contained in the paste used as the ink are thin films Phenomenon of penetrating into the interior of the resin and easily diffusing, resulting in deterioration of printability. On the other hand, if the thickness is less than 2 nm, the pore diameter becomes too small, and the solvent contained in the ink cannot penetrate and the printability deteriorates.

The aggregate particles are formed by bonding two or more primary particles made of the metal oxide, and the number of primary particles in the aggregate particles is preferably as large as 2 or more. From the viewpoint of maintaining the transparency of the substrate, 2 to 100 are preferable, 3 to 100 are more preferable, 5 to 50 are more preferable, and 7 to 30 are particularly preferable.
Confirmation of the agglomerated state can also be confirmed by a method of observing with an electron microscope or the like after drying the dispersion in an extremely diluted state.

Examples of the form of the aggregate particles include those having a long chain structure in which primary particles are bonded in a bead shape, and those in which the bonded aggregate particles are branched and / or bent.
Such aggregate particles are formed by connecting primary particles made of, for example, a spherical metal oxide with a metal ion having a valence of 2 or more, for example, Ca ²⁺ , Zn ²⁺ , Mg ²⁺ , Ba ²⁺ , Al ³⁺ , Ti ^4+, etc. Can be obtained. Further, by applying the method described in Patent Document 2, bead-like silica particles can be produced and used as the aggregate particles of the present invention.

The (A) component aggregate particle-containing material contains 25 to 100% by mass of aggregate particles formed by combining two or more primary particles, but preferably contains 40 to 100% by mass, and 60 to 100% by mass. % Containing is more preferable.
The aggregate particle-containing material of component (A) can contain monodispersed primary particles of an oxide of at least one metal selected from silicon, titanium, zirconium and aluminum, and the average particle diameter of the primary particles Is 2 to 200 nm, preferably 5 to 100 nm, more preferably 10 to 80 nm, and even more preferably 10 to 30 nm, like the average particle size of the primary particles constituting the aggregate particles.
Moreover, the content rate of the said monodispersed primary particle in the aggregate particle content of (A) component is 0-75 mass%, Preferably it is 0-60 mass%, More preferably, it is 0-40 mass%.

  In the aggregate particle-containing material of component (A), there is no particular limitation on the method for adjusting the content of the aggregate particles and the monodispersed primary particles, but for example, substantially aggregated particles and substantially aggregated particles. A method of mixing particles (primary particles) that are not formed is simple and preferable.

  In the coating liquid of the present invention, the metal oxide particles of the component (B) are made of at least one metal oxide, and the average particle size is larger than the average particle size of the primary particles constituting the aggregate particles. Metal oxide particles.

The oxide of the metal constituting the metal oxide particles of component (B) is an oxide of at least one metal selected from silicon, titanium, zirconium and aluminum from the viewpoint of stability, price, availability and the like. These may be used, and one kind may be used alone, or two or more kinds may be used in combination.
(B) The average particle diameter of the metal oxide particles of the component is larger than the average particle diameter of the primary particles constituting the aggregate particles in the aggregate particle-containing material of the component (A), for example, 50 to 3000 nm. Preferably, 100 to 2000 nm is more preferable, 200 to 1000 nm is more preferable, and 200 to 500 nm is still more preferable.
As the metal oxide particles of the component (B), when particles smaller than the particle diameter of the primary particles constituting the aggregate particles in the aggregate particles of the component (A) are used, irregularities are efficiently formed on the film surface. It is difficult to let Also, if a material having a thickness exceeding 3000 nm is used, precipitation of particles occurs when it is made into a coating liquid, which makes it difficult to handle, and when used as a receiving layer, the surface of the film and internal scattering increase. This causes a problem that the liquid becomes easily cloudy.

In the coating liquid of the present invention, the condensate of component (C) is used as a binder and has the general formula (I)
R ¹ _n M (OR ² ) _m−n (I)
The alkoxide compound represented by these is a hydrolysis-condensation reaction.

In the compound represented by the general formula (I), R ¹ represents a non-hydrolyzable group, for example, an alkyl group having 1 to 20 carbon atoms, a (meth) acryloyloxy group, or an epoxy group having 1 to 1 carbon atoms. A 20-alkyl group, an alkenyl group having 2-20 carbon atoms, an aryl group having 6-20 carbon atoms, or an aralkyl group having 7-20 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.
Examples of this alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, and cyclopentyl. Group, cyclohexyl group and the like. As a C1-C20 alkyl group which has a (meth) acryloyloxy group or an epoxy group as a substituent, the C1-C10 alkyl group which has the said 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-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. As a C6-C20 aryl group, a C6-C10 thing is preferable, for example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group etc. are mentioned. As a C7-20 aralkyl group, a C7-10 thing is preferable, for example, a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group etc. are mentioned.

In the compound represented by the above general formula (I), R ² is an alkyl group having 1 to 6 carbon atoms, and may be any of linear, branched and cyclic. Group, ethyl group, n-propyl group, 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 compound represented by the general formula (I), M represents a metal atom selected from silicon, titanium, zirconium and aluminum, m is a valence of the metal atom M, and is 3 in the case of aluminum. 4 for titanium or zirconium. n is an integer of 0 to 2 when m is 4, and an integer of 0 to 1 when m is 3.
When R ¹ are a plurality, each R ¹ may be mutually identical or different and, where OR ² there are a plurality, each OR ² may be the mutually the same, or different It may be.

  Examples of the alkoxide compound in the case where M is tetravalent silicon, m is 4, and n is an integer of 0 to 2 in the compound represented by the general formula (I) include tetramethoxysilane, Tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxy Silane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyl Triethoxysilane, .gamma.-glycidoxypropyltrimethoxysilane, .gamma. acryloyloxypropyltrimethoxysilane, .gamma.-methacryloyloxy propyl trimethoxy silane, dimethyl dimethoxy silane, and the like methylphenyl dimethoxysilane.

  Examples of the alkoxide compound in the case where M is tetravalent titanium or zirconium, m is 4, and n is an integer of 0 to 2 in the compound represented by the above general formula (I) The compound which replaced the silane in the illustrated silane compound with titanium or zirconium can be mentioned.

  Examples of the alkoxide compound represented by the general formula (I) in which M is trivalent aluminum, m is 3, and n is an integer of 0 to 1 include tri Methoxy aluminum, triethoxy aluminum, tri-n-propoxy aluminum, triisopropoxy aluminum, tri-n-butoxy aluminum, triisobutoxy aluminum, tri-sec-butoxy aluminum, tri-tert-butoxy aluminum, methyl dimethoxy aluminum, methyl Examples include diethoxyaluminum, methyldipropoxyaluminum, ethyldimethoxyaluminum, ethyldiethoxyaluminum, and propyldiethoxyaluminum.

These alkoxide compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
In the preparation of the condensate of component (C), an oligomer such as an alkoxysilane oligomer obtained by previously hydrolyzing and condensing the various alkoxide compounds can be used together with the various alkoxide compounds.

  The hydrolysis-condensation reaction of the alkoxide compound of the general formula (I) is carried out by, for example, reacting the alkoxide compound with hydrochloric acid, sulfuric acid, nitric acid or the like in an appropriate polar solvent such as alcohol, cellosolve, ketone, or ether. When the solid acid is used, it is hydrolyzed at a temperature of usually 0 to 60 ° C., preferably 20 to 40 ° C. under acidic conditions using a cation exchange resin as a solid acid or a solid acid. After the removal, it can be carried out by further distilling off or adding the solvent, if desired. By the above reaction, a condensate having a repeating unit of MO (M is the same as above) as the main skeleton ( A liquid (binder liquid) containing C) at a predetermined concentration can be obtained.

  In the coating liquid of this invention, the ratio of content of (B) component with respect to the total amount of (A) component and (B) component is 5-90 mass% on solid content basis, (A) component, It is preferable that the ratio of the total amount of the component (A) and the component (B) to the component (B) and the component (C) is 40 to 95% by mass on the solid content basis.

  The ratio of the content of the component (B) to the total amount of the component (A) and the component (B) is preferably 40 to 90% by mass and more preferably 70 to 90% by mass based on the solid content. preferable.

Moreover, it is preferable that the ratio of the total amount of (A) component and (B) component with respect to (A) component, (B) component, and (C) component is 50-95 mass% on the solid content basis, 60 More preferably, it is -95 mass%.
By controlling each ratio within the above-described range, it is possible to control the balance of printability such as the adhesion of the wiring to the organic substrate and the ink absorbability within a favorable range.
Moreover, the solid content concentration in the coating liquid of the present invention is not particularly limited as long as it is a concentration suitable for coating, but is usually 2 to 30% by mass, preferably 5 to 20% by mass.

The coating liquid of the present invention may further contain an antistatic agent. As the antistatic agent, a dispersion containing particles of conductive metal oxide, metal, carbon, etc., conductive polymers, ionic liquids, surfactants, etc. can be used. It is preferable to select one that does not inhibit the sex. The content of the antistatic agent may be appropriately adjusted according to the type of antistatic agent and the principle of performance expression and within a range that does not impair the effects of the present invention.
For example, when using a conductive tin-based oxide such as antimony-tin oxide, indium-tin oxide, titanium oxide / tin-antimony oxide as component (A), antistatic performance is also provided at the same time It will be possible.
Moreover, within the range which does not inhibit the effect of this invention, a well-known additive, for example, film-forming auxiliary agent, a plasticizer, a lubricant, surfactant, a heat-resistant agent, a weathering agent etc., can also be contained.

Next, a method for producing a coating liquid for forming an ink receiving film of the present invention (hereinafter sometimes referred to as a process for producing a coating liquid of the present invention) will be described.
The production method of the coating liquid of the present invention is as follows:
(A) a step of preparing a dispersion of the aggregate particle-containing material (A),
(B) preparing a dispersion of the metal oxide particles (B),
(C) a step of preparing a binder liquid containing the condensate (C) having a repeating unit of MO as a main skeleton, and (d) a dispersion of the aggregate particle-containing material (A), metal oxide particles The method includes a step of mixing a dispersion liquid of (B) and a binder liquid containing a condensate (C) having a repeating unit of MO as a main skeleton.

  In the step (a), preferred embodiments of the aggregate particle-containing material (A) and the method for preparing the same include the same embodiments as those described in the ink-receiving film-forming coating solution of the present invention. Examples of the dispersion medium for dispersing the aggregate particle-containing material include alcohol solvents such as methanol, ethanol, propanol, butanol and cyclohexanol, polyhydric alcohol solvents such as ethylene glycol and derivatives thereof, methyl cellosolve, ethyl cellosolve, and butyl cellosolve. Examples include cellosolve solvents and derivatives thereof, and ketone solvents such as acetone, methyl isobutyl ketone, and cyclohexanone. Other examples include toluene, xylene, hexane, dimethylacetamide, ether, ethyl acetate, butyl acetate, and water. be able to.

  In the step (b), examples of the metal oxide particles (B) include the same as those described in the ink-receiving film-forming coating liquid of the present invention. Examples thereof include the same as those described in the step (a).

  In the step (c), the condensate (C) having a main skeleton of a MO repeating unit obtained by hydrolysis-condensation reaction of the compound represented by the general formula (I) Examples thereof may be the same as those described in the ink-receiving film-forming coating solution of the invention.

  As a method for obtaining a binder liquid containing the condensate, for example, in an appropriate polar solvent such as an alcohol, cellosolve, ketone, or ether, an alkoxide compound represented by the general formula (I) is treated with hydrochloric acid, In the case of using a solid acid after hydrolysis at a temperature of usually 0 to 60 ° C., preferably 20 to 40 ° C. under acidic conditions using an acid such as sulfuric acid or nitric acid, or a cation exchange resin as a solid acid In the method, after removing it, a method of further removing or adding a solvent as desired may be mentioned. By the above reaction, a binder containing a condensate having a repeating unit of M-O as a main skeleton at a predetermined concentration. A liquid can be obtained.

  In the step (d), the dispersion medium used when mixing the components (A) to (C) includes alcohol solvents such as methanol, ethanol, propanol, butanol and cyclohexanol, and polyhydric alcohols such as ethylene glycol. Solvents, derivatives thereof, cellosolve solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, derivatives such as ethylene glycol-t-butyl ether, propylene glycol-mono-methyl ether, solvents such as acetone, methyl isobutyl ketone, cyclohexanone Other examples include toluene, xylene, hexanedimethylacetamide, ether, ethyl acetate, butyl acetate, and water.

  In the step (d), when the dispersion obtained in the step (a) and the dispersion obtained in the step (b) are mixed, the aggregate particles containing the component (A) in the mixture are contained. The ratio of the content of the metal oxide particles of the component (B) to the total amount of the product and the metal oxide particles of the component (B) is preferably 5 to 90% by mass, and 40 to 90% by mass. Is more preferable, and it is further more preferable that it is 70-90 mass%.

  Further, the ratio of the total amount of the aggregate particle content of the component (A) and the metal oxide particles of the component (B) to the components (A), (B) and (C) in the coating liquid is 40. It is preferable to set it as -95 mass%, It is more preferable that it is 50-95 mass%, It is further more preferable that it is 60-95 mass%.

  Moreover, in the said (d) process, it is preferable to make solid content concentration in a coating liquid into the density | concentration suitable for coating, Although there is no restriction | limiting in particular, Solid content concentration shall usually be 2-30 mass%. It is more preferable, and it is more preferable to set it as 5-20 mass%. Here, the weight of the condensate (C) in the binder liquid may be calculated on the assumption that the hydrolysis-condensation reaction of the alkoxide compound represented by the general formula (I) is completely completed.

  0-60 degreeC is preferable, the temperature at the time of mixing has more preferable 5-40 degreeC, and 10-30 degreeC is further more preferable. The mixing time is preferably 5 to 180 minutes, more preferably 15 to 150 minutes, and further preferably 30 to 120 minutes.

  Further, in the step (d), an antistatic agent is further mixed into the dispersion liquid containing the aggregate particles (A), the dispersion liquid of the metal oxide particles (B), and the binder liquid containing the condensate (C). May be.

Examples of the antistatic agent include the same antistatic agents as those described in the ink-receiving film-forming coating liquid of the present invention. The amount of the antistatic agent added depends on the type and the principle of performance expression. Accordingly, it can be appropriately set within a range that does not impair the effects of the present invention.
In addition, a known additive such as a film-forming auxiliary, a plasticizer, a lubricant, a surfactant, a heat-resistant agent, a weathering agent, etc. is mixed within a range not impairing the effect of the coating liquid obtained by the production method of the present invention. be able to.

Next, the ink receiving film of the present invention will be described.
The ink receiving film of the present invention is characterized in that the ink receiving film forming coating liquid of the present invention is applied.

  Examples of the ink-receiving film-forming coating liquid include the same ones as described in the ink-receiving film-forming coating liquid of the present invention.

  The ink receiving film is preferably formed by applying a coating liquid on an organic substrate and drying it. The organic substrate has a balance of lightness, flexibility, resistance to cracking, mechanical properties, economy, and the like. In view of the above, a plastic film is preferable. Examples of the plastic film include polyester film, polycarbonate film, triacetyl cellulose film, cellophane film, polyamide film, polyimide film, polyphenylene sulfide film, polyetherimide film, polyethersulfone film, aromatic polyamide film, polysulfone film, and polyolefin. A film, a polycycloolefin, etc. can be mentioned. However, it is preferable to use a polyester film, a polycarbonate film, a polyphenylene sulfide film, or a polycycloolefin from the viewpoints of mechanical characteristics, thermal characteristics, and price.

Polyester film is a general term for polymer films having an ester bond as the main bond chain, and a particularly preferred polyester is polyethylene terephthalate (PET).
Polyethylene naphthalate (PEN), polyethylene α, β-bis (2-chlorophenoxy) ethane 4,4′-dicarboxylate, polybutylene terephthalate and the like are preferable.

  Further, known additives in these plastic films, such as heat stabilizers, oxidation stabilizers, weathering stabilizers, ultraviolet absorbers, organic lubricants, pigments, dyes, organic or inorganic fine particles, fillers, You may mix | blend an antistatic agent, a nucleating agent, etc.

There is no restriction | limiting in particular in the thickness of the board | substrate consisting of a plastic film etc., Although it changes according to a use, Usually, 1-500 micrometers, Preferably it is 10-300 micrometers, More preferably, it is 20-250 micrometers.

  Further, the surface of the plastic film may be subjected to surface treatment or primer treatment by an oxidation method or a concavo-convex method, if desired, for the purpose of improving adhesion with an ink receiving film provided on the surface of the plastic film. it can. Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like. Examples include solvent processing methods. These surface treatment methods are appropriately selected according to the type of the plastic film, but in general, the corona discharge treatment method is preferably used from the viewpoints of effects and operability.

  In the above example, the case where an organic substrate such as a plastic film is used as the substrate has been described in detail. However, in the present invention, an inorganic substrate made of glass, silicon, or the like may be used.

  The coating liquid of the present invention described above is applied to the surface of a substrate such as the plastic film substrate by a conventionally known method, for example, dip coating method, spin coating method, spray coating method, bar coating method, knife coating method, roll coating method. The ink receiving film of the present invention is formed on a substrate by coating by a blade coating method, a die coating method, a gravure coating method, etc., forming a film, and then naturally drying or heat drying. In the case of heat drying, a temperature of 200 ° C. or lower can be adopted.

  The thickness of the ink receiving film of the present invention is preferably from 0.3 to 50 μm, more preferably from 0.3 to 30 μm, still more preferably from 0.5 to 20 μm, from the viewpoint of film strength and ink absorbability. More preferably, it is 5-3 micrometers.

  When used for applications that require transparency, the net haze value (Hz) of the ink receiving film is preferably 6% or less, more preferably 4% or less, and preferably 2% or less. Further preferred. However, the haze value may be 6% or more when used for applications that do not substantially require transparency.

When the coating solution contains an antistatic agent, the surface resistance of the obtained ink receiving film is preferably 10 ⁵ to 10 ¹³ Ω / cm ² , and preferably 10 ⁷ to 10 ¹² Ω / cm ^2. More preferably, it is 10 ⁹ to 10 ¹¹ Ω / cm ² . When the surface resistance value is within the above range, it is possible to prevent dust and foreign matters from adhering to the substrate after the ink receiving layer is formed, and to suppress the generation of static electricity.

In the ink receiving film of the present invention, the aggregated particle containing component (A) and the metal oxide particles (B) are mixed and exist three-dimensionally with a certain thickness on the substrate. it is conceivable that.
In the above ink-receiving film, it is considered that the aggregate particle-containing component (A) can improve the ink absorbability (printing characteristics) by forming pores on the surface of the ink-receiving film because of its three-dimensional structure. It is done. Further, the presence of the aggregate particles in the ink receiving film can suppress the generation of cracks after the film formation.
In addition, since the metal oxide particles (B) have a larger average particle diameter than the primary particles constituting the aggregate particles containing the component (A), irregularities are formed on the surface of the ink receiving film. Thus, it is considered that the anchor effect is exerted on the wiring on the surface of the ink receiving film, and the adhesion of the wiring can be improved.

Next, the laminated substrate of the present invention will be described.
The laminated substrate of the present invention is characterized in that the ink receiving film of the present invention is formed on a substrate.
Examples of the ink receiving film of the present invention include the same ones as described above, and the substrate used in the laminated substrate of the present invention includes the same ones as described for the ink receiving film of the present invention. Among them, the organic substrate described above is preferable, and a substrate made of a polyester film is more preferable.
The method for forming the ink receiving film on the substrate is the same as the method described for the ink receiving film of the present invention.

Next, the wiring material of the present invention will be described.
The wiring material of the present invention is characterized in that wiring is formed on the surface of the ink receiving film on the laminated substrate of the present invention.

  The wiring material of the present invention is preferably formed by screen printing, inkjet printing, flexographic printing, gravure printing, or printing by a dispenser, and is formed by screen printing or inkjet printing. It is more preferable.

As a manufacturing method of the wiring material of the present invention, for example,
(X) A step of coating the coating liquid of the present invention on a substrate, particularly a substrate made of a polyester film, and drying to form a laminated substrate having an ink receiving film,
(Y) The method of printing on the ink-receiving film surface on this laminated substrate using an ink, and (z) The method of baking at the temperature of 160-250 degreeC in the said order can be mentioned.

In the step (y), as the ink for forming the wiring on the ink receiving film, a metal paste such as a silver paste or an ink containing metal nanoparticles can be used.
As a printing method, it is preferable to print in a predetermined pattern shape on the ink receiving film using a screen printing method, an ink jet printing method, or the like.
Next, in the step (z), the wiring according to the present invention, in which wiring of a predetermined pattern is formed on the surface of the ink receiving film by baking at a temperature of 160 to 250 ° C., preferably 170 to 200 ° C. for about 30 to 60 minutes. Material can be obtained.

  In the present invention, since the ink receiving film is formed using the coating liquid of the present invention using a specific inorganic binder, cracks are generated even after the wiring is printed and fired as described above. Generation of discoloration, discoloration, cloudiness, etc. can be suppressed, and a wiring material with good quality can be obtained.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Example 1 (Example of production of coating liquid)
(1) Preparation of Aggregate Particle-Containing Dispersion Liquid Using an aggregate particle-containing material composed only of silica aggregate particles in which two or more silica particles having an average primary particle diameter of 15 nm are combined, the content is 15 A dispersion containing mass% (hereinafter referred to as (A) -1 component dispersion) was prepared.
(2) Preparation of metal oxide particle dispersion A dispersion containing 15% by mass of silica primary particles having a particle size of 480 nm (hereinafter referred to as (B) -1 component dispersion) was prepared.
(3) Preparation of condensate-containing binder solution 307 g of glycidoxypropyltrimethoxysilane and 277 g of titanium tetraisopropoxide are dissolved in 257 g of ethyl cellosolve, and a mixed solution of 101 g of concentrated nitric acid, 32 g of water and 37 g of ethyl cellosolve is added dropwise thereto. Then, by reacting at 30 ° C. for 4 hours, the solid content concentration is 30% by mass, and the condensate (C) containing liquid (hereinafter referred to as (( C) -1 component-containing binder liquid) was prepared.
(4) Mixing and stirring treatment In 240 g of cyclohexanone, 560 g of (A) -1 component dispersion obtained in (1) above and 160 g of (B) -1 component dispersion obtained in (2) above were added with stirring. Then, 40 g of the (C) -1 component-containing binder liquid obtained in (3) above was dropped into this mixed liquid and stirred at room temperature for 1 hour to prepare a coating liquid having a solid content concentration of 12% by mass. did. The composition of the obtained coating liquid is shown in the “Coating liquid” column of Table 1.

Example 2 (Example of production of coating liquid)
In 240 g of cyclohexanone, 400 g of (A) -1 component dispersion obtained in (1) of Example 1 and 320 g of (B) -1 component dispersion obtained in (2) of Example 1 were added with stirring. Then, 40 g of the (C) -1 component-containing binder liquid obtained in (3) of Example 1 was dropped into this mixed liquid and stirred at room temperature for 1 hour, whereby a coating liquid having a solid content concentration of 12% by mass was obtained. Was prepared. The composition of the obtained coating liquid is shown in the “Coating liquid” column of Table 1.

Example 3 (Production Example of Coating Liquid)
In 240 g of cyclohexanone, 160 g of (A) -1 component dispersion obtained in (1) of Example 1 and 560 g of (B) -1 component dispersion obtained in (2) of Example 1 were added with stirring. Then, 40 g of the (C) -1 component-containing binder liquid obtained in (3) of Example 1 was dropped into this mixed liquid and stirred at room temperature for 1 hour, whereby a coating liquid having a solid content concentration of 12% by mass was obtained. Was prepared. The composition of the obtained coating liquid is shown in the “Coating liquid” column of Table 1.

Example 4 (Production Example of Coating Liquid)
To 280 g of cyclohexanone, 356 g of (A) -1 component dispersion obtained in (1) of Example 1 and 284 g of (B) -1 component dispersion obtained in (2) of Example 1 were added with stirring. Then, 80 g of the (C) -1 component-containing binder liquid obtained in (3) of Example 1 was dropped into this mixed liquid and stirred at room temperature for 1 hour, whereby a coating liquid having a solid content concentration of 12% by mass was obtained. Was prepared. The composition of the obtained coating liquid is shown in the “Coating liquid” column of Table 1.

Example 5 (Production Example of Coating Liquid)
Into 360 g of cyclohexanone, 269 g of the (A) -1 component dispersion obtained in (1) of Example 1 and 211 g of the (B) -1 component dispersion obtained in (2) of Example 1 were added with stirring. Then, 160 g of the (C) -1 component-containing binder solution obtained in (3) of Example 1 was dropped into this mixed solution and stirred at room temperature for 1 hour, whereby a coating solution having a solid content concentration of 12% by mass was obtained. Was prepared. The composition of the obtained coating liquid is shown in the “Coating liquid” column of Table 1.

Example 6 (Production Example of Coating Liquid)
(1) Preparation of Aggregate Particle-Containing Dispersion Liquid Silica aggregate particles in which two or more silica particles having a primary particle diameter of 15 nm are combined with silica primary particles having a particle diameter of 15 nm are 60/40 in weight ratio. Using the agglomerated particle-containing material thus mixed, a dispersion liquid (hereinafter referred to as (A) -2 component dispersion liquid) containing 15 mass% of the inclusion material was prepared.
(2) Mixing and stirring treatment In 240 g of cyclohexanone, 400 g of the (A) -2 component dispersion obtained in (1) above and 320 g of the (B) -1 component-containing liquid obtained in (2) of Example 1 were stirred. Then, 40 g of the (C) -1 component-containing binder solution obtained in (3) of Example 1 was added dropwise to this mixed solution, and the mixture was stirred at room temperature for 1 hour, whereby the solid content concentration was 12% by mass. A coating solution was prepared. The composition of the obtained coating liquid is shown in the “Coating liquid” column of Table 1.

Example 7 (Production Example of Coating Liquid)
(1) Preparation of Aggregate Particle-Containing Dispersion Liquid Silica aggregate particles in which two or more silica particles having a primary particle diameter of 15 nm are bonded to silica primary particles having a particle diameter of 15 nm are 40/60 by weight. Using the aggregated particle-containing material thus mixed, a dispersion containing 15% by mass of the inclusion (hereinafter referred to as (A) -3 component dispersion) was prepared.
(2) Mixing and stirring treatment In 240 g of cyclohexanone, 400 g of (A) -3 component dispersion obtained in (1) above and 320 g of (B) -1 component-containing liquid obtained in (2) of Example 1 were stirred. Then, 40 g of the (C) -1 component-containing binder solution obtained in (3) of Example 1 was added dropwise to this mixed solution, and the mixture was stirred at room temperature for 1 hour, whereby the solid content concentration was 12% by mass. A coating solution was prepared. The composition of the obtained coating liquid is shown in the “Coating liquid” column of Table 1.

Example 8 (Production Example of Coating Liquid)
(1) Preparation of Condensate-Containing Liquid 307 g of glycidoxypropyltrimethoxysilane and 147 g of tetramethoxysilane oligomer (average tetramer) were dissolved in 257 g of methanol, and 32 g of nitric acid having a concentration of 0.1 mol / L was dissolved therein. Containing a condensate (C) having a repeating unit of Si—O having a solid content concentration of 30% by mass as a main skeleton by adding a mixture of 221 g of water and 37 g of methanol dropwise and then reacting at 30 ° C. for 24 hours. A liquid (hereinafter referred to as (C) -2 component-containing binder liquid) was prepared.
(2) Mixing and stirring treatment In 240 g of cyclohexanone, 400 g of (A) -1 component dispersion obtained in (1) of Example 1 and (B) -1 component dispersion obtained in (2) of Example 1 320 g was added with stirring, and then 40 g of the (C) -2 component-containing binder solution obtained in (1) above was added dropwise to the mixture, followed by stirring at room temperature for 1 hour, whereby a solid content concentration of 12% by mass was obtained. A coating solution was prepared. The composition of the obtained coating liquid is shown in the “Coating liquid” column of Table 1.

Example 9 (Production Example of Coating Liquid)
(1) Preparation of metal oxide particle dispersion A dispersion containing 30% by mass of silica primary particles having a particle diameter of 50 nm (hereinafter referred to as (B) -2 component dispersion) was prepared.
(2) Mixing and stirring treatment In 521 g of cyclohexanone, 158 g of (A) -1 component dispersion obtained in (1) of Example 1 and 281 g of (B) -2 component dispersion obtained in (1) above were stirred. Then, 40 g of the (C) -1 component-containing binder solution obtained in (3) of Example 1 was added dropwise to this mixed solution, and the mixture was stirred at room temperature for 1 hour, whereby the solid content concentration was 12% by mass. A coating solution was prepared. The composition of the obtained coating liquid is shown in the “Coating liquid” column of Table 1.

Example 10 (Production Example of Coating Liquid)
(1) Preparation of metal oxide particle dispersion A dispersion (hereinafter referred to as (B) -3 component dispersion) containing 30% by mass of silica primary particles having a particle diameter of 100 nm was prepared.
(2) Mixing and stirring treatment In 521 g of cyclohexanone, 158 g of (A) -1 component dispersion obtained in (1) of Example 1 and 281 g of (B) -3 component dispersion obtained in (1) above were stirred. Then, 40 g of the (C) -1 component-containing binder solution obtained in (3) of Example 1 was added dropwise to this mixed solution, and the mixture was stirred at room temperature for 1 hour, whereby the solid content concentration was 12% by mass. A coating solution was prepared. The composition of the obtained coating liquid is shown in the “Coating liquid” column of Table 1.

Example 11 (Production Example of Coating Liquid)
(1) Preparation of Aggregate Particle-Containing Dispersion Liquid Using an aggregate particle-containing material composed only of silica aggregate particles in which two or more silica particles having an average primary particle diameter of 60 nm are combined, the content is 15 A dispersion containing mass% (hereinafter referred to as (A) -4 component dispersion) was prepared.
(2) Mixing and stirring treatment In 240 g of cyclohexanone, 400 g of the (A) -4 component dispersion obtained in (1) above and 320 g of the (B) -1 component-containing liquid obtained in (2) of Example 1 were stirred. Then, 40 g of the (C) -1 component-containing binder solution obtained in (3) of Example 1 was added dropwise to this mixed solution, and the mixture was stirred at room temperature for 1 hour, whereby the solid content concentration was 12% by mass. A coating solution was prepared. The composition of the obtained coating liquid is shown in the “Coating liquid” column of Table 1.

Example 12 (Production Example of Coating Liquid)
(1) Preparation of Aggregate Particle-Containing Dispersion Liquid Silica aggregate particles in which two or more silica particles having a primary particle diameter of 15 nm are bonded to zirconia primary particles having a particle diameter of 30 nm are 40/60 by weight. Using the agglomerated particle-containing material thus mixed, a dispersion liquid (hereinafter referred to as (A) -5 component dispersion liquid) containing 15 mass% of the inclusion material was prepared.
(2) Mixing and stirring treatment In 240 g of cyclohexanone, 400 g of the (A) -5 component dispersion obtained in (1) above and 320 g of the (B) -1 component-containing liquid obtained in (2) of Example 1 were stirred. Then, 40 g of the (C) -1 component-containing binder solution obtained in (3) of Example 1 was added dropwise to this mixed solution, and the mixture was stirred at room temperature for 1 hour, whereby the solid content concentration was 12% by mass. A coating solution was prepared. The composition of the obtained coating liquid is shown in the “Coating liquid” column of Table 1.

Example 13 (Production Example of Coating Liquid)
(1) Preparation of Aggregate Particle-Containing Dispersion Liquid Silica aggregate particles in which two or more silica particles having a primary particle diameter of 15 nm are bonded to primary alumina particles having a particle diameter of 25 nm are 40/60 by weight. Using the agglomerated particle-containing material thus mixed, a dispersion liquid (hereinafter referred to as (A) -6 component dispersion liquid) containing 15 mass% of the inclusion material was prepared.
(2) Mixing and stirring treatment In 240 g of cyclohexanone, 400 g of the (A) -6 component dispersion obtained in (1) above and 320 g of the (B) -1 component-containing liquid obtained in (2) of Example 1 were stirred. Then, 40 g of the (C) -1 component-containing binder solution obtained in (3) of Example 1 was added dropwise to this mixed solution, and the mixture was stirred at room temperature for 1 hour, whereby the solid content concentration was 12% by mass. A coating solution was prepared. The composition of the obtained coating liquid is shown in the “Coating liquid” column of Table 1.

Example 14 (Example of production of coating liquid)
(1) Preparation of Aggregate Particle-Containing Dispersion Liquid Silica aggregate particles in which two or more silica particles having a primary particle diameter of 15 nm are bonded to titania primary particles having a particle diameter of 40 nm are 40/60 by weight. Using the agglomerated particle-containing material thus mixed, a dispersion liquid (hereinafter referred to as (A) -7 component dispersion liquid) containing 15 mass% of the inclusion material was prepared.
(2) Mixing and stirring treatment In 240 g of cyclohexanone, 400 g of (A) -7 component dispersion obtained in (1) above and 320 g of (B) -1 component-containing liquid obtained in (2) of Example 1 were stirred. Then, 40 g of the (C) -1 component-containing binder solution obtained in (3) of Example 1 was added dropwise to this mixed solution, and the mixture was stirred at room temperature for 1 hour, whereby the solid content concentration was 12% by mass. A coating solution was prepared. The composition of the obtained coating liquid is shown in the “Coating liquid” column of Table 1.

Comparative Example 1 (Example of coating liquid production)
720 g of the (A) -1 component dispersion obtained in (1) of Example 1 was added to 240 g of cyclohexanone with stirring, and then the (C) -1 component-containing binder solution obtained in (3) of Example 1 was added. 40 g was added dropwise and stirred at room temperature for 1 hour to prepare a coating solution having a solid content concentration of 12% by mass. The composition of the obtained coating liquid is shown in the “Coating liquid” column of Table 1.

Comparative Example 2 (Production Example of Coating Liquid)
In 240 g of cyclohexanone, 36 g of (A) -1 component dispersion obtained in (1) of Example 1 and 684 g of (B) -1 component dispersion obtained in (2) of Example 1 were added with stirring. Then, 40 g of the (C) -1 component-containing binder liquid obtained in (1) of Example 1 was added dropwise and stirred at room temperature for 1 hour to prepare a coating liquid having a solid content concentration of 12% by mass. The composition of the obtained coating liquid is shown in the “Coating liquid” column of Table 1.

Comparative example 3 (manufacture example of coating liquid)
(1) Mixing and stirring treatment 90 g of (A) -1 component dispersion obtained in (1) of Example 1 and 520 g of cyclohexanone and (B) -1 component dispersion obtained in (2) of Example 1 above 70 g of the liquid was added with stirring, and then 320 g of the (C) -1 component-containing binder liquid obtained in (1) of Example 1 was added dropwise to this mixed liquid, followed by stirring at room temperature for 1 hour to obtain a solid content. A coating solution having a concentration of 12% by mass was prepared. The composition of the obtained coating liquid is shown in the “Coating liquid” column of Table 1.

Example 15 (Example of manufacturing ink receiving film and laminated substrate)
Using the coating liquids obtained in Examples 1 to 14, a polyethylene naphthalate (PEN) film (manufactured by Teijin DuPont Films, trade name “Teonex Q51”, thickness 188 μm) was dried to a thickness after bar coating. The coating liquid was applied so that the thickness was 1.5 μm, and after heating at 120 ° C. for 1 minute, each ink receiving film was formed by aging at 60 ° C. for 3 days to produce a laminated substrate.
Using the obtained laminated substrate, the presence or absence of cracks in the ink receiving film was evaluated by observing with an optical microscope (magnification 1250 times). The obtained results are shown in the “Characteristic” item in the “ink-receiving film” column of Table 1. The evaluation results of the properties (cracks) of the ink receiving film shown in Table 1 are described so as to correspond to the coating liquids of Examples 1 to 14.

Comparative Example 4 (Production example of ink receiving film and laminated substrate)
Each ink receiving film was formed on the PEN film in the same manner as in Example 15 except that the coating liquid obtained in Comparative Examples 1 to 3 was used instead of the coating liquid obtained in Examples 1 to 14. A laminated substrate was produced.
Using the obtained multilayer substrate, the presence or absence of cracks in the ink receiving film was evaluated by the same method as in Example 15. The obtained results are shown in the “Characteristic” item in the “ink-receiving film” column of Table 1. The evaluation results of the properties (cracks) of the ink receiving film shown in Table 1 are described so as to correspond to the coating liquids of Comparative Examples 1 to 3.

Example 16 (Example of production of wiring material)
On the ink-receiving film of the laminated substrate obtained in Example 15 using the coating liquid obtained in Examples 1 to 14, an Ag paste [Silver nanopaste manufactured by ULVAC, Inc., trade name “Ag1TeH”] was ink-jetted. The wiring material was produced by printing in the predetermined pattern shape by the printing method, and baking for 60 minutes at 230 degreeC.
In the obtained wiring material, the presence or absence of cracks and printability were evaluated by the following methods. The result is shown in the “Characteristic” item in the “Wiring material” column of Table 1.
Further, a wiring material was prepared by the same method as described above except that printing was performed by a spin coat method instead of the ink jet printing method, and the adhesion of the obtained wiring material was evaluated by the following method. The result is shown in the “Characteristic” item in the “Wiring material” column of Table 1.
In Table 1, the evaluation results of the characteristics (cracks, printability, adhesion) of the obtained wiring material are described so as to correspond to the coating liquids of Examples 1-14.

(1) Presence / absence of cracks Observation with an optical microscope (magnification 1250 times) was performed to examine the presence or absence of cracks.
(2) Printability Obtain the spread width X when the printing width of the commercially available inkjet media [Pictrico Co., Ltd., trade name “Pictrico (TPX-1766 / 2)]” is 1, and print according to the following criteria. Sex was evaluated.
○: 0.1 ≦ X ≦ 1.2
Δ: 1.2 <X ≦ 1.5
×: 1.5 <X
(3) Adhesiveness Adhesiveness tests were performed in accordance with JISK5600 (cross-cut tester: “C222” manufactured by Yoshimitsu Seiki Co., Ltd., tape: cello tape (registered trademark) manufactured by Nichiban Co., Ltd.).
For the adhesion evaluation, the presence or absence of peeling was confirmed with an optical microscope (magnification 1250 times), and the following evaluation was performed based on the area of the peeling portion.
○: 8 to 10 points Δ: 6 to 8 points ×: 0 to 6 points As shown in Table 1, in each wiring material obtained in Example 16, generation of cracks was not recognized, and printability and adhesion The properties were all good.

Comparative Example 5 (Example of manufacturing wiring material)
Wiring was formed in the same manner as in Example 16 on the ink receiving film of the laminated substrate obtained in Comparative Example 4 using the coating liquids of Comparative Examples 1 to 3, thereby obtaining a wiring material.
The performance of each obtained wiring material was evaluated in the same manner as in Example 16. The result is shown in the “Characteristic” item in the “Wiring material” column of Table 1. In Table 1, the evaluation results of the characteristics (cracks, printability, adhesion) of the obtained wiring material are described so as to correspond to the coating liquids of Comparative Examples 1 to 3.
As shown in Table 1, each wiring material obtained in Comparative Example 5 was inferior in adhesion.

  The ink-receiving film-forming coating liquid of the present invention includes an inorganic condensate obtained by subjecting a specific aggregate particle-containing material, a specific metal oxide particle, and a specific alkoxide compound to a hydrolysis-condensation reaction, In particular, it is suitably used when producing a wiring material through a process of printing and baking a metal paste or ink containing metal nanoparticles on an organic substrate.

Claims (11)

An aggregate particle-containing material (A) comprising 25 to 100% by mass of an aggregate particle composed of at least one metal oxide and having two or more primary particles having an average particle diameter in the range of 2 to 200 nm; ,
Metal oxide particles (B) comprising an oxide of at least one metal and having an average particle size larger than the average particle size of primary particles constituting the aggregate particles;
Formula (I)
R ¹ _n M (OR ² ) _m−n (I)
Wherein R ¹ is a non-hydrolyzable group, R ² is an alkyl group having 1 to 6 carbon atoms, M is a metal atom selected from silicon, titanium, zirconium and aluminum, and m is a metal atom The valence of M is 3 or 4, and n is an integer of 0 to 2 when m is 4, an integer of 0 to 1 when m is 3, and each R when there are a plurality of R ^{1 1} may be different even identical to each other, if the OR ² there are a plurality, each OR ² may be different even identical to each other.)
A condensate (C) having, as a main skeleton, a repeating unit of MO obtained by subjecting an alkoxide compound represented by the following hydrolysis-condensation reaction:
A coating liquid for forming an ink receiving film, comprising:   The metal oxide constituting the aggregate particles in the aggregate particle-containing material (A) contains an oxide of at least one metal selected from silicon, titanium, zirconium and aluminum, and the metal oxide particles ( 2. The ink-receiving film-forming coating solution according to claim 1, wherein the metal oxide constituting B) includes at least one metal oxide selected from silicon, titanium, zirconium, and aluminum.   The aggregate particle-containing material (A) contains monodispersed primary particles of an oxide of at least one metal selected from silicon, titanium, zirconium and aluminum, and the average particle size of the primary particles is 2 to 200 nm. The ink receiving film-forming coating solution according to claim 1 or 2.   The coating liquid for forming an ink receiving film according to claim 3, wherein the average particle diameter of the primary particles contained in the aggregate particle-containing material (A) is in the range of 5 to 100 nm.   The ratio of the content of the component (B) to the total amount of the component (A) and the component (B) is 5 to 90% by mass based on the solid content, and the components (A), (B) and (C) The ratio of the total amount of the component (A) and the component (B) to the total amount of the ink is 40 to 95% by mass on the basis of the solid content, for forming an ink receiving film according to any one of claims 1 to 4. Coating liquid. In the method for producing a coating liquid for forming an ink receiving film according to any one of claims 1 to 5,
(A) a step of preparing a dispersion of the aggregate particle-containing material (A),
(B) a step of preparing a dispersion of metal oxide particles (B),
(C) a step of preparing a binder liquid containing a condensate (C) having a repeating unit of MO as a main skeleton, and (d) a dispersion of aggregated particle-containing material (A), metal oxide particles (B And a binder liquid containing a condensate (C) having a repeating unit of M-O as a main skeleton, and a method for producing a coating liquid for forming an ink receiving film.   An ink receiving film comprising the coating liquid according to claim 1.   A laminated substrate comprising the substrate and the ink receiving film according to claim 7 formed thereon.   The multilayer substrate according to claim 8, wherein the substrate is an organic substrate.   A wiring material comprising a wiring formed on the surface of the ink receiving film on the multilayer substrate according to claim 8. The wiring material according to claim 10, wherein the wiring is formed by any one of screen printing, ink jet printing, flexographic printing, gravure printing, and printing by a dispenser.