KR20070033990A - Method for forming pattern film, unit and material, and product obtained by said method - Google Patents

Abstract

It is an object of the present invention to provide a method of forming a patterned film, and to provide such methods, units, materials and products, wherein the method is a wet process and allows film formation at low temperatures, film base materials, eg It can also be applied to resin films, for example, and also enables direct patterning, for example, and makes it possible to form a film having a uniform thickness inexpensively and easily. As a means for achieving the above object, the method of forming a patterned film according to the present invention is a method of forming a film having a desired pattern on the surface of a base material, and the ink 2 containing the film forming material is nozzled 1a. To form the desired pattern 8 on the surface of the base material 7 mentioned above by supplying it to the surface of the base material 7 with heat applied to the base material 7 mentioned above. It is done. The pattern film forming unit according to the invention is also characterized in that it comprises means for supplying ink containing a film forming material from the nozzle to the surface of the base material and means for heating the base material.

Pattern film, unit, wet process, film base material

Description

Forming method, unit and material of a pattern film, and a product obtained by the method {FORMING METHOD, UNIT AND MATERIAL FOR PATTERN FILMS, AND PRODUCT GAINED BY SAID METHOD}

[Technical Field]

The present invention relates to a method of forming a pattern film, for example a metal oxide film having a desired pattern, the units and materials used in the method, and the product obtained by the method.

[Background]

Metal oxides such as ITO and SnO ₂ are used in conductive thin films that form electrodes (including transparent electrodes) used in display devices such as LCDs, PDPs and touch panels. Such conductive thin films typically produce metal oxide as a continuous film first by a vapor phase process, such as sputtering or vapor deposition under vacuum, on a substrate such as a glass plate, and then It was produced by forming a desired pattern by a post process, for example an etching process using photo-resist masks. However, the vapor phase process described above has the problem that its productivity is poor due to the loss of a large amount of metal material caused by volatilization, and furthermore, its cost is very high, which is great for reducing the product price for the display device. It becomes an obstacle. In addition, the necessity of the post process further leads to a greater cost increase and the necessity of time, thus these are large factors of the disorder.

In view of the foregoing, metal oxide films (ceramic films) which can be used as such as transparent conductive films, high dielectric element films or resistor element films are described above. In recent years, the development of a film forming technology by a wet process that can be efficiently and easily formed on a substrate by heating the film forming material in a liquid form applied to the base material without consuming metal materials has been in great demand. It has been required, which has led to the proposal of various techniques such as:

(1) a coating liquid containing a metal complex, a metal alkoxide and the like and capable of producing a metal oxide as a result of applying heat (see, for example, Patent Documents 1 to 5 below);

(2) film forming method for crystallization of metal oxide at low temperature, which is achieved by changing the excitation method after application (see, for example, Patent Documents 6 and 7 below); And

(3) Film forming method for crystallization of metal oxide by changing the coating method (thermal plasma spray method or spray thermal decomposition method) (for example, Patent Document 8 below) To 11).

[Patent Document 1] JP-A-279437 / 1999 (Publication)

[Patent Document 2] JP-A-207059 / 2000 (public publication)

[Patent Document 3] Japanese Patent No. 2136606

[Patent Document 4] Japanese Patent No. 3161471

[Patent Document 5] JP-A-169800 / 1996 (Publication)

[Patent Document 6] JP-A-157855 / 1997 (Publication)

[Patent Document 7] JP-A-256862 / 2000 (Publication)

[Patent Document 8] JP-A-009003 / 1993 (Publication)

[Patent Document 9] Japanese Patent No. 3271906

[Patent Document 10] Japanese Patent No. 3286954

[Patent Document 11] JP-A-078779 / 2002 (Publication)

However, the following problems exist with the above-mentioned proposals regarding the film forming technique by the wet process, and a solution to these problems is required.

That is, in recent years, miniaturization of each electronic device, increase in density, energy conservation and cost reduction have been demanded, and the demand in the semiconductor field that is loaded on a printed wire board, which is regarded as a key component of electronic technology. Has been particularly high, and therefore technology development has been pursued to form electronic circuits easily and with high density. In order to increase the density of electronic circuits, it is important to reduce the thickness of each passive element forming the electronic circuit, and also to reduce the size (thickness) and weight of the substrate, for example, the ceramic, which forms these elements. It is becoming increasingly important to change into a film (especially a resin film) substrate which can be made. As can be expected, metal oxides have been used as materials for forming the passive elements described above. For example, barium titanate and the like are used in high dielectric devices, and ruthenium oxide, tin oxide and the like are used in resistor devices in which a predetermined surface resistance value in the range of approximately 10 ⁰ to 10 ⁸ Ω / square is obtained. However, any of the above methods (1) to (3) has a problem that it is difficult to provide a base material in the form of a film and other problems disclosed below.

According to the above-described technique (1) for producing a metal oxide film using a coating liquid, the photo-resist mask in a dipping manner (by immersing method) is applied to a coating layer having a desired pattern. In a manner obtained at once by an etching process using a conventional application method without modification, it is necessary to thermally decompose all of the material compounds throughout the application layer at the same time, and thus, for practical use It is necessary to heat the base material to a considerably high temperature for a long time after completion of the application in order to form a metal oxide film having properties suitable for the application), and thus this technique is likely to form a film on a film base material such as a resin film. Considering this, there is little practicality.

According to the film forming method (2) described above, the application layer on the base material is irradiated with a UV or excimer laser having a short wavelength. However, also in this method, similarly to the case of (1) described above, in such a manner that an application layer having a desired pattern is obtained at once by an etching process using a photo-resist mask in an immersion method (by immersion method). Using conventional application methods without modification, and simultaneously converting all of the material compounds throughout the application layer into metal oxides, thus increasing the energy density of the radiation to form a metal oxide film having properties suitable for practical use. Or increase the research time. Therefore, the application of heat at low temperatures has not yet been achieved in practice, and thus similar to the case (1) described above, it is considered to be of little practicality in view of the possibility of film formation on the film base material.

With regard to the film forming method (3) described above, there is a problem associated with the technique using the thermal plasma spray method, in which case the unit is expensive and difficult to produce continuously, and in the case of the technique using the spray pyrolysis method, In addition, an application layer having a desired pattern is obtained by an etching method using a photo-resist mask simultaneously with a spraying method and converts all material compounds of the entire application layer into metal oxides simultaneously, thereby forming a metal oxide film having practicality There is a problem that the temperature of the substrate needs to be maintained at a considerably high temperature (for example, approximately 400 ° C.) for a long time. In addition, it is difficult to convert the base material into the film form, and also for both the thermal plasma spraying method and the spray pyrolysis method, the amount of adhesion to the base material is small compared to the amount of raw material liquid used (high yield). And increase costs. In addition, in the case of the technique using the thermal plasma spray method or the spray pyrolysis method, there is a problem that it is difficult to adjust the thickness in order to make the film thickness uniform from the microscopic viewpoint (for example, with respect to the surface resistance value).

Furthermore, similar to the steam process described above, the techniques (1) to (3) described above are all methods for forming a continuous film on a base material and, as can be expected, form a desired pattern. In order to achieve this, post-processing, for example, an etching process using a photo-resist mask is required after film formation, and thus, the above techniques cannot be referred to as high productivity methods in terms of cost and time required.

The above-mentioned problems with the wet process are not limited to the case where the film includes a metal oxide, and similarly occur when the film includes a material such as a metal or resin other than the metal oxide.

[Initiation of invention]

Purpose of the Invention

Accordingly, it is an object to be achieved by the present invention to provide a method of forming a pattern film, a unit and a material used in the method, and a product obtained by the method, wherein the method is a wet process and a film base material, eg It can also be applied to resin films, for example, and moreover, it allows for example direct patterning and makes it possible to form a film having a uniform thickness inexpensively and easily.

Summary of the Invention

The present inventors conducted earnest research to solve the above-mentioned problems. In the process, it was decided to focus on the method of supplying the coating liquid to the base material in order to carry out the formation of the pattern film by the wet process and the excitation method to obtain the desired film from the coating layer on the base material.

Therefore, with respect to the above-mentioned supply method, the coating liquid can be supplied to the base material by the microscopic nozzle in a state of fine liquid droplets (microscopic liquid droplets) (the end of the nozzle and the base at this time) The distance between the surfaces of the materials is very short, i.e., so-called inkjet method), whereby the coating liquid supply method for obtaining the desired pattern through the repeated supply of the coating liquid at the same place, i.e., the repeated supply method. It has been found that the amount of waste of the coating liquid to be used can be eliminated by adopting and the amount of coating liquid supplied per one can be reduced to avoid prolonged heating at a high temperature.

Pattern formation (direct patterning), which cannot be performed by the application layer forming method using a conventional dipping (immersion) method, is applied by a coating liquid supply method, for example, inkjet method, which ejects the coating liquid from the nozzle in the form of micro liquid droplets. Simultaneously with layer formation can be carried out very easily, whereby the relative positional relationship between the nozzle and the base material described above is adjusted at the time of application liquid supply in such a manner as to arbitrarily and strictly obtain the supply point of the application liquid, thereby It has been found that pattern formation can be performed arbitrarily and reliably as in an inkjet printer.

A coating layer having a desired thickness can be formed very precisely and uniformly by, for example, an inkjet method, by a coating liquid supplying method in which the coating liquid is ejected from the nozzle in the form of micro liquid droplets, wherein the coating liquid is formed as described above. It has also been found that it can be supplied to the base material with almost no disposal, whereby it is possible to strictly control the feed rate of the coating liquid from the nozzle and the adjusting speed of the above-described positional relationship (moving speed and number of coatings in the same place).

On the other hand, in connection with the above-mentioned excitation method, the base material is attached to a device capable of heating the base material, preheated before application, and then the coating liquid reaches the surface of the base material. When the metal oxide is crystallized immediately. In this way, the entire application layer is not heated at the same time as in the prior art, so that the desired patterned film is easily formed in a short time at a significantly lower temperature (for example, lower temperature from 150 to 300 ° C) than conventional technology. It was found to be possible.

The present invention has been completed based on this knowledge.

Accordingly, the method of forming the pattern film according to the present invention is a method of forming a film having a desired pattern on the surface of the base material, wherein the ink containing the film forming material is mentioned above from the nozzle to the surface of the base material mentioned above. By supplying a base material with heat applied thereto, a desired pattern is formed on the surface of the base material.

The unit for forming a patterned film according to the present invention is a unit used for carrying out the method for forming the patterned film according to the present invention, which means for supplying ink containing a film forming material from a nozzle to the surface of the base material and the base. And means for heating the material.

The ink according to the present invention is a material used to carry out the method of forming the patterned film according to the present invention, and is characterized by including a film forming material.

Further, the thin film element and the electronic circuit according to the present invention are products obtained by the method of forming the pattern film according to the present invention.

Effects of the Invention

By the method for forming a patterned film according to the present invention, even when a resin film (polymer film) containing polyimide, polyester or the like is used as a base material, not to mention a ceramic substrate such as a glass substrate or alumina, Formation of the patterned film can be easily performed by a wet process at a film forming temperature that the base material can withstand, and direct patterning and forming of a film having a uniform thickness can be performed in a short time at a low cost and at a high yield. . Therefore, this is very useful in the field of manufacturing products such as thin film devices and electronic circuits as a technique for forming a pattern film having properties necessary for transparent electrodes, device films for electronic circuits and the like at low cost. In addition, the commonly used inks can also be applied to the formation of the coating layer, so that the industrial demand for such a technique is very high and the industrial wavelength effect is also very large.

The above-mentioned functional effects on the method of forming the pattern film according to the present invention are not limited to the loading of the electronic circuit, but rather can also be obtained in the formation of a film other than the film for loading the electronic circuit.

The above-described pattern film forming method according to the present invention can be easily performed when using the pattern film forming unit and the ink according to the present invention.

[Brief Description of Drawings]

1 shows a manner of supplying ink from a nozzle, wherein (a) the ink is in direct contact with the base material from the nozzle; And (b) causing ink to flow from the nozzle in the form of micro liquid droplets to reach the surface of the base material.

2 shows an example of a unit according to the invention used for carrying out the method according to the invention.

3 shows the main part of another example of a unit according to the invention used for carrying out the method according to the invention.

4 shows SEM images of the surface (a) and the cross section (b) of the glass substrate having the pattern film obtained in Example 1. FIG.

5 is a view showing an example of a pattern film obtained in Example 18, wherein (b) is an enlarged view of (a).

(Explanation of reference numerals)

1: inkjet head with jet nozzle 1a

2: ink

3: ink bottle

5: XY stage

6: base material holder with burner

7: donation material

8: pattern

9: CO ₂ laser irradiation means

Detailed description of the invention

In the following, the present invention is described in detail, but the scope of the present invention is not limited to this description, and modifications suitable to the present invention can be made in addition to the following examples unless the scope is departed from the spirit of the present invention.

[Formation method of pattern film]

In the method of forming the patterned film according to the present invention (hereinafter sometimes referred to as the "method according to the present invention"), as described above, when a film having a desired pattern is formed on the surface of the base material, the film forming material It is important to form a desired pattern on the surface of the base material by supplying an ink comprising a from the nozzle to the surface of the base material mentioned above, with heat applied to the base material.

(ink)

In the process according to the invention, a film-forming material, i.e. a liquid comprising a metal oxide precursor which becomes a metal oxide through the application of heat, a solution in which the resin is dissolved, an ultrafine metal particle or an ultrafine particle comprising nanofine particles A dispersion liquid containing resin particles or the like is used as an ink used in a nozzle ejecting supply manner, for example, an inkjet method.

In the following, first, a film forming material among the components constituting the ink according to the present invention is disclosed.

The film forming material includes a main material and a sub-material. The main material is a material which becomes a film when the material itself causes a chemical change, for example a metal oxide precursor disclosed in detail below, or a material which becomes a film having the same composition, for example metal oxide particles, metal particles, resin Particles, or particle-resin composites. On the other hand, the minor material may be used to improve the solubility of the main material, to promote chemical change of the main material, or to improve the properties of the main material to assist in the conversion of the main material into ink. It is a substance.

Metal oxide precursors, a type of material that can be used as the main material, are commonly known to act as so-called precursors, without any particular limitation with respect to their type and react the metal oxide to the end of the film in response to heat applied to the base material. It can be any of a variety of metal compounds that can be produced in form, and preferred examples are organometallic complexes, metal alkoxides and inorganic metal complexes.

As the organometallic complexes described above, for example, metal carboxylates such as metal formate, metal acetate, metal propionate, metal stearate, metal naphthenate and metal oxalate, as well as basic salts of these metal carboxylates, Various monodentate ligands or multidentate ligands may be enumerated complexes on metal atoms, only one type of which may be used, or two or more types may be used together, There is no limit. Bidentate ligands such as dicarboxylic acids, oxy carboxylic acids, dioxy compounds, oxy oximes, oxy aldehydes and derivatives thereof, dioxy compounds, diketone compounds, keto ester compounds, oxy quinones, tropons, N-oxide compounds, Amino carboxylic acids and similar compounds thereof, hydroxyl amines, oxines, aldimines, oxy oximes, oxy azo compounds, nitrosonaphthols, triazenes, biurets, formazanes, ditizones, acetabolites Amides, glyoximes, dioxy compounds, benzoin oximes, diamines, hydrazine derivatives and dithioethers; Tridentate ligands such as aspartic acid and diethylenetriamine; Tetradentate ligands such as porphine, azaporpine and phthalocyanine; And pentadentate ligands such as ethylenediaminetetraacetic acid and trissalicylaldehydediimine as examples of the above-mentioned multidentate ligands, of which only one type is used, or two or more types Can be used together, there is no particular limitation.

Metal alkoxide monomers such as titanium tetra-n-butoxide, zirconium tetra-n-butoxide, indium tris-methoxy propoxide, tin (IV) tetraisobutoxide and aluminum tris-isopropoxide Sides and their (partial) hydrolysates as well as their hydrolyzed and condensed products (eg titanium tetra-n-butoxide tetramers) can be listed as examples of the metal alkoxides described above, and these Of these, only one type may be used, or two or more types may be used together, and there is no particular limitation.

Inorganic salts such as metal sulphates, metal carbonates, metal nitrates and metal halides as well as metal amine complexes can be listed as examples of the above-mentioned inorganic metal complexes, in particular metal nitrates, metal carbonates and metal amine complexes are low temperature. Preference is given to considering that few acid radicals remain in the.

In addition, compounds in which the valence of the metal atom is changed by heating the above-mentioned various metal compounds commonly known in the solvent as necessary, and compounds in which a part of the ligand is substituted with another group (for example, metal alkoxy carboxylate) Also listed as preferred as metal oxide precursors.

Among these metal oxide precursors, organometallic complexes and metal alkoxides are preferred in view of the fact that the components of the metal oxide film, other than the metal oxide, obtained by the process according to the present invention can be easily removed through the application of heat. In addition, organometallic complexes are more preferred given the low temperatures and the easy formation of metal oxide crystals at low temperatures during the above-mentioned heat applications, among which metal carboxylates and their basic salts as well as complexes of oxy carboxylic acids and diketone compounds are particularly preferred. desirable.

The following may be listed as specific examples classified according to the metal species of the metal oxide precursor. That is, when ruthenium oxide (RuO ₂ ) is produced as a metal oxide, the Ru compound complexes, for example ruthenium trisacetylacetonate, in which the ligand is ß-diketone, ß-keto ester and ß-dicarboxylic acid, as well as the following disclosure Enumerated are compounds obtained by heat treatment of the above in a solvent such as an alcohol. When zinc oxide (ZnO), indium oxide (In ₂ O ₃ ) or ferrite is produced, metal carboxylates, for example Zn, In or Fe (on the other hand, Co, Ni, Mn, Ba, etc.) formate, acetate , Propionate and oxalate, Zn compound complex, In compound complex, or Fe compound complex (wherein Co compound complex, Ni compound complex, Mn compound complex, and Ba compound complex) may be listed. . Where ITO is produced, metal carboxylates such as In formate, acetate, propionate and oxalate as well as In compound complexes in which the ligand is an oxy carboxylic acid can be enumerated, Sn (IV) carboxylate and Sn (IV) alkoxides may also be listed. When cerium oxide (CeO ₂ ) is produced, metal carboxylates such as Ce acetate, Ce compound complexes whose ligand is oxycarboxylic acid, Ce nitrate and the like can be enumerated. In the case where titanium oxide (TiO ₂ ) is produced, metal alkoxide compounds such as Ti tetrabutoxide, metal carboxylates such as Ti acetate, Ti compound complexes whose ligand is ß-diketone, and the like can be enumerated.

In the product obtained by the method for forming a pattern film according to the present invention, it is not necessary to form the pattern film only by metal oxide (ceramic), rather the pattern film comprises metal or resin, or metal or resin Can be mixed with the metal oxide in the pattern film. In passive device films, for example, the dielectric is a layered body of barium titanate / metal. Depending on the desired resistance value, examples of resistors include films of metals such as nickel; Films of electrically conductive oxides derived from, for example, ruthenium oxide and tin oxide; And composite films comprising a dispersion of electrically conductive particles (eg carbon black) in a resin.

The electrodes and wires can be, for example, electrically conductive films derived from metals or oxides; Or films comprising electrically conductive polymers.

In the present invention, the metal oxide particles may also be adopted as the main material of the film forming material. However, in order to form a metal film from the above at low temperature, it is preferable that the particle diameter is fine. Specifically, the particle diameter is advantageously 20 nm or less, more preferably 10 nm or less.

For metal oxide particles, those usually dispersed and contained in a solvent are used as the film forming material.

Examples of the main material from which the metal film is obtained are metal precursors, and in addition, metal particles.

Advantageous examples of metal precursors are organometallic complexes, metal alkoxides, and compounds as mentioned above as specific examples of inorganic metal complexes of metals such as copper, silver, gold and platinum group metals, ie metal oxide precursors. In addition, it may also be advantageous to employ the use of a reducing agent for metallization promotion as a sub-raw material in the ink, if necessary. For metal precursors, those which are usually dissolved in or dispersed and contained in the solvent are used as the film forming material.

Moreover, in order to form a metal film from the above with respect to a metal particle from above, it is preferable that the particle diameter is fine. Specifically, the particle diameter is advantageously 20 nm or less, more preferably 10 nm or less.

As metal particles, usually those dispersed and contained in a solvent are used as the film forming material.

Examples of the main material from which the resin film is obtained include the resin itself, the resin precursor, and the resin particles. Examples of resin precursors include polymerization, condensation or crosslinking; And various monomers and oligomers (eg acrylic type, styrene type, epoxy type) capable of forming resins by crosslinking agents. For these main materials, those which are usually dissolved in a solvent or dispersed and contained therein are used as the film forming material. In addition, in the case of the raw material system as described above, since the curing thereof proceeds in the step of mixing the raw materials forming the resin film together, the film forming material is divided into at least two parts, and It is advantageous to feed spraywise from each different nozzle. Moreover, in order to form a uniform film from the said with respect to the resin particle, it is preferable that said particle diameter is fine. Specifically, the particle diameter is advantageously 50 nm or less, more preferably 20 nm or less. For resin particles, those dispersed and contained in a solvent are usually used as the film forming material.

As another main material, the present invention may also employ carbon black, metal sulfides, metal nitrides, metal oxide nitrides, and precursors or particles capable of forming alloys, for example.

Furthermore, in the case of so-called composite films such as composite films containing dispersions of particles (for example metal oxide particles, metal particles or other particles) in resins and composite films comprising metals and metal oxides, each of the film-forming materials It is permissible to use materials obtained in such a way that the precursor of the component is used as the main material and dissolved or dispersed in the ink, and as a film forming material, a so-called paint in which the above-mentioned particles are dispersed and contained and the above-mentioned resins are dissolved. Paint compositions can also be used.

Incidentally, many types are also used together in one pattern film for the main material. When a pattern film containing a metal oxide together with a metal and / or a resin is obtained, a metal oxide precursor is used together with the ultrafine metal particles and / or the ultrafine resin particles as the main material (the resin may be a resin in solution form). have).

Examples of the secondary substances include reaction promoters and additives disclosed below, and these secondary substances may be used in combination of two or more kinds as necessary.

Examples of those which promote film formation by chemical excitation, such as oxidation reaction of the main material, with respect to the reaction promoter as secondary material are the following 1) to 3):

1) When a metal oxide film is obtained: an oxidizing agent such as hydrogen peroxide (incidentally, when a metal alkoxide is used as a precursor: a catalyst for hydrolysis and condensation);

2) when a metal film is obtained: as mentioned above, reducing agents such as aldehydes and organic amines; And

3) When a resin film is obtained: initiators and catalysts for promoting polymerization and condensation reactions.

Additives as secondary materials are added to the ink as necessary to improve the solubility stability of the main material or to make the main material soluble at high concentrations and mixed within a range in which the effects of the present invention are not impaired. With respect to such additives, basic substances such as amines, acid substances such as carboxylic acids, nonionic, anionic, cationic and amphoteric surfactants, aromatic rings with π electrons, unsaturated bonds, Unsaturated aliphatic hydrocarbons having a double bond of C = C, for example, and the above-mentioned compounds listed as polydentates, for example, bidentate ligands, are listed as preferred. These additives are preferable considering that they can take a great effect even in small amounts. For example, the use amount of 0.01 to 5 in a molar ratio to metal atoms in the metal compound precursor can also take effect of increasing solubility, and it is also preferable considering that these additives do not adversely affect the crystallinity of the obtained film.

The solvent for preparing the metal oxide precursor, the resin, the ultrafine metal particles, or the ultrafine resin particles contained in the liquid is not particularly limited, but any solvent as long as the solvent is maintained in the liquid state in a manner suitable for being supplied as ultra liquid droplets in an inkjet manner as a whole. It can be a solvent of, and can achieve excellent application to the base material. For example, water and / or organic solvents are preferably used as the solvent. In view of the high affinity with the metal compound precursor and the ease of dissolving the whole, organic solvents having a relatively high polarity, such as alcohols, ketones, aldehydes and esters, are preferred as the above-mentioned organic solvents. In particular, ethanol is preferred in view of low toxicity, and a solvent having a low boiling point such as methanol, ethanol and isopropanol is preferable in view of allowing easy formation of a film without solvent residue at low temperatures. In the case of using a base material having high heat resistance, a film having excellent crystallinity can be easily obtained by containing a solvent having a high boiling point as the solvent component, and it is preferable to adopt such a solvent.

The content of the main material of the film forming material in the ink, i.e., the metal oxide precursor, resin, ultrafine metal particles or ultrafine resin particles (as calculated as metal oxide in the case of a metal oxide film) is determined by the nozzle ejection method described above, e. There is no particular limitation as long as a suitable liquid state can be maintained and an applicability suitable for the base material can be obtained, and the content is preferably 0.01 to 20% by weight, more preferably 0.1 to 20%, based on the total ink. 10% by weight, even more preferably 0.5 to 3% by weight. The amount of main material or solvent of the film forming material may be adjusted so that the main material content of the film forming material is in the above-described range. If the above-mentioned content is less than 0.01% by weight, there is a risk that the productivity is lowered, and if the content exceeds 20% by weight, there is a risk that the film does not have a uniform thickness or has low crystallinity.

The manufacturing method of the ink containing a metal oxide precursor is illustrated as follows according to the type of metal oxide obtained.

For RuO ₂ film:

It is preferable to dissolve the above-described Ru oxide precursor in a solvent, and it is particularly preferable to heat-dissolve the precursor as alcohol as a solvent.

For In ₂ O ₃ film:

It is preferable to heat-dissolve the above-described In oxide precursor in an organic solvent (specifically, alcohol). Furthermore, it is desirable to coexist additives such as amines as dissolution aids in the preparation.

For ITO film:

It is preferable to mix Sn (IV) carboxylate and / or Sn (IV) alkoxide in the ratio of Sn / In = 0.1 to 10 atomic% in the above-mentioned liquid prepared in the case of In ₂ O ₃ film. Furthermore, it is desirable to coexist additives such as amines as dissolution aids in the preparation.

For ferrite film:

It is preferable to heat-dissolve any of the metal oxide precursors of (i) to (v) below in an organic solvent (specifically an alcohol) depending on the type of said metal oxide. Furthermore, it is desirable to coexist additives such as amines as dissolution aids in the preparation. (i) In the case of magnetite (Fe ₃ O ₄ ) films, it is preferred to use an iron compound, for example basic iron (III) acetate or iron (III) acrylate. (ii) In the case of a nickel ferrite (NiFe ₂ O ₄ ) film, it is preferable to use the above-described iron compound and a metal carboxylate, for example nickel (II) acetate together. (iii) In the case of cobalt ferrite (CoFe ₂ O ₄ ) films, it is preferred to use the above-mentioned iron compounds and metal carboxylates, for example cobalt (II) acetate together. (iv) In the case of manganese ferrite (MnFe ₂ O ₄ ) films, it is preferred to use the above-mentioned iron compounds and metal carboxylates, for example manganese (II) acetate together. (v) In the case of barium ferrite (BaFe ₂ O ₄ ), the use of the above-mentioned iron compounds and metal carboxylates, such as barium (II) acetate, or hydroxides, for example barium hydroxide, together desirable.

For ZnO Films:

It is preferable to heat-dissolve the above-described Zn oxide precursor in an organic solvent (specifically, alcohol). Furthermore, it is desirable to coexist additives such as amines as dissolution aids in the preparation.

For ZnO (M) film:

In the case of a solid solution oxide (ZnO (M)) film obtained by doping Zn with a metal element M of a different type from Zn, a carboxylate or alkoxide of a metal element M of a different type of Zn is added to M / Zn = 0.1 to 10. It is preferable to mix in the above-mentioned liquid prepared in the case of ZnO film in the ratio of atomic%. It is preferable that the metal element M of the type different from Zn is a metal element of III valence, for example In or Al. Furthermore, it is desirable to coexist additives such as amines as dissolution aids in the preparation.

For CeO ₂ film:

It is preferable to dissolve the above-described Ce oxide precursors in a solvent of water, alcohols such as ethanol or mixtures thereof.

For TiO ₂ film:

It is preferable to dissolve the above-described Ti oxide precursor in an organic solvent (specifically, alcohol, for example ethanol). Furthermore, it is preferable to coexist with additives such as acetylacetone as dissolution aids in the preparation as required.

The viscosity of the ink including the film forming material is not particularly limited, but is preferably, for example, 0.1 cm poise to 100 cm poise, and 1 cm poise to 50 so as to satisfactorily supply the ink in an inkjet manner. It is more preferable that it is cm poise. If the above-mentioned viscosity is less than 0.1 cm poise, there is a risk of obtaining a film having a very small line width, and if it exceeds 100 cm poise, there is a risk of obtaining a film having a low density or low physical strength. have.

Although the surface tension of the ink including the film forming material is not particularly limited, it is preferably 1 dy / cm to 200 dy / cm, for example, 10 dy / cm to satisfactorily supply the ink in an inkjet manner. It is more preferable that it is 100 dy / cm. When the surface tension mentioned above is less than 1 dy / cm or exceeds 200 dy / cm, it becomes difficult to generate liquid droplets in a piezo manner by the inkjet method.

(Donation material)

Materials of the base material that can be used in the process according to the invention are not particularly limited, but include inorganic materials such as ceramics such as oxides, nitrides, carbonates, and the like; Various resins such as polyester resins such as PET, PBT and PEN, polycarbonate resins, polyphenylene sulfide resins, polyether sulfone resins, polyether imide resins, polyimide resins, amorphous polyolefin resins, poly Allylate resins, aramid resins, polyether ether ketone resins, heat resistant resins such as liquid crystal polymers, and other commonly known resins such as (meth) acrylic resins, PVC resins, PVDC resins, PVA resins, EVOH Resins, polyimide resins, polyamide imide resins, fluororesins such as PTFE, PVF, PGF and ETFE, epoxy resins and polyolefin resins, and, for example, the deposition of aluminum, alumina or silica on these various resins Materials obtained by (eg films, sheets); Various metals such as silver, copper and silicon; And composites of organic and inorganic materials, such as glass fiber composite epoxy resins and silica composite epoxy resins. In addition, the materials of the base material described above are not particularly limited in terms of function, and examples thereof include optically transparent and opaque materials; Electrically insulators, conductors, p-type or n-type semiconductors, low dielectrics and high dielectrics; And magnetic and non-magnetic materials, depending on the use, purpose of use, and the like.

Various resins are suitable for use as the material of the base material, but considering the effect of lowering the film forming temperature as a result of the use of the ink according to the present invention, still heat-resistant resins are preferred, and resins having excellent insulation, for example Polyimide resin is more preferable.

As the shape and form of the base material, film form (including sheet form), plate form, fiber form, layer form, and the like can be enumerated, and these can be selected according to the use, the purpose of use, etc. Although not particularly limited, a film form or the like is preferable in view of miniaturization and weight reduction of the system.

So-called secondary processed products such as copper-clad films and printed circuit boards such as glass epoxy layer substrates and built up layer boards can also be used as base materials.

(Formation of Pattern Film)

When carrying out the method according to the invention, the above-mentioned ink and base material are used, and the ink is supplied from the nozzle to the surface of the base material, with heat applied to the base material, thereby providing a desired pattern. Is formed on the surface of the base material.

The method of supplying ink from the nozzle to the surface of the base material is not particularly limited. For example, the following method may be adopted: a manner as shown in Fig. 1 (a) in which the ink 2 discharged from the nozzle 1a is in direct contact with the base material 7; And further causing ink (2) to fly from the nozzle (1a) in the form of micro liquid droplets to reach the surface of the base material (7). In the latter case, the liquid droplets ejected from the outlets of the nozzles have a liquid droplet diameter maintained almost in size or by evaporation of volatile components (e.g. solvents) in the ink or removal of ligands constituting precursors in the ink. May reach the surface of the base material, accompanied by microminiaturization. In addition, the liquid droplets may be split into two or more during the blowing. By thermal radiation from the surface of the base material or the like, the material that has reached the surface of the base material has already been converted into a material different from the precursor in the liquid droplets ejected from the outlet of the nozzle.

However, what is important in the present invention is a feature of the present invention that directly forms an application layer having the desired pattern. Therefore, it is important that the liquid droplets ejected from the nozzle, or the active ingredient in the liquid droplets, reach only the pattern film forming place on the surface of the base material.

In order to achieve the above, it is necessary to appropriately select the nozzle diameter, the feeding speed from the nozzle, the distance between the nozzle and the base surface, the surface temperature of the base material, the solvent composition of the ink, and the like. Each of these advantageous conditions is mentioned below.

Examples of the obtained pattern include a single independent pattern in the form of dots, for example a resistor, a high dielectric or transparent electrode in an electronic circuit, a pattern in the form of dots arranged at uniform intervals, for example photonic crystals. , A pattern in the form of a stripe, a pattern in the form of a rectangle, a parallel pattern, a grid pattern, a pattern of concentric circles, a pattern in which a grid is formed in each mesh of the grid, and the like.

The supply of ink to the surface of the base material is advantageously carried out by repeatedly supplying ink to the same place on the surface of the base material, except that a single single pattern in the form of dots, such as a single independent pattern in the form of dots among the various patterns, is provided. The case where a minute pattern is to be formed from a single micro liquid droplet ejected from the outlet of the nozzle is excluded. The supply of ink to the surface of the base material is repeatedly performed in the form of micro liquid droplets, whereby the micro liquid droplets reaching the surface of the base material are converted directly into the film by receiving heat from the base material before the next supply. For example, if the film is a metal oxide film, the metal oxide precursor receives heat from the base material and converts it directly into the film. In the case of using a dispersion containing ultrafine metal particles or ultrafine resin particles as an ink, the ink reaching the surface of the base material receives heat from the base material and thereby the solvent evaporates, so that the metal film or resin film Remains. In this way, the next ink is supplied very thinly on the obtained very thin film, and then the micro liquid droplets of the supplied ink are directly converted to a very thin film by receiving heat from the base material and converting it into a very thin film in advance. Stacked on. The ink is repeatedly supplied to the surface of the base material, for example by reciprocating a jet nozzle with respect to the base material, so that the above-described process is repeated, whereby the desired film thickness with the desired pattern is achieved. Can be obtained.

By the process according to the invention, a pattern film having the desired thickness can be formed perfectly in this manner at low heating temperatures in a short time.

When carrying out the above-described method according to the present invention, ink containing different types of film forming materials can be supplied from the same nozzle. However, there are cases where it is better not to mix different types of film forming materials in one ink, and there are also cases where it is desirable to change the type of solvent or the viscosity of the ink depending on the type of film forming material. Thus, in such a case, ink containing different types of film forming materials can be supplied separately from a plurality of separate nozzles into different systems. For example, ink containing only the main material of the film forming material is supplied from the nozzle in the first system, and ink containing only the minor material is supplied from the nozzle in the second system. If the first main material is a metal oxide precursor and a main material other than the above is also desired to be added to the patterned film, ink containing the second main material is further supplied from the nozzle in the third system. For example, when forming a compound film containing two or more kinds of metal components (for example, ferrites, alloys), the materials may be defined as long as they define two or more film forming materials, each containing a precursor of each component. By supplying them from their respective different nozzles at their desired speeds, metals having various metal compositions can be formed. According to the composition of the film, there is an advantage that it is not necessary to manufacture the film forming materials one by one. In this way, even when separately supplying different main materials, for example ink containing metal particles, resin particles, carbon black and resin, as well as inks containing minor substances, the first main material and These can be blended and thus the desired film can be formed.

Although heating is the only source of energy for forming the film from the supplied film forming material, i.e. the only means of excitation, in the above description, additional excitation means other than heating via thermal conduction from the base material, for example light, heat, electromagnetic waves ( Local irradiation means such as, for example, microwaves) and ultrasonic waves and other excitation means reduce the heat capacity, promote film formation not only caused by heating, and even good quality films on base materials with low thermal conductivity. It may be used simultaneously with or before or after supplying ink to the surface of the base material to obtain. For example, laser irradiation means, such as an ultraviolet laser, a visible light laser, and an infrared laser; And ultraviolet lamp irradiation means such as a mercury lamp.

In the following, nozzles as ink supply means, and heating means as film forming excitation means are described in detail.

Any nozzle may be used in the method for forming a patterned film according to the present invention, as long as the nozzle is a nozzle capable of supplying ink in the form of micro liquid droplets, and the nozzle is not particularly limited to an ink jet nozzle. In the following description, citations are made by way of example for the purpose of facilitating their understanding.

In general, a part provided with jet nozzles is called an ink jet head, and the number of jet nozzles provided on the ink jet head is not particularly limited, that is, only one jet nozzle is provided on the ink jet head (single head) or two The above jet nozzles may be provided to the ink jet head (multi head). In the case of the multiple heads, the number of jet nozzles can be suitably selected according to the ratio of the width of the film line to be manufactured to the size of the liquid droplet to be sprayed (the size of the line width / liquid droplet). The film having the desired pattern can be easily formed by adopting the inkjet method without any resistance, and this method can also provide a very precise pattern formation in terms of time and cost, and very excellent productivity.

When supplying ink in a reciprocating motion in an inkjet method, any application unit can be used without particular limitation, as long as it is a unit capable of ejecting ink in the form of micro liquid droplets from a jet nozzle. However, it is preferable to apply ink in the manner described above by using the forming unit disclosed below for the film according to the present invention.

The size of the liquid droplets of the ink ejected from the jet nozzle varies depending on the tube diameter (inner diameter) of the nozzle, the viscosity and surface tension of the ink, the ink supply speed, and the like, and is not particularly limited. However, in view of easily forming metal oxide crystals having a uniform form and a uniform film thickness distribution at lower temperatures, the maximum diameter is preferably 2000 μm or less, more preferably 500 μm or less, particularly 100 μm or less. desirable. In general, although the size of the liquid droplets has a lower limit of micrometers in accordance with current inkjet technology, the formation of liquid droplets with nanometer size will also be possible in the future, and the method according to the invention may also be applied in such cases. It may be considered that it can provide a much larger effect in terms of drop in film forming temperature and the like.

Although the speed of supplying ink to the surface of the base material from the jet nozzle is not particularly limited, the speed is preferably 1 picoliter / minute to 10 milliliters / minute, and 10 picoliters per jet nozzle considering the range of high practicality. / Min to 50 microliters / min are more preferred. The thickness of the obtained metal oxide film can be adjusted by adjusting the ink supply speed and suitably adjusting the number of times of application when the system allows repeated application (layering) on the portion where the ink is once applied. For example, when forming a metal oxide film as a resistor element, a resistance value can be easily adjusted by adjustment of the said thickness. At this time, reducing the ink supply speed to less than 1 femtor / min may involve developing a technique for minimizing the tube diameter of the jet nozzle and controlling the increasing speed of the support on which the inkjet head or base material is fixed. It can be considered that the method according to the invention can also be applied in such a case and can provide a much greater effect in terms of the film forming temperature drop. In addition, the method according to the invention can be applied in a preferred manner even when the ink is supplied through a high speed jet exceeding 10 milliliters / minute.

When ink is supplied from a jet nozzle, ejection (jet) is generally repeated at regular intervals, which is called a pulse supply. In pulse supply, the pulse width (ie the time interval for one jet) is preferably 1 microsecond to 1 millisecond, more preferably 20 microseconds to 50 microseconds. On the other hand, the pulse interval (ie, the time interval from the start of the nth jet to the start of the (n + 1) th jet) is preferably 1 microsecond to 1 millisecond, more preferably 40 microsecond to 100 microsecond. . It is preferable to adjust the pulse width and the pulse interval in the above-described range in that a film uniform in terms of crystal structure (diameter of crystal grains and crystal orientation) and film thickness distribution can be easily obtained.

Supply of ink to the surface of the base material is performed with heat supplied to the base material. That is, heat is applied to the base material in advance and / or successively (continuously or intermittently) to obtain a state having the desired temperature when the base material applies ink to the surface of the base material. In this way, a method of obtaining a state in which heat is applied only to the surface of the base material on which ink is applied is adopted as an excitation method of the metal oxide precursor, whereby the temperature at which the film of the metal oxide or the like is formed is determined as a whole. It can be remarkably lower compared with the case of heating after forming an application layer. Therefore, damage to the base material as a result of the heating can be effectively reduced, for example, when the above-mentioned various resins are used as the base material. In particular, in the manufacture of electronic circuits by forming metal oxides as various element films, it can be said that the method according to the invention is very suitable since it generally uses an insulating resin such as polyimide resin as the base material.

The temperature of the base material generally varies slightly depending on the type of ink supplied (more specifically, the type of components of the metal oxide described above), but the temperature is preferably in the range of 100 to 400 ° C., The range of 100-300 degreeC is more preferable, and the range of 100-250 degreeC is the most preferable. If the above-mentioned temperature is lower than 100 ° C., there is a risk that the formation of a film of a desired metal oxide (crystal) or the like is insufficiently achieved, whereas if the temperature exceeds 400 ° C., damage to the base material will be significant. And there is also a risk of low productivity in terms of time and cost.

The heating method of the base material is not particularly limited and known heating units and methods can be adopted. For example, a method of heating the base material by placing the base material on a sheet-shaped heater such as a hot plate and heating the base material by a hot air and a hot air fan heater are generally known. Is not limited to these, and means such as a method of heating the base material by irradiating the base material with ultraviolet light may also be adopted.

By the method according to the invention, for example, a metal oxide film or a metal film can be formed substantially simultaneously with the ink supply to the base film surface, and the ink can be supplied in small amounts in small amounts, and also layered. Therefore, it is possible to promote ideal crystal formation and crystal growth, and moreover, to form a strong metal oxide film having a high physical strength.

(Type of film)

Films formed by the process according to the invention are useful as films with various functions depending on the type of metal oxide produced.

For example ruthenium oxide (RuO ₂ ), tin oxide-derived metal oxides such as antimony doped tin oxide, indium oxide-derived metal oxides such as tin doped indium oxide, zinc oxide-derived metals Oxides such as In and / or Al doped zinc oxide, titanium oxide-derived metal oxides and the like are useful as resistor device films.

Tin oxide-derived metal oxides such as antimony doped tin oxide, indium oxide-derived metal oxides such as tin doped indium oxide, zinc oxide-derived metal oxides such as In and / or Al Doped zinc oxide, and titanium oxide-derived metal oxides are useful as transparent conductor films.

The above-described metal oxides useful as layered films and transparent conductive films of ferrite-derived metal oxides such as magnetite, cobalt ferrite and nickel ferrite as well as any of these ferrite-derived metal oxides One of them is useful as a magnetic film and an electromagnetic noise blocking film.

Titanate-derived metal oxides such as barium titanate and strontium titanate are useful as high dielectric films.

Hafnium oxide, zirconium oxide, cerium oxide and aluminum oxide are useful as insulating films.

Titanium oxide, zirconium oxide and bismuth oxide are useful as high refractive films.

Metal oxides obtained by doping magnetic ions such as Fe, Co, Ni and Mn to semiconductor materials such as titanium oxide and zinc oxide are useful as thin magnetic semiconductor films.

Metal oxides obtained by doping lanthanoid-derived metal ions or metal ions such as Mn, Ag and Cu in yttrium oxide or zinc oxide are useful as fluorescent films.

The method according to the invention is preferably employed in the manufacturing method of an electronic device or a semiconductor mounting board for forming a functional metal oxide film, for example a conductive film or a high dielectric film.

For example, in the method of manufacturing a semiconductor loading substrate, the present invention preferably uses a high dielectric device film, for example barium titanate, a resistor device film, for example a film of RuO ₂ , SnO ₂ or ITO, or electromagnetic noise blocking. Films, for example ferrites, may be formed of metal wires, such as wires of Ag or Cu, and / or semiconductor components, such as LSI, insulated substrates such as alumina substrates, polyimide substrates or glass epoxy layers. epoxy layered board) It can be adopted when forming on a loading substrate (as a base material) loaded on a substrate.

In addition, the present invention preferably uses a material obtained by forming an electrode wire, for example, an Ag electrode on a portion such as a PET film or glass, as a base material and forms a transparent conductive film pattern thereon, or It can be adopted when the capacitor element is formed by layering a metal film and a barium titanate film (for example, a high dielectric film such as barium titanate is formed on a surface on which a metal film on a base material is formed). .

In addition to the metal oxide film, examples of the film obtained in the present invention include other films such as metal films, organic films, and composite films. Their field of application is not particularly limited but includes many different fields. However, when the film is exemplified in the field of semiconductor loading, the film is exemplified as follows.

Films of metals such as silver, copper, gold and platinum groups are useful as electrodes and electrical wiring.

Films of metals such as nickel and ruthenium are useful as resistor device films.

Composite films in which an electrically insulating material (such as a resin) and electrically conductive particles (such as carbon black particles and tin-doped indium oxide particles) are dispersed and contained are useful as a resistor element film.

Films of resins such as polyimide resins are useful as electrical insulating films.

Films comprising an electrically conductive polymer are useful as resistor element films, transparent electrically conductive films and electrical wirings, depending on their electrical resistance.

[Forming Unit of Pattern Film]

The pattern film forming unit according to the present invention (hereinafter sometimes referred to as “unit according to the present invention”) is a unit used to form a pattern film as described above and, as a specific means, forms a film on the surface of the base material from the nozzle. Means (A) for supplying ink comprising a material and means (B) for heating the base material.

The unit according to the present invention can be suitably used to carry out the above-described pattern film forming method according to the present invention.

In the unit according to the invention, the ink and base material are mentioned above.

The means for supplying ink A provided to the unit according to the invention is a means for supplying ink to the surface of the base material (i.e., the base material through a jet nozzle capable of ejecting ink in the form of micro liquid droplets, for example). Means for supplying ink by spraying onto the surface of the ink), and various supply methods adopted for a conventionally known coating unit of the inkjet method can be used. Piezo method for controlling the ejection of ink (e.g. supply timing) by piezoelectric film (adjusted by changing on / off of voltage application), ejection of ink by air pressure and electromagnetic valve ( For example, a method of adjusting the supply timing), an electrostatic method, and the like, and the like, and in particular, it is preferable to supply ink in a piezo manner in that the liquid droplets can be easily ejected at short pulse intervals.

For example, specifically speaking, the ink supply means A includes an ink bottle 3 containing ink 2 in addition to the inkjet head 1 having the jet nozzle 1a, as shown in FIG. A pipe (supply line) 4 is provided for sending the ink 2 from the ink bottle 3 to the jet nozzle of the ink jet head 1. In Fig. 2, the XY stage is represented by (5), and the base material holder having a heater fixed to the top of the XY stage is represented by (6), and the base material attached to the top of the base material holder 6 is shown. represented by (7), exhibiting a pattern formed on a surface of the base material (7) to (8), indicates a CO ₂ laser irradiation means which is used as needed to 9. The ink bottle 3 is provided with a back pressure regulator 13 of the ink jet head 1, a pipe regulator 14 is provided with a pipe (supply line) 4, and an XY direction 5 with an XY end 5. Controller 15 is provided. The laser controller is shown at 16. In addition, an adjustment signal is input to the controllers by the personal computer 10.

Specifically, the inkjet head 1 may be provided with only one jet nozzle (single head) or two or more jet nozzles (multihead), and there is no particular limitation on the number of jet nozzles or the number of systems. In the case of multiple heads, the number of jet nozzles can be suitably selected according to the ratio of the line width of the film to be manufactured to the size of the liquid droplets to be sprayed (the size of the line width / liquid droplets).

The tube diameter (inner diameter) of the jet nozzle is not particularly limited, and any diameter in the range of several microns to several millimeters may be applied, and an application for obtaining a pattern film having a uniform shape and a uniform film thickness distribution is possible. The diameter is preferably 1000 µm or less, more preferably 100 µm or less, in that the layer can be easily formed at a lower temperature. At this time, the present invention also, in the future, the development of ultra-miniaturization of the nozzle tube diameter and the technical improvement of the ink ejection apparatus to meet the miniaturization of the electronic device, the increase of the loading density on the semiconductor loading substrate and the ultra-small size of the passive element and the metal wire As a result of the saturation, the tube diameters capable of forming dots or nanometers or angstroms or thin lines at the atomic level can be sufficiently preferably applied to such tube diameters.

The base material heating means (B) provided in the unit according to the invention may be a means capable of applying heat to the base material 7 at a desired temperature, and is usually selected and adopted suitably from known heating units. Can be. In general, as can be seen in Figure 2, by placing the base material (7) to heat the base material by sending a sheet-like heater, for example hot plate, and hot or hot air to the base material A base material holder 6 comprising a fan heater capable of applying heat to the base material may be employed as an example of the above means, but is not limited to these, for example the base material may be ultraviolet light, for example UV. Heating means for irradiating with the irradiation unit can also be adopted.

Specifically, it is preferable that the base material heating means B is a base material holder capable of fixing the base material in addition to the unit capable of applying heat as described above.

The unit according to the invention is further advantageously provided with means (C) for adjusting the relative positional relationship between the base material and the nozzle. In the mode of operation in which the means C are further provided in the unit according to the invention, the unit is provided with an XY stage 5 as the means C, for example as can be seen in FIG. It is possible to move the base material holder 6 which can scan the inkjet head 1 of the ink supply means A and / or which can apply heat in the base material heating means B described above, so that the above-described inkjet The relative position of the head 1 and the base material holder 6 can be arbitrarily adjusted very accurately at high speed (preferably at least in the reciprocating direction, more preferably in both the X and Y directions). Therefore, the coating layer having the pattern of the desired form can be easily formed by adjusting the relative position described above and adjusting the ink supply by the ink supply means A described above. At this time, in the above-described adjustment of the relative position, the relative speed between the inkjet head 1 and the base material holder 6 is preferably in the range of 0.1 mm / sec to 1000 mm / sec, considering the high practical use range. The speed is not particularly limited.

3 shows another example of a means C for adjusting the relative positional relationship between the base material and the nozzle in the unit according to the invention, wherein the inkjet head 1 has a shape drawn along the rail 11. It can move in a reciprocating direction. In FIG. 2, the base material holder with the heater is shown as 6, the base material attached to the top of the base material holder 6 is shown as 7, and the surface temperature of the base material 7 is measured. A thermocouple is shown by (12), and a personal computer for inputting a control signal to the regulator of the inkjet head 1 is shown by (10). In this example, the base material 7 does not move, and the point where the ink is supplied changes only by the movement of the inkjet head 1.

Also included in the manner of operation of the unit according to the invention are the types comprising the combination of FIGS.

In the unit according to the invention, the gap between the nozzle 1a of the inkjet head of the ink supply means A described above and the base material fixed to the base material holder to which heat can be applied in the base material heating means B described above. (Distance) The size is not particularly limited, but considering the high practical use range, the interval is preferably set in the range of 0.1 to 50 mm, and the upper limit of the interval is more preferably 20 mm, and the upper limit is 10 mm. Is even more preferred. If the distance between the nozzle 1a of the inkjet head and the base material 7 is too small, the temperature of the jet nozzle 1a (inkjet head 1) rises due to the heat radiated from the base material 7 Metal oxide formation reactions and the like are induced in the jet nozzle, and the solvent in the ink evaporates, increasing the viscosity or depositing the film forming material, resulting in clogging of the jet nozzle or low crystallinity of the obtained metal oxide film. There is a risk of losing or uniformity of the film thickness distribution of the application layer. In order to avoid such a situation, it is effective to cool the jet nozzle (ink jet head). If the unit according to the invention is provided with a device capable of very precisely adjusting the gap between the nozzle and the base material and is provided with a device capable of cooling the jet nozzle 1a (inkjet head 1), Moreover, it can fully apply also to film formation in which the above-mentioned space | interval is smaller than 0.1 mm.

Means for irradiating the unit according to the present invention to light, heat, electromagnetic waves, ultrasonic waves, and the like mentioned above in addition to the ink supply means (A), base material heating means (B), and positional relationship adjusting means (C) described above. (E.g., CO ₂ laser irradiation means 9) and other excitation means may be provided.

With regard to the configuration of the unit according to the present invention, not only the respective means of the ink supply means (A), the base material heating means (B), and the positional relationship adjusting means (C) described above, It may be provided in an integrated state, or may be provided in an independent state from each other, and the manner of providing these means to the unit is not particularly limited.

In the case of forming a pattern film containing a metal oxide or the like using the unit according to the present invention, the ink supply speed, the liquid droplet size of the ink, and the number of times of repeating the ink supply can be suitably adjusted, and obtained in this manner. The film thickness of the resulting film can be adjusted to be in the range of millimeters at the ultralattice level.

Advantages of the method and unit of the present invention

When using the unit according to the invention, film formation, for example the production of metal oxide crystals, can be carried out on the surface of the base material substantially simultaneously with supplying ink from the jet nozzle to the surface of the base material and thus obtaining The film structure in the obtained film, for example, the crystal structure (that is, the diameter of crystal grains and the orientation of crystals) can be sufficiently controlled. In this regard, the method for forming a patterned film according to the present invention includes a method for obtaining a crystal film which excites the ink by applying heat after applying the ink once, and an ink containing metal nanoparticles. It can be said to be a technology far superior to the conventional technique of sketching by inkjet.

A pattern film having a desired shape and a desired structure can be easily formed as well as a film having a large area and a long film as long as the method according to the present invention is carried out using the unit according to the present invention. For example (i) primary structural patterns such as dots, thin lines, two-dimensional continuous films (daubing) and disc shaped films, and (ii) secondary structural patterns, such as A structure in which thin lines are arranged at predetermined intervals, a structure in which thin lines are two-dimensionally intersected (lattice form or mesh form), and a structure in which dots, discs, and square films are regularly arranged, and (iii) ) A layered structure including a pattern film of any shape different in composition and function, and a pattern film having a structure in which pattern films of any shape different in composition and function are alternately arranged or intersected with each other. Can be formed.

[Product containing pattern film]

Various thin film elements, electronic circuits, etc. can be enumerated as a product obtained by the formation method of the above-mentioned pattern film which concerns on this invention.

Examples of the product according to the present invention including various metal oxides (ceramic) and the like, that is, as an example of a pattern film actually used, a pattern in which a dot-shaped film is formed alone or a plurality of films are formed arbitrarily or at predetermined intervals. Cases of film can be used as dot-shaped resistors and high dielectric bodies or as transparent electrodes in electronic circuits, and elsewhere, uniformly spaced dot arrays can be used as photon crystals. In addition, a display device, for example, an LCD, an organic EL or a touch panel, or a light emitting device, in which a thin film having an arbitrary width is formed alone or a pattern film in which a plurality of films are formed arbitrarily or at predetermined intervals is used. It can be used as a transparent electrode, and can be used as a resistor device film and a high dielectric device film in electronic circuits.

Furthermore, in the method and unit according to the invention, conventional functional parts and electronic circuits can be formed as thin film elements by combining two or more film patterns. For example, TiO ₂ films or metal oxides (eg barium titanate) -derived dielectric films and metal films are alternately layered in a direction perpendicular to the base material or alternately arranged in an in-plane direction of the base material. Film is useful as a capacitor element. A transparent electrically conductive film (including tin-doped indium oxide or aluminum doped zinc oxide, etc.) is formed into an XY matrix shape and then the film is deposited on a metal (e.g. silver) film used as a collector. To combine; Or by bonding a metal film to a ruthenium oxide film or a film comprising a composite of carbon black and resin, a wiring having a regulated resistance value and the like can be formed. Electronic circuits can be formed by forming the above-mentioned passive element film (for example, a resistor film) or a capacitor element film and electrical wiring in the base material.

[ Example ]

Hereinafter, the present invention is more specifically illustrated by comparison of examples of some preferred embodiments below with comparative examples not according to the present invention. However, the present invention is not limited to these. In the following, for convenience, the units of "weight part (s)" and "liter (s)" may simply be referred to as "part (s)" and "L", respectively. In addition, "weight%" unit may be called "wt%".

The measuring method and evaluation method of an Example and a comparative example, and the formation unit of the pattern film used for the Example and the comparative example are shown below.

<Presence or absence of fine particulate metal oxide in ink>

The obtained ink was observed using a transmission electronic microscope to confirm whether any fine particulate matter was present. If any fine particulate material was recognized, elemental analysis by EDX was performed under electron microscopy to confirm the inclusion of any fine particulate metal oxide.

<Crystallinity of Film>

The presence or absence of the crystallinity of the film portion of the obtained base material with the film was measured using the thin film X-ray diffraction unit (manufactured by Mac Science Company, trade name: MXP-3VA (model)). Confirmed, demonstrated, and evaluated by performing thin film X-ray diffraction measurements under. Specifically, the following measurement conditions were used:

(Measuring conditions):

X-ray: CuKα1 line (wavelength: 1.54056 Hz), 40 kV, 40 mA

Scan range: 2 θ = 20 ° to 80 °

Scan Speed: 1 ° / min

X-ray angle of incidence: 0.5 °

At this time, when the diffraction peak intensity is low or the peak is wide in the above-described measurement, Raman spectrometry was also performed on the evaluation as necessary to improve the reliability of the evaluation. The Raman spectroscopy was performed using a Raman analyzer (manufactured by Atago Bussan Co., Ltd., product name: T64000), wherein a visible or ultraviolet laser was used as the measurement excitation light.

<Film thickness>

The cross section of the obtained base material with the film was observed using SEM or measured using a surface shape measuring unit (manufactured by ULVAC, Inc., trade name: Dektak 3030).

<Appearance of film>

The transparency and color tone of the film portion of the obtained base material having a film were visually observed.

<(Surface) resistance value of film>

The surface resistance of the film portion of the obtained base material with the film was measured using a low resistivity meter (trade name: Lorester GP) manufactured by Mitsubishi Chemical Corporation (limiter voltage of 10 V). ) Was measured by a four-terminal four-probe method.

In addition, when the film portion has a microscopic pattern, and as a result, the measurement using the low resistance meter described above is difficult, the electrode is formed by sputtering or formed from a conductive paste, and the resistance value of the film portion (Ω / □ ) Was measured using a tester and converted to surface resistance as needed. When electrodes (facing electrodes) are provided to the film portion by wiring and conductive paste, the resistance value between the two electrodes is measured by the above-described tester, the resistance value is measured, and the surface resistance value as necessary. Switched to

<Temperature of the donated material>

When the base material was heated, the temperature of the base material was measured by thermocouple.

<Forming unit of pattern film>

Two types of inkjet sketching units disclosed below were prepared as forming units of pattern films.

The inkjet sketching unit 1 is an inkjet printable unit, comprising the following components: a base material holder having a heater for heating the base material; An inkjet head provided over said base material holder and continuously moving (scanning) in a reciprocating manner; And an ink bottle and ink supply line for supplying ink (e.g., a liquid form material comprising a metal oxide precursor) to a (60) jet nozzle (inner diameter: 65 mu m) constituting the ink jet head. At this time, the ink supply line can be branched to correspond to the number of jet nozzles, and the distance between the inkjet head and the base material holder can be determined and arbitrarily changed in the range of 1 to 50 mm. When the unit is used, the precursor solution introduced into the ink bottle is supplied to the jet nozzle constituting the ink jet head through an ink supply line, and the ink is ejected from the nozzle end while moving the ink jet head, so that the ink It is ejected to the surface of the base material fixed to the base material holder, whereby an application layer of a desired pattern shape is formed on the surface of the base material.

Another inkjet sketching unit (No. 2) is a unit capable of printing in an inkjet manner and comprising the following components: a base material holder having a heater for heating the base material, which can be continuously moved (scanned); An inkjet head fixed on the base material holder (not movable); And an ink bottle and an ink supply line for supplying ink (e.g., a liquid form material comprising a metal oxide precursor) to a (one) jet nozzle (inner diameter: 60 mu m) constituting the ink jet head. At this time, the base material holder is movable with precision of 10 μm in both the X direction and the Y direction with respect to the position of the ink jet head while adjusting the moving speed and the time interval in accordance with the timing of ejecting ink from the ink jet head. . The distance between the inkjet head and the base material holder can be arbitrarily determined and varied in the range of 1 to 50 mm. When the unit is used, the precursor solution injected into the ink bottle is supplied to the jet nozzle constituting the inkjet head through an ink supply line, and the ink is ejected from the nozzle end while the base material holder on which the substrate is fixed moves. To form a desired patterned application layer on the surface of the base material.

Ink Synthesis Example 1

A reactor made of pressure-resistant glass that could be heated externally and provided with a mixer, reflux cooler, thermometer and nitrogen or air gas inlet was prepared.

1 part of cerium (III) nitrate hexahydrate and 231 parts of ion-exchanged water were continuously added to the above-described reactor and stirred in air for 1 hour at 25 ° C., whereby 232 parts of Ce-containing precursor solution (CeO ₂ concentration: 0.14) Wt%) was obtained and used as the ink S1 for ink jet. At this time, fine particulate metal oxide was not recognized in the obtained precursor solution.

Ink Synthesis Example 2

6 parts of titanium tetraisopropoxide, 192 parts of ethanol (used as a solvent), and 2 parts of acetylacetone were continuously added to the same reactor as in Ink Synthesis Example 1 and stirred for 1 hour at 25 ° C. under a nitrogen atmosphere, This resulted in 200 parts of Ti-containing precursor solution (TiO ₂ concentration: 0.9 wt%), which was used as ink jet ink (S2). At this time, fine particulate metal oxide was not recognized in the obtained precursor solution.

Ink Synthesis Example 3

18 parts of zinc acetate, 0.29 parts of indium acetate, 281 parts of 2-butoxyethanol (used as solvent), and 20 parts of triethylamine (used as additive) were continuously charged into the same reactor as in Ink Synthesis Example 1 Stir under nitrogen atmosphere with increasing temperature from 25 ° C., and then the resulting mixture was kept at 110 ° C. for 30 minutes, then cooled, whereby 319 parts of Zn and In containing precursor solution (ZnO concentration: 2.5 weight %, In / Zn = 1 atomic%) was obtained, which was used as ink jet ink (S3). At this time, fine particulate metal oxide was not recognized in the obtained precursor solution.

Ink Synthesis Example 4

14 parts of indium acetate, 1 part tetraisobutoxytin (IV), 245 parts 2-butoxyethanol (used as solvent), and 6 parts n-propylamine (used as additive) were the same as in Ink Synthesis Example 1 Continuously charged into the reactor and stirred under a nitrogen atmosphere while raising the temperature from 25 ° C., and then the resulting mixture was kept at 120 ° C. for 30 minutes, then cooled, whereby 266 parts of In and Sn containing precursor solution (Concentration as In ₂ O ₃ : 2.5 wt%, Sn / In = 5 atomic%) was obtained. The obtained solution was diluted with ethanol to have a concentration of In ₂ O ₃ of 0.25% by weight, and the resulting diluent was used as an ink jet ink (S4). At this time, fine particulate metal oxide was not recognized in the obtained precursor solution.

Ink Synthesis Example 5

Ink Synthesis Example 1 11.46 parts of basic salt of iron (III) acetate, 7.47 parts of nickel (II) acetate anhydride, 205 parts of benzyl alcohol (used as solvent), and 11 parts of n-propylamine (used as additive) Was continuously charged to the same reactor and stirred under a nitrogen atmosphere while the temperature was raised from 25 ° C., and the resulting mixture was kept at 110 ° C. for 30 minutes, then cooled, thereby containing 234 parts of Ni and Fe A precursor solution (NiFe ₂ O ₄ concentration: 3% by weight, Ni / Fe = 1/1 (atomic ratio)) was obtained, which was used as an ink jet ink S5. At this time, fine particulate metal oxide was not recognized in the obtained precursor solution.

Ink Synthesis Example 6

20 parts ruthenium (III) trisacetylacetonate, 196.6 parts benzyl alcohol (used as solvent), and 6 parts acetic acid (used as additive) were continuously charged into the same reactor as in Ink Synthesis Example 1 and the temperature was 25 ° C. The mixture was stirred under a nitrogen atmosphere while rising from and then the resulting mixture was kept at 140 ° C. for 20 minutes and then cooled. Then 222.6 parts of 2-butoxyethanol were added and mixed, whereby 445 parts of Ru containing precursor solution (RuO ₂ concentration: 1.5% by weight) was obtained. The resulting solution was diluted with 2-propanol to have a RuO ₂ concentration of 0.5% by weight, and the resulting diluent was used as ink jet ink (S6). At this time, fine particulate metal oxide was not recognized in the obtained precursor solution.

Ink Synthesis Example 7

Ink Synthesis In the same manner as in Example 6, 445 parts of a Ru containing precursor solution (RuO ₂ concentration: 1.5 wt%) were obtained. The same amount of 2-propanol as the obtained solution was added to the obtained solution, which was diluted to a concentration as 0.75% by weight RuO ₂ , and the resulting diluent was used as ink jet ink (S7).

Example 1

1) The ink jet sketch unit (No. 1) was used, and ink S1 was put into the ink bottle thereof.

2) The glass substrates were fixed to the base material holder and pre-heated to have a surface temperature of 150 ° C.

3) The distance between the surface of the glass substrate and the inkjet head was fixed at 10 mm.

4) The ink S1 is supplied at a feed rate of 1 ml / min from the ink bottle while moving the inkjet head in a manner of reciprocating at a speed of 360 mm / sec over a distance of 180 mm, whereby the ink is jet nozzle Was blown out on the glass substrate. At this time, the reciprocating number was 100, and the ejection of the ink S1 from the jet nozzle was performed only for a specific portion having a length of 20 mm at a moving distance of 180 mm only when the head moved in the forward or reverse direction.

In this way, steps 1) to 4) were carried out, thereby obtaining a substrate (glass substrate having a film) in which a rectangular film having a length of 20 mm and a width of 7 mm was formed on the surface of the glass substrate.

The appearance of the film portion of the obtained glass substrate with the pattern film was almost transparent, but slightly white and the thickness of the film portion was 8 μm. 4 shows the surface and cross-sectional SEM images of a glass substrate with a film. In addition, thin film X-ray diffractometry of the film portion confirmed that cerium oxide (IV) (CeO ₂ ) crystals were formed.

Comparative Example 1

A glass substrate having a film was obtained by the same procedure as in Example 1 except that the glass substrate was not heat-maintained in advance in step 2), and the glass substrate was heated in a heating furnace at 150 ° C. for 180 minutes after step 4). It was. The film portion of the glass substrate having the film thus obtained had an irregularly spread form, the appearance of the film portion was white, and the thickness of the film portion was 0.6 mu m.

As a result of the thin film X-ray diffraction analysis of the film portion of the glass substrate having the obtained film, no diffraction peak designated as cerium oxide (IV) crystal was recognized.

Comparative Example 2

Ink S1 was applied to the surface of the glass substrate by a bar coater and dried at a normal temperature, and then heated in a heating furnace at 300 ° C. for 10 minutes, whereby a glass substrate having a film was obtained. . The appearance of the film portion of the glass substrate having the obtained film was white, its surface was powdery, and its adhesion to the glass substrate was so low that the film was easily peeled off from the glass substrate.

As a result of the thin film X-ray diffraction analysis of the film portion of the glass substrate having the obtained film, no diffraction peak designated as cerium oxide (IV) crystal was recognized.

[Examples 2 to 6]

Base materials having various films were obtained by the same process as in Example 1, except that the type of ink and base material as well as the film forming conditions were selected as shown in Table 1. Table 1 shows the results of the evaluation of the appearance, thickness, length and width of the film portion of the base material having the obtained pattern film.

Thin film X-ray diffraction analysis of the film portion of each of the base materials having the films obtained in Examples 3 to 6 confirmed the formation of metal oxide crystals as shown in Table 1.

In addition, thin film X-ray diffraction analysis of the film portion of the base material having the film obtained in Example 2 showed that a diffraction pattern designated as anatase type TiO ₂ was recognized, but the diffraction peak was wide, thus Raman spectroscopy. Measurements were carried out with caution. As a result, it was confirmed that anatase type TiO ₂ crystals were formed.

The evaluation results for the surface resistance of each film of Examples 3 and 4 are also shown in Table 1.

TABLE 1

Example 7

1) An inkjet sketching unit (No. 2) was used, and ink S7 was put into its ink bottle.

2) The glass substrate was fixed to the base material holder and preheated to have a surface temperature of 260 ° C. At this time, the glass substrate was a glass substrate having a wire electrode, two wire electrodes made of silver having a width of 1 mm and a length of 10 mm are formed at intervals of 1 mm in the length direction of the wires, and a tester The self resistance of each wire electrode measured by was 3 Ω, where the space between the wire electrodes was not conductive and had a resistance of 1 MΩ or more.

3) The distance between the surface of the glass substrate and the inkjet head was fixed at 10 mm.

4) Position the base material holder 0.5 mm inward from the position of the inkjet head (the position of the jet nozzle end) from which one end of one wire electrode is closer to the other wire electrode on the glass substrate (based on the position And position it so that it is above position (0,0).

5) The ejection of the ink S7 was started, and at the same time as the start, the base material holder was moved from the position of the inkjet head from above the reference position to the above-described other wire electrode (the direction of this movement is the X axis Direction), and then after 5 seconds, the base material holder was stopped (total travel distance: 2 mm), and the ejection of the ink S7 was also stopped. During this movement, ejection of the ink was performed intermittently. Specifically, the ink was ejected every 30 μm movement of the base material holder (splitting amount per stroke: 200 picoliters). Thereafter, the base material holder was moved so that the position of the inkjet head returned to the jet start position (reference position) again. In this manner, the operation from the start of ink ejection to the return of the inkjet head position is called one cycle.

6) After completion of the first cycle, the base material holder was moved so that the position of the inkjet head was moved from the reference position to 30 μm in the direction perpendicular to the X axis direction (Y axis direction). The position of the inkjet head after this movement is called position (0,1). Operation of the second cycle was performed starting from the reference position (0,1) in the same manner as in step 5) above.

7) Thereafter, the same steps as in 6) were repeated to perform operations up to the nth period (a period in which the ejection is started from the position (0, n-1)).

In this manner, steps 1) to 7) were carried out, whereby a rectangular film having a length of approximately 2 mm and a width corresponding to the number of cycles was formed between two wire electrodes on the glass substrate surface. Having a glass substrate).

The appearance of the film portion of the glass substrate having the obtained pattern film was in the form of black lines. Also, due to the size of the area, X-ray diffraction analysis was difficult for a film of n ≦ 100. Thus, a film of n = 500 was prepared, and thin film X-ray diffraction analysis was performed on the film portion of the film, and as a result confirmed the formation of ruthenium oxide (RuO ₂ ) crystals.

Next, the resistance value between the two wire electrodes (including the resistance value of the wire electrode itself (3 Ω)) was measured. The results are shown in Table 2.

TABLE 2

Number of cycles (n) Resistance value between two wire electrodes 0 > 1 MΩ 5 50 kΩ 100 65 Ω

Example 8

The same procedure as in Example 7 was carried out except that ink S1 was used in place of ink S7, and a metal silicon substrate was used in place of the glass substrate (but wire electrodes were installed in the same manner) at 150 ° C. It was pre-heated to have a surface temperature. As a result, a substrate (metal silicon substrate having a film) was formed in which a rectangular film having a length of approximately 2 mm and a width corresponding to the number of cycles was formed between the two wire electrodes on the metal silicon substrate surface.

The appearance of the film portion of the metal silicon substrate having the obtained pattern film was in the form of semitransparent lines. Further, thin film X-ray diffraction analysis of the film portion of n = 500 confirmed the formation of cerium oxide (IV) crystals.

Examples 9 to 11 below are examples in which oxide complexes were obtained by simultaneously supplying multiple types of inks from different nozzles.

Example 9

The same manner as in Example 1 was performed, except that the number of ink supply lines was 60, of which 10 had ink bottles containing aqueous hydrogen peroxide (H ₂ O ₂ content: 0.5 wt%) as an ink source, The remaining 50 had ink bottles containing ink S1 (obtained in Ink Synthesis Example 1) as an ink source.

Thin film X-ray diffraction analysis was performed on the film portion of the substrate having the pattern film obtained above. As a result, it was confirmed that cerium oxide (IV) crystals were formed. The X-ray diffraction peak designated cerium oxide was sharper than the X-ray diffraction peak of the film portion of the substrate with the film obtained in Example 1, thus confirming the excellent crystallinity.

Example 10

The same manner as in Example 5 was performed, except that the number of ink supply lines was 60, of which 40 had ink bottles containing ink S8 (obtained in Synthetic Example 8 described below) as an ink source. Ten have ink bottles containing ink S9 (obtained in Synthetic Example 9 described below) as the ink source, and the remaining ten have ink S10 (in Synthetic Example 10 disclosed below) as the ink source. Having an ink bottle).

Thin film X-ray diffraction analysis was performed on the film portion of the substrate having the pattern film obtained above. As a result, no diffraction peak designated with a single oxide of Co, Ni or Fe was observed, but rather a diffraction pattern designated with ferrite was obtained. Compositional analysis was performed on the film portion. As a result, Co: Ni: Fe atomic ratio of 1: 1: 4 was confirmed and therefore the composition of the film was _{Co 0 .5 Ni 0 .5 O ·} Fe 2 O 3.

Example 11

The same manner as in Example 10 was carried out, except that 40 out of 60 ink supply lines had ink bottles containing ink S8 as ink source and five had ink bottles containing ink S9 as ink source. And the remaining 15 had ink bottles containing ink S10 as an ink source.

Thin film X-ray diffraction analysis was performed on the film portion of the substrate having the pattern film obtained above. As a result, no diffraction peak designated with a single oxide of Co, Ni or Fe was observed, but rather a diffraction pattern designated with ferrite was obtained. Compositional analysis was performed on the film portion. As a result, Co: Ni: Fe atomic ratio of 3: 1: 5 was confirmed, and thus the composition of the film was _{Co 0 .75 Ni 0 .25 O ·} Fe 2 O 3.

Ink Synthesis Example 8

The same reactor as in Synthesis Example 1 was used, and continuously charged with 19 parts of a basic salt of iron (III) acetate, 213 parts of benzyl alcohol as a solvent, and 18 parts of n-propylamine as an additive, Stir under nitrogen atmosphere with increasing temperature from 25 ° C., then keep the resulting mixture at 110 ° C. for 30 minutes, then cool, thereby obtaining 250 parts of Fe containing precursor solution (Fe concentration: 0.4 mol / kg) It was. The solution was used as ink jet ink (S8). At this time, fine particulate metal oxide was not recognized in the obtained precursor solution.

Ink Synthesis Example 9

The same reactor as in Synthesis Example 1 was used, and 25 parts of nickel (II) acetate tetrahydrate, 213 parts of ethanol as a solvent, and 12 parts of n-propylamine as an additive were continuously added to the reactor, and the materials were Stirred under nitrogen atmosphere with rising from 25 ° C., then the resulting mixture was kept at 110 ° C. for 30 minutes, then cooled, whereby 250 parts of Ni containing precursor solution (Ni concentration: 0.4 mol / kg) were obtained. The solution was used as ink jet ink (S9). At this time, fine particulate metal oxide was not recognized in the obtained precursor solution.

Ink Synthesis Example 10

The same reactor as in Synthesis Example 1 was used, and 18 parts of cobalt (II) acetate anhydride, 220 parts of 1-propanol as solvent, and 12 parts of n-propylamine as an additive were continuously added to the reactor, and the materials were Was stirred under nitrogen atmosphere with rising from 25 ° C., then the resulting mixture was kept at 110 ° C. for 30 minutes, then cooled, whereby 250 parts of Co containing precursor solution (Co concentration: 0.4 mol / kg) were obtained. . The solution was used as ink jet ink (S10). At this time, fine particulate metal oxide was not recognized in the obtained precursor solution.

Examples 12 to 13 below are examples in which other excitation means are used together with excitation means by the application of heat from the substrate.

Example 12

A base material having a pattern film was obtained in the same manner as in Example 4 except that the substrate was changed to polyimide, and infrared laser beam was continuously applied to the ink ejected portion while ejecting ink from the jet nozzle onto the glass substrate surface. (CO ₂ gas laser, wavelength: 0.6 mu m, 100 W).

Thin film X-ray diffraction analysis was performed on the film portion of the substrate with the film obtained above. As a result, it was confirmed that the film contained In ₂ O ₃ crystals. The surface resistance of the film was measured and the result was found to be 0.5 × 10 ² Ω / □ (1 × 10 ³ Ω / □ in Example 4, see Table 1), thus the film was used in Example 4 It was found that the conductivity was better than that of the obtained film.

Example 13

A base material having a pattern film was obtained in the same manner as in Example 3 except that the entire substrate was continuously irradiated with light from a mercury lamp (1000 mJ / cm 2) while ejecting ink from the jet nozzle onto the glass substrate surface. .

Thin film X-ray diffraction analysis was performed on the film portion of the substrate with the film obtained above. As a result, it was confirmed that the film contained ZnO crystals. The surface resistance of the film was measured, and the result was found to be 5 x 10 ⁴ Ω / □ (1 × 10 ⁶ Ω / □ in Example 3, see Table 1), thus the film was used in Example 3 It was found that the conductivity was better than that of the obtained film.

Examples 14 to 17 and Comparative Example 3 below are examples using a material other than a metal oxide precursor as a film forming material.

Example 14

A base material having a pattern film having a rectangular film having a length of 20 mm and a width of 7 mm was obtained in the same manner as in Example 1 except that the ink was an Ag ultrafine particle dispersion in which the Ag ultrafine particle powder was dispersed in ethanol. (Ag average particle diameter: 8 nm, Ag concentration: 0.1 wt%), the base material is changed to a polyimide film, the surface temperature of the base material is changed to 180 ° C., and the number of round trips of the inkjet head is 50 The circuit was changed.

The surface resistance of the obtained film was measured and found to be 10 Ω / square or less, thus the film had excellent adhesion to the base material.

Comparative Example 3

A base material having a pattern film was obtained in the same manner as in Example 14, except that the base material was not heated (surface temperature of the base material: 25 ° C.), and instead the heating process was patterned on the surface of the base material. After forming a coating layer having a coating was carried out at 100 ℃ to remove the solvent from the coating layer.

The length and width of the obtained film did not stay within the operating range of the inkjet head, i.e. 20 mm in length and 7 mm in width, rather the film obtained was unfolded both in the longitudinal direction and the width direction, and also the film thickness It was also uneven (film thickness taper outwards near the opposite ends in the width direction). Therefore, the surface resistance value of the film deviated a lot without stability during the measurement, and thus the film could not be called a conductive coating film. The obtained film was also easily peeled from the base material because the adhesion to the base material was too low.

Example 15

A base material having a pattern film having a rectangular film having a length of 20 mm and a width of 7 mm was obtained in the same manner as in Example 1 except that the ink was ZnO ultrafine in which ZnO ultrafine particle powders were dispersed in 1-butanol. It was changed to a particle dispersion (average particle diameter: 10 nm, ZnO concentration: 0.1% by weight), and the surface temperature of the base material was changed to 400 ° C.

The obtained film was a film having excellent ultraviolet absorbency, good transparency excellent in visible light transmittance, and uniformity of film thickness distribution.

Example 16

A base material having a pattern film having a rectangular film having a length of 20 mm and a width of 7 mm was obtained in the same manner as in Example 1 except that the ink was In ₂ O ₃ (ITO) containing 2 wt% of Sn. ITO ultrafine particle paint (average particle diameter of ITO: 25 nm, ITO: acrylic resin (weight ratio) = 7: 2, solid component concentration: 0.1% by weight, solvent: toluene-1, in which ultrafine particles were dispersed in an acrylic resin solution) -Butanol-mixed solvent) and the surface temperature of the base material was changed to 120 ° C.

The obtained film was a film having excellent conductivity in which ITO ultrafine particles were dispersed in a substrate of an acrylic resin, excellent in visible light transmittance, transparency and infrared ray blocking, and having a uniform film thickness distribution and a surface resistance of 3 × 10 ⁵ .

Example 17

A base material having a pattern film having a rectangular film having a length of 20 mm and a width of 7 mm was obtained in the same manner as in Example 1 except that the ink was an acrylic emulsion (solid component concentration: 0.1 wt%, solvent: water) Changed to.

The film obtained was a film containing acrylic resin and having excellent transparency and uniform film thickness distribution.

Examples 18 and 19 below are examples using an inkjet head having a plurality of jet nozzles.

Example 18

As an inkjet unit (No. 1), an inkjet head having a total of 60 jet nozzles having a pore diameter of 60 µm in which 10 nozzles in the lateral direction and six nozzles in the longitudinal direction are arranged at intervals of 400 µm in both the longitudinal and the lateral directions. Having an inkjet unit. Ink S1 of Synthesis Example 1 was used as ink.

Adjust the ink supply speed and head scanning speed (40 mm / sec or more as scanning speed) so that the ejection speed is 360 dpi (drops / in) and jet nozzles over a length of 20 mm in the lateral direction (X direction) While moving in a reciprocating manner, ink was sent to a glass substrate (whose surface temperature was previously maintained at 285 ° C.), so that the ink was ejected and supplied from the jet nozzle onto the glass substrate surface. At this time, the reciprocation number was 20, and ink ejection from the jet nozzle was performed only when the head moved in the forward direction.

As a result of the above operation, a base material having a film having a pattern in which six films in the form of lines having a width of 130 μm and a length of 20 mm were arranged at regular intervals was obtained.

After the above-described operation, the same six film patterns were obtained as a result of the same operation at positions moved 7 mm in the Y direction on the base material surface.

Subsequently, the same operation was performed, but the moving direction of the head was changed in the Y direction. This obtained a base material having a film having a pattern in which a film having a width of 130 mu m was formed in the longitudinal direction. The optical microscope images of the obtained patterned grating film are shown in Figs. 5 (a) and (b).

Raman spectroscopy was performed on the films obtained above. As a result, it was confirmed that the material of the films was CeO ₂ .

Example 19

A base material having a pattern film having a width of 130 μm and a length of 20 mm in the form of a lattice was obtained in the same manner as in Example 18 except that the ink was changed to the ink S4 obtained in Synthesis Example 4 And the surface temperature of the substrate was changed to 250 ° C.

From the results of electron beam diffraction and elemental analysis, it was confirmed that the obtained film was an In ₂ O ₃ crystal film containing Sn in a ratio of 5 atomic% to In.

[ Industrial availability ]

The method of forming the patterned film according to the present invention comprises a high dielectric element film as well as an electronic circuit, for example a transparent electrode, on the surface of a resin film base material and other base material comprising, for example, polyimide or polyester, and the like; It is suitable as a method of forming various metal oxide pattern films and other pattern films which can be used as element films (thin film elements) for electronic circuits such as resistor element films.

The pattern film forming unit and the ink according to the present invention can be suitably used to carry out the method according to the present invention described above.

Claims (12)

In the pattern film formation method which is a formation method of the film which has a desired pattern on the surface of a base material, Forming a pattern film, characterized in that the ink containing the film-forming material is supplied to the surface of the base material from the nozzle in the state that heat is applied to the base material, to form a desired pattern on the surface of the base material Way. The method of claim 1, And supplying ink from the nozzle in an inkjet manner. The method according to claim 1 or 2, Providing a plurality of nozzles each identical, and separately supplying ink containing different types of film forming materials from each of the number of nozzles separately. The method of claim 3, wherein A method of forming a pattern film, wherein one type of the above film forming material is a material which becomes a film when the material itself causes a chemical reaction, and another type is a reaction promoter. The method according to any one of claims 1 to 4, A pattern wherein the coating layer and / or film formed on the base material is irradiated with at least one selected from the group consisting of light, heat, electromagnetic waves and ultrasonic waves simultaneously with and / or after receiving heat from the base material Film formation method. The method according to any one of claims 1 to 5, The base material is a resin film Pattern film forming method. A pattern film forming unit, which is a unit used to carry out a pattern film forming method as recited in any one of claims 1 to 6, And means for supplying ink containing a film forming material from the nozzle to the surface of the base material and means for heating the base material. The method of claim 7, wherein And a means for adjusting the relative positional relationship between the base material and the nozzle. The method according to claim 7 or 8, And a means for irradiating the coating layer and / or the film formed on the base material with at least one selected from the group consisting of light, heat, electromagnetic waves and ultrasonic waves. An ink, which is a material used to carry out a pattern film forming method as recited in any one of claims 1 to 6, Ink comprising a film forming material. The thin film element obtained by the pattern film formation method as quoted in any one of Claims 1-6. An electronic circuit obtained by the pattern film forming method as recited in any one of claims 1 to 6.

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