JP4737386B2 - Manufacturing method of circuit board for electronic device, circuit board for electronic device, and display device - Google Patents

Description

  The present invention relates to a method for manufacturing a resin film holding substrate, a method for manufacturing a circuit board for an electronic device using the substrate obtained thereby, and a display device including the circuit substrate obtained thereby.

A circuit board for electronic equipment (hereinafter sometimes referred to as “circuit board”) includes a glass substrate, a synthetic resin substrate or the like, or a substrate having an insulator layer formed on at least a surface thereof, and a number of these thin film transistors. The electrical wiring layers for connecting the transistors to each other or the power source and the input / output terminal are arranged in a single layer or multiple layers. One of the typical uses of a circuit board is a display device such as an active matrix liquid crystal display device or an organic electroluminescence (hereinafter referred to as “organic EL”) display device. The entire substrate including the scanning lines and signal lines is also called an active matrix substrate, and is composed of an insulating layer formed in a reduced-pressure atmosphere on the surface of the circuit substrate and a plurality of circuit pattern layers formed by photolithography or the like. However, since the manufacturing method of the active matrix substrate is complicated, there is a demand for simplification by reducing the number of film forming steps and photolithography steps in a reduced pressure atmosphere.
In particular, in the process of forming the wiring by sputtering, the wiring material formed on the entire surface is processed by the photolithography method to form the wiring portion, so that the target is larger than the substrate area for the purpose of making the film thickness uniform. Sputtering or removing most of the material by etching. For this reason, the utilization efficiency of the wiring material is remarkably low, which complicates the circuit board manufacturing process and causes a large amount of waste.

In order to solve such a problem, a technique has been developed in which wiring is formed only in a necessary portion by a printing method to increase the utilization efficiency of the wiring material. For example, Patent Document 1 discloses a method of forming a wiring at a predetermined location using an inkjet method. By using such a printing method, the reduced pressure film forming step can be reduced.
By the way, when a wiring is formed on a substrate using an ink jet method, it is usually called a convex partition member (“convex portion” or “bank”) made of a resin film on the substrate on which the wiring is to be formed. ) (Hereinafter, referred to as “concave portion”) is filled with a liquid conductive material. At this time, when the partition member is lyophilic with respect to the conductive material, the partition member is pulled by the partition member and spreads to the outer periphery of the partition member, and a desired fine wiring width cannot be obtained. On the other hand, in order for the liquid conductive material to uniformly spread on the entire bottom surface of the recess, the bottom surface of the recess (substrate surface) needs to have high wettability with respect to the conductive material. If the bottom surface is inferior in wettability with respect to the conductive material, the conductive material does not spread out in the recess, which may cause disconnection.
In response to this wettability problem, Patent Documents 2 to 4 propose surface treatment techniques in which the upper part of the partition member is made liquid-repellent and the other parts are made lyophilic. The lyophobic surface treatment technology for the upper part of the partition member is a technology such as irradiating plasma of a gas containing a fluorine compound under a reduced pressure atmosphere or an atmospheric pressure atmosphere. The surface treatment technology for making the bottom surface of the recess lyophilic includes a method of applying a hydrophilic group-containing surfactant and a method of irradiating with ultraviolet rays.

  However, when a fine width wiring having a width of 10 μm or less is formed by the inkjet method, it is necessary that the difference in lyophilicity (wetting property) with respect to the liquid conductive material on the substrate surface is larger, but it is still sufficient. Often this difference cannot be realized, resulting in overflow of the conductive material and excessive wetting and spreading. The large difference between the lyophilic and lyophobic properties has not been obtained due to the following circumstances. For example, when the liquid repellent part is formed by plasma irradiation of a gas containing a fluorine compound, if the partition member is made of an organic material, only a certain liquid repellent property can be obtained because the fluoride etching proceeds simultaneously with the fluoride formation. . In general, a procedure is adopted in which a lyophilic part is formed by applying a surfactant solution or by irradiating ultraviolet rays, and then irradiating the fluorine compound with plasma to form a lyophobic part. There is a problem that fluoride is formed and the effect of increasing the lyophilic contrast is reduced. Further, since the plasma treatment is performed from the vertical direction, only the upper surface of the partition member is fluorinated, and the side wall portion of the partition member remains low in liquid repellency. Due to these circumstances, when fine wiring is formed, the storage property of the liquid conductive material on the bottom surface of the recess on the substrate is poor. In addition, since the plasma apparatus is very expensive, there is a problem that the manufacturing method of the circuit board that frequently uses plasma increases the manufacturing cost.

  As another method of liquid repellency, a technique for forming a fluoride by exposing an organic material for a partition member to a fluorine gas atmosphere has been known. For example, Patent Document 5 proposes a technique for forming a fluororesin film by exposing a photosensitive resin to a fluorine gas atmosphere. In this method, the C—H bond in the resin is converted to a C—F bond by exposure to a fluorine gas atmosphere, and fluorine is added to the carbon-carbon unsaturated bond to obtain a fluororesin. However, when the method of Patent Document 5 is performed, hydrofluoric acid may be generated, and the generated hydrofluoric acid may cause deterioration of a resin film or a silicon-based substrate that is a partition member made of an organic material.

JP 2002-026014 A JP-A-9-203803 Japanese Patent Laid-Open No. 9-230129 JP 2000-353594 A JP-A-6-69190

  An object of the present invention is to provide a method for obtaining a resin film holding substrate having sufficient contrast for the wettability of the liquid conductive material between the resin film and the substrate without deteriorating the resin film as a partition member, and the substrate Another object of the present invention is to provide a method for manufacturing a circuit board for electronic equipment capable of realizing fine wiring formation by an ink-jet method in the pattern recess, and to provide a display device using the circuit board.

As a result of intensive research aimed at achieving the above object, the present inventors have found that a cleaning treatment with an alkaline solution performed after exposing a partition member made of a photosensitive resin formed on a substrate to fluorine gas is effective for making the substrate surface lyophilic. It has been found that a high contrast of the wettability with respect to the conductive material between the partition member and the substrate is obtained, the wiring can be miniaturized, and further, the deterioration of the partition member and the substrate is prevented. Based on this, the present invention has been completed.
Thus, according to the present invention, the following 1 to 14 are provided.
1. A resin film holding substrate comprising: forming a patterned resin film on a substrate; exposing the surface of the resin film to a fluorine gas atmosphere; and then bringing an alkaline solution into contact with the surface having the resin film Manufacturing method.
2. After the resin film forms a thermosetting uncured resin film on the substrate, the uncured resin film is developed or exposed after exposure through a mask, and the remaining resin film is heat cured. Then, the method for producing a resin film holding substrate according to 1 above, which is dried.
3. 3. The method for producing a resin film holding substrate according to 1 or 2, wherein the alkaline solution is a 0.1 to 5% by weight tetramethylammonium hydroxide aqueous solution.
4). 3. The method for producing a resin film holding substrate according to 2 above, wherein the resin film is heat-cured in an inert gas atmosphere.
5. On the resin film holding substrate obtained by the manufacturing method according to any one of the above 1 to 4, an electrical wiring is formed by filling a concave portion surrounded by the convex portion of the resin film with a conductive material. A method for manufacturing a circuit board for electronic equipment.
6). 6. The method for manufacturing a circuit board for electronic equipment according to 5 above, wherein the conductive material is filled by a plating method or a printing method.
7). 7. The method for producing a circuit board for an electronic device according to 6 above, wherein the printing method is an inkjet printing method or a screen printing method.
8). 8. The method for manufacturing a circuit board for an electronic device according to any one of 5 to 7, wherein the upper surface of the electrical wiring and the upper surface of the resin film are substantially in the same plane.
9. 9. The method for manufacturing a circuit board for electronic equipment according to any one of 5 to 8 above, wherein the substrate is a glass substrate or a silicon wafer.
10. 10. The method for manufacturing a circuit board for electronic equipment according to any one of 5 to 9 above, wherein the conductive material contains an organic substance.
11. 11. The method for producing a circuit board for an electronic device according to any one of 5 to 10 above, wherein the resin film is a film obtained using a resin having an acidic group.
12 The method for producing a circuit board for an electronic device according to any one of 5 to 11 above, wherein the resin film is formed of a photosensitive resin composition containing a carboxyl group-containing alicyclic olefin-based resin and a radiation-sensitive component. .
13. The circuit board for electronic devices obtained by the manufacturing method in any one of said 5-12.
14 The display apparatus provided with the circuit board for electronic devices obtained by the manufacturing method in any one of said 5-12.

  According to the present invention, it is possible to obtain a resin film holding substrate having sufficient contrast for the wettability of the liquid conductive material between the partition member and the substrate without deteriorating the resin film as the partition member. Also, a circuit board having fine electrical wiring can be easily obtained by forming electrical wiring with a conductive material by an ink jet method or the like in a region partitioned by the convex portions of the resin film on the substrate. Furthermore, by using the circuit board, a low-cost display device such as a liquid crystal display device, an organic EL display device, or a plasma address display device is provided.

  The best mode of the method for manufacturing a resin film holding substrate and the method for manufacturing a circuit board for electronic equipment according to the present invention will be described with reference to the drawings. FIG. 1 and FIG. 2 are first and second of process explanatory views showing one embodiment of the best mode of the method for producing the resin film holding substrate and the electronic device circuit board of the present invention.

(1) Resin Film Forming Step FIG. 1A shows a step of forming a thermosetting and uncured resin film 2 on the substrate 1.
The substrate used in the present invention is not limited as long as it is usually used for a circuit substrate used in an electronic apparatus such as a liquid crystal display device, an organic EL display device, a plasma address display device, and the like. Examples thereof include an inner layer substrate having a layer and an insulating layer.
The resin film used in the present invention is preferably a thermosetting photosensitive resin film. The resin film is not limited as long as it is composed of a resin composition whose solubility in a developing solution is changed by light irradiation and can be cured by heating. Usually, an alkali-soluble polymer, a radiation-sensitive component, a crosslink It is formed by applying a photosensitive resin composition containing an agent, a solvent and the like.
Alkali-soluble polymers include acrylic resins, silicon resins, fluorine resins, polyimide resins, polyolefin resins, alicyclic olefin resins, epoxy resins having acidic groups such as carboxyl groups and phenolic hydroxyl groups. Resin is used. Of these, alkali-soluble alicyclic olefin resins such as carboxyl group-containing alicyclic olefin resins (for example, carboxyl group-containing norbornene resins) are preferable from the viewpoint of excellent patternability, mechanical properties, and heat resistance.

Examples of the radiation sensitive component include quinone diazide sulfonate, onium salt, acetophenone compound, azide compound and the like, and naphthoquinone diazide compound is preferable.
As the crosslinking agent, one having two or more, preferably three or more functional groups that react with the resin in the molecule is used. Examples of the functional groups include amino groups, carboxyl groups, hydroxyl groups, epoxy groups, An isocyanate group, a vinyl group, etc. are mentioned, Preferably an amino group, an epoxy group, an isocyanate group, More preferably, an epoxy group etc. are illustrated. As a preferable crosslinking agent, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (trade name “EHPE3150” manufactured by Daicel Chemical Industries, Ltd.) and the like Is mentioned.
The solvent is not particularly limited in its boiling point, but is usually 100 ° C. or higher, preferably 130 to 300 ° C., more preferably 150 to 250 ° C., most preferably 160 to 220 ° C. Ethers and ketones. And organic solvents such as esters and polyhydric alcohols. Preferable solvents include propylene glycol monoethyl ether acetate, diethylene glycol ethyl methyl ether, N-methyl-2-pyrrolidone and the like.
The content of the alkali-soluble polymer in the photosensitive resin composition is usually 10% by weight or more, preferably 30 to 100% by weight, more preferably 40 to 100% by weight. The content of the radiation-sensitive component is usually 1 to 100% by weight, preferably 5 to 50% by weight, and more preferably 10 to 40% by weight with respect to 100 parts by weight of the alkali-soluble polymer.
Specific examples of the photosensitive resin composition include a radiation-sensitive resin composition described in JP-A No. 2004-4733, a radiation-sensitive composition described in JP-A No. 2003-288991, and JP-A No. 2003-302642. Radiation-sensitive resin composition, radiation-sensitive resin composition described in JP-A-10-26829, radiation-sensitive resin composition described in JP-A-9-230596, and sensitivity described in JP-A-9-146276 Radiation-sensitive resin composition, radiation-sensitive resin composition described in JP-A-8-262709, radiation-sensitive resin composition described in JP-A-10-10734, radiation-sensitivity described in JP-A-8-240911 Examples thereof include a resin composition and a radiation sensitive resin composition described in JP-A-8-183819. Further, the resin film may contain metal oxide fine particles such as silica and alumina, and inorganic substances such as glass fiber in order to improve mechanical properties and heat resistance.
A method for forming the thermosetting and photosensitive resin film is not particularly limited, and examples thereof include a method in which the photosensitive composition is applied by spin coating, slit coating, or screen printing and then heated and dried. When a thin film of 5 μm or less is to be formed, it is preferably applied by spin coating or slit coating. In particular, in order to make the film thickness in the substrate uniform, spin coating is more preferable.

(2) Exposure process FIG.1 (b) irradiates the resin film 2 formed by apply | coating the photosensitive resin composition and drying the radiation 4 through the mask 3 which has a predetermined | prescribed pattern, The process of forming the resin exposure part 21 and the resin light-shielding part 22 in a resin film is shown. There are photosensitive resin films in which the resin exposed portion 21 is easily removed with a developer (positive type) and those in which the resin exposed portion 21 is difficult to remove with a developer (negative type). FIG. 1 shows an example of a positive type, but the resin film in the present invention is not limited to a positive type.
The irradiation of radiation is appropriately selected according to the fineness of the pattern. For example, irradiation with ultraviolet light having a wavelength of 365 nm and a light intensity of 10 mW / cm ² is performed in air at an energy amount of 100 mJ / cm ² . In order to increase the development resolution after exposure by irradiation with radiation, it is preferable to pre-bake for about 1 minute on a hot plate at 120 ° C., for example.

(3) Development Step or Etching Step FIG. 1C shows a development step in which the resin exposed portion 21 is dissolved and removed (developed) with a developer and a pattern is formed by the remaining resin light shielding portion 22. As the developer, conventionally known ones can be used, and examples thereof include alkaline organic developers such as amines and organic ammonium salts, and alkaline inorganic developers such as sodium hydroxide and potassium hydroxide. After developing with a developer, a rinsing treatment can be added.

  Instead of being formed by exposure and development, the pattern may be formed by etching. Specifically, a positive or negative photoresist is formed on the resin film, a pattern is formed by exposure and development, the resin film is patterned by dry or wet etching, and then the resist is peeled off. Do.

(4) Heat-curing process FIG.1 (d) shows the process of fixing the pattern by heat-curing the developed or etched resin film after exposure. The heating method is not particularly limited. For example, it heats for 30 minutes on a 240 degreeC hotplate. The patterned resin light-shielding part 22 is cured by heating. From the viewpoint of maintaining transparency, the heat curing step is preferably performed in an inert gas atmosphere such as nitrogen or argon.

(4a) Oxygen Plasma or Ultraviolet Irradiation Treatment Step FIG. 1E shows a step of performing oxygen plasma treatment or ultraviolet irradiation treatment on the substrate surface. Although this step is not essential for the method of manufacturing the resin film holding substrate of the present invention, the contrast of the wettability with respect to the liquid conductive material between the upper surface of the resin film and the substrate surface can be expanded. It is preferable to install as a pre-process of the fluorine gas treatment process of the light shielding part 22. This step is also effective for removing the resin residue remaining on the substrate surface when the pattern is formed on the thermosetting resin film by the exposure and development or etching. If the fluorine gas treatment described below is performed with the resin residue remaining on the exposed portion of the substrate, a fluorine compound may be formed on the surface of the resin residue, which may reduce the difference in wettability between the surface of the thermosetting resin and the opening portion. is there.
The oxygen plasma treatment and the ultraviolet irradiation treatment are performed under atmospheric pressure or reduced pressure.

(5) Step of exposing to fluorine gas atmosphere after resin film drying (fluorination step)
FIG. 2F shows a process of exposing the dried resin film holding substrate to a fluorine gas atmosphere. The drying condition of the resin film holding substrate is usually 50 to 300 ° C., preferably 150 to 250 ° C., usually 10 to 200 minutes, preferably 30 to 150 minutes. By drying, the moisture content of the resin film is preferably 1% by weight or less, more preferably 0.1% by weight or less, and particularly preferably 0.05% by weight or less. When the moisture content is high, fluorine gas reacts with moisture to produce hydrogen fluoride, which hinders the surface treatment of the resin and may cause problems such as deterioration of the resin film and peeling from the substrate.

  The fluorine gas in the fluorine gas atmosphere is preferably diluted with an inert gas such as a rare gas or nitrogen. The fluorine gas concentration is not particularly limited, but is preferably 0.1 to 50% by volume, more preferably 0.3 to 30% by volume, and particularly preferably 0.5 to 20% by volume. If the fluorine gas concentration is too low, the generation of fluoride on the surface of the resin film may be insufficient. On the other hand, if the concentration is too high, the reaction between fluorine and the resin film is too rapid, which may cause an undesirable situation. There is no particular limitation on the method of exposing the resin film holding substrate to the fluorine gas atmosphere. For example, the resin film holding substrate is placed in a container and fluorine gas is allowed to flow at normal pressure, or fluorine gas is filled in a pressurized state under sealing.

A smaller moisture content in the fluorine gas atmosphere is more effective for the surface treatment of the resin film. The moisture content in the fluorine gas atmosphere is preferably 100 ppm or less, more preferably 10 ppm or less, and particularly preferably 1 ppm or less. When the moisture concentration is in the above range, hydrogen fluoride is hardly generated.
The temperature of the resin film holding substrate in the fluorination step is usually 23 to 300 ° C, preferably 50 to 250 ° C.

(5a) Heating process (annealing process)
FIG. 2G shows a step of heating (annealing) the resin film holding substrate in an inert gas in order to enhance the liquid repellency of the resin surface after exposure to a fluorine gas atmosphere. Although this step is not essential for the method for producing the resin film holding substrate of the present invention, annealing has the effect of promoting the fluorination of the portion where the fluorination is insufficient and volatilizing excess fluorine. It is preferable to be performed subsequent to the conversion step. The type of inert gas used for annealing is not particularly limited, and examples thereof include rare gases such as helium, neon, argon, krypton, xenon, and radon, and nitrogen. The annealing temperature varies depending on the softening point of the cured resin used, but is preferably 50 to 350 ° C, more preferably 200 to 300 ° C. When the annealing temperature is within the above range, the above-mentioned effects of annealing are sufficiently exhibited, and the generated fluoride is not likely to volatilize.

In the method for producing a resin film holding substrate of the present invention, the step of developing the resin film on the substrate after exposure through a mask or the step of etching [the developing step or the etching step (3)], heating the resin film There is no limitation on the order of the three steps of the step of curing [the heat curing step (4)] and the step of exposing the resin film to a fluorine gas atmosphere after drying [the fluorination step (5)]. Can do.
1 and 2, the three steps (3), (4) and (5) are performed in this order as one embodiment of the best mode of the method for producing a resin film holding substrate of the present invention.
When an oxygen plasma treatment or an ultraviolet irradiation treatment step (4a) is added, it is preferably provided as a pre-step of the fluorination step (5). Moreover, when adding an annealing process (5a), it is preferable to provide as a next process following a fluorination process (5).

(6) Cleaning Step with Alkaline Solution FIG. 2 (h) shows a substrate on which a resin film having a surface exposed to a fluorine gas atmosphere is placed in order to increase the wettability contrast between the resin surface and the substrate surface. Is a step of cleaning by contacting with an alkaline solution. In this process, even if the resin residue is removed by the above-mentioned oxygen plasma treatment or ultraviolet irradiation treatment, a fluorine compound layer is often formed in the opening of the substrate in the fluorination process, so this is removed by contact with an alkaline solution. It is a process to do.
The alkaline solution to be used is not limited as long as the alkaline compound is dissolved in water or an organic solvent, but is preferably dissolved in water from the viewpoint of operability. Examples of alkaline compounds include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; diethylamine, di- Secondary amines such as n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutyl Quaternary ammonium salts such as ammonium hydroxide and choline; pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] nona-5 Ene, N- cyclic amines such as methyl pyrrolidone; and the like, in particular tetramethylammonium hydroxide aqueous solution is preferred. Tetramethylammonium hydroxide is excellent in terms of recycling because its aqueous solution can be easily recovered by electrodialysis. The concentration of the alkaline solution is preferably 0.1 to 5% by weight, more preferably 0.1 to 3% by weight. When the concentration of the alkaline solution is within the above range, the effect of removing the fluorine compound layer in the opening can be sufficiently obtained, and the resin film is not deteriorated or peeled off from the substrate. Although there is no limitation in the contact method with an alkaline solution, the method of immersing a resin film holding board | substrate in the alkaline solution in containers, such as a fluororesin, the method of spraying or spraying an alkaline solution on a resin film holding board | substrate, etc. are mentioned.

The resin film holding substrate washed with an alkaline solution is washed with a rinse solution, a stripping solution, water, and the like, and then dried. Thus, a resin film holding substrate having a sufficient contrast in the wettability of the liquid conductive material between the partition member and the substrate can be obtained without deteriorating the partition member.
Next, a method for producing the circuit board of the present invention using the resin film holding substrate obtained by the method of the present invention will be described based on the embodiments shown in the drawings.

(7) Wiring formation process FIG.2 (i) shows the process of filling an electroconductive material in the recessed part enclosed by the convex part of the resin film on a board | substrate, and baking and forming an electrical wiring. .
The filling of the concave portion with the conductive material is preferably performed by a plating method or a printing method, and the printing method is preferably an ink jet printing method or a screen printing method. In particular, according to the ink-jet printing method, since the difference in wettability with respect to the liquid conductive material between the upper surface of the partition member and the exposed surface of the opening of the substrate is large, the conductive material can be selectively filled into the recess. Therefore, it is preferable.

Although the kind of conductive material is not specifically limited, It is preferable that the metal seed | species to contain contains gold | metal | money, platinum, silver, copper, nickel, palladium, manganese, chromium, or aluminum. In particular, gold, silver, copper, nickel, and the like can be used as fine particles of 1 μm or less, which is preferable for forming fine wiring.
When the conductive material contains an organic substance such as tetradecane, dodecylamine, or oleic acid, the metal is preferably dispersed in the solvent. The content of the organic substance is preferably 25 to 90% by weight, more preferably 60 to 80% by weight with respect to the metal.
The solvent for the conductive material is not limited to water, an organic solvent, or a mixture thereof, but it is preferable to use a solvent species that expresses clearer wettability between the partition member and the substrate surface.

  The board | substrate with which the electroconductive material was filled into the recessed part is normally baked at 200-500 degreeC for 10 to 120 minutes, Preferably it is 30 to 60 minutes at 250-350 degreeC, and the circuit board for electronic devices is formed.

  In the electronic device circuit board of the present invention obtained by the production method of the present invention, it is preferable that the upper surface of the electrical wiring and the upper surface of the resin film (partition member) are substantially in the same plane. By making the both substantially the same plane, occurrence of disconnection, short circuit, etc. can be reduced.

  The electronic device circuit board obtained by the method for manufacturing an electronic device circuit board according to the present invention is capable of fine wiring and is less likely to be disconnected or short-circuited, so that it can be used as a TFT, STN, TFD, etc. By incorporating it into an EL display device or a plasma address display device, a display device with few missing dots can be obtained.

  As an example of the liquid crystal display device of the present invention, a cross-sectional view showing the structure of an active matrix liquid crystal display device is shown in FIG. A scanning line formed on the glass substrate, a signal line, and a gate electrode is connected to the scanning line in the vicinity of an intersection of the scanning line and the signal line, and a source or drain electrode is connected to the signal line The planarization layer is formed so as to surround the signal line, the source electrode, and the drain electrode, and the signal line, the source electrode, the drain electrode, and the planarization layer form substantially the same plane. ing. A pixel electrode is disposed on this plane via an interlayer insulating film to constitute an active matrix substrate, and a liquid crystal is sandwiched between the opposite substrate. As the scanning line and the gate electrode wiring, a fine wiring is formed by applying the method for manufacturing a circuit board for electronic equipment of the present invention.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In the examples, parts and% are based on mass unless otherwise specified.
Moreover, the test and evaluation in an Example and a comparative example were based on the following.
(1) Thermal desorption analysis (hereinafter abbreviated as “TDS analysis”)
The moisture content of the cured resin film was measured using a TDS analyzer (EMD-WA1000S / W, manufactured by Electronic Science Co., Ltd.).

(2) Contact angle The contact angle of the droplet on the substrate surface was measured using a contact angle measuring device (CA-D, manufactured by Kyowa Interface Science Co., Ltd.). Tetradecane was used as the liquid, and it was defined as a value when 30 seconds had passed after the droplet contacted the substrate.
(3) Conductive material storage limit width Five types of widths of 10, 20, 30, 40 and 50 μm, and the conductive material dropped into a straight groove with a length of 50 mm are observed to protrude from the groove of each width. The lower limit width that does not protrude was defined as the storage limit width.

Example 1
100 g of thermosetting resin (carboxyl group-containing alicyclic olefin-based resin), 25 g of crosslinking agent EHPE3150 (manufactured by Daicel Chemical Industries), 1,1,3-tris (2,5-dimethyl) as a radiation sensitive compound 25 g of condensate of -4-hydroxyphenyl) -3-phenylpropane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (1.9 mol), γ-glycidoxypropyl as an adhesion assistant 200 g of propylene glycol monoethyl ether acetate, 5 g of trimethoxysilane, 1 g of antioxidant Irganox 1010 (manufactured by Ciba Specialty Chemicals) and 0.05 g of surfactant KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) 100 g of diethylene glycol ethyl methyl ether, 100 g of N-methyl-2-pyrrolidone It was dissolved in Ranaru mixed solvent, to prepare a radiation-sensitive resin composition was filtered through a pore size of 0.45μm Millipore filter.
The obtained radiation-sensitive resin composition was washed in advance and heated in high-purity nitrogen for dehydration, and then a hexamethylene disilazane (HMDS) vapor was applied to form an HMDS adhesion layer ( 40 mm in length, 10 mm in width, and 1 mm in thickness) by spin coating, and placed in an oven at 100 ° C. for 10 minutes and baked to form a resin film having a thickness of 1 μm. The half surface of the alkali-free glass substrate on which the resin film is formed is shielded with a mask, exposed at 200 mJ / cm ² with a mask aligner, and then developed in an aqueous 2.38% tetramethylammonium hydroxide (TMAH) solution at 25 ° C. for 70 seconds. Then, a rinse treatment was performed with ultrapure water for 30 seconds. Thereby, since the said radiation sensitive resin composition was a positive type, the resin exposure part melt | dissolved and the resin film of the glass substrate upper half surface was removed. This was washed with water and dried, and then heated at 280 ° C. for 60 minutes in a 99.99999% by volume high-purity nitrogen atmosphere using the baking apparatus shown in FIG. 3, to cure the resin film, and to 500 mJ / cm ² with a mask aligner. The entire surface of the substrate was irradiated with ultraviolet rays. Thereafter, the resin film holding substrate sample was put into an electric furnace shown in FIG. 4, and high purity nitrogen gas was circulated, and dried by heating at 150 ° C. for 60 minutes. When the moisture content of the cured resin film was analyzed by TDS analysis for a part of the dried sample, it was 0.02%. Next, while the sample was continuously heated to 180 ° C. with the same apparatus, 10 vol% fluorine gas diluted with high-purity argon gas was introduced at a rate of 200 ml per minute, and fluorination treatment was performed for 1 minute. After the fluorination treatment, the sample was annealed in high-purity nitrogen gas at 300 ° C. for 10 minutes using the same apparatus. The sample after annealing was immersed in a 2.38% TMAH aqueous solution for 10 seconds, then rinsed with pure water for 5 minutes and dried to obtain a resin film holding substrate. Table 1 shows the results of measuring the contact angle with tetradecane on the resin surface and glass surface of the substrate.

(Comparative Example 1)
In Example 1, the resin film holding substrate sample was processed in the same manner as in Example 1 except that the operation was completed at the stage where the heat curing process in the high-purity nitrogen gas atmosphere in the baking apparatus shown in FIG. A film holding substrate was obtained. Table 1 shows the results of measuring the contact angle with tetradecane on the resin surface and glass surface of the substrate.

(Comparative Example 2)
In Example 1, a resin film holding substrate was obtained in the same manner as in Example 1 except that the operation was completed when the fluorination treatment and annealing were performed on the resin film holding substrate sample. Table 1 shows the results of measuring the contact angle with tetradecane on the resin surface and glass surface of the substrate.

(Comparative Example 3)
In Example 1, after performing the fluorination treatment and annealing of the resin film holding substrate sample, instead of the operation of immersing the resin film holding substrate sample in the 2.38% TMAH aqueous solution, the oxygen plasma treatment was performed. In the same manner as in Example 1, a resin film holding substrate was obtained. Table 1 shows the results of measuring the contact angle with tetradecane on the resin surface and glass surface of the substrate.
In the oxygen plasma treatment, the resin film holding substrate sample was put in an RF plasma apparatus, and after being filled with oxygen, plasma treatment was performed at a pressure of 2.67 Pa for 10 seconds.

(Comparative Example 4)
In Example 1, instead of the operation of immersing the resin film holding substrate sample in the 2.38% TMAH aqueous solution, a lyophilic coating film was formed with a fluorosurfactant on the exposed glass surface after the resin film was removed. Others were carried out in the same manner as in Example 1 to obtain a resin film holding substrate. Table 1 shows the results of measuring the contact angle with tetradecane on the resin surface and glass surface of the substrate.
In addition, the lyophilic coating film using a fluorosurfactant is prepared by spin coating a 3% aqueous solution of a fluorosurfactant (product name: Fluorard FC-170C, manufactured by Sumitomo 3M) on the exposed glass surface after removing the resin film. After coating by heating at 100 ° C. for 5 minutes, a coating film having a thickness of 0.1 μm was obtained.

As shown in Table 1, the tetradecane contact angle on the top surface of the resin film cured in a pattern exposed to a fluorine gas atmosphere is 62 degrees, indicating extremely low wettability, and the insulation on which the resin film is placed By bringing the substrate into contact with the TMAH aqueous solution, the contact angle of tetradecane on the glass surface was 9 degrees, and extremely wettability was exhibited. As a result, the difference between both contact angles was 53 degrees, and a high wettability contrast was achieved (Example 1).
On the other hand, if only the TMAH aqueous solution contact treatment with respect to the insulating substrate on which the resin film was placed was omitted, the wettability of the glass surface was not improved, and the difference in the tetradecane contact angle was reduced to 49 degrees (Comparative Example 2). When the oxygen plasma treatment was performed instead of the TMAH aqueous solution contact treatment, the wettability of the resin surface was improved, and the difference in the tetradecane contact angle was reduced to 31 degrees (Comparative Example 3). Even when a lyophilic film was formed on the glass surface using a fluorosurfactant instead of the TMAH aqueous solution contact treatment, the effect of lyophilicity was small, and the difference in the tetradecane contact angle was reduced to 27 degrees (Comparative Example 4). ).
Moreover, if the fluorination treatment for the resin film and the TMAH aqueous solution contact treatment for the insulating substrate on which the resin film is placed are not performed together, the difference in tetradecane contact angle is 1 degree, and the wettability of the resin surface and the substrate surface is almost the same. It became equivalent (comparative example 1).

(Example 2)
After forming a thermosetting resin film having a thickness of 1 μm on an alkali-free glass substrate in the same manner as in Example 1, five types of widths of 10, 20, 30, 40, and 50 μm and a straight line having a length of 50 mm are used. After exposure at 200 mJ / cm ² with a mask aligner through a mask having a belt-like pattern, development was performed in the same manner as in Example 1. Thereby, the resin exposure part melt | dissolved and the resin film which has a width | variety of 10-50 micrometers and a linear groove pattern of length 50mm was formed. This was exposed, developed and heat-cured in the same manner as in Example 1, and then subjected to oxygen plasma treatment at a pressure of 2.67 Pa for 10 seconds using an RF plasma apparatus. A resin film holding substrate sample is placed in the electric furnace shown in FIG. 4 and dried in the same manner as in Example 1 after drying under an argon gas flow, followed by fluorination treatment, annealing, TMAH aqueous solution contact treatment, water washing and drying. Got.
A conductive material (silver ink, manufactured by Fujikura Kasei Co., Ltd.) was dropped into the linear groove portion of the resin film of the substrate sample using a micro syringe. Table 2 shows the results of examining the storage limit width of the conductive material.

(Comparative Example 5)
In Example 2, the operation of the resin film holding substrate sample was completed at the stage where the heat curing process in the high purity nitrogen gas atmosphere in the baking apparatus shown in FIG. The TMAH aqueous solution contact treatment with respect to the insulating substrate on which the film was placed was also performed in the same manner as in Example 2 except that the resin film holding substrate prepared without being carried out was obtained to obtain a substrate filled with a conductive material. Table 2 shows the results of examining the storage limit width of the conductive material.

(Comparative Example 6)
In Example 2, instead of fluorination treatment with fluorine gas, a resin film holding substrate sample was placed in an RF plasma apparatus, filled with carbon tetrafluoride, and then plasma-treated at a pressure of 6.67 Pa for 1 minute to hold the resin film. A substrate filled with a conductive material was obtained in the same manner as in Example 2 except that the substrate was used. Table 2 shows the results of examining the storage limit width of the conductive material.

As shown in Table 2, the resin film holding substrate having a partition member made of a resin film having a surface exposed to a fluorine gas atmosphere and a groove bottom made of a glass surface in contact with the TMAH aqueous solution has a width of 10 μm. It was shown that the conductive material did not protrude even in the groove, and fine wiring was possible (Example 2).
On the other hand, if neither the fluorination treatment with a fluorine gas for the resin film nor the TMAH aqueous solution contact treatment for the substrate on which the resin film is placed is performed, the conductive material protrudes over the entire surface even in the groove having a width of 50 μm. Was impossible (Comparative Example 5). Even if the surface of the resin film is subjected to lyophobic treatment with carbon tetrafluoride plasma instead of being exposed to fluorine gas, and then subjected to lyophilic treatment in which the resin film holding substrate is brought into contact with the TMAH aqueous solution, the conductive material can be stored. The limit width was 30 μm, and the fine area storage was insufficient (Comparative Example 6).

(Example 3)
A photosensitive transparent resin film having a thickness of 1 μm with a carboxyl group-containing alicyclic olefin-based resin was formed on the surface of the glass substrate by spin coating. This photosensitive resin film has a function as a photoresist film. Next, by selectively exposing, developing, and heat-curing the resin film using actinic radiation, a resin in which a transparent resin film having a wiring groove is placed on the glass substrate shown in FIG. A film holding substrate was obtained. This resin film holding substrate was subjected to oxygen plasma treatment at 2.67 Pa for 10 seconds with an RF plasma apparatus, then exposed to a fluorine gas atmosphere to treat the surface with fluorine, and then immersed in a 2.38% TMAH aqueous solution at 23 ° C. for 10 seconds. did.

Next, the groove material was filled with a conductive material by an ink jet printing method. In this example, as a conductive material, a commercially available silver dispersion of ultrafine particles (Perfect Silver, manufactured by Vacuum Metallurgical Company; 100 parts of silver fine particles with an average particle diameter of 8 nm, 15 parts of dodecylamine, 75 parts of terpineol) Prepared by mixing 6.8 parts of methylhexahydrophthalic anhydride, 5 parts of resol type phenolic resin (PL-2211, Gunei Chemical Co., Ltd.) and 35 parts of toluene with 100 parts, followed by filtration with a 0.5 μm filter. Wiring was formed using the prepared silver paste ink. After filling with the conductive material, it was baked for 30 minutes at a temperature of 250 ° C. to form scanning lines and gate electrode wirings (FIG. 6B). Next, a silicon nitride film (SiN _x film) was formed using SiH ₄ gas, H ₂ gas, N ₂ gas, and Ar gas by plasma CVD using microwave excitation plasma.

Next, at 300 ° C. by plasma CVD using microwave excitation plasma, SiH ₄ gas is vented to pass through the amorphous silicon layer, then SiH ₄ gas, PH ₃ gas and Ar gas are vented to form n + type amorphous. Silicon layers were sequentially formed [FIG. 6 (c)]. Next, a photoresist was applied to the entire surface by spin coating, and dried on a hot plate at 100 ° C. for 1 minute to remove the solvent. Next, it exposed with the energy amount of 36 mJ / cm < ² > using the g line | wire stepper. At the time of exposure, a mask was formed so as to leave the element region, and the exposure amount was adjusted by using a slit mask for a portion corresponding to the channel region inside the element region. As a result of performing paddle development for 70 seconds using a 2.38% TMAH aqueous solution, a sample having the photoresist shape shown in FIG. 6D was obtained.

Next, the n + type amorphous silicon layer and the amorphous silicon layer were etched using a plasma etching apparatus. At this time, the photoresist was also slightly etched to reduce the film thickness, so that the resist in the channel region where the photoresist film thickness was thin was removed by etching, and the n + silicon layer was also etched. When the n + type amorphous silicon layer and the amorphous silicon layer other than the element region are removed by etching and the n + type amorphous silicon layer in the channel region is removed by etching, the etching process is finished, and the shape shown in FIG. A sample with was obtained. With the photoresist on the n + -type amorphous silicon layer of the source electrode portion and the drain electrode portion remaining, microwave excitation plasma treatment is performed using Ar gas, N ₂ gas, and H ₂ gas, and the channel portion A nitride film was formed directly on the amorphous silicon surface [FIG. 7 (f)].

  Next, the photoresist film remaining on the source and drain electrode regions was subjected to oxygen plasma ashing, and then removed with a resist stripping solution or the like to obtain a sample having the shape of FIG. Subsequently, as a partition member required when forming signal lines, source electrode wirings and drain electrode wirings by a printing method such as an ink jet printing method or a plating method, a carboxyl group-containing alicyclic olefin system which is an alkali-soluble polymer 100 g of resin, 25 g of crosslinking agent EHPE3150 (manufactured by Daicel Chemical Industries, Ltd.), 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane (1 mol) as a radiation sensitive compound ) And 1,2-naphthoquinonediazide-5-sulfonic acid chloride (1.9 mol), 5 g of adhesion promoter γ-glycidoxypropyltrimethoxysilane, and Irganox 1010 antioxidant (Ciba) 1 g of Specialty Chemicals) and 0.05 g of surfactant KP-341 (Shin-Etsu Chemical Co., Ltd.) Radiation-sensitive resin obtained by filtering a solution prepared by dissolving a solution of propylene glycol monoethyl ether acetate 200 g, diethylene glycol ethyl methyl ether 100 g and N-methyl-2-pyrrolidone 100 g with a Millipore filter having a pore size of 0.45 μm The composition was washed and heated in high-purity nitrogen for dehydration, and then a non-alkali glass substrate (40 mm long, 40 mm long, HMDS adhesion layer formed by applying a vapor of hexamethylene disilazane (HMDS). (10 mm wide, 1 mm thick) by spin coating, placed in an oven at 100 ° C. for 10 minutes and baked to form a 1 μm thick resin film, using a photomask for signal lines, source electrode wiring and drain electrode wiring Exposure, development and heat curing to form a transparent resin layer. As described in FIG. 7 (h), to give a signal line, a sample having a groove serving as a source electrode wiring and the drain electrode wiring region.

  After the oxygen plasma treatment, the sample was exposed to a fluorine gas atmosphere to treat the surface with fluorine, and then immersed in a 2.38% TMAH aqueous solution. Next, the conductive material of the silver paste ink was filled in the groove by an ink jet printing method. After filling the conductive material, it was baked at a temperature of 250 ° C. for 30 minutes to form a wiring [FIG. 6 (i)]. In this way, the formation of the TFT was completed.

Next, as the interlayer insulating film, a photosensitive and transparent resin film was formed from a carboxyl group-containing alicyclic olefin-based resin, and exposure and development were performed to form a contact hole from the pixel electrode to the TFT electrode. In order to increase the light transmittance of the photosensitive transparent resin, the photosensitive transparent resin is cured by using a heating device in which the inner surface of the device is electropolished with SUS316, and the residual oxygen concentration is controlled to 10 ppm. Bake for minutes. Subsequently, ITO was sputtered on the entire surface of the substrate and patterned to form a pixel electrode. A polyimide film was formed on the surface as a liquid crystal alignment film, and the liquid crystal was sandwiched between the opposite substrate and an active matrix liquid crystal display device having the structure shown in FIG. 5 was obtained.
Since the flattening layer has high transparency, the display device has high luminance and low power consumption.

It is process explanatory drawing (the 1) which shows one embodiment of the manufacturing method of the resin film holding | maintenance board | substrate of this invention, and the circuit board for electronic devices. It is process explanatory drawing (the 2) which shows one embodiment of the manufacturing method of the resin film holding | maintenance board | substrate of this invention, and the circuit board for electronic devices. It is a conceptual diagram of the baking apparatus used by this invention Example. It is a conceptual diagram of the electric furnace for drying, a fluorine gas process, etc. which are used by the Example of this invention. It is sectional drawing which shows the structure of the active matrix liquid crystal device of an example of this invention. It is process explanatory drawing (the 1) of this invention Example 4. FIG. It is process explanatory drawing (the 2) of this invention Example 4. FIG.

Explanation of symbols

1. Substrate 2. 3. Resin film Mask 4. Ultraviolet light 5. Oxygen plasma or ultraviolet light 6. Fluoride layer Fluorine gas 8. 8. Tetramethylammonium hydroxide aqueous solution Metal wiring 10. Inkjet nozzle

Claims (13)

After forming a patterned resin film on the substrate, the surface of the resin film is exposed to a fluorine gas atmosphere to make a liquid repellent treatment, and then an alkaline solution is brought into contact with the surface having the resin film to make a lyophilic treatment by be Rukoto to obtain a resin film holding substrate, on the resin film support substrate, a concave portion surrounded by the convex portions of the resin film, to form an electrical wiring by filling a conductive material in a liquid phase A method for manufacturing a circuit board for electronic equipment, which is characterized . After the resin film forms a thermosetting uncured resin film on the substrate, the uncured resin film is developed or exposed after exposure through a mask, and the remaining resin film is heat cured. The method for producing a circuit board for an electronic device according to claim 1 , wherein the circuit board is then dried. The method for producing a circuit board for an electronic device according to claim 1, wherein the alkaline solution is a 0.1 to 5 wt% tetramethylammonium hydroxide aqueous solution. The method for manufacturing a circuit board for an electronic device according to claim 2, wherein the heat curing of the resin film is performed in an inert gas atmosphere. Method of manufacturing a circuit board for an electronic device according to claim 1 for performing filling of the conductive material by printing method. The method for manufacturing a circuit board for an electronic device according to claim 5 , wherein the printing method is an inkjet printing method or a screen printing method. Method of manufacturing a circuit board for an electronic device according to any one of claims 1 to 6, the upper surface of the upper surface and the resin film of the electric wiring is in a substantially coplanar. Method of manufacturing a circuit board for an electronic device according to any one of claims 1-7 wherein the substrate is a glass substrate or a silicon wafer. The method for manufacturing a circuit board for electronic equipment according to any one of claims 1 to 8 , wherein the conductive material contains an organic substance. The method for manufacturing a circuit board for an electronic device according to any one of claims 1 to 9 , wherein the resin film is a film obtained using a resin having an acidic group. The circuit board for electronic devices according to any one of claims 1 to 10 , wherein the resin film is formed of a photosensitive resin composition containing a carboxyl group-containing alicyclic olefin-based resin and a radiation-sensitive component. Method. A circuit board for an electronic device obtained by the production method according to any one of claims 1 to 11. Display device having a circuit board for an electronic device obtained by the production method according to any one of claims 1 to 11.

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