JP2006045294A - Printing ink composition, coating film, its forming method, electronic component and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a printing ink composition which, when a printing method is used as a method of forming fine patterns used in manufacturing electronic components, improves the uniformity of the coating film surface that forms the patterns and the accuracy and profile of the patterns. <P>SOLUTION: The printing ink composition contains: as component (a), a resin soluble in an organic solvent; as component (b), an organic solvent having a surface tension of ≤30 mN/m at 20°C; and as component (c), an organic solvent having a vapor pressure of ≤2.0 hPa at 20°C. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a printing ink composition, a coating film and a method for forming the same, and an electronic component and a method for manufacturing the same.

  As a method for forming a fine pattern used in electronic parts such as a display member, an optical member, and a wiring board, a photolithography method using a photoresist is generally used. This photolithography method is a method in which, on a substrate on which a processed film to be etched is formed, a photoresist is applied, exposed, developed, an etching process for the processed film, and the photoresist is removed in this order. In particular, the photolithography method can be used for forming a wiring pattern or an element in a manufacturing process of a liquid crystal display LCD because it can form a precise pattern.

  However, in recent years, in order to carry out the photolithography method with the increase in the size of the substrate, a large exposure machine, a developing device, a baking furnace and a clean room in which these are installed are necessary, and the capital investment is increased. It tends to be prominent. In addition, in the photolithography method, it is difficult to apply a resist with a spin coater on a substrate of 1 m square or more, and as an alternative, a coating apparatus such as a slit coater is used. However, it is difficult to form a resist coating film with a uniform thickness on the entire coated surface, and the operation is laborious and expensive. In recent years, there has been a strong demand for reduction in manufacturing cost, and a method for manufacturing an electronic component that does not use a photolithography method that requires expensive equipment and cost is desired.

  As a method for forming a fine pattern other than the photolithography method, application of a conventional electrodeposition method or a printing method has been proposed. In particular, the printing method is attracting attention because it is a relatively inexpensive method.

  As a specific example of the printing method, for example, as disclosed in Patent Document 1, it is possible to eliminate roughness, improve resolution and flatness, and eliminate ghosting by completely eliminating ink film thickness unevenness. Intentionally, an application process in which a resin is applied to the silicon resin surface to form an application surface, and a removal in which the resin is transferred to and removed from the convex portion of the relief plate by pressing the relief plate formed in a predetermined shape against the application surface. There has been proposed an image forming method including a process and a transfer process in which the resin remaining on the coated surface is transferred to a substrate.

Further, as disclosed in Patent Document 2, there is provided an image forming method capable of obtaining a high-quality printed matter that does not cause a stringing phenomenon and does not cause ink film thickness unevenness (melon pattern). Intended to form a functional resin coating surface on the silicon blanket, press the intaglio or relief to the coating surface, remove the pressure-bonded resin from the silicon blanket, and leave the remaining resin unprinted There has been proposed an image forming method which is transferred onto a body.
JP-A-11-58921 JP 2000-289320 A

  However, even if such a conventional method is used for forming a fine pattern used in the manufacture of electronic components, it is not always sufficient to smooth the surface of the coating film forming the fine pattern and to increase the precision of the pattern size and shape. However, there is still room for improvement in order to obtain good electronic components.

  Therefore, the present inventors have investigated the cause and focused on the printing ink composition. And it discovered that the printing ink composition was not fully adaptable to the manufacturing method of an electronic component by the conventional printing method, especially the offset printing method.

  The present invention has been made in view of the above circumstances, and when a printing method is used as a method for forming a fine pattern used in the manufacture of electronic components, the uniformity of the coating film thickness that forms the pattern, and the coating film surface Ink composition for improving the smoothness, pattern accuracy and shape of the coating film, coating film using the printing ink composition and method for forming the same, and method for producing electronic components using the printing ink composition and the electronic parts The purpose is to provide.

  The printing ink composition of the present invention comprises (a) component: a resin soluble in an organic solvent (hereinafter referred to as “a component”), and (b) component: a surface tension at 20 ° C. of 30 mN / m or less. An organic solvent (hereinafter referred to as “component b”) and (c) component: an organic solvent having a vapor pressure at 20 ° C. of 2.0 hPa or less (hereinafter referred to as “component c”) are included. And

  Here, in the printing ink composition of the present invention, the surface tension of the b component is, for example, in accordance with a method defined in JIS K-2241 (2000; cutting oil test method) under a constant temperature condition (20 ° C.). Originally, it can be measured using a Dunui surface tension meter. In addition, the vapor pressure of component c should be measured using a vapor pressure tester in accordance with, for example, the method specified in JIS K-2258 (1998; crude oil and fuel oil vapor pressure test method (Reed method)). Can do.

  According to the printing ink composition of the present invention, since the component a which is a resin is soluble in an organic solvent, it can be dissolved in the components b and c. When this b component is contained in the composition, the surface tension of the b component satisfies the above condition, so that the wettability of the solvent with respect to the silicon resin film is improved, and the printing ink composition of the present invention is made into silicon. When applied to the surface of the resin film, a coating film having a sufficiently uniform film thickness can be formed. The component c is an organic solvent having a low evaporation rate and low volatility, as is clear from the fact that the vapor pressure satisfies the above conditions. For this reason, when the component c is included, the printing ink composition of the present invention is applied to a silicon resin surface such as a silicon blanket to form a coating film, and then transferability when the coating film is transferred to a substrate or the like. Can be improved. Therefore, when the printing ink composition of the present invention is used when a printing method is used as a method for forming a fine pattern used in the manufacture of electronic components, the uniformity of the coating film thickness that forms the pattern and the smoothness of the coating film surface And the accuracy and shape of the pattern in the coating film can be improved.

  In the printing ink composition of the present invention, the component a is preferably at least one resin selected from the group consisting of a novolac resin, a polyhydroxystyrene resin, and an acrylic resin. Thereby, when implementing the manufacturing method of the electronic component mentioned later, tolerance characteristics, such as suppressing a deformation | transformation of a pattern at the time of an etching process, can be improved.

  The method for forming a coating film of the present invention is a method for forming a coating film patterned into a predetermined shape, and forms the coating film by applying the above-described printing ink composition onto the surface of the silicon resin film. A coating film forming step, a peeling removal step for peeling and removing from the silicon resin film by transferring a part of the coating film onto the convex surface of the relief plate, and a coating film remaining on the silicon resin film after the peeling removal step And a coating film transfer process for transferring the film onto the surface of the substrate.

  Moreover, the coating film of this invention is provided on the board | substrate, and is formed by said formation method of a coating film, It is characterized by the above-mentioned.

  Since the coating film of the present invention and the method for forming the same use the printing ink composition of the present invention, the coating film thickness uniformity and the coating film surface smoothness are excellent, and the pattern accuracy and shape are excellent. A coated film can be formed on the substrate.

  Moreover, the manufacturing method of the electronic component of this invention is a manufacturing method of the electronic component by which the wiring pattern was formed on the board | substrate, Comprising: The coating film of Claim 4 is formed on the to-be-processed film provided on the board | substrate. A coating film pattern forming process to be formed, a resin film forming process for drying the coating film to form a resin film, an etching process for etching an exposed region of the film to be processed, and a resin film removing process for removing the resin film; It is characterized by providing.

  The electronic component of the present invention is an electronic component having a wiring pattern formed on a substrate, and is manufactured by the above-described electronic component manufacturing method.

  Since the electronic component of the present invention and the method for producing the same use the above-described printing ink composition of the present invention, a sufficiently good etching process can be performed even when the pattern interval is narrowed, and the productivity is improved. In addition to being excellent, it is possible to increase the density and resolution of the wiring of electronic components.

  According to the present invention, when a printing method is used as a method for forming a fine pattern used for manufacturing an electronic component, the uniformity of the thickness of the coating film forming the pattern, the smoothness of the coating film surface, the pattern accuracy, and the shape A printing ink composition can be provided that improves the above. Moreover, the coating film using this printing ink composition, its formation method, the manufacturing method of an electronic component using this printing ink composition, and its electronic component can be provided.

  Hereinafter, embodiments of the present invention will be described in detail. In the present invention, (meth) acrylic acid means acrylic acid or methacrylic acid, (meth) acrylate means acrylate or a corresponding methacrylate, and (meth) acryloyl group means acryloyl group or methacryloyl group. means.

  Moreover, the weight average molecular weight given below is a value measured by gel permeation chromatography and converted using a standard polystyrene calibration curve.

  The printing ink composition of the present invention has a resin soluble in an organic solvent as component a, an organic solvent having a surface tension at 20 ° C. of component b of 30 mN / m or less, and a vapor pressure at 20 ° C. of component c. It contains an organic solvent of 2.0 hPa or less.

(Component a)
The component a is a resin that is soluble in an organic solvent and is not particularly limited as long as the film-forming property and transferability are not impaired when a printing ink composition is obtained.

  Examples of the component a include novolak resins, polyhydroxystyrene resins, acrylic resins, amide resins, polyester resins, polycarbonate resins, polyphenylene ether resins, and the like.

  Among these, novolak resin, acrylic resin, and polyhydroxystyrene resin are particularly preferable in that they have excellent resistance characteristics such as suppression of pattern deformation during an etching process described later.

  Examples of novolak resins include polycondensates of phenol, cresol, xylenol and the like with formaldehyde.

  As acrylic resins, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, glycidyl methacrylate, bisglycidyl methacrylate, dimethylaminoethyl methacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, lauryl methacrylate, stearyl methacrylate, benzyl methacrylate, benzyl Acrylic acid ester such as acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl methacrylate, hexyl acrylate, octyl methacrylate, octyl acrylate, phosphorus-containing methacrylate, etc. Le or methacrylic acid esters. Also, styrene, styrene derivatives, homopolymers or copolymers of other polymerizable monomers, (meth) acrylic acid, itaconic acid, maleic acid, maleic anhydride, monoalkyl maleate, citraconic acid, citraconic anhydride, A copolymer of a carboxyl group-containing polymerizable monomer such as citraconic acid monoalkyl ester and (meth) acrylic acid ester, a styrene derivative of styrene, other polymerizable monomers, or the like can be used.

  Examples of the polyhydroxystyrene resin include homopolymers such as hydroxystyrene and α-methylstyrene, as well as copolymer compositions with the aforementioned polymerizable monomers.

  When a novolak resin is used, the weight average molecular weight is preferably in the range of 1000 or more, and more preferably in the range of 2000 or more. When the weight average molecular weight is less than 1000, the resistance characteristic during the etching process tends to be lowered.

  Moreover, when using an acrylic resin, it is preferable that a weight average molecular weight exists in the range of 1500-200000, It is more preferable in the range of 5000-100000, It is especially in the range of 10000-50000. preferable. When the weight average molecular weight is less than 1,500, the resistance characteristic during the etching process tends to be lowered, and when the weight average molecular weight exceeds 200000, the solubility in the solvent of the present invention tends to be lowered.

  When using a polyhydroxystyrene resin, the weight average molecular weight is preferably in the range of 1000 to 100,000, more preferably in the range of 2000 to 50000, and in the range of 5000 to 30000. It is particularly preferred. When the weight average molecular weight is less than 1000, the resistance characteristic during the etching process is lowered, and when the weight average molecular weight exceeds 200000, the solubility in the solvent of the present invention tends to be lowered.

  Moreover, you may use resin which has a light or a thermopolymerizable unsaturated bond as a component of the printing ink composition of this invention. Thereby, after forming the coating film patterned into the predetermined shape of this invention, a coating film can be hardened easily by performing light irradiation or heat processing.

  Preferred examples of such resins include high acid value carboxy group-containing acrylic resins, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, α-ethyl glycidyl acrylate, crotonyl glycidyl ether, itaconic acid monoalkyl glycidyl ether. A compound having one oxirane ring and one ethylenically unsaturated bond; allyl alcohol, 2-buten-4-ol, furfuryl alcohol, oleyl alcohol, cinnamyl alcohol, 2-hydroxyethyl acrylate, 2-hydroxy Resins in which a hydroxyl group such as ethyl methacrylate or N-methylolacrylamide and a compound each having one ethylenically unsaturated bond (unsaturated alcohol) are reacted; a carboxyl group-containing resin having a hydroxyl group Resin obtained by reacting an unsaturated compound containing an isocyanate group; Resin obtained by reacting an addition reaction product of an epoxy resin and an unsaturated carboxylic acid with a polybasic acid anhydride; Conjugated diene polymer or conjugated diene copolymer and unsaturated Examples thereof include a resin obtained by reacting an addition reaction product with a dicarboxylic acid anhydride with a hydroxyl group-containing polymerizable monomer.

  Examples of the monomer having two or more photopolymerizable unsaturated bonds in the molecule include EO (ethylene oxide) modified bisphenol A diacrylate, ECH (epichlorohydrin) modified bisphenol A diacrylate, bisphenol A dimethacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol diacrylate, EO-modified phosphate diacrylate, ECH-modified phthalic acid diacrylate, polyethylene glycol 400 Acrylate, polypropylene glycol 400 dimethacrylate, tetraethylene glycol diacrylate, ECH-modified 1,6-hexanediol diacrylate, toner Methylolpropane triacrylate, pentaerythritol triacrylate, EO modified phosphoric acid triacrylate, EO modified trimethylolpropane triacrylate, PO (propylene oxide) modified trimethylolpropane triacrylate, tris (methacryloxyethyl) isocyanurate, pentaerythritol tetraacrylate Acrylates such as dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and methacrylates corresponding to these. These monomers can be used alone or in combination of two or more.

  When the printing ink composition is cured with ultraviolet rays, it is also possible to use a photopolymerization initiator. For example, as a photopolymerization initiator, benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, benzyl, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether , Benzoin isobutyl ether, benzyldimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1- Propane, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10- Enantorakinon, 1,2-anthraquinone, 1,4-dimethyl anthraquinone, 2-phenyl anthraquinone, 2- (o-chlorophenyl) -4,5 the like and diphenyl imidazole dimer. These photoinitiators are used individually or in combination of 2 or more types.

(Component b)
Component b is an organic solvent having a surface tension at 20 ° C. of 30 mN / m or less, and is not particularly limited as long as the film formability and transferability are not impaired when a printing ink composition is obtained.

  Examples of the component b include ester solvents and ketone solvents whose surface tension satisfies the above conditions.

  Examples of ester solvents include methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, i-propyl acetate, n-propyl acetate, i-butyl acetate, n-butyl acetate, methyl propionate, and ethyl propionate. Can be mentioned. Examples of the ketone solvent include acetone and methyl ethyl ketone.

  Although b component will not be specifically limited if the said conditions are satisfy | filled, the surface tension in 20 degreeC is more preferable in it being 28 mN / m or less, and it is still more preferable in it being 26 mN / m or less.

(Component c)
The component c is an organic solvent having a vapor pressure at 20 ° C. of 2.0 hPa or less, and is not particularly limited as long as the film formability and transferability are not impaired when a printing ink composition is obtained.

  Examples of the component c include alkylene glycol compounds and alkylene glycol ether compounds whose vapor pressure satisfies the above conditions.

  Examples of the alkylene glycol compound include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, and dipropylene glycol.

  Examples of alkylene glycol ether compounds include ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol Propylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate Over DOO, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate and the like.

  The component c is not particularly limited as long as the above conditions are satisfied, but the vapor pressure at 20 ° C. is more preferably 1.0 hPa or less, and further preferably 0.5 hPa or less.

  The a component, b component, and c component may be any combination, but as a suitable combination example, the a component is a cresol novolac resin, a polyhydroxystyrene resin, or poly t-butyl methacrylate, and the b component is The combination which is ethyl acetate and c component is diethylene glycol is mentioned.

  The b component and the c component may be the same component as long as the above conditions are satisfied.

(Ratio of each component)
In the printing ink composition containing the a component, the b component, and the c component, the total amount of the a component, the b component, and the c component is preferably 100 parts by mass, and preferably includes 1 to 70 parts by mass, and 5 to 40 masses. It is more preferable to include a part. When the component a is less than 1 part by mass, it tends to be difficult to form a coating film by applying the printing ink composition of the present invention to a silicon resin surface such as a silicon blanket. There is a tendency for the solubility of to deteriorate.

  Moreover, in the said total amount, it is preferable that b component is included 5-95 mass parts, and it is more preferable that 10-80 mass parts is included. When the component b is less than 5 parts by mass, the coating ink composition of the present invention is applied to a silicon resin surface such as a silicon blanket to form a coating film, and the coating film tends to have unevenness, and 95 parts by mass. If it exceeds 1, the coating film is dried too quickly, and it tends to be difficult to transfer the coating film to a substrate or the like.

  Moreover, in the said total amount, it is preferable that 1-40 mass parts of c components are included, and it is more preferable that 2-30 mass parts is included. When the c component is less than 1 part by mass, the coating ink composition of the present invention is applied to a silicon resin surface such as a silicon blanket to form a coating film, and then the coating film is dried too quickly. It tends to be difficult to transfer to a substrate or the like, and if it exceeds 40 parts by mass, the coating tends to be broken during the transfer. In particular, when the component c is a high boiling alcohol organic solvent, the component c is preferably contained in an amount of 50 parts by mass or less, and preferably 40 parts by mass or less. If the c component in this case exceeds 50 parts by mass, the transferability to the substrate tends to be reduced.

  The printing ink composition of the present invention may further comprise a hydrocarbon solvent such as pentane, hexane, heptane, octane, decane, dodecane, isopentane, isohexane, isooctane, cyclohexane, methylcyclohexane, cyclopentane, methanol, if necessary. , Ethanol, propanol, isopropanol, secondary butanol, tert-butanol and the like can contain about 1 to 10 parts by mass with respect to the total amount. . Thereby, the uniformity, drying property, transferability, etc. of the coating film can be adjusted.

  In addition, the printing ink composition of the present invention has a titanate coupling agent (vinyl group, epoxy group, amino group, mercapto group, etc.) for improving the adhesion to the substrate within the range that does not interfere with the above effects. Silane coupling agents, isopropyltrimethacryloyl titanate, diisopropylisostearoyl-4-aminobenzoyl titanate, etc.), surfactants for improving the smoothness of the film (fluorine-based, silicon-based, hydrocarbon-based, etc.) and others, Various additives such as an ultraviolet absorber and an antioxidant can be appropriately contained as necessary.

(Method for forming a coating film patterned into a predetermined shape)
A method of forming a coating film patterned into a predetermined shape according to the present invention includes a coating film forming step of coating the above-described printing ink composition on the surface of a silicon resin film to form a coating film, The film is transferred to the surface of the substrate by transferring the film remaining on the silicon resin film after the peeling and removing process to the surface of the substrate. A process. Hereinafter, an embodiment will be described with reference to FIGS.

  First, an a component, a b component, and a c component are prepared, and a printing ink composition 10 is prepared by dissolving a resin that is the a component in a mixed solution of the b component and the c component using a flask or the like.

  Next, as shown in the schematic end view of FIG. 1A, a reservoir 20 for storing the printing ink composition 10 and a cylindrical cap coater in which one end is immersed in the printing ink composition 10 of the reservoir 20. 30 and a main cylinder 40 disposed on the other end side of the cap coater 30 for applying the printing ink composition 10 to the surface. Here, the main cylinder 40 has a drum shape, and a blanket 42 made of a silicon resin film is formed on the roll surface of the drum. The upper and other ends of the cap coater 30 are disposed slightly apart from the surface of the blanket 42.

  In the coating film forming process, the printing ink composition 10 of the reservoir 20 is applied to the blanket 42 while the main cylinder 40 is rotated in the direction of the arrow in FIG. . In this way, the coating ink composition 10 is applied to the entire blanket 42 and then air-dried for several minutes, whereby the coating film 12 made of the printing ink composition 10 is formed on the blanket 42.

  Subsequently, as shown in FIG. 1C, a plate cylinder 50 having a drum shape substantially the same size as the main cylinder 40 and being a relief plate is prepared. The main cylinder 40 and the plate cylinder 50 are arranged such that the rotation axes of the rolls are parallel to each other and the roll surfaces face each other. The surface of the plate cylinder 50 has a convex portion 52.

  In the peeling and removing step, the convex portion 52 of the plate cylinder 50 is pressed against the coating film 12 formed on the main cylinder 40, and the main cylinder 40 and the plate cylinder 50 are respectively rotated in the direction of the arrow in FIG. Then, the coating film area unnecessary for the target pattern is transferred to the convex portion 52 and removed from the blanket 42. In this way, a patterned coating film 14 is formed.

  Subsequently, as shown in FIG. 1D, a substrate 60 is prepared.

  In the coating transfer process, the patterned coating film 14 is transferred from the roll-shaped blanket 42 to the surface of the substrate 60 while the main cylinder 40 is rotated in the direction of the arrow in FIG. Thereby, the coating film patterned into the desired shape on the substrate 60 can be formed.

  The substrate 60 is selected depending on the application. For example, a transparent glass plate such as white plate glass, blue plate glass, and silica coated blue plate glass, a sheet made of a synthetic resin such as a polyester resin, a polycarbonate resin, an acrylic resin, and a vinyl chloride resin, a film Alternatively, a metal plate such as a plate, an aluminum plate, a copper plate, a nickel plate, and a stainless plate, a ceramic plate, a semiconductor substrate having a photoelectric conversion element, and the like can be given. The substrate 60 may be a single layer or may have a laminated structure.

(Method for manufacturing electronic parts)
An electronic component manufacturing method of the present invention is an electronic component manufacturing method in which a wiring pattern is formed on a substrate, and the coating film pattern that forms the above-described coating film on a film to be processed provided on the substrate. A forming step; a resin film forming step for drying the coating film to form a resin film; an etching step for etching an exposed region of the film to be processed; and a resin film removing step for removing the resin film. . Hereinafter, an embodiment will be described with reference to FIGS.

  The first coating film pattern forming step is the same as the method for forming the coating film patterned into the predetermined shape described above. However, instead of the substrate 60, a laminate 70 in which a film to be processed 74 is formed on the surface of the electronic component substrate 72 is used. The electronic component substrate 72 may be any of those listed for the substrate 60 and is not particularly limited as long as it is applied to the electronic component and does not interfere with the following steps.

  That is, in the coating film pattern forming process, first, after performing the coating forming process and the peeling removing process in the above-mentioned coating film forming method, as shown in FIG. The coating film 14 is transferred from the roll-shaped blanket 42 to the processed film 74 surface of the laminate 70.

  Next, in the resin film forming step, the coating film 14 patterned on the laminate 70 is sufficiently dried by heat treatment for 1 to 15 minutes in a temperature environment of 100 to 150 ° C., and the coating film 14 is cured. Thus, the resin film 16 is formed. When a resin having a photopolymerizable unsaturated bond is used as the component a, the coating film 14 can be sufficiently cured by performing light irradiation before the heat treatment. The thickness of the resin film 16 thus formed is appropriately determined depending on the application, but is preferably in the range of 0.1 to 10 μm, and more preferably in the range of 0.2 to 5 μm.

  Subsequently, in the etching step, an etching solution of a phosphoric acid aqueous solution, a nitric acid aqueous solution, an acetic acid aqueous solution, or a mixed solution thereof is supplied to the surface of the laminate 70 on the resin film 16 side, and the resin film 16 is formed thereon. An exposed region of the unprocessed film 74 is etched (see FIG. 2B). Examples of the etching method include a dip etching method.

  Thereafter, the etching surface is rinsed with an organic solvent such as ethanol, and in the resin film removal step, the resin film 16 used as a mask in the etching step is removed by a dipping method, a spray method, or the like (see FIG. 2C). Thereby, the to-be-processed film | membrane 74 of the laminated body 70 can be processed into the same pattern as the pattern by the resin film 16, ie, the pattern by the coating film 14. FIG. Thus, an electronic component can be manufactured by manufacturing a circuit on a substrate.

  Specific examples of electronic components manufactured using such a manufacturing method include a liquid crystal display LCD.

  The preferred embodiments of the printing ink composition of the present invention, the method of forming a coating film patterned into a predetermined shape, and the method of manufacturing an electronic component have been described above, but the present invention is limited to the above-described embodiment. It is not a thing.

  For example, in the peeling and removing process, a plate-shaped plate is used instead of the drum-shaped plate cylinder, the convex portion of the plate-shaped plate is pressed against the coating film 12 of the main cylinder 40, and the main cylinder 40 is rotated in the roll direction. While moving the plate-shaped plate horizontally in the same direction as the roll direction of the main cylinder 40 on the contact surface, the coating film area unnecessary for the target pattern is transferred to the convex portion and removed from the blanket 42. Also good.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

[Example 1]
First, 125 g of cresol novolak resin (Maywa Kasei Co., Ltd., weight average molecular weight 5000, p-cresol: m-cresol = 60: 40 (molar ratio)) was weighed and put into a 1 L four-necked flask. Subsequently, 200 g of ethyl acetate, 250 g of 2-acetoxy-1-methoxypropane (propylene glycol monomethyl ether acetate) and 50 g of diethylene glycol are added to this four-necked flask, and the resin is dissolved by stirring for 6 hours in a nitrogen atmosphere. It was. Table 1 shows the vapor pressure and surface tension of these additives. Thereafter, the resin solution in the four-necked flask was pressure filtered through a 2 micron polytetrafluoroethylene filter to produce the printing ink composition of Example 1.

[Examples 2-3]
The printing ink compositions of Examples 2 to 4 were prepared in the same manner as in Example 1 except that the amounts of cresol novolac resin, ethyl acetate, 2-acetoxy-1-methoxypropane and diethylene glycol were changed as shown in Table 2. Produced.

[Example 4]
The printing ink composition of Example 4 was the same as Example 1 except that 2-acetoxy-1-methoxypropane was not added and the amounts of cresol novolac resin, ethyl acetate and diethylene glycol were changed as shown in Table 2. A product was made.

[Example 5]
Table 2 shows the amounts of ethyl acetate, 2-acetoxy-1-methoxypropane and diethylene glycol using 100 g of polyhydroxystyrene (manufactured by Maruzen Chemical Co., Ltd., trade name: Marcalinker, weight average molecular weight Mw 15000) instead of cresol novolac resin. A printing ink composition of Example 5 was produced in the same manner as in Example 1 except that the above was changed.

[Example 6]
Except for using 100 g of poly-t-butyl methacrylate (manufactured by Polysciences, molecular weight Mw 40000) instead of cresol novolac resin, the amounts of ethyl acetate, 2-acetoxy-1-methoxypropane and diethylene glycol were changed as shown in Table 2. In the same manner as in Example 1, the printing ink composition of Example 6 was produced.

[Comparative Example 1]
The printing ink composition of Comparative Example 1 was prepared in the same manner as in Example 1 except that diethylene glycol was not added and the amounts of ethyl acetate and 2-acetoxy-1-methoxypropane were changed as shown in Table 2. Produced.

[Comparative Example 2]
A printing ink composition of Comparative Example 1 was prepared in the same manner as in Example 1 except that ethyl acetate was not added and the amount of 2-acetoxy-1-methoxypropane was changed as shown in Table 2.

(Coating appearance evaluation)
The printing ink compositions of Examples 1 to 6 and Comparative Examples 1 and 2 were applied using a cap coater on a silicon resin surface (blanket) according to the method for forming a coating film according to the above-described embodiment. And it was made to dry for 2 to 3 minutes, and the coating film with a film thickness of 1.0 micrometer was formed. Then, it transferred to the glass substrate surface, and observation of the coating-film external appearance was performed using visual observation and an optical microscope. In addition, when it was not able to transfer to the glass substrate surface, the coating-film external appearance was observed before transfer. The results are shown in Table 2. In addition, in the coating film appearance of Table 2, A indicates that no repelling or unevenness is confirmed, and B indicates that repelling is confirmed on the coated surface.

  In the case of Examples 1 to 6 and Comparative Example 1, no repelling or unevenness was observed in the appearance of the coating film, but in the case of Comparative Example 2, repelling was recognized in the appearance of the coating film.

(Pattern shape evaluation)
The printing ink compositions of Examples 1 to 6 and Comparative Example 1 were applied using a cap coater on a silicon resin surface (blanket) according to the method for forming a coating film according to the above-described embodiment. And it was made to dry for 2 to 3 minutes, and the coating film with a film thickness of 1.0 micrometer was formed. Subsequently, an unnecessary portion of the coating film was removed using a plate cylinder to form a pattern. Furthermore, the coating film after this pattern formation was transferred to the glass substrate surface. Thereafter, the accuracy and shape of the transferred pattern were observed with a microscope. The results are shown in Table 3.

  In the case of Examples 1 to 6, a stripe pattern having a width of 50 microns could be formed. However, in the case of Comparative Example 1, the drying time of the printing ink composition was early and could not be transferred to the plate copper and the substrate.

(Gate film wiring evaluation)
The printing ink composition of Examples 1-6 was apply | coated using the cap coater on the silicone resin surface (blanket) according to the formation method of the coating film concerning the above-mentioned embodiment. And it was made to dry for 2 to 3 minutes, and the coating film with a film thickness of 1.0 micrometer was formed. Subsequently, an unnecessary portion of the coating film was removed using a plate cylinder to form a pattern. Further, the coating film after the pattern formation was transferred to a base gate film substrate for TFT electrode (Mo / Al Nd). Then, using this coating film as a mask, the underlying gate film of the substrate was etched with phosphoric acid / nitric acid / acetic acid aqueous solution (phosphoric acid 70 mass%, nitric acid 5 mass%, acetic acid 10 mass%, water 15 mass%). (40 ° C., 2 minutes). Thereafter, it was evaluated whether or not a gate film wiring was formed. The results are shown in Table 3.

In any of Examples 1 to 6, a wiring having a width of 50 microns could be formed.

(A)-(c) is a figure for demonstrating the manufacturing method of the pattern by the coating film of this invention. (A)-(c) is a figure for demonstrating the manufacturing method of the electronic component of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 10 ... Printing ink composition, 12, 14 ... Coating film, 16 ... Resin film, 42 ... Blanket (silicone resin film), 60 ... Substrate, 74 ... Processed film.

Claims (6)

(A) component: resin soluble in organic solvent;
(B) component: an organic solvent having a surface tension at 20 ° C. of 30 mN / m or less,
(C) Component: an organic solvent having a vapor pressure at 20 ° C. of 2.0 hPa or less,
A printing ink composition comprising:   The printing ink composition according to claim 1, wherein the component (a) is at least one resin selected from the group consisting of a novolac resin, a polyhydroxystyrene resin, and an acrylic resin. A method of forming a coating film patterned into a predetermined shape,
A coating film forming step of forming a coating film by applying the printing ink composition according to claim 1 or 2 on the surface of the silicon resin film; and
A peeling removal step of peeling and removing from the silicon resin film by transferring a part of the coating film onto the convex surface of the relief plate,
A coating film transfer step of transferring the coating film remaining on the silicon resin film after the peeling removal step onto the surface of the substrate;
A method of forming a coating film, comprising:   A coating film provided on a substrate and formed by the coating film forming method according to claim 3. A method of manufacturing an electronic component having a wiring pattern formed on a substrate,
A coating film pattern forming step for forming a coating film according to claim 4 on a film to be processed provided on the substrate;
A resin film forming step of drying the coating film to form a resin film;
An etching step of etching the exposed region of the film to be processed;
A resin film removing step for removing the resin film;
An electronic component manufacturing method comprising: An electronic component having a wiring pattern formed on a substrate,
An electronic component manufactured by the method for manufacturing an electronic component according to claim 5.

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