JP2006037058A - Printing ink composition, method for letterpress reversed offset, method for forming resist pattern, method for producing electronic component and electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a printing ink composition suppressing defective disconnection caused by lowering of etching resistance due to insufficient thickness of a formed resist causing problems in a method for printing, improving uniformity of a coated film, pattern accuracy and shape and having good etching resistance and release properties. <P>SOLUTION: The printing ink composition is used in a method for letterpress reversed offset comprising a coating layer-forming step of coating the top surface of a base material for forming the coating layer with the printing ink composition and forming the coating layer of the printing ink composition, a removing step of bringing the coating layer into contact with a letterpress of a prescribed shape, transferring the coating layer to protruding parts of the letterpress and removing the coating layer and a transfer step of transferring the coating layer remaining on the base material for forming the coating layer to a substrate. The printing ink composition comprises (A) a resin soluble in an organic solvent, (B) the organic solvent and (C) a silica sol. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a printing ink composition, a letterpress inversion offset method, a resist pattern formation method, a method for manufacturing an electronic component, and an electronic component.

  A fine pattern forming method used for electronic parts such as a display member, an optical member, and a wiring plate is generally a photolithography method using a photoresist. For example, in the wiring pattern and the element formation in the manufacturing process of the liquid crystal display LCD, the liquid crystal display LCD is manufactured by processing a resist with photolithography, etching, or the like. In recent years, with the increase in size of substrates, a large exposure machine, a developing device, a baking furnace, and a clean room in which these are installed are required, and the capital investment has become enormous. In addition, it is difficult to apply a substrate of 1 m square or more with a spin coater. For this reason, a coating device such as a slit coater is used, but it is difficult to ensure the uniformity of the coating film. Further, there is a strong demand for reduction in manufacturing cost, and a method for manufacturing electronic components other than the photolithography method using expensive equipment such as the above exposure machine is desired. Electrodeposition methods and printing methods have been conventionally proposed as methods for producing electronic components other than the photolithographic method. Among these, the printing method has attracted attention as an inexpensive manufacturing method, but it has been difficult to manufacture a wiring pattern having good surface smoothness and high-definition pattern dimensions and shape by the conventional printing method. It was. For example, in the offset printing method, since the printing ink composition uses a high-viscosity colored paste, it is difficult to obtain a high-definition pattern or a uniform coating surface.

  Further, in this printing method, when the solvent component of the ink is increased, a uniform coating film can be easily obtained, but the resist film that can be formed at the same time becomes thin, and there is a problem that the etching resistance is lowered. On the other hand, if the solvent component of the ink is reduced, the resist film can be made thicker, but there is a problem that a uniform coating film is difficult to obtain and the pattern property with fine lines is deteriorated.

JP-A-11-58921 Japanese Patent Laid-Open No. 11-97032

The present invention provides a composition for printing ink that can suppress a disconnection failure caused by a decrease in etching resistance due to insufficient thickness of a formed resist, which is a problem in a printing method. This invention provides the composition for printing inks which improves the uniformity of a coating film, pattern precision, and a shape, and has favorable etching tolerance and peelability.

  The present invention provides a resist pattern forming method having high etching resistance that can be transferred with good pattern accuracy and shape. The present invention provides a method of manufacturing an electronic component and an electronic component capable of accurately etching a base with a resist pattern having improved pattern accuracy and shape. The present invention provides a method of manufacturing an electronic component capable of accurately etching a base with a resist pattern having improved pattern accuracy and shape, and provides an electronic component equivalent to that manufactured by a photolithography method. It is.

  The present invention includes a coating layer forming step in which a printing ink composition is applied onto a coating layer forming substrate to form a coating layer of the printing ink composition, and a relief plate having a predetermined shape is brought into contact with the coating layer. A printing ink composition for use in a relief reversal offset method comprising a removal step of transferring and removing the coating layer on a convex portion and a transfer step of transferring the coating layer remaining on the coating layer-forming substrate to a substrate The printing ink composition relates to a printing ink composition comprising (A) a resin soluble in an organic solvent, (B) an organic solvent, and (C) a silica sol.

  Moreover, this invention relates to the printing ink composition of Claim 1 whose addition amount of the said (C) silica sol is 1 to 40 weight% with respect to the printing ink composition whole quantity.

  The present invention also relates to (A) the printing ink composition wherein the resin soluble in an organic solvent contains a resin soluble in an alkaline solution.

  Moreover, this invention relates to the said printing ink composition whose resin soluble in an alkaline solution is a novolak resin.

  The present invention also relates to the printing ink composition, wherein the resin soluble in an alkaline solution is a polyhydroxystyrene resin.

  The present invention also includes a coating layer forming step of coating the printing ink composition on a coating layer forming substrate to form a coating layer of the printing ink composition, and bringing a relief plate having a predetermined shape into contact with the coating layer. And a transfer step of transferring the coating layer remaining on the coating layer forming substrate to a substrate, and a transfer step of transferring the coating layer to the substrate. Regarding the law.

  The present invention also includes a coating layer forming step of coating the printing ink composition on a coating layer forming substrate to form a coating layer of the printing ink composition, and bringing a relief plate having a predetermined shape into contact with the coating layer. A resist pattern comprising: a removal step of transferring and removing the coating layer on the convex portion of the relief plate; and a transfer step of transferring the coating layer remaining on the coating layer-forming substrate to the substrate. It relates to the forming method.

  The present invention is also a method for producing an electronic component having a wiring pattern formed on a substrate, wherein the printing ink composition is applied on a coating layer forming substrate to form a coating layer of the printing ink composition. A coating layer forming step, a removing step of bringing a relief plate of a predetermined shape into contact with the coating layer and transferring and removing the coating layer on a convex portion of the relief plate, and the coating layer remaining on the coating layer forming substrate The present invention relates to a method for producing an electronic component, comprising: a transfer step of transferring the substrate to a substrate; and a processing step of performing etching or plating using the transferred printing ink composition as a resist.

  The present invention also relates to an electronic component having a wiring pattern formed on a substrate, which is manufactured by the electronic component manufacturing method according to claim 8.

  The above printing ink composition, resist pattern forming method and manufacturing method can form a resist pattern with good pattern accuracy and pattern shape, excellent etching resistance, and an inexpensive manufacturing method. The inventors have found that an equivalent electronic component can be obtained and have reached the present invention. The composition for printing ink of the present invention can suppress disconnection failure caused by a decrease in etching resistance due to insufficient thickness of the formed resist, which is a problem in the printing method. Moreover, the composition for printing ink of this invention can improve the uniformity of a coating film, a pattern precision, and a shape, and can improve etching tolerance and peelability.

  Moreover, the relief reversal offset method of this invention can improve the uniformity and peelability of a coating film. The resist pattern forming method of the present invention can be transferred with good pattern accuracy and shape, and can improve etching resistance. In addition, the method of manufacturing an electronic component according to the present invention can accurately perform etching or plating of a base with a resist pattern having improved pattern accuracy and shape. By such a manufacturing method, an electronic component equivalent to a photolithography method can be obtained. Obtainable.

  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.

  The present invention provides a coating layer forming step in which a printing ink composition is applied onto a coating layer forming substrate to form a coating layer, and a printing plate having a predetermined shape is brought into contact with the coating layer to print the convex portion on the relief printing plate. A printing ink composition for use in a letterpress reversal offset method comprising a removal step of transferring and removing an ink composition, and a transfer step of transferring the printing ink composition remaining in the coating layer to a substrate. The ink composition contains (A) a resin soluble in an organic solvent, (B) an organic solvent, and (C) a silica sol.

  By including a silica sol in the printing ink composition of the present invention, it is possible to improve applicability to the coating layer-forming substrate and to improve etching resistance. Here, the silica sol refers to all soluble silica compounds, such as polymethylsilsesquioxane, polyphenylsilsesquioxane, poly-p-chloromethylphenylsiloxane, polyallylsil nsesquioxane, polyvinylsilsesquioxane, and the like. From the viewpoint of etching resistance, high molecular weight polysilicon having a molecular weight exceeding 1000 is preferable. Of these, poly-p-phenylsilsesquioxane is preferably used from the viewpoint of etching resistance. The amount of (C) silica sol added in the present invention is preferably 1 to 40% by weight, more preferably 3 to 30% by weight, and particularly preferably 5 to 20% by weight based on the total amount of the printing ink composition. If the amount of silica sol added exceeds 40% by weight, the printability and transferability tend to be poor, and if it is less than 1% by weight, the etching resistance tends to be poor.

  The resin soluble in the organic solvent (A) used in the present invention is preferably soluble in an alkaline solution, and preferably has a film-forming property and transferability when used as a printing ink composition. . Here, the alkaline solution is a solution containing a basic compound. Examples of the basic compound include sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and sodium metasilicate. And tetramethylammonium hydroxide.

  Examples of the resin include novolak resin, polyhydroxystyrene resin, acrylic resin, amide resin, polyester resin, polycarbonate resin, and polyphenylene ether resin. When a printing ink composition is used and a resist pattern is formed by a photolithography method, it is preferable to use a novolak resin, an acrylic resin, a polyhydroxystyrene resin, or the like from the viewpoint of etching resistance.

  As the novolak resin, for example, a polycondensate of phenol, cresol, xylenol or the like with formaldehyde can be used. These may be used alone or in combination of two or more. The weight average molecular weight of the novolak resin is preferably 1,000 or more, and more preferably 2,000 or more. When the weight average molecular weight is less than 1000, the etching resistance tends to be lowered. The upper limit of the weight average molecular weight of the novolak resin is preferably 200,00 or less, and if it exceeds 200,000, the solubility in a solvent tends to be lowered. The weight average molecular weight in the present invention is a value measured by gel permeation chromatography and converted using a standard polystyrene calibration curve.

  Examples of the acrylic resin include 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, bis-glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, and trimethylolpropane. Tri (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl ( Homopolymerization of (meth) acrylates such as (meth) acrylate, octyl (meth) acrylate, and phosphorus-containing (meth) acrylate, styrene, styrene derivatives and other polymerizable monomers Or a copolymer, (meth) acrylic acid, itaconic acid, maleic acid, maleic anhydride, maleic acid monoalkyl ester, citraconic acid, citraconic acid anhydride, citraconic acid monoalkyl ester, (Meth) acrylic acid esters, styrene derivatives of styrene, copolymers with other polymerizable monomers, and the like. These may be used alone or in combination of two or more. The weight average molecular weight of the acrylic resin is preferably 1,500 to 200,000, more preferably 5,000 to 100,000, and particularly preferably 10,000 to 50,000. If the weight average molecular weight is less than 1,500, the etching resistance tends to decrease, and if it exceeds 200,000, the solubility in a solvent tends to decrease.

  Examples of the polyhydroxystyrene resin include homopolymers such as hydroxystyrene and α-methylstyrene, and copolymers with the above-described polymerizable monomers. These may be used alone or in combination of two or more. The weight average molecular weight of the polyhydroxystyrene resin is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and particularly preferably 5,000 to 30,000. If the weight average molecular weight is less than 1000, the etching resistance tends to decrease, and if it exceeds 200,000, the solubility in a solvent tends to decrease.

  In addition, as the resin soluble in the organic solvent (A), a resin having a photopolymerizable unsaturated bond in the molecule can be used. Examples of such resins include glycidyl (meth) acrylate, allyl glycidyl ether, α-ethyl glycidyl (meth) acrylate, crotonyl glycidyl ether, itaconic acid monoalkyl glycidyl ether, etc. A compound containing an oxirane ring and an ethylenically unsaturated bond, allyl alcohol, 2-buten-4-ol, furfuryl alcohol, oleyl alcohol, cinnamyl alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N- Resin obtained by reacting a hydroxyl group such as methylolacrylamide with a compound containing an ethylenically unsaturated bond (unsaturated alcohol), a carboxyl group-containing resin having a hydroxyl group and a free isocyanate group-containing unsaturated compound Resin, epoxy resin and unsaturated carboxylic acid addition reaction product, polybasic acid anhydride reaction, conjugated diene polymer or conjugated diene copolymer and unsaturated dicarboxylic acid anhydride addition reaction Examples thereof include resins obtained by reacting a product with a hydroxyl group-containing polymerizable monomer. These may be used alone or in combination of two or more.

  In addition, when a thermoplastic (meth) acrylic resin or polyester resin is used as the resin used in the printing ink composition of the present invention, a polyfunctional monomer having two or more photopolymerizable unsaturated bonds in the molecule. Can be contained. Moreover, it can be set as a thermosetting composition by using together a thermosetting epoxy resin, a urethane resin, a melamine resin, etc.

  Examples of the monomer having two or more photopolymerizable unsaturated bonds in the molecule include EO-modified bisphenol A di (meth) acrylate (EO means ethylene oxide; the same applies hereinafter), ECH-modified bisphenol A di (meta) ) Acrylate (ECH means epichlorohydrin; the same applies hereinafter), bisphenol A di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, diethylene glycol Di (meth) acrylate, glycerol di (meth) acrylate, neopentyl glycol di (meth) acrylate, EO modified phosphoric acid di (meth) acrylate, ECH modified phthalic acid di (meth) acrylate, polyethylene glycol 400 di (meth) acrylate , Poly Lopylene glycol 400 di (meth) acrylate, tetraethylene glycol di (meth) acrylate, ECH modified 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, EO Modified tri (meth) acrylate phosphate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate (PO means propylene oxide, the same applies hereinafter), tris ((meth) acryloxy) Ethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaeryth Penta (meth) acrylate. These may be used alone or in combination of two or more.

  In the present invention, the amount of the resin soluble in the organic solvent (A) is preferably 1 to 50% by weight, more preferably 3 to 30% by weight, more preferably 5 to 30% by weight based on the total amount of the printing ink composition. Particularly preferred is 20% by weight. (A) When the blending amount of the resin soluble in the organic solvent exceeds 50% by weight, the transferability tends to decrease, and when it is less than 1% by weight, the thickness of the coating layer of the printing ink composition becomes too thin. Etching resistance tends to decrease.

  Examples of the organic solvent (B) in the present invention include nonpolar hydrocarbon organic solvents such as pentane, hexane, heptane, octane, decane, dodecane, isopentane, isohexane, isooctane, cyclohexane, methylcyclohexane, and cyclopentane. Is mentioned. Of course, it is also possible to use these mixed solvents. It is also possible to use commercially available solvents such as ISOPAR H, ISOPAR H Fluid, ISOPAR G, ISOPAR L, ISOPAR L Fluid (hereinafter, trade names) manufactured by Exxon Chemical Co., Ltd. From the viewpoint of the drying property of the coating film, a low boiling hydrocarbon solvent having a boiling point of 100 ° C. or lower is preferable. Hydrocarbon solvents used for general offset printing are used to control the adhesion of ink to the hydrophobic and hydrophilic surfaces on the plate, but the present inventors have obtained a uniform coating film. We have found that it is preferable to use hydrocarbon solvents.

  Examples of solvents other than hydrocarbon solvents include low boiling ester solvents having a boiling point of less than 100 ° C., alcohol solvents, and ketone solvents. 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. Etc. Examples of the alcohol solvent include methanol, ethanol, propanol, isopropanol, secondary butanol, tertiary butanol and the like. Examples of the ketone solvent include acetone and methyl ethyl ketone. These solvents are important for the drying property of the coating film, and when the solvent has a high boiling point of 100 to 250 ° C., the drying property of the coating film tends to decrease. Further, since the hydrocarbon solvent alone is poorly compatible with various resins, a combination with an ester solvent, an alcohol solvent or a ketone solvent is preferable.

  On the other hand, in order to improve the transfer to the substrate, a high-boiling alkylene glycol compound or alkylene glycol ether compound having a boiling point of 100 to 250 ° C. can be added. Examples of the alkylene glycol compound include diethylene glycol and piper glycol. Moreover, as an alkylene glycol ether compound etc., an alkylene glycol ether compound etc. are mentioned, for example. Examples of these alkylene glycol ether compounds include diethylene glycol ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ether acetate. , Diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol isopropyl ether acetate, diethylene glycol butyl ether acetate, diethylene glycol-t-butyl ether acetate, triethylene glycol methyl acetate Acetate, triethylene glycol ethyl ether acetate, triethylene glycol propyl ether acetate, triethylene glycol isopropyl ether acetate, triethylene glycol butyl ether acetate, triethylene glycol-t-butyl ether acetate, dipropylene glycol dimethyl ether, dipropylene glycol monobutyl ether, etc. Can be mentioned. These may be used alone or in combination of two or more.

  (B) The blending amount of the organic solvent is preferably 50 to 99% by weight, more preferably 70 to 97% by weight, particularly preferably 80 to 95% by weight based on the total amount of the printing ink composition. (B) If the blending amount of the organic solvent exceeds 99% by weight, the thickness of the coating layer of the printing ink composition tends to be too thin, and the etching resistance tends to decrease. Tend to. However, the amount added when using a high-boiling alkylene glycol compound or alkylene glycol ether compound is 50% by weight or less, preferably 40% by weight or less, based on the total amount of the printing ink composition. When the addition amount exceeds 50% by weight, the transferability to the substrate tends to be lowered, and the lower limit is preferably 1% or more.

  In the present invention, a plasticizer can be added as necessary. The plasticizer is a component for increasing the flexibility of the resin, and examples thereof include polyethylene glycol, polypropylene glycol, polysilicon, etc., and polysilicon is preferable from the viewpoint of improving adhesion to a glass substrate or a silicon substrate. . When using polysilicon as a plasticizer, it is preferable to use low molecular weight polysilicon having a molecular weight of 1000 or less. By increasing the flexibility of the resin with this plasticizer, there is an effect of improving the adhesion between the printing ink composition layer and the substrate and suppressing cracking of the pattern. These may be used alone or in combination of two or more. In addition, when the plasticizer is used, the amount of the plasticizer is preferably 0.01 to 20% by weight, more preferably 0.05 to 15% by weight, based on the total amount of the printing ink composition. It is particularly preferably 1 to 10% by weight. When the blending amount of the plasticizer exceeds 20% by weight, the etching resistance tends to decrease, and when it is less than 0.01% by weight, the transferability tends to decrease.

  When the printing ink composition of the present invention is cured with ultraviolet rays, it is preferable to use a photoinitiator. Examples of the photoinitiator include benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, benzyl, 2,2-diethoxyacetophenone, benzoin, and 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, 9,1 - phenanthraquinone, 1,2-anthraquinone, 1,4-dimethyl anthraquinone, 2-phenyl anthraquinone, 2- (o-chlorophenyl) -4,5-diphenyl imidazole dimer, and the like. These may be used alone or in combination of two or more.

  Also, titanate cups such as silane coupling agents, isopropyl trimethacryloyl titanate, diisopropylisostearoyl-4-aminobenzoyl titanate having vinyl group, epoxy group, amino group, mercapto group, etc. to improve adhesion to the substrate Surfactants (fluorine-based, silicon-based, hydrocarbon-based, etc.) can be used to improve the smoothness of the film, and other additives such as ultraviolet absorbers and antioxidants can be used. It can be appropriately used as necessary.

  Next, the printing method of a printing ink composition is demonstrated. As shown in FIG. 1, the printing ink composition 1 is applied onto a roll-shaped coating layer forming substrate 3 using a cap coater 7 or the like to form a coating layer of the printing ink composition 1. The surface of the coating layer forming substrate 3 on which the coating layer is formed preferably has releasability.

  The cap coater 7 supplies the printing ink composition 1 using capillary action. After air-drying for several minutes, the roll-shaped or flat convex plate 5 is brought into contact, and an unnecessary coating layer of the printing ink composition 1 is transferred and removed. The contact of the convex plate 5 is preferably pressing. Thereafter, the remaining coating layer of the printing ink composition 1 is transferred from the roll-shaped coating layer forming substrate 3 to the surface of the substrate 6 to obtain a desired pattern.

  As the relief plate 5, for example, a photosensitive resin such as a water-developable nylon photosensitive resin relief plate (Toyobo Printite; Toyobo Co., Ltd., trade name) can be used. Further, a reverse pattern of a pattern having a target shape is formed on the relief plate 5. Since the coating layer of the printing ink composition 1 is transferred to and removed from the convex portions, it is preferable that the composition has a large surface tension, or the convex portions are roughened to increase the contact area with the coating layer of the printing ink composition 1. . In order to increase the surface tension, for example, a large amount of polar groups are contained in the constituent resin. Moreover, the coating layer of the printing ink composition 1 that has been transferred and removed may be removed by, for example, scraping with a blade or the like, pressing and removing it onto porous paper or the like, or washing and removing with a solvent. Can do. Although the transfer of the layer of the printing ink composition 1 remaining on the coating layer forming substrate 3 to the substrate 6 is affected by the release performance of the surface on which the coating layer forming substrate 3 is formed, the direction of the pattern to be formed May be affected. When transferring in the vertical direction temporally, the vertical line is transferred without interruption, but the horizontal line tends to be inferior in transferability, so that the vertical and diagonal lines increase, It is preferable to use a pattern with few horizontal lines. For example, in the lattice pattern, the lattice of the printing ink composition 1 transferred to the substrate 6 becomes a lattice pattern by rotating the lattice and devising the shape of the relief plate 5 so as to be transferred in a rhombus shape in the vertical direction. It is also possible to take products at different angles. Even without this, the problem may be solved by adjusting the mold release performance of the mold release surface, or may be solved by blending a filler or the like with the printing ink composition 1.

  The surface on which the coating layer of the coating layer forming substrate 3 is formed is preferably a surface having releasability. For example, a roll having a release surface applied to the roll surface, or the film itself is releasable. And a film subjected to a release treatment.

  When the coating layer forming substrate 3 is a film, a continuous coating layer can be formed and productivity can be improved. In the case of a film, a coating layer can be formed continuously and along the surface of the main cylinder 2 of FIG. 1, the removal process and transfer process of the next process can be performed.

  Examples of roll-shaped rolls that have been subjected to release treatment on the roll surface include, for example, metal, rubber, resin, ceramic rolls that have been released with a release agent, and those that have a release treatment layer. It is done. Plating, vapor deposition, plasma, baking, etc. with a low surface tension, such as a layer coated with a fluorine resin, silicon resin, polyolefin resin or oligomer, metal composite oxide layer, ceramic layer, etc. And the like formed by, for example. Among these, a roll made of a silicon resin that is flexible and excellent in releasability and a roll coated with a silicon resin are preferable.

  Examples of the film having releasability include a resin film having a low surface tension such as a fluororesin and a polyolefin resin. Specifically, polytetrafluoroethylene, polytrifluoroethylene, polyethylene, Examples include polypropylene. These films preferably have a surface tension of 20 to 30 dyne / cm. The surface tension can be measured by, for example, a surface tension / interfacial tension measuring unit by a drop volume method.

  The mold release treatment is, for example, a treatment with a mold release agent. Examples of the mold release agent include mineral oil-based mold release agents such as liquid paraffin, polyolefin wax, partial oxides thereof, fluorides and chlorides, Fatty acid release agents such as stearic acid and oleic acid, fat release agents such as animal and vegetable oils and natural waxes, fatty acid ester release agents such as ethylene glycol fatty acid esters, sorbitol fatty acid esters, polyoxyethylene fatty acid esters, poly Alcohol release agents such as oxyalkylene glycol, glycols, polyoxyethylene higher alcohol ether, higher aliphatic acid alcohol, amide release agents such as polyoxyethylene alkylene amide and fatty acid amide, polyoxyalkylene phosphoric acid Phosphate release agents such as esters, calcium stearate , And metal soap-based releasing agent such as sodium oleate and the like, which is preferably used in combination a releasing agent and a fluorine-based release agent silicon because poor heat resistance. Thus, there is a tendency that heat resistance and releasability can be increased by using a silicon release agent or a fluorine release agent in combination. Examples of such a silicon release agent or fluorine release agent include dimethyl silicone oil, dimethyl silicone rubber, silicone resin, organically modified silicone, polytetrafluoroethylene, and the like.

  The SP value (solubility parameter) between the printing ink composition 1 and the releasable surface is preferably separated, and specifically, it is particularly preferably 2 or more. Since the SP value is difficult to measure in the case of a composition or the like, see, for example, Polym. Eng. Sci. , Vol. 14 is used in accordance with the method of Fedors described on pages 147 to 154 [unit: (MJ / m3) 1/2]. The SP value (solubility parameter) is generally called a solubility parameter, and is a scale indicating the degree of hydrophilicity or hydrophobicity of a resin, and is an important scale for judging compatibility between resins. In the case of silicon mold release agent, the surface tension of dimethylpolysiloxane is 20 to 21.5 dyne / cm. Therefore, the release property was adjusted by blending and copolymerizing with various resins as a base polymer. It can be a mold release agent. From the viewpoint of preventing the release agent from migrating, for example, paint-type methylphenyl silicone oil, long-chain alkyl-modified oil, a mixture of a fluorine compound and a silicone polymer, fluorine-modified silicone, and the like can also be used. Silicone mold release agents include silicone oil (dimethyl resin, dimethyl / silicone resin, modified silicone oil, phenyl group / long chain alkyl group-containing silicone oil as base resin), and curable type (dimethylsilicone as base polymer). System (condensation reaction, addition reaction type), methyl silicon varnish).

  The thinner the coating layer, the easier it is to repel the printing ink. In order to eliminate repelling, pinholes, etc., it is preferable to increase the surface tension of the surface on which the coating layer of the coating layer forming substrate 3 is formed or to roughen the surface. This roughening may be roughening the surface of the surface, using roughening of the base, or porous. For example, a blanket made of silicon resin is suitable.

  The substrate 6 to which the printing ink composition 1 is transferred is selected depending on the application. For example, a transparent glass plate such as white plate glass, blue plate glass, silica coated blue plate glass, polyester resin, polycarbonate resin, acrylic resin, vinyl chloride. Examples thereof include a synthetic resin sheet such as a resin, a film or plate, an aluminum plate, a copper plate, a nickel plate, a metal plate such as a stainless plate, other ceramic plates, and a semiconductor substrate having a photoelectric conversion element. When etching is performed in a later step, for example, a substrate having a metal layer on the surface of a copper clad laminate or the like is preferable.

  The thickness of the coating layer of the printing ink composition 1 thus formed is appropriately determined depending on the use, but is preferably 0.1 to 10 μm and preferably 0.2 to 5 μm from the viewpoint of etching resistance. Is more preferable. The coating layer of the printing ink composition 1 formed on the substrate 6 is sufficiently dried by heat treatment at 100 to 150 ° C. for about 1 to 15 minutes. If necessary, it can be photocured and / or thermally cured. Next, the pattern of the coating layer of the printing ink composition 1 formed on the substrate 6 is used as a resist, and a circuit pattern can be formed on the substrate 6 by performing etching or plating by a known method. Since the printing ink composition of the present invention is suitable for forming a thin film, it is preferably applied to an etching method.

EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not restrict | limited by these.
Example 1
125 g of cresol novolac resin (Maywa Kasei Co., Ltd., weight average molecular weight 5,000, p-cresol: m-cresol = 60: 40 (molar ratio)) was weighed in a 1 L four-necked flask. 25 g of silsesquioxane, 600 g of ethyl acetate, 250 g of 2-acetoxy-1-methoxypropane and 50 g of diethylene glycol were added, and the mixture was stirred for 6 hours in a nitrogen atmosphere to dissolve the resin. The solution was subjected to pressure filtration with a 2 micron fluororesin filter to obtain a printing ink composition solution of Example 1.

  As shown in FIG. 1, this printing ink composition is applied onto a silicon resin blanket as a coating layer forming substrate 3 using a cap coater 7 and dried for 2 to 3 minutes to obtain a film thickness of 0.3 μm. The coating layer of the printing ink composition 1 was formed. Thereafter, an unnecessary portion of the coating layer was removed using the plate cylinder 4 having the relief plate 5, transferred to the glass substrate surface, and the accuracy and shape of the pattern transferred to the glass substrate surface were observed with a microscope. A micron-width resist stripe pattern could be formed. Apart from this, in order to observe the appearance (unevenness, repellency, etc.) of the coating layer, the step of removing unnecessary portions of the coating layer using the plate cylinder 4 having the relief plate 5 is omitted, and printing with a film thickness of 0.3 μm is performed. After forming the coating layer of the ink composition 1, it was directly transferred to a glass substrate, and the appearance of the coating film was observed visually and with a microscope. As a result, the coating film appearance was not repelled or uneven. Separately, the coating layer was transferred to the surface of the TFT electrode base gate film substrate (Mo / Al Nd) to form a resist pattern, and then the substrate was etched with an aqueous solution of phosphoric acid / nitric acid / acetic acid (40 ° C. (2 minutes) However, a wiring having a width of 50 microns could be formed.

(Comparative Example 1)
A printing ink composition solution was obtained in the same manner as in Example 1 except that silsesquioxane was not added, and was evaluated under the same conditions as in Example 1. In all cases, the appearance of the coating film repelled and was not uneven. A stripe pattern of 50 micron width resist could be formed. When this resist pattern was used to etch an underlying gate film substrate for TFT electrodes (Mo / Al Nd) with an aqueous solution of phosphoric acid / nitric acid / acetic acid (40 ° C., 2 minutes), resist peeling was observed.

Schematic explaining the process of transferring a printing ink composition to a board | substrate using a printing ink composition.

Explanation of symbols

1: Printing ink composition 2: Main cylinder 3: Coating layer forming substrate (silicone resin blanket)
4: Plate cylinder 5: Convex plate 6: Substrate 7: Cap coater

Claims (9)

  A coating layer forming step of forming a coating layer of the printing ink composition by applying the printing ink composition onto the coating layer forming substrate; A printing ink composition used for a relief reversal offset method having a removal step of transferring and removing a coating layer, and a transfer step of transferring the coating layer remaining on the coating layer forming substrate to a substrate, The printing ink composition comprising (A) a resin soluble in an organic solvent, (B) an organic solvent, and (C) a silica sol.   (C) The printing ink composition according to claim 1, wherein the amount of silica sol added is 1 to 40% by weight based on the total amount of the printing ink composition.   (A) The printing ink composition according to claim 1 or 2, wherein the resin soluble in an organic solvent contains a resin soluble in an alkaline solution.   The printing ink composition according to claim 3, wherein the resin soluble in the alkaline solution is a novolak resin.   The printing ink composition according to claim 3, wherein the resin soluble in the alkaline solution is a polyhydroxystyrene resin.   A coating layer forming step of coating the printing ink composition according to any one of claims 1 to 5 on a coating layer forming substrate to form a coating layer of the printing ink composition, and a predetermined shape with respect to the coating layer A removing step of transferring and removing the coating layer on a convex portion of the relief plate by bringing the relief plate into contact; and a transferring step of transferring the coating layer remaining on the coating layer-forming substrate to the substrate. The letterpress inversion offset method.   A coating layer forming step of coating the printing ink composition according to any one of claims 1 to 5 on a coating layer forming substrate to form a coating layer of the printing ink composition, and a predetermined shape with respect to the coating layer A removing step of transferring and removing the coating layer on a convex portion of the relief plate by bringing the relief plate into contact; and a transferring step of transferring the coating layer remaining on the coating layer-forming substrate to the substrate. Forming a resist pattern. A method of manufacturing an electronic component having a wiring pattern formed on a substrate,
A coating layer forming step of coating the printing ink composition according to any one of claims 1 to 5 on a coating layer forming substrate to form a coating layer of the printing ink composition, and a predetermined shape with respect to the coating layer A removing step of transferring and removing the coating layer on the convex portion of the relief plate by contacting the relief plate, a transferring step of transferring the coating layer remaining on the coating layer forming substrate to the substrate, and the transferred printing ink And a processing step of etching or plating using the composition as a resist. An electronic component having a wiring pattern formed on a substrate, wherein the electronic component is manufactured by the method for manufacturing an electronic component according to claim 8.

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