JP2006037060A - 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 a defective pattern due to formation of pinholes causing problems in a printing method, 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 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 forming the coating layer to a substrate. The printing ink composition comprises (A) a resin soluble in an organic solvent and (B) the organic solvent. The printing ink composition contains the organic solvent having ≤15° contact angle of (B) the organic solvent on the base material forming the coated surface at 25°C. <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.

  In addition, in this printing method, depending on the ink used, when used in the coating process, ink repellency occurs on the silicon resin, and when it is transferred to the substrate in that state, pinholes are generated on the formed pattern. There has been a problem that defects such as disconnection occur during pattern formation.

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

  The present invention provides a printing ink composition capable of suppressing pattern defects due to the occurrence of pinholes, which is a problem in the printing method. The present invention provides a composition for printing ink that does not generate pinholes, improves the uniformity, pattern accuracy and shape of the coating film, and has good etching resistance and peelability.

  The present invention provides a resist pattern forming method that can transfer with good pattern accuracy and shape without generating pinholes. 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 contains (A) a resin soluble in an organic solvent and (B) an organic solvent, and the (B) contact of the organic solvent on the coated surface forming substrate at 25 ° C. The present invention relates to a printing ink composition containing an organic solvent having an angle of 15 ° or less.

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

  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 onto a coating layer forming substrate to form a coating layer of the printing ink composition. A coating layer forming step, a removing step in which a relief plate having a predetermined shape is brought into contact with the coating layer, and the coating layer is transferred to and removed from the 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 manufacturing an electronic component, comprising: a transfer step of transferring a substrate to a substrate; and a processing step of 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 method for manufacturing the electronic component.

  It was discovered that the above printing ink composition and manufacturing method have good pattern accuracy and shape, a low pinhole generation rate, and an inexpensive manufacturing method can provide an electronic component equivalent to the photolithography method. It came.

The printing ink composition of the present invention can suppress pattern defects due to the occurrence of pinholes, which is a problem in the printing method. The composition for printing ink of the present invention does not generate pinholes, improves the uniformity, pattern accuracy and shape of the coating film, and has good etching resistance and peelability.

  The relief reversal offset method of the present invention does not generate pinholes and can improve the uniformity and peelability of the coating film. The resist pattern forming method of the present invention can be transferred with good pattern accuracy and shape without generating pinholes.

  The method for manufacturing an electronic component according to the present invention can perform etching of a base with a resist pattern with improved pattern accuracy and shape without generating pinholes. By such a manufacturing method, it is equivalent to a photolithography method. An electronic component can be obtained.

  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 contains (A) a resin soluble in an organic solvent and (B) an organic solvent, and the contact angle of the organic solvent (B) on the coated surface forming substrate at 25 ° C. is 15 °. It contains the following organic solvent.

  In this invention, the organic solvent whose contact angle in 25 degreeC on a coating surface formation base material is 15 degrees or less is used. By using such an organic solvent, it is possible to improve the coating property to the coated surface forming base material and uniformly apply without repelling, and to improve the transfer to the substrate. If the contact angle exceeds 15 °, pinholes tend to be formed, and if the contact angle is less than 5 °, the releasability tends to be inferior. In addition, the contact angle in this invention is the value measured at 25 degreeC on the coating surface formation base material using the static contact angle measuring apparatus based on prescription | regulation of JIS-K-2396.

  Examples of the organic solvent having a contact angle of 15 ° or less include methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, i-propyl acetate, n-propyl acetate, i-butyl acetate, n-butyl acetate, Ester solvents such as methyl propionate and ethyl propionate, ketone solvents such as acetone and methyl ethyl ketone, 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 ether 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. An alkylene glycol ester solvent is preferred.

  Further, as the organic solvent having a contact angle of 15 ° or less, an organic solvent having a contact angle of more than 15 ° and a solvent having a contact angle of 15 ° or less are mixed in order to suppress overdrying of the ink. It can also be used. At this time, the contact angle of the mixed organic solvent may be 15 ° or less. Even when two or more kinds of organic solvents are mixed and used, the contact angle of the mixed organic solvent may be 15 ° or less. Examples of the organic solvent having a contact angle exceeding 15 ° to be mixed in order to suppress overdrying of the ink include, for example, diethylene glycol ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, Examples thereof include high-boiling alcohol organic solvents such as propylene glycol monobutyl ether. As the high-boiling alcohol organic solvent, a solvent having a boiling point of 150 ° C. or higher is preferably used.

  In addition to these solvents, pentane, hexane, heptane, octane, decane, dodecane, isopentane, isohexane, isooctane, cyclohexane, methylcyclohexane, cyclopentane are used to adjust the uniformity, drying and transfer properties of the coating film. These may be used in combination with hydrocarbon solvents such as methanol, ethanol, ethanol, propanol, isopropanol, secondary butanol, tertiary butanol and the like.

  (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, and if it is less than 50% by weight, the transferability decreases. Tend to. However, the amount added when using a high-boiling alcohol organic solvent or the like 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 addition, as the coating layer forming substrate, a fluorine resin, a silicon resin, a polyolefin resin or an oligomer-coated one, a metal composite oxide layer, a ceramic layer, or the like is formed by plating, vapor deposition, plasma, baking, or the like. Among them, a coating layer forming substrate made of silicon resin is preferable, and a silicon blanket is particularly preferable.

  The resin soluble in the organic solvent (A) used in the present invention is preferably soluble in an alkali solution, and preferably has a film-forming property and a transfer property 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 200,000 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. Here, (meth) acrylic acid means acrylic acid and its corresponding methacrylic acid, (meth) acrylate means acrylate and its corresponding methacrylate, (meth) acryloyl group means acryloyl group and its corresponding Means a methacryloyl group. 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.

  As said polyhydroxystyrene resin, it is good also as a copolymer composition with the polymerizable monomer mentioned above other than homopolymers, such as hydroxystyrene and (alpha) -methylstyrene, for example. 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. preferable. 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.

  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 lines are transferred without interruption, but the horizontal lines tend 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
In a 1 L four-necked flask, 125 g of cresol novolak resin (Maywa Kasei Co., Ltd., weight average molecular weight 5,000, p-cresol: m-cresol = 60: 40) was weighed. 200 g of ethyl acetate, 250 g of 2-acetoxy-1-methoxypropane and 50 g of diethylene glycol were added, and the resin was dissolved by stirring for 6 hours in a nitrogen atmosphere. The solution was subjected to pressure filtration with a 2 micron fluororesin filter to obtain a printing ink composition solution of Example 1. Table 1 shows the contact angle of the organic solvent used on the silicon blanket. The contact angle was measured at 25 ° C. using a static contact angle measuring device, and the results are shown in Table 3.

  This printing ink composition was applied on a silicon blanket surface using a cap coater as shown in FIG. The film was dried for 2 to 3 minutes to form a film having a thickness of 1.0 μm. Then, the coating film of the unnecessary part was removed using the plate cylinder, and transcribe | transferred to the glass substrate surface. The accuracy and shape of the transferred pattern were observed with a microscope. When observing the coating film appearance (unevenness, repelling, etc.) on the silicon resin surface, the coating film removal step was omitted, and the coating film appearance was observed visually and under a microscope by transferring it to the glass substrate surface. . Table 2 shows the evaluation results. In Example 1, the appearance of the coating film was free of repellency and unevenness, and a 50 micron width resist stripe pattern could be formed. Using this resist pattern, an underlying gate film substrate for TFT electrode (Mo / Al Nd) was etched with phosphoric acid / nitric acid / acetic acid aqueous solution (40 ° C., 2 minutes), and a wiring with a width of 50 microns could be formed.

(Example 2)
Except having changed to each composition shown in Table 1, the solution of the printing ink composition was obtained like Example 1, and it evaluated on the conditions similar to Example 1. FIG. In any case, there was no cissing or unevenness in the appearance of the coating film. A stripe pattern of 50 micron width resist could be formed. Using this resist pattern, an underlying gate film substrate for TFT electrodes (Mo / Al Nd) was etched with an aqueous solution of phosphoric acid / nitric acid / acetic acid (40 ° C., 2 minutes), and a wiring with a width of 50 microns could be formed.

(Comparative Example 1)
Except having changed to each composition shown in Table 1, the solution of the printing ink composition was obtained similarly to Example 1, and it evaluated by the method similar to Example 1. FIG. Unevenness and repelling occurred on the coating film on the silicone resin surface (blanket). When pattern transfer was performed, pinholes were found on the entire pattern surface.

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 surface forming substrate (silicone resin blanket)
4: Plate cylinder 5: Convex plate 6: Substrate 7: Cap coater

Claims (8)

  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 contains (A) a resin soluble in an organic solvent and (B) an organic solvent, and the contact angle of the organic solvent (B) on the coated surface forming substrate at 25 ° C. is 15 °. The printing ink composition containing the organic solvent which is the following.   (A) The printing ink composition according to claim 1, comprising a resin soluble in an alkaline solution as a resin soluble in an organic solvent.   The printing ink composition according to claim 2, wherein the resin soluble in the alkaline solution is a novolak resin.   The printing ink composition according to claim 2, 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 4 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 4 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 4 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 performing 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 7.

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