JP5195337B2 - Etching resist ink and resist pattern forming method using the same - Google Patents

Description

  The present invention relates to an etching resist ink and a method of forming a resist pattern using the same.

  Until now, photolithography (photolithography) capable of high-definition patterning has been used for manufacturing various electrical components. For example, when forming an electrode pattern for a touch panel using a conductor such as ITO (indium tin oxide), a resist film is applied on the entire surface of the conductor film, exposed using a mask, and an uncured portion. After removing the resist, unnecessary conductor film is removed by etching, and used resist is removed. However, the photolithography method has many problems such as a long production process, use of a mask, exposure, and application of a resist on the entire surface, resulting in an increase in running cost. In order to shorten the production process, it is desired to manufacture various electronic components by a printing method.

  As a technique related to the photolithographic method, a resist ink (photo-curable printing ink) for forming a circuit pattern of a wiring board by an etching method is known (see, for example, Patent Documents 1 to 4). The resist ink is a pattern that is printed by screen printing, gravure printing, or the like, and then cured by ultraviolet curing, so that a resist pattern is not required. However, a fine pattern comparable to the photolithography method cannot be formed by screen printing or gravure printing. Moreover, the ink used for these is unsuitable for the relief printing method.

Patent Document 5 (particularly Example 4) uses a photolithographic method by performing resist pattern formation by a letterpress reverse printing method in applications such as etching of metal-clad laminates such as copper and solder masks. It is described that a printed wiring board having a fine pattern can be manufactured with simple equipment. Although it is described that the material used for these includes a particulate material that is excellent in printing accuracy, there is no description of a specific particle shape. Further, when the particle component is not included as in Example 4, the linearity of the image line comparable to the photolithography method cannot be achieved if the pressure pressing the relief is weak, and the linearity is increased by increasing the pressure pressing the relief. However, in this case, there are problems such as insufficient positional accuracy.
The inventors of the present application tried to obtain an image line from a resist ink by a letterpress reversal printing method. When a particulate material exceeding 1,000 nm was included, the smoothness of the coating film was poor, and pinholes also appeared. It has been found that simply adding a particle component is insufficient for a resist by practical printing.

  In Patent Document 6, as a technique related to the letterpress reverse printing method, for the purpose of printing a precise pattern such as a color filter, a colorant such as a pigment, a fluorescent color former, or a powdery material such as gold, silver or aluminum is used. An ink composition is described which comprises a conductive agent, a solvent, a resin soluble in the solvent, and may contain a surface energy adjusting agent as required. It describes that excellent image quality can be obtained when a pixel is formed on a substrate to be printed with a liquid crystal display element or conductor circuit of a color filter. However, even when trying to obtain an image line by using a letterpress reversal printing method as a resist ink in combination with the described solvent or resin, application to a reversal printing blanket, transfer to a substrate, or resist properties were not sufficient. . In some cases, the resist property of the resist ink with respect to the substrate may not be sufficiently exhibited, and the resist ink still has a practical problem.

JP-A-11-172176 JP-A-11-172177 JP-A-11-172178 JP-A-11-172179 Japanese Patent Laid-Open No. 2005-057118 JP 2005-126608 A

  This invention is made | formed in view of the said situation, and makes it a subject to provide the formation method of the resist pattern using the ink for etching resists by the relief printing reverse printing method which can form a fine pattern.

  In order to solve the above problems, the present invention provides a constitutional component having an average particle diameter of 100 nm or less, a first resin having an acid value of 200 or more, and a second resin having a Tg of 25 ° C. or less. There is provided an ink for etching resist by a letterpress reverse printing method, comprising a mold, a surface energy adjusting agent, and a solvent. The present invention also provides a method for forming a resist pattern, characterized in that an etching resist pattern is formed by a letterpress reverse printing method using the above-described etching resist ink.

  According to the present invention, a fine pattern can be formed and a resist pattern having excellent etching resistance can be formed.

  The present invention will be described below based on the best mode.

<Ink for etching resist>
The ink for etching resist of the present invention comprises a constitutional component (A) having an average particle diameter of 100 nm or less, a first resin (B) having an acid value of 200 or more, and a second Tg of 25 ° C. or less. It contains a resin (C), a release agent (D), a surface energy adjusting agent (E), and a solvent (F).

  The ink for etching resist of the present invention can be used for forming an etching resist pattern by a letterpress reverse printing method. As each component used in the ink of the present invention, it is desirable to appropriately select and use a component that can be chemically resistant to the etching solution. However, as a whole composition, if the formed pattern has a desired etching resistance, It can be used.

  In the present invention, the letterpress reverse printing method is a method in which an ink is applied on a blanket to form an ink application surface, and after pressing the letterpress on the ink application surface, the portion of the ink contacting the letterpress is removed from the blanket. And a printing method for transferring the ink remaining on the blanket to a printing medium.

As the extender component (A), extender pigments having an average particle diameter of 100 nm or less are preferably used. According to this, the linearity of the image line comparable to that of the photolithography method can be achieved even with a low pressure by the letterpress reverse printing method. Examples thereof include silica (SiO ₂ ), calcium carbonate (CaCO ₃ ), magnesium fluoride (MgF ₂ ), and the like. The average particle size is more preferably 10 to 60 nm. A material of 10 to 20 nm is particularly preferable. As the particle diameter is smaller, a smooth image line can be formed even if the film thickness is made thinner. In addition, the adjustment of the printed film thickness is easy, and an image line with a narrower interval can be suitably achieved. The average particle diameter of these constitutional components can be measured as a volume average particle diameter by a measuring device using laser diffraction and scattering.

As the first resin (B), a resin having an acid value of 200 or more (hereinafter referred to as “high acid value resin (B)”) is used. Here, the acid value of the resin refers to the number of milligrams of potassium hydroxide necessary to neutralize 1 g of the resin content (mgKOH / g). The high acid value resin (B) can be selected from resins having a carboxyl group (COOH group). Specific examples include rosin-modified maleic resin.
The first resin (B) is not particularly limited as long as the acid value is a resin having an acid value of 200 or more, but the high acid value resin itself is used even when crosslinked using a low molecular weight resin or a monomer. However, both can be suitably used. When the high acid value resin itself is used, it is particularly preferable that the Tg is higher than 25 ° C., since an ink having a high softening point can be obtained, and the coating film on the printing medium can achieve high film strength.

  The second resin (C) is a resin having a glass transition temperature (Tg) of 25 ° C. or lower (hereinafter referred to as “low Tg resin (C)”). Examples of the low Tg resin (C) include a liquid acrylic resin. The liquid acrylic resin is a liquid at room temperature among resins containing one or more acrylic monomers such as acrylic ester and methacrylic ester as monomers.

  As the release agent (D), a low molecular silicone (molecular weight of about 148 to 2220) which is a 2 to 30 mer of silicone is preferable because it has little influence on ink patterning. In particular, a modified silicone modified with a substituent having a higher polarity than an alkyl group is more preferable from the viewpoint of printability in letterpress reverse printing. Particularly suitable release agents include silicone oils such as SH28 manufactured by Toray Dow Corning (both are trade names). In particular, the content of the release agent is preferably 0.05 to 5.0% by mass, and more preferably 0.1 to 1.0% by mass in the total ink composition. By adding this release agent, even if the wettability of the ink to the blanket is increased by adjusting the solvent or the surface energy, the peelability from the blanket can be ensured. Thereby, the transferability in the relief printing method can be improved.

  As the surface energy adjusting agent (E), a silicone type or a fluorine type can be suitably used. In particular, the addition of a small amount of a fluorine-based surface energy regulator is preferable because of its great effect. As the fluorine-based surface energy adjusting agent, for example, DIC's MegaFace (trade name) series is preferably used. The content of the surface energy adjusting agent is preferably 0.05 to 5.0% by mass, more preferably 0.1 to 1.5% by mass in the total ink composition.

  Examples of the solvent (F) include various organic solvents such as hydrocarbons, alcohols, ketones, ethers, esters, and water. You may mix and use these suitably.

  In particular, the organic solvent is more preferably used in combination with a fast-drying organic solvent and a slow-drying organic solvent described later. Water may be used in combination with a fast drying organic solvent and / or a slow drying organic solvent.

Examples of the fast-drying organic solvent include ester solvents, alcohol solvents, carbonate solvents, ketones having a vapor pressure at 20 ° C. of not less than 11.3 × 10 ² Pa (8.0 mmHg) and a boiling point of less than 115 ° C. under atmospheric pressure. Any one or more of a solvent and a hydrocarbon solvent are suitably selected and used, and the quick-drying organic solvent is preferably contained in an amount of 5 to 90% by mass in the total ink composition, and 30 to 80 % By mass is more preferable, and 40 to 70% by mass is particularly preferable.

  This quick-drying organic solvent is used because the ink composition has good fluidity when an ink coating film is formed on a blanket. After application, before being imaged on the relief printing plate, it is volatilized in the air or absorbed by the blanket, so that the ink viscosity increases, so that it has optimum viscosity, adhesiveness and cohesive force for imaging. Is formulated for. Moreover, the compounding quantity will be easily adjusted if it is the range of 5-90 mass% in all the ink compositions with the printing speed of a relief printing method.

These quick-drying organic solvents may be appropriately selected in consideration of the solubility of the vehicle and the affinity for the pigment dispersion system, and the following solvents may be used as examples.
Ethyl acetate, normal propyl acetate, isopropyl acetate (IPAc) as ester solvents, methanol, ethanol, 1-propanol, 2-propanol (IPA) as alcohol solvents, diethyl carbonate as carbonate solvents, methyl ethyl ketone as ketone solvents Examples of (MEK) and hydrocarbon solvents include pentane, hexane, cyclohexane, methylcyclohexane, and toluene. These may also be a mixture of each system and a plurality of systems. Of these, isopropyl acetate, ethanol and 2-propanol are preferable in view of their evaporation rate and surface tension.

As the slow-drying organic solvent, an ester solvent, an alcohol solvent, an ether solvent and a carbonized carbon having a vapor pressure at 20 ° C. of less than 11.3 × 10 ² Pa (8.0 mmHg) and a boiling point of 115 ° C. or higher under atmospheric pressure. Any one or more of hydrogen-based solvents are preferably used. The slow-drying organic solvent is preferably contained in the total ink composition in an amount of 5 to 90% by mass, more preferably 10 to 60% by mass, and particularly preferably 20 to 40% by mass.

  This slow-drying organic solvent remains on the blanket until the ink film formed and imaged on the blanket by the relief printing is transferred onto the substrate to be printed, so that the viscosity of the ink rises above a certain level. This is preferably used because a good image can be obtained on the substrate to be printed. The blending amount may be appropriately changed depending on the printing speed of the letterpress reverse printing method, and can be easily adjusted as long as it is in the range of 5 to 90% by mass in the total ink composition.

These slow-drying organic solvents may further be appropriately selected in consideration of the solubility of the vehicle and the affinity for the pigment dispersion system. For example, the following solvents may be used.
As ester solvents, propylene glycol monomethyl ether acetate (PGMAc), 3-methoxy-3-methyl-butyl acetate (“Solfit AC” trade name; manufactured by Kuraray Co., Ltd.), ethoxyethyl propionate (EEP), alcohol As a solvent, 1-butanol, Diadol 135 (trade name; manufactured by Mitsubishi Rayon Co., Ltd.), 3-methoxy-3-methyl-1-butanol, 1-hexanol, 1,3-butanediol, 1-pentanol 2-methyl-1-butanol, 4-methyl-2-pentanol, nonanediol, ether solvents such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol tertiary butyl Ether, dipropylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, polytetramethylene ether glycol [formula _{HO (CH 2 CH 2 CH 2} CH ₂ O) Oligomer represented by _n H], as hydrocarbon solvents, Solvesso 100, Solvesso 150 (trade name; manufactured by Exxon Chemical Co., Ltd.), N-methylpyrrolidone, polypropylene glycol, and propylene carbonate are also included. Can be mentioned. These may also be a mixture of each system and a plurality of systems.

  Among these slow-drying organic solvents, alkylene polyols, polyoxyalkylene polyols, or ethers or alcohols thereof have a polar group, have a low blanket permeability, a low evaporation rate, and a property that remains moderately in ink. This is preferable.

Examples of such solvents include 1-butanol, 3-methoxy-3-methyl-1-butanol, 1-hexanol, 1,3-butanediol, 1-pentanol, 2-methyl-1-butanol, and 4-methyl. -2-pentanol, nonanediol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol tertiary butyl ether, dipropylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol mono ether, diethylene glycol monoethyl ether, polytetramethylene ether glycol [formula _{HO (CH 2 CH 2 CH 2} CH 2 O oligomer represented by _{n H],} polypropylene glycol, also include propylene carbonate.
Among these, polytetramethylene ether glycol and propylene glycol monomethyl ether are particularly preferable in view of their evaporation rate and the degree of permeability to the blanket. These may be a mixture added to another solvent.

  In the ink for etching resist of the present invention, in addition to the above-described essential components (A) to (F), coloring components such as dyes and pigments, pigment dispersants, antifoaming agents, plasticizers, adhesion to the substrate to be printed An appropriate amount of various additives such as an imparting agent can be appropriately blended.

  The ink for etching resist of the present invention can be produced by kneading and homogenizing the above raw materials. Printing of the resist pattern on the printing material using the etching resist ink is performed by a letterpress reverse printing method. There are no particular limitations on the substrate to be printed, and examples thereof include plastic, paper, glass, ceramics, and metal.

<Letterpress reverse printing method>
In the letterpress reverse printing method, first, ink is applied on a blanket to form an ink application surface. As the blanket, a silicone blanket made of silicone is preferable. By forming the ink application surface on the surface of the blanket and leaving it for a predetermined time, the low boiling point solvent volatilizes and is absorbed into the blanket, thereby increasing the viscosity of the ink. At this time, the high surface energy solvent remains in the ink, and appropriate cohesiveness of the ink is maintained.

  When a relief plate on which a plate corresponding to a predetermined pattern is formed on the ink application surface is pressed, the portion of the ink contacting the relief plate is removed from the blanket. At this time, since the ink has an appropriate cohesive property, the ink can be reliably peeled off from the blanket and adhered to the relief plate without structural breakage, and undesirable residue on the blanket can be suppressed. As a result, an ink pattern corresponding to the relief pattern is formed on the blanket by the ink remaining on the blanket.

  The wet or semi-dry ink remaining on the blanket is transferred to the printing medium. At this time, since the ink has appropriate cohesiveness, peeling from the blanket and adhesion to the printing medium are reliably performed. As a result, a resist pattern is formed on the substrate to be printed by a pattern inverted with respect to the pattern formed on the relief printing plate.

  For example, when a resist pattern is to be formed using ITO as a substrate to be printed, the etching resist ink of the present invention is reverse printing using a cylinder having a blanket and a relief plate having a specific line width using the ITO layer as a base material. When baked with the resist ink pattern printed by the above, the solvent that has formed the coating film evaporates, and the resist coating strength increases. If the ITO film is etched with an etchant, a good fine pattern of the ITO glass substrate can be obtained.

  When the etching resist ink contains the constitutional component (A) having an average particle diameter of 100 nm or less and the low Tg resin (C), a fine pattern can be formed. By containing the constitutional component (A) having an average particle diameter of 100 nm or less, an increase in film forming property due to the high acid value resin (B) having a high Tg can be suppressed, and patterning can be facilitated. Even if the high acid value resin (B) is blended and the constitutional component (A) is not blended, it cannot be transferred with a normal printing pressure, but it may be transferred with a strong printing pressure that is substantially impossible. In this case, it is considered that a fine pattern cannot be obtained.

  In addition, since the etching resist ink contains the low Tg resin (C), it is possible to remove the unnecessary ink coating film by pressing the relief plate and adhere to the printing medium by providing a tack.

  Furthermore, according to the present invention, the ink for etching resist contains the high acid value resin (B), so that alkali solubility and etching resistance can be improved. Therefore, a fine resist pattern can be etched as it is, and the etching resist ink of the present invention can be easily removed after etching.

  Hereinafter, the present invention will be specifically described with reference to examples. Here, “%” is “% by mass” unless otherwise specified.

Example 1
Silica sol IPA-ST (trade name; manufactured by Nissan Chemical Industries, average particle size 10 nm; solid content 30% (IPA 70%)) 19.7 g as extender pigment component and rosin modified maleic resin J-896 (high acid value resin) Product name: 6.1 g of DIC, acid value of 200 or more adjusted to 50% solid content by IPA, and liquid acrylic resin CBB-3098 (trade name; manufactured by Soken Chemical, Tg is 25 ° C. or lower) as a low Tg resin ) Was adjusted to a resin content of 50% by IPA, and the dye Orazole Blue GN (trade name; manufactured by Ciba Specialty Chemicals) was used as a coloring component in an isopropyl acetate / propylene glycol monomethyl ether 1/1 solution. 11.8 g adjusted to a solid content of 5%, and fluorine-based surface energy adjusting agent TF- as a surface energy adjusting agent 303 (trade name; manufactured by DIC, solid content 30% (MEK 70%)) 0.5 g and silicone oil SH28PA (trade name; manufactured by Toray Dow Corning) as a release agent adjusted to 10% solid content by IPAc 2.0 g, 2.0 g of polytetramethylene ether glycol having a weight average molecular weight of about 650 and 16.1 g of propylene glycol monomethyl ether as slow-drying organic solvents, and 35.5 g of isopropyl acetate as quick-drying organic solvents were carried out. The ink for etching resist of Example 1 was obtained.

  Using an ITO glass substrate (ITO thickness 10 nm) as a substrate to be printed, the above etching resist ink is printed in a matrix form by a letterpress reverse printing method using a cylinder having a silicone blanket and a letterpress with a line width of 18 μm. The printed matter was obtained. After the printed matter was baked at 230 ° C. for 15 minutes, the ITO film was etched with a mixed acid etching solution that is generally commercially available, and then the etching resist was removed with a 10% aqueous solution of monoethanolamine (MEA). When the surface shape of the ITO glass substrate thus obtained was measured with a surface roughness measuring device, etching resist patterning (interval between patterns of about 18 μm) of an ITO film having a thickness of 10 nm was observed (FIG. 1). From this result, this ink is an etching resist ink suitable for the relief printing method.

(Comparative Example 1) System not containing high acid value resin Silica sol IPA-ST (trade name; manufactured by Nissan Chemical Industries, average particle size 10 nm; solid content 30%) 19.7 g as an extender pigment component and liquid as a low Tg resin 12.3 g of an acrylic resin CBB-3098 (trade name; manufactured by Soken Chemical Co., Ltd., Tg of 25 ° C. or less) adjusted to a resin content of 50% by IPA, and dye Orazole Blue GN (trade name; Ciba Specialty) as a coloring component 11.8 g of Tea Chemicals) adjusted to 5% solid content with isopropyl acetate / propylene glycol monomethyl ether 1/1 solution, and fluorine-based surface energy modifier TF-1303 (trade name; DIC) as a surface energy modifier Made, 30% solids) and silicone oil SH28PA (trade name; Toray Dowko as a release agent) 2.0 g of IPN adjusted to a solid content of 10%, 2.0 g of polytetramethylene ether glycol and 16.1 g of propylene glycol monomethyl ether as a slow-drying organic solvent, and isopropyl acetate 35 as a fast-drying organic solvent The ink for etching resist of Comparative Example 1 was obtained. That is, the composition of Comparative Example 1 is the same as that of Example 1 except that the content of the low Tg resin is equal to the sum of the high acid value resin and the low Tg resin of Example 1 instead of not containing the high acid value resin. It is.

  In the same manner as in Example 1, an ITO glass substrate (ITO thickness 10 nm) was used as a substrate to be printed, and etching of Comparative Example 1 was performed by a letterpress reverse printing method using a cylinder having a silicone blanket and a letterpress having a line width of 18 μm. When the resist ink was printed, since there was no film-forming property and the wet state continued, unnecessary portions remained on the silicone blanket when unnecessary portions were removed by the matrix plate, and a fine pattern was not obtained.

(Comparative example 2) System sol IPA-ST (trade name; manufactured by Nissan Chemical Industries, average particle size 10 nm; solid content 30%) 19.7 g as an extender pigment component containing no second resin having a Tg of 25 ° C. or less And 12.3 g of a rosin-modified maleic resin J-896 (trade name; manufactured by DIC, acid value of 200 or more) adjusted to a solid content of 50% by IPA as a high acid value resin, and dye Orazole Blue as a coloring component 11.8 g of GN (trade name; manufactured by Ciba Specialty Chemicals) adjusted to a solid content of 5% with isopropyl acetate / propylene glycol monomethyl ether 1/1 solution, and a fluorine-based surface energy modifier as a surface energy modifier TF-1303 (trade name; manufactured by DIC, solid content 30%) 0.5 g and silicone oil SH28PA (trade) as a release agent Product name; manufactured by Toray Dow Corning) adjusted to 10% solid content by IPAc, 2.0 g of polytetramethylene ether glycol and 16.1 g of propylene glycol monomethyl ether as a slow-drying organic solvent, fast-drying organic As a solvent, 35.5 g of isopropyl acetate was added to obtain an ink for etching resist of Comparative Example 2. That is, the composition of Comparative Example 2 is the same as that of Example 1 except that the content of the high acid value resin is equal to the sum of the high acid value resin and the low Tg resin of Example 1 instead of containing the low Tg resin. It is.

  In the same manner as in Example 1, an ITO glass substrate (ITO thickness of 10 nm) was used as a substrate to be printed, and etching of Comparative Example 2 was performed by a letterpress reverse printing method using a cylinder having a silicone blanket and a letterpress with a line width of 18 μm. When the resist ink was printed, the film was hard and there was no tack, so the non-image area on the matrix plate could not be removed and a fine pattern could not be obtained.

(Comparative Example 3) A system that does not contain an extender component having an average particle diameter of 100 nm or less. A rosin-modified maleic resin J-896 (trade name; manufactured by DIC, acid value 200) is used as a high acid value resin without using an extender component. 7.6 g of the above adjusted to a solid content of 50% by IPA and liquid acrylic resin CBB-3098 (trade name; manufactured by Soken Chemical Co., Ltd., Tg of 25 ° C. or less) as a low Tg resin to a resin content of 50% by IPA 7.7 g of the adjusted product and the dye Orazol Blue GN (trade name; manufactured by Ciba Specialty Chemicals) as a coloring component, adjusted to a solid content of 5% with an isopropyl acetate / propylene glycol monomethyl ether 1/1 solution 14 .7 g and a fluorine-based surface energy adjusting agent TF-1303 (trade name; manufactured by DIC, solid content 30%) as a surface energy adjusting agent 0.6 g, 2.5 g of silicone oil SH28PA (trade name; manufactured by Toray Dow Corning) adjusted to 10% solid content by IPAc, 2.5 g of polytetramethylene ether glycol and propylene glycol as slow-drying organic solvents An etching resist ink of Comparative Example 3 was obtained by adding 20.1 g of monomethyl ether and 44.3 g of isopropyl acetate as a fast-drying organic solvent. That is, the composition of Comparative Example 3 is the same as that of Example 1 except that the constitutional component is not included and the content of other components is increased by 25% from Example 1.

  In the same manner as in Example 1, an ITO glass substrate (ITO thickness of 10 nm) was used as a substrate to be printed, and etching of Comparative Example 3 was performed by a letterpress reverse printing method using a cylinder having a silicone blanket and a letterpress having a line width of 18 μm. When the resist ink was printed, the film-forming property was strong, the non-image area on the matrix plate could not be removed, and a fine pattern could not be obtained. Here, the pressure was further increased to obtain linearity, but a fine pattern as in Example 1 was not obtained.

(Comparative Example 4) Without using the extender component and the extender component that does not contain the second resin, the rosin-modified maleic resin J-896 (trade name; manufactured by DIC, acid value of 200 or more) is used as the high acid value resin. ) Adjusted to a solid content of 50% by IPA, and dye Orazole Blue GN (trade name; manufactured by Ciba Specialty Chemicals) as a coloring component in an isopropyl acetate / propylene glycol monomethyl ether 1/1 solution 14.7 g adjusted to 5% solid content, 0.6 g of fluorine-based surface energy adjuster TF-1303 (trade name; manufactured by DIC, 30% solid content) as a surface energy adjuster, and silicone oil as a release agent 2.5g of SH28PA (trade name; manufactured by Toray Dow Corning) adjusted to 10% solid content with IPAc, with slow drying Etching resist ink of Comparative Example 4 was obtained by adding 2.5 g of polytetramethylene ether glycol and 20.1 g of propylene glycol monomethyl ether as machine solvents and 44.3 g of isopropyl acetate as a quick-drying organic solvent. That is, the composition of Comparative Example 4 did not contain a constitutional component and a low Tg resin, and the content of other components was uniformly increased by 25% from Example 1 (however, the content of the high acid value resin was higher than that of Example 1). The others are the same as in Example 1 except that the total amount of the acid value resin and the low Tg resin is increased by 25%.

  In the same manner as in Example 1, an ITO glass substrate (ITO thickness 10 nm) was used as a printing medium, and etching of Comparative Example 4 was performed by a letterpress reverse printing method using a cylinder having a silicone blanket and a letterpress with a line width of 18 μm. When the resist ink was printed, unnecessary portions remained on the printing medium when unnecessary portions were removed by the matrix plate, and the linearity of the image line could not be achieved. Further, sufficient linearity could not be obtained even if the pressure for pressing the relief plate was increased. The pattern was worse than Comparative Examples 2 and 3.

(Comparative Example 5)
19.7 g of Sicilia Grade # 530 (trade name; manufactured by Fuji Silysia Chemical Co., Ltd., average particle diameter of over 5200 nm) adjusted to a solid content of 30% by IPA, and rosin-modified maleic resin J -896 (trade name; manufactured by DIC, acid value of 200 or more) adjusted to 50% solid content by IPA, and liquid acrylic resin CBB-3098 (trade name; manufactured by Soken Chemical, Tg as a low Tg resin) 25 g or less) adjusted to a resin content of 50% by IPA, and dye Orazole Blue GN (trade name; manufactured by Ciba Specialty Chemicals) as a coloring component, isopropyl acetate / propylene glycol monomethyl ether 1 / 11.8g of solid content adjusted to 5% with one solution, and fluorine-based surface energy regulator Surface energy adjusting agent TF-1303 (trade name; manufactured by DIC, solid content 30%) 0.5 g and silicone oil SH28PA (trade name; manufactured by Toray Dow Corning) as a release agent are adjusted to 10% solid content by IPAc. The etching resist of Comparative Example 5 was added 2.0 g of the product, 2.0 g of polytetramethylene ether glycol and 16.1 g of propylene glycol monomethyl ether as the slow-drying organic solvent, and 35.5 g of isopropyl acetate as the fast-drying organic solvent. Ink was obtained. That is, the composition of Comparative Example 5 is the same as that of Example 1 except that the constitutional component has an average particle diameter of more than 100 nm.

  In the same manner as in Example 1, an ITO glass substrate (ITO thickness of 10 nm) was used as a substrate to be printed, and etching of Comparative Example 5 was performed by a letterpress reverse printing method using a cylinder having a silicone blanket and a letterpress having a line width of 18 μm. When the resist ink was printed, the coating film on the printing substrate was not smooth, and a pattern with insufficient edge linearity was obtained.

  In the present invention, the letterpress reversal printing method is, as described above, by applying ink on a blanket to form an ink application surface, and pressing the letterpress on the ink application surface to inject the ink in a portion in contact with the letterpress. In this printing method, after the ink is removed from above, the ink remaining on the blanket is transferred to a printing medium.

(Evaluation method)
(1) Pattern When the ink remaining on the blanket is transferred to the substrate, the printed material is observed with an optical microscope (750x) and the pattern of the plate is faithfully reproduced (◯). The case where defects such as the above were observed was taken as (x).
(2) Film-forming property After applying ink on a blanket to form an ink-applied surface, it is evaluated by touching a finger after a certain period of time, and when a film is formed (O), no film is formed The case was set as (x).
(3) Remaining blank After pressing the relief plate on the ink application surface and removing the ink in the portion in contact with the relief plate from the blanket, the step of transferring the ink remaining on the blanket to the printing medium is visually observed. In the case where all of the ink was transferred and no ink remained on the blanket (O), the case where a portion of the ink was not transferred and the ink remained on the blanket was indicated as (X).
(4) Tackiness After applying ink on a blanket to form an ink application surface, evaluation was made by contacting a finger after a certain period of time, and the case where the film did not dry and had tackiness (○ ), The case where the film dries and does not have tackiness, and was marked (x).
The results are shown in Table 1.

  The present invention can be used for manufacturing various electric parts and electronic parts. For example, an electrode for a touch panel or a pixel electrode for a display can be used.

2 is a graph showing patterning of an ITO film etched in Example 1. FIG.

Claims (6)

  A constitutional component having an average particle diameter of 100 nm or less, a first resin having an acid value of 200 or more, a second resin having a Tg of 25 ° C. or less, a release agent, a surface energy adjusting agent, and a solvent An ink for etching resist by a letterpress reverse printing method, comprising:   The etching resist ink according to claim 1, wherein an average particle diameter of the constitutional component is 10 to 60 nm.   The ink for etching resist according to claim 1, wherein the first resin is a resin having a carboxyl group.   The ink for etching resist according to claim 1, wherein the first resin is a rosin-modified maleic acid resin having a carboxyl group.   The ink for etching resist according to any one of claims 1 to 4, wherein the second resin is a liquid acrylic resin.   A resist pattern forming method, wherein the resist pattern is formed by a letterpress reverse printing method using the etching resist ink according to claim 1.

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