KR20090062510A - Ink composition - Google Patents

Abstract

An ink composition is provided to act on pattern supporter by being applied to imprint lithography and pattern formation, and to increase precision of pattern formation by minimizing swelling phenomenon. An ink composition comprises (a) polymer resin 5-45 parts by weight, (b) tackifier 5-45 parts by weight and (c) organic solvent 50-90 parts by weight. The ink composite is used for imprint lithography or pattern formation using roll print. The polymer resin is selected from the group consisting of novolac resin, acrylic resin and their mixture. The ink composition further includes silicon-based surfactant or fluorine-based surfactant.

Description

Ink composition

The present invention relates to an ink composition, and more particularly, it is applied to pattern formation using imprint lithography and roll printing to minimize the occurrence of swelling caused by the ink composition as well as the role of the pattern support, thereby increasing the precision of pattern formation. The present invention also relates to an ink composition for imprint lithography and roll printing, which can improve the yield and improve the efficiency of the process by increasing the pattern transfer rate.

In general, a process of forming a micro pattern applied to information storage, a small sensor, a photonic crystal and an optical device, a microelectromechanical device, a display device, a display, and a semiconductor uses photolithography that forms a micro pattern using light. This is the method used.

In the conventional photolithography method, the circuit line width or pattern line width is determined by the wavelength of light used in the exposure process. Given the current state of the art, photolithography processes are difficult to form fine patterns of 70 nm or less on a substrate because of light interference. In addition, as the pattern becomes very fine, the initial investment costs increase due to expensive equipment such as exposure equipment, and the price of high-resolution masks soars, resulting in inefficiency. The problem of using expensive equipment is the cost. It is another factor causing the rise.

In addition, since the exposure, the post-exposure bake, the development, the post-development bake, the etching process, the cleaning process, and the like must be performed every time the pattern is formed, the process takes a long time and the productivity decreases because a plurality of photo processes must be repeated. The problem that comes up is highlighted.

Imprint lithography and roll printing techniques have emerged as a way to solve this problem. Imprint lithography is the first method invented by Stephen chou of Princeton University in order to imprint nanoscale, and prefabricates the shape needed on the surface of inorganic or polymer with high strength. The fine pattern is formed by painting. Specifically, a method of forming a pattern by bonding to a curable composition coated on a metal film or an organic film using an inorganic material or a polymer mold in which a desired fine pattern is formed in advance, and thermally or photocuring to form a pattern, as compared with the conventional photolithography method. There is an advantage to simplify the process and to form a fine pattern.

In addition, the roll printing method is disclosed in the Republic of Korea Patent Application No. 2006-0005482 (Patent Publication No. 10-2007-76292) with respect to the roll printing apparatus and the manufacturing method of the display device using the same. The prior art mentions that the roll printing method can be applied to FED (Field Emission Display), organic EL (ElectroLuminescent), PDP (Plasma Display Panel) devices, and the manufacturing process will be simple. It is disclosed that will be secured.

In the roll printing method, direct pattern transfer is formed on a substrate to form a fine pattern using a silicon polymer and a cliché instead of a high-resolution mask used to form a pattern in conventional photolithography. The roll printing method uses a silicone polymer, which is a stamp, to improve alignment and mold release properties, and to improve productivity and work efficiency by applying a thermosetting process. In addition, it has been proposed as an alternative that can drastically reduce the complicated process that proceeds through various processes, such as photolithography exposure or development work, and the resulting process costs.

However, when using a fluid ink composition used for forming a fine pattern, there was a problem in transferring the pattern precision and excellent pattern formation with a single polymer resin. Specifically, it is difficult to completely transfer the pattern on the substrate on which the fine pattern is to be formed, and because the ink composition has fluidity, the pattern thickness is inconsistently formed, and thus the pattern line width is changed and the silicon polymer is repeatedly used. There was a difficulty in improving the yield by increasing the pattern precision.

In addition, the swelling phenomenon (swelling phenomenon) between the silicon polymer and the organic solvent used in the roll printing apparatus to form a fine pattern severely changes the circuit line width and pattern thickness, making it difficult to repeatedly use the silicon polymer. In order to remove the foreign matter of the ink composition caused by the swelling phenomenon, if the cleaning operation is performed by physical contact, the surface is easily damaged by friction, etc., and the imprint and the roll of the silicon polymer ink composition are not removed. When the printing operation is performed, there is a problem that a fine pattern of the ink composition is incorrectly formed on the side of the substrate to be formed, or that a defect quality is excessively generated. Therefore, there is a limit in transferring the fine pattern continuously, and there is a difficulty in improving the precision of the fine pattern.

In order to solve the problems of the prior art as described above, the present invention is applied to the pattern formation using the imprint lithography and roll printing to minimize the occurrence of swelling phenomenon due to the ink composition with the role of the pattern support to have an excellent pattern forming ability The purpose is to provide.

In addition, an object of the present invention is to provide an ink composition for imprint lithography and roll printing that can increase the precision of pattern formation, and can improve the yield and process efficiency by increasing the pattern transfer rate.

In order to achieve the above object, the present invention

a) 5 to 45 parts by weight of the polymer resin;

b) 5-45 parts by weight of a tackifier; And

c) 50 to 90 parts by weight of organic solvent

It provides an ink composition comprising a.

The ink composition of the present invention may further comprise 0.01 to 3 parts by weight of the surfactant.

In addition, the ink composition may further include 0.01 to 8 parts by weight of the additive.

The ink composition of the present invention is applied to pattern formation using imprint lithography and roll printing to minimize the occurrence of swelling caused by the ink composition as well as the role of the pattern support to increase the precision of the pattern formation, and also to increase the pattern transfer rate Improved yield and process efficiency can be improved.

Hereinafter, the present invention will be described in detail.

The ink composition of the present invention comprises a) 5 to 45 parts by weight of a polymer resin; b) 5-45 parts by weight of a tackifier; And c) 50 to 90 parts by weight of an organic solvent, and in particular, by adding a tackifier that can increase viscosity and maintain stickiness, it has excellent pattern forming ability as well as the role of pattern support, and also improves the yield by increasing the pattern transfer rate. The efficiency of the process can be improved.

In the ink composition of the present invention, the a) polymer resin may be a novolak resin, an acrylic resin, or the like used in a conventional ink composition. The novolac resin is synthesized by reacting formaldehyde or paraformaldehyde with an aromatic alcohol such as meta cresol, para cresol, 2,3,5-trimethylphenol, 2,3-xylene, 3,5-xylene, and the like. Polymers can be used. Moreover, what superposed | polymerized unsaturated carboxylic acid, an aromatic monomer, an acryl monomer, etc. can be used for the said acrylic resin.

The molecular weight of the polymer resin is preferably 2,000 to 40,000, more preferably 2,000 to 15,000.

The polymer resin is preferably included in 5 to 45 parts by weight, more preferably 7 to 12.5 parts by weight based on 100 parts by weight of the total composition. If it is in the above range it can improve the yield and process efficiency by increasing the role and pattern transfer rate of the pattern support.

In addition, the ink composition of the present invention, b) the tackifier to increase the viscosity of the ink composition, to maintain sticky tack, to increase the releasability with the imprint and roll print, to increase the role of the pattern support and the pattern transfer rate yield Improvement and process efficiency can be improved.

Specific examples of the tackifiers include butyrate hydroxyanisole, 2,6-di-tert-butyl-4-hydroxymethylphenol, butyrate hydroxytoluene, propyl gallate, lauryl gallate, octylgal Late, 2,4,5-trihydroxybutyrophenone, tert-butylhydroquinone; Phenols such as 3-aminophenol, 4-aminophenol, 4-methoxyphenol, 2,3,5-trimethylphenol, 2,4-dimethylphenol, poly (4-vinylphenol), and 4-bromophenol; Ethers such as ethyl vinyl ether, poly (methyl vinyl ether) and poly (isobutyl vinyl ether); Poly- (p-hydroxy) styrene, 1,1-bis (4-hydroxyphenyl) decane, 4,4- [1- [4- [1- (1,4-hydroxyphenyl) -1-methyl Ethyl] phenyl] ethylidene] bisphenol, 4,4- [2-hydroxyphenyl] methylene] bis [2,6-dimethylphenol], urethane acrylate having a weight average molecular weight of 1,000 to 5,000, a urethane oligomer or the like alone or It can mix and use 2 or more types.

It is preferable that the tackifier is included in the ink composition of the present invention 5 to 45 parts by weight, more preferably 7 to 12.5 parts by weight. Within the above range, the tackiness of the ink composition and the releasability of the imprint and the roll print may be increased, and the role of the pattern support and the pattern transfer rate may be increased to improve the yield and the efficiency of the process.

In addition, in the ink composition of the present invention, c) the organic solvent may preferably be used to dissolve an additive such as a polymer resin and a tackifier and a visible compound which can be additionally used as necessary.

Specifically, the organic solvent may be alcohol such as methanol, ethanol, ethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, diethylene glycol, butanediol, benzyl alcohol, hexyl alcohol; Ethers such as propylene carbonate, tetrahydrofuran, methoxybenzene, 1,4-dioxane, 1-methoxy-2-propanol, methoxybenzene, dibutyl ether and diphenol ether; Ethyl acetate, propyl acetate, butyl acetate, ethyl propion, ethyl ester, butyl ester, methyl-2-hydroxyisobutyrate, 2-methoxy-1-methylethyl ester, 2-methoxyethanol acetate, 2-ethoxy Esters such as ethanol acetate; Ethylene glycol alkyl ether acetates such as ethylene glycol methyl ether acetate and ethylene glycol ethyl ether acetate; Ethylene glycol alkyl ether propionates such as ethylene glycol methyl ether propionate and ethylene glycol ethyl ether propionate; Ethylene glycol monoalkyl ethers such as ethylene glycol methyl ether and ethylene glycol ethyl ether; Diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol propyl ether acetate; Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate and propylene glycol propyl ether propionate; Propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, and propylene glycol butyl ether; Dipropylene glycol alkyl ethers such as dipropylene glycol dimethyl ether and diporoethylene glycol diethyl ether; Butylene glycol monomethyl ether, such as butylene glycol monomethyl ether and butylene glycol monoethyl ether; Dibutylene glycol alkyl ethers, such as dibutylene glycol dimethyl ether and dibutylene glycol diethyl ether, etc. can be used individually or in mixture of 2 or more types. In particular, the organic solvent is better for pattern transfer to use a mixture of two or more solvents than to use a single solvent to improve the coating performance to the silicone polymer.

The organic solvent is preferably included in an amount of 50 to 90 parts by weight, more preferably 70 to 80 parts by weight with respect to the ink composition. If it is in the above range can contribute simultaneously to the solubility, the efficiency of the process.

The ink composition for implant lithography and roll printing of the present invention comprising the above components may further include a surfactant or an additive.

The surfactant serves to prevent stains and marks on ink materials generated from the silicone polymer and to ensure smooth coating property.

The surfactant may be a fluorine-based surfactant such as a silicone-based surfactant or perfluoroalkyl oligomer, the content of which is 0.01 to 3 parts by weight, preferably 0.1 to 1.5 parts by weight based on 100 parts by weight of the total ink composition. It is good to be used as wealth.

As said additive, an adhesive sensitizer and a visibility compound can be used.

The adhesive sensitizer is used to improve the adhesiveness to the underlayer. The adhesive sensitizer may be used a common melanin crosslinking agent, the melanin crosslinking agent is a condensation product of urea and formaldehyde, a condensation product of melamine and formaldehyde, methylol urea alkyl ethers or methylol melamine alkyl ethers obtained from alcohol Etc. can be used.

Specifically, monomethylol urea, dimethylol urea, or the like may be used as a condensation product of the urea and formaldehyde. Hexamethylol melamine may be used as the condensation product of melamine and formaldehyde, and other partial condensation products of melamine and formaldehyde may be used. In addition, the methylol urea alkyl ethers are obtained by reacting a condensation product of urea with formaldehyde with alcohols in part or all of the methylol groups, and specific examples thereof include monomethyl urea methyl ether, dimethyl urea methyl ether, and the like. Can be used. The methylol melamine alkyl ethers are obtained by reacting a condensation product of melamine and formaldehyde with alcohols in part or in all of methylol groups, and specific examples thereof include hexamethylol melamine hexamethyl ether and hexamethylol melamine hexabutyl ether. Etc. can be used. Moreover, the compound of the structure where the hydrogen atom of the amino group of melamine was substituted by the hydroxy methyl group and the methoxy methyl group, the compound of the structure where the hydrogen atom of the amino group of melamine was substituted by the butoxy methyl group and the methoxy methyl group, etc. can also be used, Especially methylol Preference is given to using melamine alkyl ethers.

When the adhesive sensitizer is used as the additive, the content thereof is preferably used in an amount of 0.01 to 5 parts by weight, and preferably 0.5 to 2.5 parts by weight, based on 100 parts by weight of the total composition. In the above range, the ink composition of the present invention has excellent adhesion with the lower substrate, and serves to protect the metal layer under the pattern in an etching process later.

In addition, the visibility compound may secure the visibility of the ink composition by using a dye, a pigment, or a photosensitive compound, dissolving it with a polymer resin to form an excellent pattern transfer ability, and to facilitate the adhesion of the substrate to the desired It works.

As the visible compound, 2,3,4-trihydroxybenzophenone-1,2 prepared by esterifying a trihydroxy benzophenone and 2-diazo-1-naphthol-5-sulfonic acid as a diazide compound 2,3,4,4-tetrahydroxybenzophenone prepared by esterifying naphthoquinone diazide-5-sulfonate, tetrahydroxy benzophenone and 2-diazo-1-naphthol-5-sulfonic acid -1,2-naphthoquinone diazide-5-sulfonate etc. can be used individually or in mixture.

When the visibility compound is used as the additive, the content thereof is preferably used in an amount of 0.1 to 3 parts by weight, preferably 0.5 to 2.0 parts by weight, based on 100 parts by weight of the ink composition of the present invention.

The ink composition of the present invention comprising such a component is a known conventional imprint process (for example, Korea Patent Publication No. 10-2005-0019557) and roll printing process (for example, Korea Patent Publication No. 10-2007 -0076292) can be applied to form a pattern to form a pattern on the substrate.

As a specific example, using a suitable method such as spin coating, roller coating, slit coating, etc., the coating is applied in a thickness of 0.5 to 10 μm, and in the imprint process, the silicon substrate is brought into contact with a silicon polymer stamp having a pattern of a shape to be formed. Can be transferred onto a substrate such as a ceramic substrate, a metal layer, or a polymer layer. In a roll printing process, a silicon substrate, a ceramic substrate, and a metal layer are contacted with a silicon polymer by using a cliché having a pattern of a shape to be formed. The pattern can be transferred onto a substrate such as a polymer layer or the like.

Subsequently, the photocuring process can be performed using ultraviolet rays, or the thermosetting process which heat-processes at the temperature of 90-200 degreeC can be implemented, or a photocuring process and a thermosetting process can be performed in parallel. The heat treatment step is performed to evaporate the solvent without pyrolyzing the solid component in the ink composition. In general, it is preferable to minimize the concentration of the solvent through the heat treatment process, and it is preferable to carry out until the ink film having a thickness of 10 μm or less remains on the substrate. Such a process enhances the adhesion and chemical resistance of the ink film and the substrate. The substrate having the above process is treated with a corrosion solution or a gas plasma to treat the exposed substrate portion, wherein the unexposed portion of the substrate is protected by an ink film. After treating the substrate as described above, a fine circuit pattern can be formed on the substrate by removing the ink film with an appropriate stripper.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

EXAMPLE

Example 1

The ink compositions of Example 1 or 2 and Comparative Examples 1 or 2 were prepared by mixing the components and compositions as shown in Table 1 below, and uniformly mixing at room temperature for at least 24 hours. The unit in Table 1 is parts by weight.

The polymer resin used in Table 1 is a novolak resin, the organic solvent is methanol, the surfactant is a silicone surfactant, and the additive is hexamethylolmelamine hexamethyl ether.

TABLE 1

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Polymer resin 10 10 10 20  Tackifier 10 10 10  - Butyrate hydroxyanisole Poly- (p-hydroxy) styrene Urethane acrylate Organic solvent 80 80 80 80 Surfactants One One One One additive 3 3 3 -

The physical properties of the ink compositions of Examples 1 or 2 and Comparative Examples 1 or 2 prepared in Table 1 were evaluated in the following manner.

end. Fine Pattern Transfer Rate

The ink compositions of Examples 1-2 and Comparative Examples 1-2 were coated on the silicone polymer having no pattern. After the natural drying for 20 seconds, the silicon polymer is transferred to the substrate to be formed while passing through the cliché, the fine pattern is transferred, the transfer rate of the pattern is shown in Table 2 below. The transfer rate of the pattern was specified as 0-100% depending on the pattern formation in 100 cells having a size of 1 × 1 mm.

TABLE 2

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Pattern Transfer Rate (%) 96 95 70 30

As shown in Table 2, the ink compositions of Example 1 and Example 2 using the tackifier according to the present invention was confirmed that the excellent pattern transfer rate of 95% or more.

I. Pattern shaping precision

The ink compositions of Examples 1-2 and Comparative Examples 1-2 were coated on the silicone polymer having no pattern. After drying for a predetermined time, the micro pattern was transferred onto the substrate to be formed while the silicon polymer passed through the cliché. Subsequently, the substrate on which the micropatterns have been transferred is heat-treated at a high temperature for a predetermined time, dipped in an aluminum etching solution at 40 ° C. for a predetermined time, and then subjected to surface analysis of the micropatterns through a scanning electron microscope. 1 to 4 are shown. In addition, it is shown in Table 3 by measuring the adhesion between the fine pattern portion and the lower substrate. The adhesion between the fine pattern portion and the lower substrate was specified to be 0 to 100% depending on the degree.

As shown through FIGS. 1 to 4, it was confirmed that the ink compositions of Example 1 (FIG. 1) and Example 2 (FIG. 2) according to the present invention form a uniform pattern and have excellent precision of pattern formation. On the other hand, in Comparative Examples 1 and 2 it can be seen that the pattern formation does not appear precisely.

TABLE 3

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Adhesion (%) 98 97 5 2

In addition, as shown in Table 3, the ink compositions of Examples 1 (FIG. 1) and Example 2 (FIG. 2) according to the present invention are significantly better in adhesion with the fine pattern portion and the lower substrate than Comparative Examples 1 and 2. I could confirm it.

1 and 2 are scanning electron micrographs observing the surface after forming a fine pattern using the ink composition prepared according to an embodiment of the present invention.

3 and 4 are scanning electron micrographs of the surface after forming a fine pattern using the ink composition prepared according to the comparative example.

Claims (8)

a) 5 to 45 parts by weight of the polymer resin; b) 5-45 parts by weight of a tackifier; And c) 50 to 90 parts by weight of organic solvent Ink composition comprising a. The method of claim 1, Wherein said ink composition is used for pattern formation using imprint lithography or roll printing. The method of claim 1, The polymer resin is ink composition, characterized in that at least one selected from the group consisting of novolak resin, acrylic resin and mixtures thereof. The method of claim 1, The tackifiers include butyrate hydroxyanisole, 2,6-di-tert-butyl-4-hydroxymethylphenol, butyrate hydroxytoluene, propyl gallate, lauryl gallate, octyl gallate, 2, 4,5-trihydroxybutyrophenone, tert-butylhydroquinone, 3-aminophenol, 4-aminophenol, 4-methoxyphenol, 2,3,5-trimethylphenol, 2,4-dimethylphenol, poly (4-vinylphenol), 4-bromophenol, ethyl vinyl ether, poly (methyl vinyl ether), poly (isobutyl vinyl ether), poly- (p-hydroxy) styrene, 1,1-bis (4- Hydroxyphenyl) decane, 4,4- [1- [4- [1- (1,4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 4,4- [2-hydroxy At least one selected from the group consisting of phenyl] methylene] bis [2,6-dimethylphenol] and a urethane acrylate having a weight average molecular weight of 1,000 to 5,000 and a urethane oligomer. The method of claim 1, The organic solvent is methanol, ethanol, ethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, diethylene glycol, butanediol, benzyl alcohol, hexyl alcohol, propylene carbonate, tetrahydrofuran, methoxybenzene, 1,4-di Oxane, 1-methoxy-2-propanol, methoxybenzene, dibutyl ether, diphenol ether, ethyl acetate, propyl acetate, butyl acetate, ethyl propion, ethyl ester, butyl ester, methyl-2-hydroxyisobutyrate , 2-methoxy-1-methylethyl ester, 2-methoxyethanol acetate, 2-ethoxyethanol acetate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol methyl ether propionate, ethylene glycol ethyl ether Propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol monomethyl ether Le, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol methyl ether propionate, propylene Glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol dimethyl ether, diporo ethylene glycol diethyl ether, butyl Ink composition characterized in that at least one selected from the group consisting of len glycol monomethyl ether, butylene glycol monoethyl ether, dibutylene glycol dimethyl ether, dibutylene glycol diethyl ether. The method of claim 1, The ink composition is an ink composition, characterized in that further comprises 0.01 to 3 parts by weight of a silicone-based surfactant or a fluorine-based surfactant based on 100 parts by weight of the total ink composition. The method of claim 1, The ink composition is an ink composition, characterized in that it further comprises from 0.01 to 8 parts by weight of the adhesive sensitizer or visibility compound based on 100 parts by weight of the total ink composition ink composition. The pattern formation method using the ink composition of any one of Claims 1-7.

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