KR20130016645A - A etching paste composition for etching the transparent conductive metal oxide layer using gravure offset printing process and method of forming a pattern of transparent conductive metal oxide layer using the same - Google Patents

A etching paste composition for etching the transparent conductive metal oxide layer using gravure offset printing process and method of forming a pattern of transparent conductive metal oxide layer using the same Download PDF

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KR20130016645A
KR20130016645A KR1020110078704A KR20110078704A KR20130016645A KR 20130016645 A KR20130016645 A KR 20130016645A KR 1020110078704 A KR1020110078704 A KR 1020110078704A KR 20110078704 A KR20110078704 A KR 20110078704A KR 20130016645 A KR20130016645 A KR 20130016645A
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South Korea
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oxide layer
transparent conductive
conductive oxide
etching
paste composition
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KR1020110078704A
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Korean (ko)
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전승훈
이종욱
백나영
정찬민
김아란
정택성
변경록
박찬석
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주식회사 동진쎄미켐
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Priority to KR1020110078704A priority Critical patent/KR20130016645A/en
Publication of KR20130016645A publication Critical patent/KR20130016645A/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
    • G03F1/80—Etching
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2014—Contact or film exposure of light sensitive plates such as lithographic plates or circuit boards, e.g. in a vacuum frame
    • G03F7/2016—Contact mask being integral part of the photosensitive element and subject to destructive removal during post-exposure processing
    • G03F7/2018—Masking pattern obtained by selective application of an ink or a toner, e.g. ink jet printing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2041—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means
    • G03F7/2043—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means with the production of a chemical active agent from a fluid, e.g. an etching agent; with meterial deposition from the fluid phase, e.g. contamination resists
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Manufacturing & Machinery (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing Of Electric Cables (AREA)

Abstract

PURPOSE: An etching paste composition is provided to form micro-patterns by a low phosphate compound content, and to form micro-patterns with a line width of 30micron or less by a simple method. CONSTITUTION: An etching paste composition comprises: 5-45 weight% of non-water soluble binder selected from an acrylic copolymer, an acrylate copolymer, and an acryl-acrylate copolymer which comprise -OH or -COO-; 15-30 weight% of phosphate compound; and a residual solvent. A patterning method of a transparent conductive oxidation layer comprises: a step of preparing a substrate with a transparent conductive oxide layer; a step of printing the etching paste composition on the transparent conductive oxide layer; a step of etching the transparent conductive oxide layer by heat-treating the substrate; and a step of washing the substrate. [Reference numerals] (AA) Oxidation layer; (BB) Gravure offset printing; (CC) Etching paste printing; (DD) Heat treatment; (EE) Washing; (FF) Alkali washing liquid DI water; (GG) Patterned transparent conductive oxidation layer

Description

An etching paste composition for etching the oxide layer and a pattern forming method of the transparent conductive oxide layer using the same, which is printed on the transparent conductive oxide layer by a gravure offset printing process. process and method of forming a pattern of transparent conductive metal oxide layer using the same}

The present invention relates to an etching paste composition of a transparent conductive oxide layer of a display using a gravure offset printing process, especially a transparent conductive oxide layer for a touch panel, and a method of forming a fine pattern of the transparent conductive oxide layer using the same.

Conventional techniques for patterning a transparent conductive layer of a display, in particular a transparent conductive oxide layer (usually an ITO layer) for a touch panel, include a photolithography method, a method of applying an etching paste to a screen method, and patterning a conductive oxide layer using a laser. The method is used.

Among these, the photolithography method is used in a conventional manner, and can be patterned with a high resolution and a complicated structure of a pattern.

1 shows a process diagram for the photolithography method, and a mask is used during exposure. As shown in FIG. 1, this process involves laminating a dry film resist (DFR) protective film or a photoresist coating on a transparent conductive oxide layer in a general manner, followed by exposure and development. Subsequently, etching is performed directly with an etching solution to remove the film, and a patterned oxide layer is formed by washing with water. By the way, the photolithography method is capable of etching fine patterns of less than 30um, but the process is complicated, there is a disadvantage that the waste solution after the etching is not environmentally friendly.

In addition, the screen method is also applied to the current process. For example, in the screen method, an etching paste is pattern-printed using a screen mask, and etching and washing processes through drying are performed to form a pattern. Although the process is simple when the screen method is used, it is generally applied to pattern formation on the order of 100 um rather than fine etching. In addition, in the screen system, as the number of print accumulation increases, the positional shift occurs due to the sagging of the screen printing mask, and thus the replacement cycle of the mask is shortened. In addition, in the mask for forming a fine pattern, the above problem is further increased. In addition, when the conventional etching paste is applied to the screen method, the manufacturing cost of the mask during the patterning of a large area significantly increases, there is a problem that the precision is also reduced. Therefore, the above method is not usually used for patterning fine patterns.

In addition, although the patterning method of the oxide layer using the laser is also mentioned, there is a problem in that the equipment is complicated, there is a problem that the deformation of the substrate is caused when the substrate is a film is not widely used.

An object of the present invention is to provide an etching paste composition that can form a fine pattern even with a content of a lower phosphoric acid compound than conventional, and can be applied to a gravure offset method.

Another object of the present invention is to use the etching paste composition and the gravure offset process, to form a fine pattern having a line width of less than 30 ㎛ in a relatively simple process, in particular to blur the pattern boundary through gravure offset printing and process control It is to provide a method of forming a fine pattern of a transparent conductive oxide layer, which has an effect of improving visibility and can form a fine pattern even in a large area.

The present invention is a water-soluble binder 5 to 45% by weight selected from the group consisting of an acrylic copolymer, an acrylate copolymer and an acrylic-acrylate copolymer containing an -OH or -COO- group,

15 to 30% by weight of a phosphoric acid compound and

Containing residual amount of solvent,

It is printed on a transparent conductive oxide layer by a gravure offset printing process to provide an etching paste composition for etching the oxide layer.

In addition, the etching paste composition of the present invention may further include at least one additive selected from the group consisting of 0.5 to 5% by weight of inorganic particles and 0.1 to 1% by weight of surfactant based on 100% by weight of the total etching paste composition. .

In addition, the present invention is to prepare a substrate on which a transparent conductive oxide layer is formed,

Printing the etching paste composition in a fine pattern on the transparent conductive oxide layer formed on the substrate through a gravure offset process;

Etching the transparent conductive oxide layer by heat-treating the substrate on which the etching paste composition is printed in a fine pattern on the transparent conductive oxide layer, and

Cleaning the substrate on which the transparent conductive oxide layer is etched in a fine pattern

It provides a pattern forming method of a transparent conductive oxide layer comprising a.

The gravure offset process may be performed in a roll-to-roll apparatus having a gravure roll having grooves at a predetermined interval and a blanket roll facing the gravure roll and rotating in a direction opposite to the rotation direction of the gravure roll. .

Hereinafter, the present invention will be described in detail.

The present invention provides a method of using an etching paste composition containing a specific amount of acid, preferably a phosphoric acid-based compound, together with a water-insoluble binder having a specific functional group and an acid value when forming a fine pattern of a transparent conductive oxide layer for a display. In particular, the etching paste composition of the present invention is a composition for etching the oxide layer is printed on the transparent conductive oxide layer by a gravure offset printing process, which can improve the etching property in a way that the acid content is at least effective than conventional.

In another aspect, the present invention provides a method for forming a pattern of a transparent conductive oxide layer to effectively form a fine pattern by applying the etching paste composition to a gravure offset printing process. That is, when using the specific etching paste composition of the present invention, it can be applied to the gravure offset printing process rather than the conventional general screen printing method to form a fine pattern on the substrate on which the transparent conductive oxide layer is formed in a relatively simpler and simpler process than the prior art. can do. Therefore, according to the present invention, it is possible to form a fine pattern having a line width of 30 um or less. In addition, the gravure offset printing and process control (preferably, drying conditions control) can be formed to blur the boundaries of the fine pattern can greatly contribute to the improvement of visibility.

According to a preferred embodiment of the present invention, 5 to 45% by weight of a water-insoluble binder, phosphoric acid, selected from the group consisting of an acrylic copolymer, an acrylate copolymer and an acrylic-acrylate copolymer including an -OH or -COO- group An etching paste composition is provided on a transparent conductive oxide layer by a gravure offset printing process, comprising 15 to 30% by weight of a phosphoric acid compound such as a salt thereof or an adduct thereof and a residual solvent, to etch the oxide layer. .

Then, each component of the etching paste composition is printed on the transparent conductive oxide layer by the gravure offset printing process to etch the oxide layer.

Water-insoluble binder

The etching paste composition of the present invention is characterized in that it comprises an acid value in order to proceed with a gravure offset process and to be easily washed in a cleaning solution (especially an alkaline developer) after heat treatment.

To this end, the present invention uses a water-insoluble binder having a specific functional group. The water-insoluble binder of the present invention having the specific functional group is used to impart compatibility to water contained in the etching paste composition and to enable smooth gravure offset printing. In this case, in the case of the water-insoluble binder that does not include the specific functional group, a problem of precipitation of the binder occurs due to the volatilization of the solvent during the gravure offset printing, and thus there is a problem in that a seamless printing pattern cannot be formed. Such water-insoluble binders include methyl acrylate; Butyl methacrylate; Hydroxyethyl methacrylate; Nonyl acrylate; Methyl methacrylate; Ethyl acrylate; Ethylhexyl acrylate; Ethyl acrylate; Acrylic acid; And an adduct of methacrylic acid, acrylic acid or methacrylic acid; one or more selected from the group consisting of these may be used, and these may be used in a copolymer form by mixing one or more kinds. In the adduct of the methacrylic acid, acrylic acid or methacrylic acid, the adduct may be an ester group, an alkyl group or a hydroxy alkyl group, etc., wherein the alkyl group may include 1 to 10 carbon atoms. In addition, the weight average molecular weight of the water-insoluble binder may be 5,000 ~ 100,000, preferably 10,000 ~ 50,000.

The content of the non-aqueous binder may include 5 to 45% by weight, preferably 15 to 40% by weight. When the water-insoluble binder content is less than 5% by weight, it is difficult to maintain a uniform printing pattern due to the high viscosity decrease of the paste composition, and when the content is more than 45% by weight, the viscosity of the paste composition is increased and the drying of the paste is rapidly increased. It is difficult to achieve a smooth print.

Phosphoric Acid Compound

Acids that can be used for gravure offset printing may advantageously be used acids that do not attack gravure rolls. The gravure roll provided in the present invention is generally plated with chromium. Any kind of acid that does not attack the chromium layer may be used, but preferably one or more phosphate-based compounds are included.

The phosphoric acid compound may be phosphoric acid, salts thereof, or adducts thereof, and preferably phosphoric acid may be used. At this time, the phosphoric acid is usually dissolved in 85% concentration in water. Thus, the etching paste composition of the present invention may comprise water. In particular, the present invention by using the content of the phosphate compound compared to the conventional 30% by weight or less, can be applied to the gravure offset process while showing an effect equal to or higher than the conventional one can form a fine pattern by a simple method. Preferably, the content of the phosphoric acid-based compound in the etching paste composition may include 15 to 30% by weight, more preferably 15 to 25% by weight. It is preferable that the phosphoric acid type compound contained in an etching paste composition in the said range is phosphoric acid of 85% concentration.

 When the content of the phosphate-based compound is less than 15% by weight, the etching rate may be reduced, so that the etching may not be smoothly achieved. When the content is more than 30% by weight, the content of water having a large surface tension in the composition is increased to give uniform fineness. Patterns can be hard to implement.

menstruum

The solvent used in the present invention can be used to adjust the viscosity of the etching paste composition. In particular, the solvent has high absorbency in the blanket roll applied in the gravure offset printing process described below, and allows the water-containing etching paste composition to have an appropriate surface tension on the blanket roll, and to maintain viscosity and fluidity at a desirable level. It is preferable to use what can be used suitably for a printing process.

In other words, in the case of the gravure offset printing process, when a long axis pattern contains a large amount of water when printing a long axis pattern, it may be in a droplet form when transferred onto a hydrophobic blanket roll (silicon rubber). Therefore, the present invention is characterized in that the fine pattern can be easily achieved by suppressing the movement of the pattern on the blanket roll as much as possible by using a solvent having high water absorption and relatively low surface tension. In particular, since the solvent is absorbed in the blanket during the printing process, the content of phosphoric acid may be increased by using the superabsorbent solvent, thereby further improving the etching property.

Examples of such a solvent include gamma butyrolactone, butyl carbitol acetate, carbitol, methoxymethyl ether propionet, terpineol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol Methyl ethyl ether, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether propionate, ethyl ether At least one selected from the group consisting of propionate, propylene glycol monomethyl ether acetate, methyl ethyl ketone, ethyl lactate and ethyl glycol butyl ether can be used. More preferably, the solvent may use a mixture.

The content of the solvent in the etching paste composition may be included in the remaining amount, but preferably 25 to 75% by weight, more preferably 35 to 65% by weight. If the content of the solvent is less than 25% by weight, there is a problem in that the viscosity of the composition is high. If the content is more than 75% by weight, the viscosity of the composition may increase, so that smooth printing may not be achieved.

In the present invention, the etching paste composition may have a viscosity of 10,000 to 50,000 cps, and may easily form a fine pattern without affecting printability when applied to a gravure offset printing process.

additive

The etching paste composition according to the present invention may further comprise optional additives for further improvement of properties. For example, small amounts of optional powder ingredients may be added to improve printability. In addition, an optional surfactant component may be further added to adjust the physical properties of the etching paste composition, and any basic material may be further included for controlling the etching property.

Preferably, the etching paste composition is 0.5 to 5 parts by weight of inorganic particles and 0.1 to 1 weight of surfactant based on 100 parts by weight of the total etching paste composition (e.g., the composition of the above-described water-insoluble binder, phosphate compound and solvent). It may further comprise one or more additives selected from the group consisting of parts.

The inorganic particles may include conventional inorganic compounds such as carbon black and silica. In addition, the surfactant may be an antifoaming agent, but is not limited thereto, and nonionic, anionic, or cationic surfactants well known in the art may be used.

In addition, the etching paste composition of the present invention may further include additives such as a fluidity regulator, a thickener, a defoaming agent, a surface tension control agent, and the content thereof is not particularly limited.

As such, the present invention can provide a stable etching paste composition having compatibility with water even without using a water-insoluble binder and without phase separation. In addition, since the present invention uses an etching paste composition containing a less amount of phosphoric acid-based compound and a super absorbent solvent, the gravure offset printing process can be applied and the etching property is improved, and in particular, the fine etching pattern can be realized.

On the other hand, the present invention provides a method of forming a pattern of a transparent conductive oxide layer using the etching paste composition and gravure offset printing process.

According to a preferred embodiment of the present invention, preparing a substrate on which the transparent conductive oxide layer is formed, and printing the etching paste composition in a fine pattern on the transparent conductive oxide layer formed on the substrate through a gravure offset process, the etching paste composition is There is provided a method of forming a pattern of a transparent conductive oxide layer comprising heat-treating the substrate printed in a fine pattern on the transparent conductive oxide layer to etch the transparent conductive oxide layer, and cleaning the substrate etched by the transparent conductive oxide layer in a fine pattern. do.

Next, a method for forming a pattern of a transparent conductive oxide layer according to an embodiment of the present invention will be described with reference to the drawings.

Figure 2 briefly illustrates a method of forming a pattern of a transparent conductive oxide layer, applying the etching paste according to the present invention in a gravure offset process.

Figure 3a is a simplified illustration of the gravure offset printing process using the etching paste of the present invention in the pattern formation method of the transparent conductive oxide layer of FIG.

First, referring to FIG. 2, the present invention prints the above-described specific etching paste on a transparent conductive oxide layer through a gravure offset printing process. Subsequently, the transparent conductive oxide layer is etched by heat treatment, and the substrate is washed with an alkali cleaning solution and DI water to remove the etching paste composition, thereby obtaining a patterned transparent conductive oxide layer.

In the method for forming a pattern of the transparent conductive oxide layer of the present invention, the gravure offset process is opposed to the gravure roll 20 and the gravure roll 20, the grooves of which a predetermined interval is patterned, as shown in Figure 3a It can proceed in the roll-to-roll apparatus provided with the blanket roll 30 which rotates in the direction opposite to the rotation direction of the gravure roll.

Referring to FIG. 3A, in the gravure offset process, a gravure roll 20 in which a blade 40 is installed is prepared by a doctoring process, and an etching paste composition 50 is provided in a groove of the gravure roll 20. And the gravure roll is rotated to transfer the etching paste composition 50 onto the surface of the blanket roll 30 which rotates in the opposite direction to the gravure roll 20. Subsequently, the substrate 10 having the transparent conductive oxide layer formed thereon is prepared, and the etching paste composition 50 which has been transferred to the blanket roll 30 while moving the blanket roll 30 over the substrate 10 is transferred to the substrate 10. The gravure offset printing process can be performed.

In a preferred embodiment, the gravure offset process is a step of filling the etching paste composition in the grooves of the gravure roll patterned grooves at regular intervals, the blanket facing the gravure roll and rotated in the direction opposite to the rotation direction of the gravure roll Providing a roll of rolls, transferring the etch paste composition to a blanket roll while rotating the gravure roll, providing a transparent substrate comprising a transparent conductive oxide layer on a table, and a blanket roll over the transparent substrate. Printing through the transparent substrate the etching paste composition transferred to the blanket roll while moving through rotation.

In addition, in the present invention, the etching paste composition 50 is moved by the rotational force of the gravure roll 20 to the blanket roll 30 away from the groove of the gravure roll.

At this time, although not shown in the drawing in the present invention, the grooves of various forms may be formed in the gravure roll according to the pattern shape of the transparent conductive oxide layer. That is, the pattern form of the transparent conductive oxide layer of the present invention may be variously changed depending on the characteristics of the device to be applied without being particularly limited in form.

For example, the groove of the gravure roll may be a groove of the mesh form. In this case, the width of the groove in the form of a mesh formed on the gravure roll is not particularly limited, but may be formed to implement a line width necessary for forming a fine pattern. In addition, in the gravure roll, the mesh groove is preferably formed in an oblique direction.

At this time, any pattern form such as a mesh form is disadvantageous when orthogonal to the rotation direction of the gravure roll. This is because the filling in gravure roll may not be performed smoothly.

In addition, the pattern shape is advantageous to form a fine pattern by obtaining a uniform pattern that coincides with the rotation direction of the gravure roll, rather than orthogonal to the rotation direction of the gravure roll. That is, when the direction of rotation of the gravure roll and the direction in which the grooves extend coincide, the etching paste composition is smoothly filled, which is advantageous for obtaining a clean pattern.

Therefore, when the groove is formed in a direction coinciding with the rotation direction of the gravure roll, a fine pattern having an opening having a uniform size may be formed in the transparent conductive oxide layer.

Meanwhile, when the gravure offset printing process is completed, the oxide layer patterning process of FIG. 3B including etching and cleaning may be performed to form a transparent conductive (ie, conductive) oxide layer having a fine pattern on the substrate. . FIG. 3b briefly illustrates an oxide layer patterning process performed through heat treatment and cleaning after the gravure printing process of FIG. 3a.

At this time, in the etching step, the etching of the printed portion may be started by heat-treating the substrate on which the etching paste composition is printed. In addition, the heat treatment is performed for 3 to 20 minutes at a temperature of 90 to 200 ℃, the temperature range can be changed according to the type and resistance of the substrate. For example, when a film having a transparent conductive oxide layer for a touch panel is formed by using a substrate having high resistance, the heat treatment may be performed at a temperature of 90 to 140 ° C. for 3 to 20 minutes. However, when the substrate is not susceptible to heat, the heat treatment temperature and time may be increased within the above range.

In addition, the etching paste composition after the etching is completed may be removed with a cleaning liquid to form a patterned oxide layer of the transparent conductive oxide film for a display. That is, the washing may include cleaning the transparent substrate on which the transparent conductive oxide layer is etched using an alkaline cleaning liquid and deionized water.

In more detail, through the heat treatment and cleaning process in the process (a)-(c) of Figure 3b, the oxide layer is patterned to obtain a transparent conductive oxide layer having a fine pattern. At this time, Figure 3b (a) shows the state of the substrate after gravure offset printing, Figure 3b (b) shows the heat treatment process of the substrate, Figure 3b (c) shows the cleaning process of the substrate after the heat treatment process It is shown.

As shown in FIG. 3B (a) through the gravure offset printing process of FIG. 3A, a substrate 10 having a transparent conductive oxide layer on which the etching paste composition 50 is printed is provided.

Thereafter, the heat treatment of FIG. 3B (b) is performed. The fine pattern printed through the heat treatment attacks the transparent conductive oxide layer 16, and etching is performed. When heat is applied to the etching paste composition 50, the attack of the transparent conductive oxide layer 16, such as an ITO layer, of the acid component contained in the etching paste by heat is activated.

Subsequently, the cleaning process of the substrate, which has undergone the heat treatment of FIG. 3B, is performed. After the etching of the transparent conductive oxide layer 16 is completed through the heat treatment, the etching paste on the transparent conductive oxide layer is removed using a cleaning solution and water to form a transparent conductive oxide layer having a fine pattern.

At this time, in the heat treatment process, the etching conditions of the transparent conductive oxide layer according to the present invention can be accelerated through the heat treatment of the etching paste composition. In addition, heat treatment conditions may vary according to the composition and the substrate of the transparent conductive oxide layer, and the method used may be variously performed. As a method to be used, various methods such as hot air drying, an IR oven, and a hot plate may be performed, and the substrate may be selected under conditions in which deformation does not occur in heat.

In particular, the etching paste composition of the present invention is capable of etching a fine pattern in spite of a low acid content.

In addition, as described above, the present invention can adjust the heat treatment temperature range for etching in accordance with the resistance of the substrate, preferably etching is possible in the temperature range of 90 to 200 ℃. If a high resistance substrate is used, the heat treatment may be performed at a low temperature, and if a low resistance substrate is used, the heat treatment may be performed at a high temperature. For example, since the touch film (270 Ω, 150) substrate) exhibits high resistance, heat treatment is possible at 90 to 140 ° C., and the touch glass (70 Ω substrate) has low resistance, so the heat treatment may be performed at about 180 ° C. have.

In addition, in the case of the present invention, since the superabsorbent solvent is used in the etching paste composition, the micropattern is relatively easily at a temperature of 90 to 140 ° C., preferably 100 to 140 ° C., which does not significantly affect the thermal deformation of the ITO film for the touch panel. Is characterized in that etching can be achieved. In the above-described etching paste composition, after the superabsorbent solvent is absorbed into the blanket roll and the acid content is relatively increased after the transition to the blanket roll, the initial low acid content is relatively increased by being transferred over the oxide layer. Etching can be easily performed even at the temperature of.

The transparent conductive oxide layer may include any one metal oxide selected from the group consisting of ITO, FTO, ZnO-Ga 2 O 3 , ZnO-Al 2 O 3 and SnO 2 -Sb 2 O 3 , preferably It includes an ITO layer.

In addition, the present invention implements a fine pattern having a semicircular cross section through a gravure offset printing process, and it is effective in improving the visibility of the pattern by blurring the boundary of the etched pattern by selecting an appropriate heat treatment condition.

In the present invention, the substrate 10 on which the transparent conductive oxide layer is formed may further include an undercoat layer between the transparent conductive oxide layer and the substrate. Accordingly, the substrate 10 on which the transparent conductive oxide layer is formed includes a transparent substrate 12, an undercoat layer 14, and a transparent conductive oxide layer 16. The transparent substrate may generally include a glass substrate or a polymer resin well known in the art, and the thickness and kind thereof are not particularly limited. In addition, the material and thickness of the undercoat layer are not limited.

In addition, the present invention can implement a fine pattern according to the pattern width of the gravure roll, in particular in the present invention to achieve a line width of the etched oxide layer at least 30um or less by appropriately adjusting the pattern width of the gravure roll within the range of 30 ~ 50um Can be.

In addition, the present invention is applied to a variety of substrates in the construction method of gravure offset printing, it is characterized in that it is possible to achieve a uniform printed body without significantly limiting the hardness and thickness of the substrate.

In addition, according to the present invention, by increasing the diameter and width of the gravure roll it is possible to continuously work for pattern formation. For example, when a pattern is formed by applying a substrate on which a touch panel ITO layer is formed, it is confirmed that a substrate of 500 * 500 size can be applied up to four chamfers, and continuous work is possible.

As described above, according to the present invention, the achievement of the fine etching line width can be achieved primarily through gravure offset printing as mentioned above, and the transparent conductive oxide layer is attacked by the appropriate heat treatment of the printed material having the fine printing line width to spread the line width. Can be etched away, and then rinsed with alkaline cleaning solution and deionized water to achieve a transparent conductive oxide layer with a high resolution etch pattern without disconnection.

That is, the present invention can implement a fine pattern of 30 μm or less through gravure offset printing, heat treatment (etching), and cleaning process using the etching paste composition. In addition, it is possible to improve visibility by blurring the boundary of the fine pattern by controlling the drying process during heat treatment. In addition, the method of the present invention is a simple process, heat treatment is possible at a temperature of 90 ~ 200 ℃ degree, it is applicable to the case that the substrate is vulnerable to heat, there is an effect that can be continuous work in large areas.

The present invention has the effect of providing an etch paste composition that is suitable for fine patterning a transparent conductive oxide layer by applying a gravure offset method and is printable. In addition, in the present invention using the etching paste composition and to form a micropattern of 30um or less through a gravure offset process, it is possible to form a micropattern through a relatively simple process even with a low acid content. In particular, the present invention is able to obscure the pattern boundary through gravure offset printing and process control (drying condition control) is effective in improving visibility. In addition, the present invention can improve the etching properties compared to the conventional by increasing the phosphoric acid content by the super absorbent solvent contained in the etching paste composition when printing.

FIG. 1 briefly illustrates a process of forming a transparent conductive oxide layer to which an etching paste using a conventional photolithography method is applied.
Figure 2 briefly illustrates a method of forming a pattern of a transparent conductive oxide layer, applying the etching paste according to the present invention in a gravure offset process.
Figure 3a is a simplified illustration of the gravure offset printing process using the etching paste of the present invention in the pattern formation method of the transparent conductive oxide layer of FIG.
FIG. 3b briefly illustrates an oxide layer patterning process performed through heat treatment and cleaning after the gravure printing process of FIG. 3a.
4 is an electron micrograph showing a surface state of a substrate on which a pattern of a transparent conductive oxide layer for a touch panel according to Example 1 of the present invention is formed.
5 is an enlarged view of the transparent conductive oxide layer pattern of FIG. 4.
6A is an electron micrograph showing an etching state of a mesh pattern formed using the etching paste of Example 1. FIG.
6B is an electron micrograph showing the etching state of an isolated line formed using the etching paste of Example 1. FIG.
7 shows a printing state of the etching paste coated on the transparent conductive oxide layer according to Comparative Example 1.
8 shows a printing state of the etching paste coated on the transparent conductive oxide layer according to Comparative Example 2.
9 shows a comparison of printing states of an etching paste coated on a transparent conductive oxide layer according to Example 1 and Comparative Example 3. FIG.

Hereinafter, the present invention will be described in more detail through experimental examples. These experimental examples are only for illustrating the present invention, and the present invention is not limited thereto.

< Example  1>

First, 316.25 g of an acrylic binder having an acid value and containing -OH group was dissolved in 783.3 g of a solvent mixture (mixed in a weight ratio of 6.5: 3.5) of butyl carbitol acetate and diethylene glycol monoethyl ether acetate to form a vehicle. Thereafter, 274.8 g of 85% phosphoric acid was added to the vehicle with vigorous stirring, followed by stirring for 3hr to prepare an etching paste. Thereafter, the etching paste was subjected to gravure offset printing on the transparent conductive oxide layer, as shown in FIGS. 2, 3A, and 3B, and printed on the pattern, followed by heat treatment to form a fine pattern of the transparent conductive oxide layer. At this time, Elvacite Co., Ltd. was used as an acrylic binder having the acid value and containing -OH group. Elvacite 9400 is a copolymer of methyl methacrylate (MMA), butyl methacrylate (BMA), hydroxyethyl methacrylate (HEMA) and methacrylic acid (MA), hybrid (OH / HEMA) / 2 It may have a urethane type of part.

* Gravure Roll Pattern: Negative 40um, Isolated Line & Mesh Pattern, Width 600, Diameter 250

* Substrate: Oike PT-50 ITO film (film coated with ITO on polymer resin, film thickness: 125um ± 12), resistance 270ohm, size 500 * 500 1 chamfered printing

* Heat treatment condition: IR oven, 110 ℃, 10min

< Experimental Example  1>

For the pattern of the transparent conductive oxide layer for the touch panel of Example 1, electron micrographs were measured, and the results are shown in FIGS. 4 to 6B. That is, FIG. 4 is an electron micrograph showing a surface state of a substrate on which a pattern of a transparent conductive oxide layer for a touch panel according to Example 1 of the present invention is formed. 5 is an enlarged photograph of the transparent conductive oxide layer pattern of FIG. 4. 6A is an electron micrograph showing the etching state of the mesh pattern formed using the etching paste of Example 1. FIG. 6B is an electron micrograph showing the etching state of an isolated line formed using the etching paste of Example 1. FIG.

As shown in FIG. 4, the present invention proceeds through a gravure offset process using an etching paste composition having a specific composition, and thus it is understood that printability is good. In addition, the pattern according to the present invention was not disconnected and the pattern was formed up to about 7 inches (18 cm).

In addition, it can be seen from the results of FIG. 5 that the boundary of the etched pattern is blurred by using appropriate heat treatment conditions and etching paste and gravure offset printing process according to the present invention, thereby improving the visibility of the pattern.

In addition, the fine pattern of the transparent conductive oxide layer of the present invention was etched in a mesh form up to a line width of 30㎛ or less, and also excellent in cleanability. That is, as shown in FIG. 6A, the left and right line widths of the fine pattern of Example 1 were 26.29 μm and 29.43 μm, respectively, and the line widths were 30 μm or less.

In addition, Figure 6b shows that when using the etching paste composition of the present invention independent long lines can be etched without disconnection. In the case of Figure 6b, the line width of the transparent conductive oxide layer has a fine line width of 26.27um, 26.89um, 24.99um.

< Example  2>

In preparing the etching paste, the above etching paste was printed on the transparent conductive oxide layer in the same manner as in Example 1 except for using DOP-4 (Ta paint Paint Co., Ltd.) as the acrylic binder to form a conductive oxide layer pattern. The DOP-4 is an acrylic copolymer composed of EA / MMA / MAA / 2-HEMA and has a weight average molecular weight of 10,300.

As a result, the fine pattern of the transparent conductive oxide layer of Example 2 was also etched to a line width of 30 μm or less, and also excellent in cleanability.

< Example  3>

The etching paste was printed on the transparent conductive oxide layer in the same manner as in Example 1 except that the size of the gravure roll pattern and the substrate was changed as follows to form a conductive oxide layer pattern.

Gravure roll pattern: width 1200, diameter 580

* Description: size 500 × 500 4 chamfer

As a result, it was confirmed that the fine pattern of the transparent conductive oxide layer of Example 3 also had a line width of 30 μm or less, and in particular, uniform etching was performed up to 100 consecutive times. Thus, by confirming that the present invention is applied to a large area, it was confirmed that there is a great effect in increasing productivity, and furthermore, it was confirmed that the conductive layer of a large display can be applied.

< Comparative example  1>

The etching paste was prepared on the transparent conductive oxide layer in the same manner as in Example 1, except that an acrylic binder (Elvacite Co., 2776, a butyl methacrylate copolymer) containing no -OH group was used to prepare the etching paste. By printing, a conductive oxide layer pattern was formed.

For Comparative Example 1, the printing state of the etching paste was measured using an optical microscope, and the results are shown in FIG. 7.

By the way, in the case of the comparative example 1, the etching paste reacts sensitively to the process in the printing process, and many pattern breaks generate | occur | produced. That is, as in FIG. 7, Comparative Example 1 had a large number of disconnection of the pattern after printing, and could not form a uniform pattern.

< Comparative example  2>

In preparing the etching paste, the etching paste was printed on the transparent conductive oxide layer in the same manner as in Example 1, except that polyvinyl alcohol (Poly (vinyl alcohol, 98-99% hydrolyzed, Aldrich) was used as the water-soluble binder. A conductive oxide layer pattern was formed.

As a result, as shown in FIG. 8, in Comparative Example 2, printing defects of the etching paste in the form of droplets occurred as in the red circle portion of the drawing, and thus, fine patterns could not be properly formed due to the etching defects. This is judged to be due to the stickiness of the etching paste of Comparative Example 2.

< Comparative example  3>

In preparing the etching paste, the etching paste was printed on the transparent conductive oxide layer in the same manner as in Example 1 except that the content of 85% phosphoric acid was increased to 40 wt% (732 g) to form a conductive oxide layer pattern. .

In this case, the content of water with a relatively large surface tension is increased so that a large number of droplets are present when printing a fine pattern, and the line width is also increased than that of Example 1 (FIG. 9).

Claims (10)

5 to 45% by weight of a non-aqueous binder selected from the group consisting of an acrylic copolymer, an acrylate copolymer and an acrylic-acrylate copolymer comprising an -OH or -COO- group,
15 to 30% by weight of a phosphoric acid compound and
Containing residual amount of solvent,
An etching paste composition for etching the oxide layer by printing on the transparent conductive oxide layer by a gravure offset printing process. The method of claim 1, wherein the water-insoluble binder is methyl acrylate; Butyl methacrylate; Hydroxyethyl methacrylate; Nonyl acrylate; Methyl methacrylate; Ethyl acrylate; Ethylhexyl acrylate; Ethyl acrylate; Acrylic acid; And an adduct of methacrylic acid, acrylic acid or methacrylic acid. The etching paste composition of claim 1, wherein the phosphoric acid compound includes phosphoric acid, a salt thereof, or an adduct thereof. The method of claim 1, wherein the solvent is gamma butyrolactone, butyl carbitol acetate, carbitol, methoxymethyl ether propionet, terpineol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, di Ethylene glycol methyl ethyl ether, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether propionate, Etch paste composition of at least one selected from the group consisting of ethyl ether propionate, propylene glycol monomethyl ether acetate, methyl ethyl ketone, ethyl lactate and ethyl glycol butyl ether. The etching paste of claim 1, wherein the etching paste composition further comprises at least one additive selected from the group consisting of 0.5 to 5 parts by weight of inorganic particles and 0.1 to 1 part by weight of surfactant based on 100 parts by weight of the total etching paste composition. Composition. Preparing a substrate on which a transparent conductive oxide layer is formed,
A step of printing the etching paste composition according to any one of claims 1 to 5 through a gravure offset process in a fine pattern on the transparent conductive oxide layer formed on the substrate,
Etching the transparent conductive oxide layer by heat-treating the substrate on which the etching paste composition is printed in a fine pattern on the transparent conductive oxide layer, and
Cleaning the substrate on which the transparent conductive oxide layer is etched in a fine pattern
Pattern forming method of a transparent conductive oxide layer comprising a. The method of claim 6, wherein the gravure offset process,
Filling the etching paste composition according to any one of claims 1 to 4 in the grooves of the gravure roll patterned grooves at regular intervals,
Providing a blanket roll facing the gravure roll and rotating in a direction opposite to the direction of rotation of the gravure roll,
Transferring the etching paste composition to a blanket roll while rotating the gravure roll,
Providing a transparent substrate on the table comprising a transparent conductive oxide layer, and
Printing the etching paste composition transferred to the blanket roll on the transparent substrate as the blanket roll moves through the rotation over the transparent substrate. The method of claim 6, wherein the washing comprises cleaning the transparent substrate on which the transparent conductive oxide layer is etched using an alkaline cleaning solution and deionized water. The transparent conductive oxide layer of claim 6, wherein the transparent conductive oxide layer comprises at least one metal oxide selected from the group consisting of ITO, FTO, ZnO-Ga 2 O 3 , ZnO-Al 2 O 3, and SnO 2 -Sb 2 O 3 . Method of forming a pattern of a conductive oxide layer. The method of forming a pattern of the transparent conductive oxide layer according to claim 6, wherein the fine pattern of the transparent conductive oxide layer has a line width of 30 μm or less.
KR1020110078704A 2011-08-08 2011-08-08 A etching paste composition for etching the transparent conductive metal oxide layer using gravure offset printing process and method of forming a pattern of transparent conductive metal oxide layer using the same KR20130016645A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019035501A1 (en) * 2017-08-18 2019-02-21 (주)프로템 Gravure offset roll for printed electronics and method for manufacturing micropatterns
KR20190109870A (en) * 2018-03-19 2019-09-27 건국대학교 산학협력단 Etching apparatus using roll-to-roll gravure printing method, and Etching method using the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019035501A1 (en) * 2017-08-18 2019-02-21 (주)프로템 Gravure offset roll for printed electronics and method for manufacturing micropatterns
KR20190109870A (en) * 2018-03-19 2019-09-27 건국대학교 산학협력단 Etching apparatus using roll-to-roll gravure printing method, and Etching method using the same

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