KR101306778B1 - Photosensitive paste composition for forming fine electrode patterns in touch panels, method of fabrication the composition and application thereof - Google Patents

Photosensitive paste composition for forming fine electrode patterns in touch panels, method of fabrication the composition and application thereof Download PDF

Info

Publication number
KR101306778B1
KR101306778B1 KR1020130035620A KR20130035620A KR101306778B1 KR 101306778 B1 KR101306778 B1 KR 101306778B1 KR 1020130035620 A KR1020130035620 A KR 1020130035620A KR 20130035620 A KR20130035620 A KR 20130035620A KR 101306778 B1 KR101306778 B1 KR 101306778B1
Authority
KR
South Korea
Prior art keywords
binder
paste composition
paste
conductive
weight
Prior art date
Application number
KR1020130035620A
Other languages
Korean (ko)
Inventor
남수용
정현욱
고명종
Original Assignee
남수용
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 남수용 filed Critical 남수용
Priority to KR1020130035620A priority Critical patent/KR101306778B1/en
Application granted granted Critical
Publication of KR101306778B1 publication Critical patent/KR101306778B1/en

Links

Images

Classifications

    • 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
    • G03F7/004—Photosensitive materials
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • 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
    • G03F7/202—Masking pattern being obtained by thermal means, e.g. laser ablation
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Theoretical Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Human Computer Interaction (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Conductive Materials (AREA)
  • Materials For Photolithography (AREA)

Abstract

PURPOSE: A paste composition is provided to prevent errors occurred during a driving process of a touch panel by residual components after hardening. CONSTITUTION: A paste composition comprises: 60-85 parts by weight of conductive powder; a first acrylate monomer selected from a group consisting of a compound denoted by chemical formula I, a compound denoted by chemical formula II, and their mixture; a second acrylate monomer with more than two functional groups without carboxylic acid (-COOH); an acylate oligomer with the number average molecular weight of 1,000-5,000, selected from a group consisting of a compound denoted by chemical formula III, a compound denoted by chemical formula IV, and their mixture; and 15-40 parts by weight of binder composition containing a binder dilution agent.

Description

PHOTOSENSITIVE PASTE COMPOSITION FOR FORMING FINE ELECTRODE PATTERNS IN TOUCH PANELS, METHOD OF FABRICATION THE COMPOSITION AND APPLICATION THEREOF}

The present invention relates to a photosensitive paste composition and a method for producing the same, and more particularly, to a photosensitive paste composition capable of realizing a fine electrode pattern on a touch panel, a method and application of the composition.

With the rapid development of electronic technology, interest in printing electronic devices related to display devices such as solar cells, as well as flat panel display panels represented by liquid crystal display (LCD) and organic light emitting transistor (OLED) It's growing. Recently, due to the demand for large screen, light weight, and slimness of electronic devices, electrodes constituting the electronic devices have to be formed, or fine patterns have to be formed in the packaging or assembly process of these electronic devices. Accordingly, research and development of conductive pastes for dispersing conductive materials such as metal particles in a resin composition have been actively conducted.

Touch screen panels, also known as touch panels, have been used in large industrial products such as ATMs and kiosks of banks, but recently, portable electronic devices such as digital cameras, as well as smart phones, navigation systems, etc. Applied to equipment. A touch screen panel is a panel that allows a person's hand or pen to touch a character or a specific location on a screen without a separate input device such as a mouse or a keyboard, and processes a specific function according to the contacted location.

The touch panel is composed of a top film and a bottom film (or glass) on which a transparent conductive thin film, such as indium oxide (ITO), is deposited. Panel, ii) a controller that converts a signal transmitted from the touch panel into a digital signal and outputs the coordinates on a display;

Ultrasonic (SAW, Surface Accoustic Wave) and Infrared (IR) methods have also been developed in connection with the implementation of the touch panel of the touch screen panel, but now two substrates coated with a transparent electrode are bonded to each other. Accordingly, a resistive method in which the upper and lower electrode layers are in contact with each other and electrically generated, and a capacitive method for detecting static electricity generated in the human body are mainly used. Currently, most capacitive systems capable of multi-touch are the mainstream.

In order to operate the capacitive touch panel with a finger, the sensor electrode required for the liquid crystal display unit, and a bezel electrode connecting the sensor electrode to the FPCB and the liquid crystal panel are required. Most of the sensor electrodes are mainly used for ITO electrodes having excellent transparency, and the bezel electrodes are formed of patterns by various methods using a conductive paste such as silver paste. The most commonly used method is a method of forming a conductive pattern by screen-printing silver paste and curing at 130-150 ° C. However, this method is impossible to form a fine pattern of 60 μm or less. In addition, if the screen printing method is applied, the loss of the expensive conductive paste is considerably increased.

Accordingly, in order to solve the problems of the screen printing as described above, the development of a photosensitive silver paste hardened by using ultraviolet (UV) energy has been actively made in recent years. After applying the conductive paste composition for touch panel, which can be cured by ultraviolet rays, onto the ITO film primarily by screen printing, the solvent is evaporated to proceed with ultraviolet curing well, and then irradiated with ultraviolet rays to undergo a curing process. This is to remove uncured components. At this time, it is necessary to completely remove the uncured silver paste. However, there is a problem in that the uncured component of the paste composition is not completely removed in the developing process and remains on one surface of the touch panel.

Therefore, fine patterning of 30/30 μm or less, which is a problem of the above screen printing method, is possible, minimizing the loss of silver paste, and developing a conductive paste having excellent developability is urgently required.

The present invention has been proposed to solve the above-mentioned problems of the prior art, and an object of the present invention is to improve developability, for example, to form a photosensitive paste composition capable of fine patterning up to 30/30 μm, a manufacturing method thereof, and a photosensitive paste. It is to provide a method for forming a fine pattern using a film for a touch panel to which the composition is applied, a touch panel on which the film is laminated, and a conductive paste composition.

Another object of the present invention is a photosensitive paste composition which can be printed or applied to a subject by, for example, screen printing, etc., which can be cured at a low temperature, a manufacturing method thereof, a film for a touch panel to which a conductive paste composition is applied, and An object of the present invention is to provide a method of forming a fine pattern using a touch panel and a conductive paste composition in which films are stacked.

Another object of the present invention is to provide a photosensitive paste composition capable of realizing a fine pattern, a method of manufacturing the same, and a method of forming a fine pattern using the conductive paste composition.

According to an aspect of the present invention having the above object, 60 to 85 parts by weight of the conductive powder; And a first acrylate monomer selected from the group consisting of a compound of formula (I), a compound of formula (II), and a combination thereof; A second acrylate monomer having two or more functional groups having no carboxylic acid (-COOH); A binder having a number average molecular weight of 1000 to 5000 and an acrylate oligomer selected from the group consisting of a compound represented by the following formula (III), a compound represented by the following formula (IV), and a combination thereof; And it provides a paste composition comprising 15 to 40 parts by weight of the binder composition containing a binder dilution solvent.

Figure 112013028528632-pat00001

Figure 112013028528632-pat00002

(In the formula (I) and formula (II), R is

Figure 112013028528632-pat00003
,
Figure 112013028528632-pat00004
,
Figure 112013028528632-pat00005
,
Figure 112013028528632-pat00006
And
Figure 112013028528632-pat00007
Selected from the group consisting of

For example, the binder may be an acrylate oligomer selected from the group consisting of a compound of formula (III), a compound of formula (IV), and a combination thereof, or an acrylate oligomer represented by formula (V) Can be.

Figure 112013064085977-pat00065

Figure 112013064085977-pat00066

Figure 112013028528632-pat00010

(In the formulas (III) and (IV), X is hydrogen or

Figure 112013064085977-pat00067
Wherein R is the same as defined in Formulas (I) and (II), and the number of substituents X other than hydrogen in the acrylate oligomer is 2 to 3; n is an integer of 3 to 10; In Formula (V), k is an integer of 40 to 50, respectively, and R is the same as defined in Formulas (I) and (II).)

According to an exemplary embodiment, the second acrylate monomer is ethylene glycol diacrylate (EGDA), neopentyl glycol hydroxy pivalate diacrylate (neopentylglycol hydroxypivalate diacrylate), neopentyl glycol hydroxy pival Neopentylglycol Hydroxypivalate diacrylate modified caprolactone, Bisphenol A diacrylate, Hexanedioldiacrylate (HDDA), Tetraethyleneglycol diacrylate (TTEGDA) ), Trimethylolpropane triacrylate (TMPTA), ethoxylated trimethylolpropane triacrylate (TMP (EO) TA), pentaerythritol tryacrylate (PETA), di Pentaerythritol triacrylate Dipentaerythritol triacrylate (DPETA), Ditrimethylolpropane tetraacrylate (DTMPTA), Dipentaerythritol hexaacrylate (DPHA), Ethoxylated Dipentaerythritol hexaacrylate (Dipentaerythritol hexaacrylate) , (EO) DPHA), dipentaerythritol hexaacrylate-modified caprolactone, and combinations thereof.

On the other hand, the conductive powder is silver (Ag), gold (Au), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), platinum (Pt), tin (Sn), zirconium oxide, oxide It may be a metal powder selected from the group consisting of tin, antimony oxide, nickel oxide, aluminum oxide, indium tin oxide (ITO), and combinations thereof.

According to an exemplary embodiment, the conductive powder is characterized in that the silver powder having a different average particle diameter mixed.

For example, the binder composition may include 5 to 20 parts by weight of solids containing the binder, the first acrylate monomer, and the second acrylate monomer, and 5 to 20 parts by weight of the binder dilution solvent. Preferably, the paste composition may further include 1 to 10 parts by weight of a polymerization initiator.

Moreover, this invention provides the electroconductive film for touch panels coat | covered using the paste composition mentioned above.

In addition, the present invention provides a touch panel including a conductive thin film in which the conductive film for the above touch panel is laminated.

Further, according to another aspect of the invention, the first acrylate monomer selected from the group consisting of the compound of formula (I), the compound of formula (II) and combinations thereof; A second acrylate monomer having two or more functional groups having no carboxylic acid (-COOH); A binder having a number average molecular weight of 1000 to 5000 and an acrylate oligomer selected from the group consisting of a compound of the formula (III), a compound of the formula (IV), and a combination thereof; And a binder composition comprising a binder dilution solvent; Mixing a conductive powder with the binder composition to obtain a primary paste; And mixing a paste dilution solvent in which a polymerization initiator is dissolved with the primary paste to obtain a secondary paste.

For example, the binder is represented by an acrylate oligomer selected from the group consisting of the compound of formula (III), the compound of formula (IV), and combinations thereof, and / or of formula (V). It may be an acrylate polymer.

In addition, according to another aspect of the invention the step of screen printing the above-mentioned conductive paste composition on the printed material to form a photoresist layer; An electrothermal (preliminary) treatment step of evaporating the solvent contained in the photoresist layer, if necessary; Performing an exposure process on the photoresist layer so that a photopolymerizable material can be formed on the photoresist layer via an exposure mask; Developing a uncured photoresist layer by supplying a developer to the photoresist layer on which the photopolymer is formed; And if necessary, rinsing the developed photoresist layer; It provides a photosensitive pattern forming method comprising the step of heat-treating the washed photoresist layer.

For example, the light irradiated in the exposing step may be ultraviolet (UV) wavelength light having a wavelength of 200 to 400 nm, and the developing solution used in the developing step is sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate Inorganic alkali selected from the group consisting of (Na 2 CO 3 ), sodium sulfite (Na 2 SO 3 ), sodium silicate, sodium metsilicate, ammonia, and combinations thereof.

In the present invention, not only can realize a fine pattern of 30 ㎛ or less, which was impossible with screen printing, but also improved developability. For example, conductive paste can be applied to a printed object such as a touch panel by screen printing. The paste composition which can be hardened by an ultraviolet-ray, and its manufacturing method are proposed.

In the conductive paste composition according to the present invention, the developability is greatly improved, for example, residual components which are not cured in the developing process after curing on the surface of the touch panel or the electronic product can be completely removed. Accordingly, the problem of defects caused during the driving of the touch panel due to the components remaining after curing can be solved.

In addition, since the conductive paste composition of the present invention can be cured by, for example, ultraviolet rays, it solves the problem of deterioration of electronic devices due to heat as compared with the heat-curing method, shortens the production process time, and improves productivity, and prints. The physical properties of the film were good and the formation of a fine electrode pattern of 30 μm or less was made possible.

In addition, since the conductive paste composition of the present invention can utilize screen printing, an electrode pattern excellent in conductive thin film printing aptitude, adhesion and electrical conductivity of a touch panel can be obtained, and in particular, fine patterns of 30 μm or less can be reproduced.

1 is a flow chart schematically showing the manufacturing process of the conductive paste composition according to the present invention.
2 is a flow chart schematically showing a process of forming a photosensitive pattern on a printed object using the conductive paste composition according to the present invention.
3A and 3B are graphs showing the results of measuring the viscosity according to the shear rate among the rheological properties of the pastes prepared in Examples 1-4 and Comparative Example 1, respectively, and the storage modulus according to the shear stress (G ′). And a graph showing the results of measuring the loss modulus (G ″).
4A and 4B are graphs showing the results of measuring the viscosity according to the shear rate among the rheological properties of the pastes prepared in Examples 5-9 and Comparative Example 2, respectively, and G ′ and G ″ according to the shear stress. It is a graph showing the result of the measurement.
Figure 5 is a photograph of the sharpness of the pattern to determine the pattern reproducibility of the film obtained by printing and curing the paste prepared in Examples 1-4 and Comparative Example 1 of the present invention, respectively. In the drawings, (a) to (e) refer to films formed from pastes prepared in Examples 1-4 and Comparative Example 1, respectively.
Figure 6 is a photograph of the sharpness of the pattern to determine the pattern reproducibility of the film obtained by printing and curing the paste prepared in Example 5-9 and Comparative Example 2 of the present invention. In the drawings, (a) to (j) refer to films formed from pastes prepared in Examples 5-13 and Comparative Example 2, respectively.
Figure 7 is a photograph measuring the adhesion test results on the ITO surface in order to determine the reproducibility of the film obtained by printing and curing the paste prepared in Examples 1-4 and Comparative Example 1 of the present invention. In the drawings, (a) to (e) refer to films formed from pastes prepared in Examples 1-4 and Comparative Example 1, respectively.
8 is a photograph measuring the adhesion test results on the ITO surface in order to determine the reproducibility of the film obtained by printing and curing the paste prepared in Examples 5-9 and Comparative Example 2 of the present invention. In the drawings, (a) to (j) refer to films formed from pastes prepared in Examples 5-13 and Comparative Example 2, respectively.
9 is a photograph of measuring the pencil hardness of the film obtained by printing and curing the paste prepared in Example 1-4 and Comparative Example 1 of the present invention. In the drawings, (a) to (e) refer to films formed from pastes prepared in Examples 1-4 and Comparative Example 1, respectively.
10 is a photograph of measuring the pencil hardness of the film obtained by printing and curing the paste prepared in Example 5-9 and Comparative Example 2 of the present invention. In the drawings, (a) to (j) refer to films formed from pastes prepared in Examples 5-13 and Comparative Example 2, respectively.

The present invention can be manufactured in a conductive pattern to be able to operate as a sensor, for example, when the touch screen is touched by a human hand, and can improve the developability of the photosensitive paste to form a fine pattern of 30 μm or less A paste composition, its manufacturing method, and application are related. EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail, referring an accompanying drawing as needed.

A. Paste Composition

The paste composition according to the present invention is a photosensitive paste composition having conductivity capable of forming a conductive pattern on a film in an electronic display panel such as a touch panel. For example, the paste composition of the present invention to enable screen printing includes a conductive powder, an ultraviolet curable binder (oligomer, monomer) composition, and an ultraviolet polymerization initiator, and may include a functional additive as necessary.

1. Conductive Powder

The conductive powder may be an inorganic conductive powder that can be used in the display device. The conductive powder in the conductive paste composition according to the present invention may use an inorganic conductive powder that can be used in the display device. The inorganic conductive powder is to impart conductivity to the electrode paste of a display element such as a touch panel, and for example, one or more metal powders may be used. Metal powders that can be used as conductive powders are silver (Ag), gold (Au), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), platinum (Pt), tin (Sn), oxide Zirconium, tin oxide, antimony oxide, nickel oxide, aluminum oxide, indium tin oxide (ITO), and combinations thereof.

When metal powder is used as the conductive powder, silver powder having an appropriate particle size distribution, morphology and average particle diameter may be used alone, or other metal powder, preferably zirconium oxide, tin oxide, antimony oxide, nickel oxide, or oxide, may be used for the silver powder. Metal powders selected from oxidized metal particles such as aluminum and indium tin oxide (ITO) may be mixed and used.

When the silver powder and the (oxidized) metal powder are mixed and used as the conductive powder, the silver powder and the other metal powder may be mixed in a weight ratio of 100: 1 to 20, preferably in a weight ratio of 100: 1 to 10. . If the content of the dissimilar metal powder mixed with silver powder is less than this, the conductivity improvement effect is insignificant, and if it is more than this, the resistivity of the film may be too high, and the content of the silver powder is reduced so that the desired effect may not be achieved.

As the conductive powder, in addition to the above-described metal powder, any other inorganic powder having conductivity can be used. Examples of such non-metallic inorganic powders may include ceramic particles such as graphite, carbon black, carbon nanotubes / carbon nanofibers / carbon nanowires, and graphene, which are conductive carbonaceous materials.

When using a metal powder containing silver powder as the conductive powder, the size and shape of the particles may affect the properties or patterns, such as the conductivity of the final paste composition to be produced, so that the size and shape suitable for the purpose of the present invention It is preferable to select the conductive powder having.

For example, the particle size of the conductive powder including silver powder may be used, for example, 0.1 ~ 5.0 ㎛. As the conductive powder, the larger the particle size of the silver powder, the lower the interfacial resistance of the particles and the larger the contact area between the particles, which is advantageous in conductivity, but in the case of the purpose of realizing a fine pattern, the larger the particles of the silver powder, the lower the printability. . On the other hand, when the particles of the silver powder is small as the conductive powder, the volume occupied by the silver powder in the entire coating is reduced, resulting in poor patterning or poor packing, which may lower conductivity.

In this case, preferably, when two or more conductive powders having different particle sizes are used, voids between the conductive powders may be reduced to increase packing density, thereby improving conductivity. Examples of two or more conductive powders having different particle sizes may include a first conductive powder having a particle size (D50) of 0.1 to 1.0 μm and a second conductive powder having a particle size (D50) of 1.5 to 5.0 μm. By way of example, the first conductive powder and the second conductive powder may be, for example, 1: 4 to 4: 1, preferably 1: 3 to 3: 1.

On the other hand, the conductive powder may be a conductive powder having any shape, such as Flake, Spherical, Agglomerate, but relatively uniform particle diameter for producing a fine pattern and good UV curing It is possible to use spherical conductive powder having a. Since spherical particles make point contact, while plate-shaped particles make surface contact, they are advantageous in forming conductive paths, thereby improving conductivity. For example, due to lack of curing due to UV blocking during pattern formation through a photosensitive process, Relatively non-uniform plate-shaped particles may cause loss of pattern in the washing process.

If desired, the particle surface of the conductive powder of the present invention may be coated with any one selected from higher fatty acids, higher fatty acid amines or derivatives thereof. As the higher fatty acid, one or more selected from linear or branched C 6 -C 22 saturated or unsaturated fatty acids can be used. For example, it may be selected from hexanoic acid, octanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, oleic acid, stearic acid, palelic acid, linolenic acid, etc. As the higher fatty acid derivative, esters such as methyl, ethyl, butyl, hexyl, etc. It may be selected from the group, but is not limited thereto. As the higher fatty acid amine, one or more selected from linear or branched C 6 -C 22 aliphatic amines can be used. For example hexyl amine, octyl amine, decyl amine, dodecyl amine, tetradecyl amine, oleyl amine, linoleyl amine and the like. As the higher fatty acid amine derivative, among amides such as mono-methyl, mono-ethyl, mono-butyl, mono-hexyl, di-methyl, di-ethyl, di-butyl, methyl-ethyl, methyl-butyl and ethyl-butyl It may be selected, but is not limited thereto. When using nano metal particles coated on the surface of the conductive powder with any one selected from higher fatty acids, higher fatty acid amines, or derivatives thereof, there is an advantage in that miscibility with a binder and a solvent is improved and dispersibility in a paste is improved.

The conductive powder may be included in the paste composition according to the present invention in an exemplary range of 60 to 85 parts by weight, preferably 70 to 80 parts by weight. If the content of the conductive powder is less than this, it is difficult to achieve the conductivity required in the touch panel, and the nonuniformity of luminance may be caused between the pixel and the sensor due to the nonuniformity of the positional conductivity. When the content of the conductive powder exceeds the above-mentioned range, dispersibility may be degraded or ultraviolet curing may not be sufficiently performed, and thus developability may be decreased during the pattern formation process. Illustratively, Table 1 below illustrates the silver powder usable as an example of the conductive powder according to the present invention. For convenience of description, each silver powder is divided into 'SP001' to 'SP006'.

Properties of Silver Powder division shape Particle Size (D50)
(탆) Particle size
Dispersion (μm) Specific surface area
(M < 2 > / g) Apparent density
(g / cc) SP001 Cohesive 1.98 0.17-7.0 3.29 4.5 to 4.7 SP002 rectangle 0.67 0.4 to 1.49 1.0 3.0 to 3.2 SP003 rectangle 0.94 0.6 to 1.8 ≤1.5 3.1 to 3.3 SP004 rectangle 1.07 0.7 to 1.9 ≤0.8 3.4 to 3.6 SP005 Plate type 1.86 1.0 to 4.0 3.69 2.6 to 4.0 SP006 rectangle 0.274 0.1 to 3.0 3.2 to 3.5

2. Binder Composition

For example, a binder composition comprising a binder that can be cured at room temperature by ultraviolet (UV) is used to impart the properties of the printed coating film and the fluidity of the paste. The binder constituting the paste composition according to the present invention may be cured by ultraviolet rays, and in the case of uncuring, to improve developability and curability with a binder in oligomer and / or polymer form which may be developed (dissolved) by an aqueous alkali solution. And a diluent solvent for imparting fluidity, screen printing aptitude, and other functions of the paste.

end. Monomer

The monomer used when preparing the conductive paste composition according to the present invention should have excellent curing properties against ultraviolet rays and compatibility with a binder described later. Particularly, in order to improve developability, some acrylate groups (functional groups) are carboxylic acids. It is preferable to use a polyfunctional (two or more functional groups) monomer (first acrylate monomer) substituted with (-COOH).

For example, a first acrylate monomer selected from the group consisting of a compound of formula (I), a compound of formula (II), and a combination thereof may be used.

Figure 112013028528632-pat00012

Figure 112013028528632-pat00013

(In the formula (I) and formula (II), R is

Figure 112013028528632-pat00014
(R1),
Figure 112013028528632-pat00015
(R2),
Figure 112013028528632-pat00016
(R3),
Figure 112013028528632-pat00017
(R4) and
Figure 112013028528632-pat00018
Selected from the group consisting of (R5))

In the present specification, for the convenience of description, the monomer of the formula (I) and the monomer of the formula (II) are abbreviated as 'monomer A' (or A) and 'monomer B' (or B), respectively. In addition, about the monomer substituted by R1-R5, it abbreviates as "monomer A1 (or A1)" to "monomer A5 (or A5)" or "monomer B1" to "monomer B5". For example, when the substituent R in the monomer of the formula (I) is R1, it is 'monomer A1', and when the substituent R in the monomer of the formula (II) is R2, it is abbreviated as 'monomer B2 (or B2)'. Monomer A, monomer B, and combinations thereof, and monomers for improving developability, for example, in an amount of 1 to 10 parts by weight, preferably 1 to 5 parts by weight, are advantageous in printability or other physical properties. .

If necessary, in addition to the monomer consisting of the above-described monomers A, B and combinations thereof, an acrylate-based second monomer capable of improving curability may be selectively used. 2-Hydroxypropyl acrylate (HPA), 4-Hydroxybutyl acrylate (4-HBA), octyl decyl acrylate (ODA), isobornyl acrylate Although a monofunctional acrylate-based second monomer such as (Isobonyl acrylate, IBOA) can be used, it is preferable to use the second acrylate monomer having a plurality of functional groups, for example three or more functional groups, Can be improved.

For example, the polyfunctional acrylate compound that can be used as the second monomer is ethylene glycol diacrylate (Ethyleneglycol diacrylate, EGDA), neopentyl glycol hydroxy pivalate diacrylate (neopentylglycol Hydroxypivalate diacrylate), neopentyl glycol Neopentylglycol Hydroxypivalate diacrylate modified caprolactone, Bisphenol A diacrylate, Hexanedioldiacrylate (HDDA), tetraethyleneglycol diacrylate (Tetraethyleneglycol) diacrylate, TTEGDA), trimethylolpropane triacrylate (TMPTA), for example, ethoxylated trimethylolpropane triacrylate (TMP (EO) 1- modified with 1-20 ethylene oxide groups 20 TA), pentaerythritol tria Pentaerythritol tryacrylate (PETA), Dipentaerythritol triacrylate (DPETA), Ditrimethylolpropane tetraacrylate (DTMPTA), Dipentaerythritol hexaacrylate (DPHA) Ethoxylated (Dipentaerythritol hexaacrylate, (EO) 1-20 DPHA), dipentaerythritol hexaacrylate-modified caprolactone, for example modified 1-20 ethylene oxide groups (Dipentaerythritol hexaacrylate modified caprolactone) and combinations thereof. Preferably, the second monomer, which may be a multifunctional acrylate monomer, may be included in the conductive paste composition of the present invention in an amount of 1 to 10 parts by weight, preferably 1 to 5 parts by weight. In this case, hardening and developability of a binder composition can be improved simultaneously.

I. bookbinder

The binder may affect the properties of the prepared paste and the properties of the coating film. The acrylate binder is easy to adjust the viscosity, and has excellent coating hardness, conductivity, adhesiveness, solvent resistance, and printability. In addition, the light-receiving part should have sensitivity to be cured even with a small amount of ultraviolet light, and developability should be easy so that the non-hardened part that is not lighted can be washed out well. For this purpose, it is preferable to use the oligomer of the form which substituted some of the functional groups of an oligomer with the carboxylic acid group (-COOH) easy to develop.

As the resin forming the oligomer binder constituting the conductive paste composition according to the present invention, it is preferable to use an ultraviolet curable acrylic acrylate oligomer having a glass transition temperature of 10 to 50 ° C. When the paste according to the present invention is applied to a touch panel, it is preferable to form a pattern through the post-exposure post-exposure process using screen printing. In general, an indium-tin-oxide (ITO) film ( Or an etching surface of an ITO film). Of course, the printed material to which the conductive paste according to the present invention is applied is not limited to the ITO film, but considering the printability of the printed material and the physical properties of the coating film, the use of the oligomers in the above-described range may cause the UV to have good printability. It is suitable as a binder having the property of being cured by.

For example, as the binder of the present invention, an acrylate oligomer having a number average molecular weight of 1000 to 5000 and 2 to 3 acrylate functional groups, and a number average molecular weight of 15000 to 25000 and 50 to 100 acrylate functional groups It may be selected from the group consisting of acrylate oligomers and combinations thereof. When the molecular weight of the oligomer as a resin solid content satisfy | fills the range mentioned above, the electrically conductive paste composition which has an appropriate viscosity and hardness can be obtained. Preferably it is an acrylate oligomer which has a number average molecular weight of 1000-5000, and has 2-3 acrylate-type functional groups.

For example, the acrylate oligomer having a number average molecular weight of 1000 to 5000 and having 2 to 3 acrylate functional groups comprises a compound of formula (III), a compound of formula (IV), and a combination thereof Can be selected from the group.

Figure 112013064085977-pat00068

Figure 112013064085977-pat00069

(In the formulas (III) and (IV), X is hydrogen or

Figure 112013064085977-pat00070
Is a substituent, wherein R is as defined in formulas (I) and (II) above
Figure 112013064085977-pat00071
(R1),
Figure 112013064085977-pat00072
(R2),
Figure 112013064085977-pat00073
(R3),
Figure 112013064085977-pat00074
(R4) and
Figure 112013064085977-pat00075
Selected from the group consisting of (R5) the same, the number of substituents X which are not hydrogen in the acrylate oligomer is 2 to 3; n is the number of unit units, an integer of 3 to 10, preferably an integer of 3 to 5)

As an example of the acrylate oligomer which has a number average molecular weight of 15000-25000, and has 50-100 acrylate functional groups, the acrylate oligomer represented by following General formula (V) is mentioned.

Figure 112013028528632-pat00027

(In Formula (V), k is an integer of 40 to 50, respectively, R is as defined in Formulas (I) and (II),

Figure 112013028528632-pat00028
(R1),
Figure 112013028528632-pat00029
(R2),
Figure 112013028528632-pat00030
(R3),
Figure 112013028528632-pat00031
(R4) and
Figure 112013028528632-pat00032
Selected from the group consisting of (R5))

In the present specification, for the convenience of description, for oligomers of formula (III), oligomers of formula (IV) and oligomers of formula (V), respectively, 'oligomer C' (or C), 'oligomer D' (or D), Abbreviated as oligomer E (or E). In addition, for oligomers each substituted with R1 to R5, 'Oligomer C1 (or C1)' to 'Oligomer C5 (or C5)'; 'Oligomer D1 (or D1)' to 'oligomer D5 (or D5)'; It is abbreviated as "oligomer E1 (or E1)" to "oligomer E5 (E5)." For example, when the substituent R in the oligomer of formula (III) is R1, it is 'oligomer C1', and when the substituent R in the oligomer of formula (IV) is R2, it is 'oligomer D2 (or D2)', When substituent R in the oligomer of V) is R3, it is abbreviated as "oligomer E3 (or E3)." In addition, any one oligomer may have substituent R substituted with two or more different functional groups. That is, in the unit unit constituting the oligomer, one unit unit may be substituted with other substituents R2 to R5 other than R1. For example, when one substituent in the substituent (R1) of the oligomer of formula (III) is R1 and the other substituent is R2, it is 'oligomer C1-2 (C1-2)' and in the oligomer of formula (IV) When one substituent is R1 and the other substituent is R3, 'oligomer D1-3 (or D1-3)', one of substituents (R) of the oligomer of formula (V) is R1, the other substituent is R2 The remaining substituents are abbreviated as 'oligomer E1-2-5 (or E1-2-5)' when R5. It may be advantageous in printability or other physical properties that the oligomer as a binder is contained in the paste composition in a ratio of 1 to 20 parts by weight, preferably 1 to 15 parts by weight, more preferably 5 to 10 parts by weight.

After all, in the solids constituting the binder composition of the present invention, an acrylate-based monomer having a relatively large amount of carboxylic acid per unit unit and an oligomeric binder having a relatively small amount of carboxylic acid are appropriately blended to improve the curability and developability of the paste. Patterns can be formed.

That is, the oligomeric binder used in the photosensitive paste by way of example according to the present invention is a material that serves to give adhesion to the substrate after printing. In the curing process, the monomer containing carboxylic acid crosslinks with the oligomeric binder, wherein a part of the reactor (functional group) in which the crosslinking reaction occurs is replaced with carboxylic acid (-COOH). Accordingly, in the developing process, the non-hardened portion reacts with a base (for example, KOH) contained in the developing solution to form a salt. The salt is easily dissolved in water, and thus can be easily removed in the developing step, thereby improving developability. .

All. (Binder) Diluent Solvent

It is preferable to use an inert or non-aqueous solvent for the dilution solvent which comprises a binder composition. At this time, it is preferable to use a dilution solvent as a liquid component of the binder so that the resin solid content can be cured within 20 seconds in an ultraviolet atmosphere, the boiling point is in the range of 80 ~ 240 ℃. Specifically, terpineol (terpineol), N-methylpyrrolidone (N-methylpyrrolidone, boiling point 202 ℃), butyl cellosolve (boiling point 171.2 ℃), ethylene glycol monobutyl ether acetate (Ethylene glycol monobutyl ether acetate, boiling point 192 ° C), ethyl carbitol (boiling point 201.9 ° C), ethyl carbitol acetate (Ethyl cabitol acetate, boiling point 217.4 ° C), butyl carbitol (boiling point 230.6 ° C), ethoxyethyl acetate ( Ethoxyethyl acetate, boiling point 156.3 ℃), ethyl cellosolve (2-ethoxyethanol, boiling point 135 ℃), ethyl cellosolve acetate (ECCA, Ethylene glycol monoethyl ether Acetate, boiling point 156 ℃), butyl Acetate (Butyl acetate, boiling point 126 ° C), Propylene glycol monomethyl ether (boiling point 121 ° C), propylene glycol monomethyl ether acetate (boiling point 146 ° C), gamma-buty Lactone may be selected from at least one selected from the group comprising a (γ-butyrolactone, boiling point 204 ℃), such as methyl ethyl ketone (methyl ethyl ketone (MEK), boiling point 80 ℃). Considering the adhesion and printability of the print film to the printed material, preferably in gamma-butyrolactone, methyl ethyl ketone (MEK), 2-ethoxyethanol (2EE) and ethyl cellosolve acetate (ECA) It is more preferred to use at least one material selected alone or in combination of two or more.

In the context of the present invention, the diluent solvent may be used, for example, in a ratio of 10 to 50 parts by weight based on the oligomeric binder described above. By way of example, the diluting solvent is 5 to 20 parts by weight, preferably 5 to 15 parts by weight, in the paste composition of the present invention. On the other hand, the solid containing the above-described monomer and oligomer binder may be 5 to 20 parts by weight, preferably 5 to 10 parts by weight in the paste composition of the present invention. In addition, the binder composition including the solid content and the diluting solvent may be contained in an amount of 15 to 40 parts by weight, preferably 15 to 25 parts by weight, in the paste composition of the present invention. It is advantageous in terms of printing suitability or other physical properties when the content of the binder composition or the solid content and the diluting solvent constituting the same satisfy the above-mentioned range. In particular, when the content of the solid content is less than this, the viscosity of the conductive paste is low, and when the content of the solid content is more than this, the adhesion is too high, the workability may be reduced in the case of screen printing for forming a film for a touch panel.

3. Polymerization initiator

For example, a polymerization initiator is used when the conductive paste composition of the present invention is utilized as a photosensitive paste. The polymerization initiator is a substance that absorbs ultraviolet energy to form radicals, and then combines the radicals with the above-described acrylate oligomer and monomer to start the reaction in series.

As the polymerization initiator in the face composition according to the present invention, any photopolymerization initiator capable of forming radicals by ultraviolet irradiation can be used. For example, an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound containing monophenyl, an oxime compound, etc. can be used as a photoinitiator.

Non-limiting examples of polymerization initiators that may be included in the conductive paste composition according to the present invention include benzophenone; Benzoinbutylether (Esacure EB3), chloroacetophenon such as trichloroacetophenone, diethoxyacetophenone (DEAP), 1-phenyl-2-hydroxy-2-methyl propane-1 On (1-phenyl-2-hydroxy-2-methyl propane-1-one), 1-hydroxycyclohexyl-phenylketone (1-Hydroxycyclohexyl-phenylketone, Irgacure-184, I-184), 2-hydride Hydroxyacetophenon such as 2-Hydroxy-2-methyl-1-phenyl-propane-1-one, Darocure 173; 2-benzyl-2- (dimethylamino) -4'-morpholinobutyrophenone, Irgacure 369, I-369); 2-benzyl-2- (dimethylamino) -4'-morpholinobutyrophenone; Alpha-aminoacetophenones (α-Amino Acetophenone, Irgacure-907, I-907); 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone (4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, Irgacure 2959, I-2959 ), 2,2-dimethoxy-1,2-di (phenyl) ethanone (2,2-dimethoxy-1,2-di (phenyl) ethanon, Irgacure 641, I-651), bis (h5-2, 4, -cyclopentadien-1-yl) bis [2,6-difluoro-3- (1H-pyrrol-1-yl) phenyltitanium (bis (h5-2,4-cyclopentadien-1-yl) bis [2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl] -titanium, Irgacure-784, I-784), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Bis (2,4,6-trimethylbenzoyl) -phenylphosphineoxide, Irgacure-819 (I-819)), 2-methyl-1- [4-methylthio] phenyl-2-morpholinopropan-1-one (2-methyl -1 [4-methylthio] phenyl-2-morphorinopropane-1-on), 2,3,6-trimethylbenzoyl phenyl ethoxyphosphine oxide (2,3,6-Trimethylbenzoyl phenyl ethoxyphosphine oxide (TPO)), 2, 4-diethylthioxanthone (DETX), isopropyl thioxthanthone (ITX), oligo [2-hydroxy 2-methyl-1- [4- (1-methylvinyl) phenyl] propanone] (Oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone, Esacure KIP150), 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione (2- (O-Benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2 -octanedione, Irgacure OXE 01, OXE 01), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) ethanone (1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) ethanone, Irgacure OXE 02, OXE 02) and combinations thereof.

Among these polymerization initiators, a photocuring initiator of an appropriate active wavelength region may be selected in consideration of the wavelength region of the light source used in the UV curing process described below. For example, the wavelength region of the UV lamp light source used for curing may be 200 to 500. In the case of nm, Irgacure-369, 819, 907, which has excellent light absorption capability in the vicinity, has a long wavelength absorption region in consideration of the difficulty of internal purification due to the high proportion of conductive powder in the pattern printed with the ultraviolet curable paste. The monomolecular forms of OXE 01 and OXE 02 can be used for solvents having excellent solubility (eg gamma butyl lactone or ECA). Alternatively, ITX or TPO TPO (2,3,6-trimethylbenzoyl diphenylphosphine oxide) may be used as a sensitizer capable of promoting a curing reaction by photoreaction.

The polymerization initiator may be used in an amount of 1 to 10 parts by weight, preferably 1 to 5 parts by weight in the paste composition of the present invention, and may be used, for example, for a paste dilution solvent having excellent solubility. If the content of the polymerization initiator is less than the above-mentioned range, the curing reaction does not start effectively, and the desired network structure is not made. Even if the above-mentioned range is exceeded, the desired effect does not increase proportionally, and developability is lowered. That is, the residue (residue paste) remains in the portion not cured by ultraviolet rays.

la. Other additives

On the other hand, the present invention may further include an additive for imparting properties such as conductivity, dispersibility, storage stability, printability to the conductive paste. As an example of such an additive, a surfactant for improving screen printing aptitude for a touch panel of a paste composition, a coupling agent (adhesive accelerator) for improving the adhesion of the paste composition to a substrate, an antioxidant, a curing accelerator, an ultraviolet absorber, At least 1 type or more additives chosen from a thermal polymerization inhibitor, a leveling agent, an acid additive, an antifoamer, and a filler are mentioned.

Examples of the surfactant include cationic surfactants such as organosiloxane polymers, (meth) acrylic acid-based (co) polymer polyflows and polyoxyethylene alkylamine glycols; Include polyoxyethylene fatty acid ethers or polyoxyethylene fatty acid esters such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether , Nonionic surfactants such as polyhydric alcohol fatty acid esters such as polyethylene glycol dilaurate, polyethylene glycol distearate and sorbitan fatty acid ester; Alkylphosphate-based anionic surfactants; Or a fluorine-based surfactant can be used.

As coupling agent, vinyltrialkoxy silane, 3-methacryloxy propyltrimethoxy silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycol Cydoxypropyltriethoxysilane and the like.

Antioxidants include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-g, t-butylphenol, and the like. Non-limiting examples of curing accelerators include 2-mers. Captobenzoimidazole, 2-mercaptobenzothiazole, pentaerythritol-tetrakis (3-mercaptopropionate). Non-limiting examples of ultraviolet absorbers include 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chloro-benzotriazole, alkoxy benzophenone, and hydroquinone as a thermal polymerization inhibitor. , p-methoxyphenol, t-butylcatechol, benzoquinone and the like.

The acid additive may be selected from stearic acid, acetic acid, formic acid phosphoric acid, malonic acid, maleic acid, hydrochloric acid, sulfuric acid, and the like, and the antifoaming agent may be selected from dimethylpolysiloxane, methylethylpolysiloxane, diethylpolysiloxane, and the like. In addition, the leveling agent may be a silicon-based leveling agent selected from silicone diacrylate, silicone polyacrylate and the like or an alcohol-based leveling agent selected from methanol, ethanol, butanol and the like. In addition, functional additives selected from hexafluoroantimonate, ammonium and inorganic fillers blocked with triflic acid may be included in the conductive paste composition of the present invention.

The present invention is not limited to the other additives described above and may be commercially available in the field of conductive pastes. At this time, such an additive may be added in a ratio of 0.1 to 3.0 parts by weight in the paste composition, and when the additive is added in an amount of less than 0.1 parts by weight, it is difficult to exert a desired function. And developability may be reduced.

The paste composition according to the present invention may have a suitable viscosity in consideration of the aptitude and workability of screen printing, and may have suitable electrical properties required in the display film. For example, the viscosity of the conductive paste according to the present invention may have a range of 5000 to 1,000,000 cps at 50 rpm using a rotatable viscometer.

B. Method of Preparation of Paste Composition

The manufacturing method of the paste composition mentioned above is demonstrated, referring FIG. First, in order to improve developability, for example, a binder composition in which an oligomer-type binder having 2-3 carboxylic acid groups (-COOH) and a solid content of a monomer having a carboxylic acid group (-COOH) and a diluting solvent are appropriately blended. To manufacture (s110). Since the oligomeric binder and monomer of this invention which comprise solid content in a binder composition have an appropriate number of carboxylic acid groups (-COOH), developability can be improved. These solids and dilution solvents can be mixed, for example, treated with an anti-foaming, and then the solids of the binder composition can be uniformly dispersed in the solvent by milling. At this time, it is preferable to adjust the content of the solid content so that the diluting solvent may be 1 to 50 parts by weight with respect to the oligomeric binder. If the solid content is too low, the viscosity of the conductive paste is low, the ultraviolet curing properties are lowered. If the solid content is too high, the viscosity is too high, for example, the conductive printed film for a touch panel is printed too thick, so that the ultraviolet curing is not sufficient. .

In particular, according to the present invention, the developability can be improved due to the carboxylic acid groups present in the oligomer binder and the monomer, but the curing properties may be degraded because some of the acrylate functional groups are substituted with the carboxylic acid groups. Therefore, in preparing the binder composition, in combination with the monomer of the present invention having a carboxylic acid group (-COOH), a second monomer of a multifunctional acrylate type, preferably having a plurality of acrylate functional groups, may be included in the binder composition. . As the diluting solvent, at least two or more dilutions preferably selected from gamma-butyrolactone, butyl cellulsolve (BCA), methyl ethyl ketone (MEK), 2-ethoxyethanol (2EE) and ethyl cellosolve acetate (ECA) Using a solvent together can improve screen printing aptitude and ultraviolet curing properties.

A conductive powder such as silver powder is mixed with the binder composition obtained in this manner, and a preliminary paste (primary paste) in which the conductive powder is uniformly dispersed in the binder composition is obtained through a defoamer treatment and milling treatment (s120). . Since the process of preparing the paste by mixing the binder composition and the conductive powder for the conductive paste for screen printing is well known, a detailed description thereof will be omitted.

Subsequently, the final paste (secondary paste) may be obtained by stirring the polymerization initiator dissolved in, for example, a paste dilution solvent, in the primary face of the inorganic powder uniformly dispersed in the binder composition (s130). The paste dilution solvent can use the same kind as the binder dilution solvent mentioned above, for example, gamma-butyrolactone excellent in solubility.

At this time, the conductive powder in the conductive paste composition of the present invention may be 60 to 85 parts by weight, preferably 70 to 80 parts by weight, and the binder composition may be 15 to 40 parts by weight, preferably 15 to 25 parts by weight. In the binder composition, the oligomeric binder is 1 to 20 parts by weight, preferably 1 to 15 parts by weight, more preferably 5 to 10 parts by weight, and the monomer having a carboxylic acid group (-COOH) is 1 to 10 parts by weight, preferably Is 1 to 5 parts by weight, and optionally the second monomer, which is a multifunctional acrylate monomer, may be 1 to 10 parts by weight, preferably 1 to 5 parts by weight.

On the other hand, the diluting solvent plays a role of adjusting the viscosity, fluidity, printability, etc. of the finally obtained conductive paste composition as well as the viscosity of the binder. This is because the viscosity of the paste may be too high or low when the solvent is out of this range, so that the printing aptitude may be poor. Therefore, the content of the solid content including the oligomeric binder and the monomer may be 5 to 20 parts by weight, preferably 5 to 10 parts by weight, and the diluting solvent may be 5 to 20 parts by weight, preferably 5 to 15 parts by weight. On the other hand, the polymerization initiator is 1 to 10 parts by weight, preferably 1 to 5 parts by weight.

C. Application of Conductive Paste Compositions

1. Conductive Film and Touch Panel

The conductive paste composition according to the present invention can be applied to a film for protecting the conductive thin film, for example, on top of a transparent conductive thin film such as ITO constituting the touch panel. This film can be largely divided into a transparent film layer which is made of a transparent material and can be used as a kind of printed material for forming a conductive paste composition, and a photoresist layer to which the conductive paste composition according to the present invention is applied.

The transparent film layer may be glass or plastic, which is transparent and easy to process thinly, preferably a plastic film or a plastic plate. Plastic materials for forming the transparent film layer include a touch such as polyethylene terephthalate (PET), polycarbonate, polymethyl methacrylate, polystyrene, polystyrene / polymetal methacrylate copolymer, triacetyl cellulose resin, cyclic olefin resin, and the like. It is possible to use materials which are well known in the context of panels. Typically, the transparent film layer may be produced in a thickness of 1 ~ 500 ㎛, preferably 1 ~ 300 ㎛. On the other hand, as described below, the paste composition according to the present invention can form a photoresist layer of 0.5 to 20 ㎛ using various printing methods.

In addition, a transparent conductive thin film may be formed on one surface of the film described above with a thickness of approximately 30 to 3000 m 3. If the thickness is thinner than this, the conductivity is poor. If the thickness is exceeded, irregularities such as patterns formed on one surface of the resin layer may not only affect the uneven structure of the transparent conductive thin film, but may also cause a decrease in transparency. The transparent conductive thin film may be a single or a composite material of an organic material such as polythiophene as well as inorganic materials such as indium tin oxide, indium titanium oxide, tin oxide, and titanium oxide. Since the process of forming the transparent conductive thin film is well known, a detailed description thereof will be omitted.

2. Method of forming photosensitive pattern

The paste composition according to the present invention can be used to form a photosensitive pattern. The photosensitive pattern forming method is a technique in which a conventional pattern forming process such as screen printing is combined with lithography processes such as exposure and development. In the case of forming a pattern through the screen printing method, screen printing is easy to work, but due to the limitation of the mesh (mesh) has a disadvantage that it is difficult to implement a fine pattern of less than L / S = 50/50, etching The method is easy to implement a fine pattern, but has the disadvantages of complex workability, low productivity, and high cost. On the other hand, when the offset printing method or the gravure printing method is used, there is a problem that the continuity of the work is inferior.

Compensating these shortcomings, the photosensitive pattern formation has advantages of relatively simple workability and easy implementation of fine patterns, and has an advantage of ensuring continuity of work. Through these advantages, iii) increased number of wirings due to multi-touch, ii) miniaturization of line width due to narrowing of bezel part, iv) extension of wiring distance due to panel enlargement, and iv) reduction of weight of printed material (Glass → Film) It is sufficient as a condition corresponding to the touch panel circuit technology trend of change. Particularly, the number of processes can be simplified compared to the etching method through the photosensitive pattern forming process, and a fine pattern of 50 μm or less, for example, 30 μm or less, for example, up to 20 μm, which is difficult with a simple screen printing method, can be realized. .

The process of forming a photosensitive pattern using the electrically conductive paste composition of this invention is demonstrated, referring FIG. 2 which is attached. First, the conductive paste composition according to the present invention is coated or printed with a thickness of approximately 0.5 to 20 μm, preferably 0.5 to 20 μm, on a printed material, for example, a transparent film layer of a touch panel, according to a predetermined pattern. A photo resist layer is formed (S210). In this case, a method such as dip coating, spin coating, roller coating, spray coating, bar coating, slit coating, gravure printing, or offset printing may be used to form the photoresist layer. You can use free silkscreen printing. The screen printing method is the most widely used method of forming a conductive pattern, and is a direct printing method printed only on a necessary portion, and has the advantage of low loss of conductive paste, simple process, and low plate making cost. Recent advances in metal mask technology enable the printing of precise patterns and increase the productivity of printing by increasing the size of equipment. However, the method for forming the electrode forming film of the touch panel using the conductive paste of the present invention is not limited to the silk screen printing method.

The transparent film layer on which the photoresist layer is printed is, for example, polyethylene terephthalate (PET), polycarbonate, polymethyl methacrylate, polystyrene, polystyrene / polymethacrylate copolymer, triacetyl cellulose resin, cyclic olefin type It is possible to use a well-known material in connection with a touch panel such as a plastic film such as resin or an ITO film (or an etching surface of the ITO film).

If necessary, pre-heating is performed for 100 to 1000 seconds, preferably 300 to 900 seconds, at a temperature of approximately 80 to 130 ° C., preferably 90 to 110 ° C., prior to the exposure process on the photoresist layer. , Soft baking, drying, and pre-curing) process s220 may be optionally performed to form a relatively robust photoresist layer. Although the solid content of the conductive paste composition of the present invention is not thermally decomposed by the electrothermal treatment, most solvent components may be evaporated to minimize the concentration of the solvent.

After performing the optional heat treatment (S220), an exposure process for curing the binder is performed (S230). In order to perform the exposure process, an exposure mask (photo mask) is disposed on the photoresist layer. Accordingly, the photoresist layer is divided into an exposure area to which light is irradiated) and a non-exposure area to which light is not irradiated.

In this case, the photoresist formed on the printed body by the conductive paste composition according to the present invention may be a so-called negative type. In this case, the photoresist corresponding to the exposure region is polymerized by the radical reaction by the polymerization initiator reacting with light, whereas no reaction occurs because no light is irradiated to the photoresist corresponding to the non-exposure region. Does not occur, and thus monomers in this region cannot be polymerized and remain in the form of monomers.

That is, in the photoresist layer corresponding to the exposure region, the polymerization initiator contained in the conductive paste composition is activated by irradiation of light to form radical molecules, and the radical molecules start photopolymerization. Thereby, the polymerization reaction by the monomer contained in the paste composition can be started to form a photopolymer.

Non-limiting examples of light sources used in the exposure process include mercury vapor arc, carbon arc micro xenon (Xe) arc. The polymer is obtained by crosslinking the monomer with the oligomer binder through the radical reaction by a polymerization initiator reacting with light of an appropriate wavelength band through the exposure step. Since the monomer of the present invention has a large number of functional groups, there is a sensitivity to sufficiently cure even a small amount of light. Although the present invention is not limited thereto, in the exposure step S130, the light source may emit ultraviolet light (UV) in a wavelength band of about 200 to 500 nm, preferably 300 to 400 nm.

When the exposure process (s230) is completed, the cured photoresist layer is treated with a developer (s240). Through the developing step, monomers and oligomers which remain unreacted by light are dissolved in the developer while reacting with the developer to form chlorides. Particularly, according to the present invention, since a part of the functional groups of the oligomeric binder and / or monomer is substituted with a carboxylic acid group, the non-hardened part can be easily washed away in the developing process since the carboxylic acid groups react with the base in the developer to form salts. And developability can be improved. For example, as a developer, inorganic alkalis such as sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na 2 CO 3 ), sodium sulfite (Na 2 SO 3 ), sodium silicate, sodium metsilicate, and ammonia Ryu; Primary amines such as ethylamine and N-propylamine; Secondary amines such as diethylamine and di-n-propylamine; Tertiary amines such as trimethylamine, methyldiethylamine and dimethylethylamine; Cyclic tertiary amines such as pyrrole, piperidine, n-methylpiperidine, n-methylpyrrolidine, 1,8-diazabicyclo [5,4,0] -7-undecene; Aromatic tertiary amines such as pyridine, corridin and counoline; Aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide (TMAH) and tetraethylammonium hydroxide can also be used.

If necessary, a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the developer. Examples of the development treatment include a shower development method, a spray development method, a dip development method, a paddle development method, and the like, and the development process may be performed, for example, about 5 to 100 seconds, preferably about 5 to 50 seconds. In addition, after the exposure and the developing process, it may further include a rinse (rinse (washing) process) for washing off the developer remaining on the pattern.

Subsequently, after the development process is completed, the post-heating treatment (post-curing, post-baking) of completely curing the transparent film layer having the cured photoresist layer at a predetermined temperature by using a heating apparatus such as a hot-plate or an oven. , Hard baking) is performed (s250). Thereby, the crack resistance, solvent resistance, etc. of the photosensitive pattern formed using the electrically conductive paste composition of this invention can be improved further. The post heat treatment process may be performed at, for example, 20 to 90 minutes, preferably 30 to 80 minutes, at a temperature of 200 to 250 ° C.

Hereinafter, the present invention will be described through exemplary embodiments, but the present invention is not limited to these examples.

Examples 1 to 4: preparing a conductive paste composition according to the oligomeric binder

Conductive paste compositions were prepared by combining the respective components according to the procedure shown in FIG. 1. Silver powder SP001 and SP002 as conductive powders are silver powders of manufacturers of domestic metal powders. The acrylate oligomers and monomers used as binders were commissioned by a domestic resin manufacturer. ECA (Ethyl Solosolve Acetate) was Samcheon Chemical and Gamma Butyrolactone was Junsei's product.

Specifically, a binder was prepared by pre-mixing each monomer with ECA and 2-Ethoxy ethanol (2EE) solvent in an ultraviolet curable acrylate oligomer resin. The metal powder paste containing the silver powder as shown in the main ingredient was added and stirred, followed by dispersing the metal powder using a 3-roll mill (ETR-6.5, a light machine). A conductive paste was prepared by dissolving ITX, I-907, and OXE-02 as a curing initiator in a gammabutylarolactone solution and then adding it to a paste. The type and content of each component according to the present embodiment are shown in Table 2 below.

Examples 5 to 13: Preparation of the conductive paste composition according to the monomer

In this example, the conductive paste composition was prepared by repeating the above procedure by changing the type of monomer. The type and content of each component constituting the conductive paste composition according to the present embodiment are shown in Table 2 below.

Comparative Examples 1-2: Use of Binder / Monomer Without Carboxylic Acid Group

In Comparative Example 1, a conductive paste composition was prepared by repeating the above procedure using a binder resin having no carboxylic acid group. Epoxy resin AA4123, which is a binder resin used in Comparative Example 1, is a resin synthesized by a solution polymerization method in FP Co., Ltd. using BCA as a base solvent. In Comparative Example 2, a conductive paste composition was prepared by repeating the above procedure using a binder composition composed only of monomers having no carboxylic acid groups. The type and content of each component constituting the conductive paste composition according to the present comparative example are shown in Table 2 below.

Composition and Ratio of Conductive Paste Composition Example Silver powder
(content) Oligomer
(content) Monomer
(content) solvent
(content) Photoinitiator
(content) One SP001 (50)
SP002 (25) C1 (12) A1 (2), B1 (1.5)
TMP (EO) 9 TA (2.5) 2-EE (4)
ECA (5) ITX (0.1), I-369 (0.9), OXE 02 (1) 2 SP001 (50)
SP002 (25) E2 (12) A1 (2), B1 (1.5)
TMP (EO) 9 TA (2.5) 2-EE (4)
ECA (5) ITX (0.1), I-369 (0.9), OXE 02 (1) 3 SP001 (50)
SP002 (25) D3 (12) A1 (2), B1 (1.5)
TMP (EO) 9 TA (2.5) 2-EE (4)
ECA (5) ITX (0.1), I-369 (0.9): OXE 02 (1) 4 SP001 (50)
SP002 (25) C4 (12) A1 (2), B1 (1.5)
TMP (EO) 9 TA (2.5) 2-EE (4)
ECA (5) ITX (0.1): I-369 (0.9): OXE 02 (1) 5 SP001 (50)
SP002 (25) C1 (12) B1 (2), DPHA (1.6)
TMP (EO) 9 TA (2.4) 2-EE (4)
ECA (5) ITX (0.1): I-369 (0.9): OXE 02 (1) 6 SP001 (50)
SP002 (25) C1 (12) A1 (1.6), TMPTA (2),
TMP (EO) 9 TA (2.4) 2-EE (4)
ECA (5) ITX (0.1): I-369 (0.9): OXE 02 (1) 7 SP001 (50)
SP002 (25) D3 (12) B1 (2), DPHA (1.6),
TMP (EO) 9 TA (2.4) 2-EE (4)
ECA (5) ITX (0.1): I-369 (0.9): OXE 02 (1) 8 SP001 (50)
SP002 (25) D3 (12) A1 (1.6), TMPTA (2)
TMP (EO) 9 TA (2.4) 2-EE (4)
ECA (5) ITX (0.1): I-369 (0.9): OXE 02 (1) 9 SP001 (50)
SP002 (25) C1 (12) A1 (1)
TMP (EO) 9 TA (2) 2-EE (4)
ECA (5) ITX (0.1): I-369 (0.9): OXE 02 (1) 10 SP001 (50)
SP002 (25) C1 (12) B1 (1)
TMP (EO) 9 TA (2) 2-EE (4)
ECA (5) ITX (0.1): I-369 (0.9): OXE 02 (1) 11 SP001 (50)
SP002 (25) C1 (12) A1 (1)
EO12-DPHA (2) 2-EE (4)
ECA (2) ITX (0.1): I-369 (0.9): OXE 02 (1) 12 SP001 (50)
SP002 (25) C1 (12) B1 (1)
EO 12 -DPHA (2) 2-EE (4)
ECA (5) ITX (0.1): I-369 (0.9): OXE 02 (1) 13 SP001 (50)
SP002 (25) C1 (12) B1 (1), DPHA (1.2)
EO 12 -DPHA (0.8) 2-EE (4)
ECA (5) ITX (0.1): I-369 (0.9): OXE 02 (1) Comparison 1 SP001 (50)
SP002 (25) AA4123 * 12 A1 (2), B1 (1.5)
TMP (EO) 9 TA (2.5) 2-EE (4)
ECA (5) ITX (0.1): I-369 (0.9): OXE 02 (1) Comparison 2 SP001 (50)
SP002 (25) C1 (12) DPHA (1.6), TMPTA (2),
TMP (EO) 9 TA (2.4) 2-EE (4)
ECA (5) ITX (0.1): I-369 (0.9): OXE 02 (1)

*: Acrylic resin (NV 40 wt%, solvent α-terpineol, Mw 20,000, acid value 150 mgKOH / g)

Experimental Example 1 Formation of Photosensitive Pattern

Photosensitive patterns were formed using the face compositions prepared in Examples 1 to 13 and Comparative Examples 1-2, respectively. First, the conductive pastes prepared in Examples 1-13 and Comparative Examples 1-2, respectively, were printed on a PET film using a screen printing method. As a 500-mesh SUS material, it printed on the screen printing machine (SW-2525, Japan Mino) using the screen making of the front surface 900 * 900 mm. The platemaking used for screen printing is mesh count SUS500, mesh angle is 22.5 kPa, tension in the X-axis is 1.0 mm / kgf, tension in the Y-axis is 1.3 mm / kgf, mesh thickness is 24 µm, emulsion thickness is 8 mu m, the total thickness was 32 mu m. Screen printing was performed on the entire surface. Screen printing was performed with the contact off gap of 2.5 mm, the squeegee angle of 80 ㅀ, and the squeegee speed of 30-50 mm / sec. Subsequently, after a pre-heating process of evaporating the solvent for 10 minutes at 90 ° C., the pattern was cured with ultraviolet (UV) UV intensity for curing with ultraviolet (UV) was 500 mJ / Then, the solution was developed in an aqueous alkali solution and washed with DI water, and for development, a 0.5% alkaline aqueous solution of sodium carbonate (Na 2 CO 3 , pH 11.5) was used, and the developing time was 10 seconds, and the washing was performed with rinse. time) was set to 10 seconds After the completion of development, a conductive coating was formed through a post-processing process at 150 ° C. for 1 hour.

Experimental Example  2: of paste Rheology  Measure

Rheology of the conductive paste prepared in Examples 1-13 and Comparative Examples 1-2 was measured using a HAAKE Rheoscope 1 (Germany) device. The measurement items are Viscosity Profile, which measures the change of viscosity according to shear rate (0.1 ~ 100s -1 ), and Amplitude Sweep, which measures the change of storage modulus (G ') and loss modulus (G ") according to shear stress (0.1 ~ 1000Pa). The sample stage was a parallel plate of 35 mm in diameter, and the sample interval was set to 0.8, and the measurement temperature was 23 degreeC.

3A and 3B are graphs showing the results of measuring the viscosity according to the shear rate among the rheological properties of the pastes prepared in Examples 1-4 and Comparative Example 1, respectively, and G ′ and G ″ according to the shear stress. In addition, Table 3 shows the results of viscosity measurements according to the shear rates of the pastes prepared in Examples 1-4 and Comparative Example 1.

On the other hand, Figures 4a and 4b is a graph showing the results of measuring the viscosity according to the shear rate in the rheological properties of the paste prepared in Example 5-9 and Comparative Example 2, respectively G 'and G according to the shear stress "Is a graph showing the results of the measurement. Table 4 below also shows the results of the viscosity measurement according to the shear rate of the paste prepared in Example 5-9 and Comparative Example 2.

As shown in Figures 3a, 3b, 4a, 4b, Table 3, Table 4, it can be seen that the viscosity of the paste prepared according to the present invention decreases from a low shear rate to a high shear rate.

Viscosity of Paste According to Oligomer Type Viscosity (cps) Example One 2 3 4 Comparative Example 1 1 1 / s 25650 140500 30320 54510 662700 5 1 / s 13970 16550 9068 17600 25810 10 1 / s 9778 9662 5729 10470 17840 50 1 / s 5494 4918 2626 3965 11950 100 1 / s 4733 4180 2072 2937 11270 TI (5/50) 2.54 3.37 3.45 4.44 2.16

Viscosity of Paste According to the Type of Monomer Viscosity (cps) Example 5 6 7 8 9 10 11 12 13 Comparison 2 1 1 / s 75460 108800 93580 107500 13000 11920 19530 18960 19230 76420 5 1 / s 20710 24670 22510 24340 8899 8320 14090 12260 12670 20180 10 1 / s 13930 15680 14090 15200 6033 5712 8348 7468 7612 14120 50 1 / s 7778 8827 7443 8298 3546 3075 3185 2938 2982 7797 100 1 / s 6709 7987 6393 7277 3108 2602 2337 2185 2235 6661 TI (5/50) 2.66 2.79 3.02 2.93 2.51 2.71 4.42 4.17 4.25 2.59

Experimental Example  3: measuring electrical conductivity of paste

The electrical conductivity of the electrode using the conductive paste obtained in Experimental Example 1 measured the surface of the electrode pattern. The surface resistance is measured according to the 4 probe method (4 prove, KSL 1619) which measures the surface resistance measuring instrument (2002 multimeter, keithley), and the thickness of the conductive pattern film is measured by the roughness meter (SJ-401, Mitutoyo) and then the resistivity is measured. Converted to. The resistance values specified for each conductive paste are shown in Table 5 below.

While the paste prepared in the comparative example is too high in resistance to be suitable as a conductive material for a display such as a touch panel, the conductive paste prepared according to the present invention has suitable electrical properties as a material for a display panel including a touch panel. It can be seen.

Result of measuring surface resistance of paste Example Surface resistance Example Surface resistance One 30 to 40 m 2 150 to 170 m 3 130 to 150 m 4 200 to 250 m 5 600 m 6 200 to 300 m 7 200 to 250 m 8 100 to 150 m 9 80 to 140 m 10 150 to 200 m 11 60 to 80 m 12 40 mΩ 13 30 to 35 m Comparative Example 1 ㏀n ↑ Comparative Example 2 ㏀n ↑

Experimental Example 4 Measurement of Pattern Sharpness

After the paste prepared in Experimental Example 1 formed a pattern coating film on the PET film, the sharpness was measured with a video micrograph of Figure 7. Results measured according to the present experimental example are shown in FIGS. 5 and 6, respectively. Figure 5 is a photograph measuring the sharpness on the ITO surface in order to determine the reproducibility of the film obtained by printing and curing the paste prepared in Examples 1-4 and Comparative Example 1 of the present invention, Figure 6 is the present invention In order to determine the reproducibility of the film obtained by printing and curing the paste prepared in Examples 5-13 and Comparative Example 2, the sharpness of the ITO surface is measured. As can be seen in the drawings, the fine pattern can be obtained because the sharpness of the film pattern obtained from the conductive paste composition according to the present invention is excellent, whereas the film pattern obtained from the paste according to the comparative example has a problem in obtaining a fine pattern. It can be seen that it occurred.

Experimental Example 5 Measurement of Adhesiveness (Adhesive Force) of Paste

The adhesive test method of the paste coating material was measured according to KS M ISO 2409. To this end, the printed coating film was cross-cut in a cross shape and then attached with a cellophane tape, and then it was determined whether or not the printed pattern cells were good as falling numbers. Adhesion measurement results are shown in FIGS. 7 and 8. 7 is a photograph of measuring the adhesiveness (adhesiveness) of the coating film obtained by printing and curing the pastes prepared in Examples 1-4 and Comparative Example 1 of the present invention. Fig. 8 is a photograph of measuring the adhesiveness (adhesiveness) of the coating film obtained by printing and curing the pastes prepared in Examples 5-13 and Comparative Example 2 of the present invention. As can be seen from the figure, the coating film obtained from the conductive paste composition prepared according to the present invention was greatly improved compared to the comparative example, the adhesion was excellent.

Experimental Example 6: Hardness Measurement

In order to measure the hardness of the paste coating film, the following method was followed. First, in the case of paint and varnish, it was measured by the pencil hardness meter of Fig. 9 according to KS M ISO15184, which is a pencil hardness measurement method of coating film. Pencil hardness means pencil hardness that is a pencil lead having a prescribed size and shape and a prescribed hardness. According to the present Example, it measured in 10 minutes at 90 degreeC of pre-heating, the amount of light 500 (mJ / cm <2>) UV-curing, and hardening at 150 degreeC for 1 hour. The results measured according to the present experimental example are shown in FIGS. 9 and 10, respectively. 9 is a photograph of measuring the pencil hardness of the film obtained by printing and curing the paste prepared in Example 1-4 and Comparative Example 1 of the present invention, Figure 10 is a comparative example and Example 5-9 of the present invention It is a photograph which measured the pencil hardness of the film obtained by printing and hardening the paste prepared in Example 2, respectively. The pencil hardness of the film obtained from the paste according to the present invention was very good in hardness from about 2H to 4H.

Claims (17)

60 to 85 parts by weight of conductive powder; And
A first acrylate monomer selected from the group consisting of a compound of formula (I), a compound of formula (II), and a combination thereof; A second acrylate monomer having two or more functional groups having no carboxylic acid (-COOH); A binder having a number average molecular weight of 1000 to 5000 and an acrylate oligomer selected from the group consisting of a compound represented by the following formula (III), a compound represented by the following formula (IV), and a combination thereof; And 15 to 40 parts by weight of the binder composition comprising a binder dilution solvent.
Figure 112013064085977-pat00033

Figure 112013064085977-pat00034

(In the formula (I) and formula (II), R is
Figure 112013064085977-pat00035
,
Figure 112013064085977-pat00036
,
Figure 112013064085977-pat00037
,
Figure 112013064085977-pat00038
, And
Figure 112013064085977-pat00039
Selected from the group consisting of
Figure 112013064085977-pat00076

Figure 112013064085977-pat00077

(In the formulas (III) and (IV), X is hydrogen or
Figure 112013064085977-pat00078
Wherein R is the same as defined in Formulas (I) and (II), and the number of substituents X other than hydrogen in the acrylate oligomer is 2 to 3; n is an integer from 3 to 10)
The paste composition of claim 1, wherein the second acrylate monomer has three or more functional groups.
The method of claim 1, wherein the second acrylate monomer is Ethyleneglycol diacrylate (EGDA), Neopentylglycol hydroxypivalate diacrylate (Neopentylglycol Hydroxypivalate diacrylate), Neopentylglycol hydroxypivalate Neopentylglycol Hydroxypivalate diacrylate modified caprolactone, Bisphenol A diacrylate, Hexanedioldiacrylate (HDDA), Tetraethyleneglycol diacrylate (TTEGDA) , Trimethylolpropane triacrylate (TMPTA), ethoxylated trimethylolpropane triacrylate (TMP (EO) TA), pentaerythritol tryacrylate (PETA), dipenta Erythritol triacrylate (Dipentaeryth) ritol triacrylate (DPETA), Ditrimethylolpropane tetraacrylate (DTMPTA), dipentaerythritol hexaacrylate (DPHA), ethoxylated dipentaerythritol hexaacrylate, (Dipentaerythritol hexaacrylate, EO) DPHA), dipentaerythritol hexaacrylate-modified caprolactone, and a combination thereof.
The method of claim 1, wherein the conductive powder is silver (Ag), gold (Au), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), platinum (Pt), tin (Sn), Paste composition, characterized in that the metal powder selected from the group consisting of zirconium oxide, tin oxide, antimony oxide, nickel oxide, aluminum oxide, ITO (Indium Tin Oxide) and combinations thereof.
The paste composition of claim 1, wherein the conductive powder is a mixture of silver powder having different average particle diameters.
According to claim 1, The binder composition, 5 to 20 parts by weight of solids containing the binder, the first acrylate monomer, and the second acrylate monomer, and 5 to 20 parts by weight of the binder dilution solvent Paste composition comprising.
The paste composition of claim 1, wherein the paste composition further comprises 1 to 10 parts by weight of a polymerization initiator.
The conductive film for touch panels coat | covered using the paste composition as described in any one of Claims 1-7.
A touch panel comprising a conductive thin film on which a conductive film for a touch panel according to claim 8 is laminated.
A first acrylate monomer selected from the group consisting of a compound of formula (I), a compound of formula (II), and a combination thereof; A second acrylate monomer having two or more functional groups having no carboxylic acid (-COOH); A binder having a number average molecular weight of 1000 to 5000 and an acrylate oligomer selected from the group consisting of a compound represented by the following formula (III), a compound represented by the following formula (IV), and a combination thereof; And a binder composition comprising a binder dilution solvent;
Mixing a conductive powder with the binder composition to obtain a primary paste; And
A method of producing a paste composition comprising the step of mixing a paste diluting solvent in which a polymerization initiator is dissolved with the primary paste to obtain a secondary paste.
Figure 112013064085977-pat00043

Figure 112013064085977-pat00044

(In the formula (I) and formula (II), R is
Figure 112013064085977-pat00045
,
Figure 112013064085977-pat00046
,
Figure 112013064085977-pat00047
,
Figure 112013064085977-pat00048
, And
Figure 112013064085977-pat00049
Selected from the group consisting of
Figure 112013064085977-pat00079

Figure 112013064085977-pat00080

(In the formulas (III) and (IV), X is hydrogen or
Figure 112013064085977-pat00081
Wherein R is the same as defined in Formulas (I) and (II), and the number of substituents X other than hydrogen in the acrylate oligomer is 2 to 3; n is an integer from 3 to 10)
The method of claim 10, wherein the second acrylate monomer has three or more functional groups.
The method of claim 10, wherein the second acrylate monomer is ethylene glycol diacrylate (Ethyleneglycol diacrylate, EGDA), neopentyl glycol hydroxy pivalate diacrylate (neopentylglycol Hydroxypivalate diacrylate), neopentyl glycol hydroxy pivalate Neopentylglycol Hydroxypivalate diacrylate modified caprolactone, Bisphenol A diacrylate, Hexanedioldiacrylate (HDDA), Tetraethyleneglycol diacrylate (TTEGDA) , Trimethylolpropane triacrylate (TMPTA), ethoxylated trimethylolpropane triacrylate (TMP (EO) TA), pentaerythritol tryacrylate (PETA), dipenta Erythritol triacrylate (Dipentaeryt) hritol triacrylate (DPETA), Ditrimethylolpropane tetraacrylate (DTMPTA), Dipentaerythritol hexaacrylate (DPHA), dipentaerythritol hexaacrylate-modified caprolactone (Dipentaerythritol hexaacrylate modified caprolactone) and a combination thereof.
The method of claim 10 or 11, wherein the binder composition in the conductive paste composition comprises 15 to 40 parts by weight, the conductive powder comprises 60 to 85 parts by weight, the polymerization initiator comprises 1 to 10 parts by weight Method for producing a paste composition, characterized in that.
Printing a conductive paste composition according to any one of claims 1 to 7 on a printed material to form a photoresist layer;
Performing an exposure process on the photoresist layer so that a photopolymerizable material can be formed on the photoresist layer via an exposure mask;
Supplying a developer to the photoresist layer on which the photopolymerizable material is formed to develop the photoresist layer; And
And heat treating the developed photoresist layer.
15. The method of claim 14, wherein the light irradiated in the exposing step has a wavelength of 200 to 500 nm.
The method of claim 14, wherein the developing solution used in the developing step is sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na 2 CO 3 ), sodium sulfite (Na 2 SO 3 ), sodium silicate, sodium metsilicate, A photosensitive pattern forming method comprising an inorganic alkali selected from the group consisting of ammonia and combinations thereof.
15. The method of claim 14, further comprising forming the photoresist layer and electrothermally treating the photoresist layer between the exposing step.
KR1020130035620A 2013-04-02 2013-04-02 Photosensitive paste composition for forming fine electrode patterns in touch panels, method of fabrication the composition and application thereof KR101306778B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020130035620A KR101306778B1 (en) 2013-04-02 2013-04-02 Photosensitive paste composition for forming fine electrode patterns in touch panels, method of fabrication the composition and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020130035620A KR101306778B1 (en) 2013-04-02 2013-04-02 Photosensitive paste composition for forming fine electrode patterns in touch panels, method of fabrication the composition and application thereof

Publications (1)

Publication Number Publication Date
KR101306778B1 true KR101306778B1 (en) 2013-09-17

Family

ID=49455686

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020130035620A KR101306778B1 (en) 2013-04-02 2013-04-02 Photosensitive paste composition for forming fine electrode patterns in touch panels, method of fabrication the composition and application thereof

Country Status (1)

Country Link
KR (1) KR101306778B1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200002386A (en) * 2018-06-29 2020-01-08 주식회사 에프이엠 Transparent electrode film for touch driving of flexible oled, method of manufacturing thereof and touch panel using the same
TWI780277B (en) * 2017-12-14 2022-10-11 日商則武股份有限公司 Photosensitive composition, composite, electronic component, and method for producing electronic component

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005097515A (en) 2003-08-22 2005-04-14 Mitsubishi Rayon Co Ltd Coating composition, coated article and outer shell for automobile
JP2010102314A (en) 2008-09-25 2010-05-06 Fujifilm Corp Lithographic printing plate precursor and process for producing lithographic printing plate
KR20120129229A (en) * 2011-05-19 2012-11-28 주식회사 에프피 Ultra Violet Curing Conductive Paste Composition for Touch Panels, Touch Panels Containing the Composition and Manufacturing Process of the Composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005097515A (en) 2003-08-22 2005-04-14 Mitsubishi Rayon Co Ltd Coating composition, coated article and outer shell for automobile
JP2010102314A (en) 2008-09-25 2010-05-06 Fujifilm Corp Lithographic printing plate precursor and process for producing lithographic printing plate
KR20120129229A (en) * 2011-05-19 2012-11-28 주식회사 에프피 Ultra Violet Curing Conductive Paste Composition for Touch Panels, Touch Panels Containing the Composition and Manufacturing Process of the Composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI780277B (en) * 2017-12-14 2022-10-11 日商則武股份有限公司 Photosensitive composition, composite, electronic component, and method for producing electronic component
KR20200002386A (en) * 2018-06-29 2020-01-08 주식회사 에프이엠 Transparent electrode film for touch driving of flexible oled, method of manufacturing thereof and touch panel using the same
KR102134793B1 (en) 2018-06-29 2020-07-16 주식회사 에프이엠 Transparent electrode film for touch driving of flexible oled, method of manufacturing thereof and touch panel using the same

Similar Documents

Publication Publication Date Title
JP5257558B1 (en) Method for forming conductive pattern, conductive pattern substrate, and touch panel sensor
JP6079645B2 (en) Photocurable resin composition containing fine metal particles and use thereof
CN102365690B (en) Photosensitive electrically conductive paste and electrode pattern
CN105244081B (en) Degradation inhibiting method, film and its manufacturing method and laminated body
JP6176295B2 (en) Method for forming conductive pattern
JP2012009383A (en) Composition for coating formation, method of manufacturing substrate having patterned transparent conductive film obtained from the composition, and use of the manufactured body
JP2013140329A (en) Photosensitive composition for transparent conductive film
JP2012009219A (en) Conductive material and touch panel
KR101306778B1 (en) Photosensitive paste composition for forming fine electrode patterns in touch panels, method of fabrication the composition and application thereof
KR101233241B1 (en) Ultra Violet Curing Conductive Paste Composition for Touch Panels, Touch Panels Containing the Composition and Manufacturing Process of the Composition
JP2013101861A (en) Photosensitive conductive paste, conductive circuit pattern, touch panel sensor, and display device
JP5569144B2 (en) Photosensitive conductive film, method for forming conductive film, and method for forming conductive pattern
CN114364532A (en) Transfer film, method for producing laminate, touch panel sensor, and touch panel
KR102292668B1 (en) Thermoplastic resin film base for optical firing, conductive circuit board using same, and method for manufacturing said conductive circuit board
JP6406618B2 (en) Reactive resin composition and its use
WO2021065322A1 (en) Transfer film, method for producing multilayer body, multilayer body, touch panel sensor, and touch panel
WO2021065331A1 (en) Transfer film, laminate production method, laminate, touch panel sensor, and touch panel
TW201533534A (en) Conductive paste, method for producing pattern, method for producing conductive pattern and sensor
WO2021065288A1 (en) Transfer film, method for producing laminate, laminate, touch panel sensor, touch panel
WO2021039187A1 (en) Transfer film, method for producing transfer film, method for producing laminate, laminate, touch panel sensor, and touch panel
JP5927004B2 (en) Conductive paste and conductive circuit
JP2017156510A (en) Photosensitive conductive film, method for forming conductive pattern, conductive pattern substrate, and touch panel
CN116841120A (en) Composition for preparing ultraviolet-sensitive photoetching silver paste, and preparation method and application thereof
WO2018138879A1 (en) Photosensitive conductive film, conductive pattern formation method, conductive pattern substrate production method, conductive pattern substrate, and touch panel sensor
KR101685743B1 (en) A photosensitive resin composition having high sensitivity and high remaining rate

Legal Events

Date Code Title Description
A201 Request for examination
A302 Request for accelerated examination
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant
FPAY Annual fee payment

Payment date: 20160701

Year of fee payment: 4

FPAY Annual fee payment

Payment date: 20170709

Year of fee payment: 5

FPAY Annual fee payment

Payment date: 20190827

Year of fee payment: 7