KR20170031854A - Photo-curable resin composition - Google Patents

Abstract

The present invention relates to a hybrid-type composite photocurable resin composition which is used in the production of electrode pastes for touch screen panels. More specifically, the present invention relates to a photocurable resin composition which contains Ag powder (A), a photosensitive resin composition (B), a solvent (C), and an additive (D). The photosensitive resin composition (B) includes: a photosensitive oligomer/polymer (a); a photopolymerizable monomer (b); a photopolymerization initiator (c); and an additive (d).

Description

{PHOTO-CURABLE RESIN COMPOSITION}

The present invention relates to a hybrid type composite photo-curing resin composition used for manufacturing an electrode paste for a touch screen panel.

Recently, with the rapid spread of electronic communication devices, attention has been paid to devices constituting these devices. There is a growing interest in printing electronic devices associated with displays such as flat panel display panels, RFID, batteries, and organic transistors. Among them, touch screen panels, which have been mainly used in industrial products such as ATMs and kiosks in the past, are being applied to portable electronic devices such as smart phones and navigation devices. A touch screen panel, also referred to as a touch panel, can be used to identify the position of a person or other object (pen) in contact with a character or specific location on the screen, without using an input device such as a keyboard or a mouse Means a panel that is to be processed.

Currently, touch screen panels are being developed as large-sized, high-permeability, slimmer, lightweight, and low-cost. The electrodes used in the touch screen panel are divided into a bezel electrode and a sensor electrode, and attention has been paid to a method of enlarging the screen within a limited size by minimizing the bezel electrode. However, as the size of the touch panel becomes larger and the size of the bezel electrode becomes smaller, it becomes impossible to form a bezel electrode or a sensor electrode as a conventional process method. Therefore, a new patterning method is required. Since the metal electrode is wired on the bezel, it can not be reduced unconditionally, and it is a key technology to minimize the line width of the wiring. In particular, as the screen size increases, the number of channels increases and the number of wirings increases, and the thickness difference of the bezel increases according to the patterning process.

Currently, screen printing, gravure offset, and laser etching method are applied to the bezel electrode forming method. The screen printing method is a technique capable of patterning at the lowest unit cost, but it is difficult to achieve patterning at 70/70 μm or less. The gravure offset printing method can be applied to 40/40 μm of film and 30/30 μm of glass. However, due to the swelling of the used silicone blanket sheet, the continuous printing is only about 100 to 150 sheets, resulting in poor mass productivity. There is a difficult problem entering the company. In addition, the laser etching method has a problem that the production cost is increased due to complicated processes. Screen printing is the simplest and most traditional method of printing patterning that is most commonly used to pattern electrical and electronic circuits. The longer the material is, the more reliable the materials and patterns are. Recently, many studies have been carried out to apply OTFT fabrication process, which requires a pattern of several micrometers wide electrode width, in accordance with the development of screen mesh technology, the development of nano metal paste manufacturing technology, and the development of precision screening equipment technology . The basic method is a process of applying a conductive paste onto a substrate through a screen mask and is an inexpensive and simple method in which only a screen mask and a paste are exchanged as needed in one screen printing equipment. The principle is simple: the squeezer acts as a brush, and the paste serves as a paint, and a film of a certain thickness can be applied by using a screen mesh made of a screen material. At present, a stable pattern has a line / space (line / space) pattern that is finer than 100/100, and technically, a technique capable of producing up to 80 and 60 탆 has been established recently. The biggest disadvantage and advantage is that the printing thickness is about 20 μm thick compared to other methods. This is difficult to overcome due to the physical limitations of the screen mesh, and it is possible to control the viscosity slightly to reduce the thickness, but the reliability of the print reproducibility is somewhat reduced.

As described above, the screen printing method has advantages such as low investment cost, material cost, simple process, and securing of reliability by long experience. However, there are limitations in the implementation of fine patterns, and laser etching method has complicated process steps and high production cost. A photosensitive silver paste method has been proposed as a solution to this problem. The photosensitive silver paste method is disadvantageous in terms of investment cost, material cost, and process number, but can realize a fine line width of less than 30 μm. The photosensitive silver paste patterning method is similar to the process used in conventional semiconductor / LCD processes (deposition → exposure → etching). Only the bezel portion is subjected to screen printing → pre-heating → UV-exposure → develpment → rinse → post-heating. The photosensitive silver paste method using a photolithography method rather than a screen printing method or a laser etching method is in the development stage in Korea and is still being adopted only by a small number of companies. Therefore, mass production verification is further required. It is one step.

KR2012-0129229 discloses a conductive paste composition for a touch panel comprising a resin solid content of a polyester-based acrylate oligomer. However, the above-mentioned prior art does not solve the above-mentioned problems and can realize high optical activity There is a continuing need for a novel photocurable resin composition having excellent sensitivity and improved heat resistance.

Further, in order to make the thickness of the metal electrode formed in the bezel region thin, a resin composition improved in patterning property which can realize a precise pattern shape using UV curing and a pattern having a fine line width is desired.

Accordingly, the inventors of the present invention have conducted various studies with a view to developing a hybrid type composite photo-curable organic oligomer / polymer resin composition capable of first curing using UV, pattern development using an aqueous alkaline solution, and then thermosetting. As a result, excellent optical activity and heat resistance The present invention has been completed.

An object of the present invention is to provide a photo-curable resin composition having excellent photoactivity and heat resistance.

Another object of the present invention is to provide a photocurable resin composition having excellent chemical resistance and low dielectric properties and excellent in fine patterning properties.

Another object of the present invention is to provide a process for producing a hybrid composite resin having improved physical and chemical properties compared with conventional linear photosensitive resin polymers.

It is another object of the present invention to provide an electrode paste for a touch screen panel having improved heat resistance and fine patternability.

Other objects and advantages of the present invention will become more apparent from the following detailed description of the invention and claims.

In the following description, for purposes of complete understanding of the present invention, various specific details are set forth, such as specific forms, compositions, and processes, and the like. Reference throughout this specification to "one embodiment" or "embodiment" means that a particular feature, form, composition, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. Accordingly, the appearances of the phrase " in one embodiment "or" the embodiment "in various places throughout this specification are not necessarily indicative of the same embodiment of the invention.

Hereinafter, the present invention will be described in detail.

According to one embodiment of the present invention, the fluorene type terpolymer composite resin is produced by the three-step heating polymerization process to improve the performance of the existing linear epoxy-urethane oligomer and to improve the heat resistance, Characteristics and oxidation resistance, and a method for producing the same. BACKGROUND OF THE INVENTION

According to one embodiment of the present invention, the present invention relates to a process for preparing an acrylate oligomer containing a fluorene group, followed by mixing a monomer of an aromatic acid anhydride and a tetracarboxylic dianhydride with a monomer of an alicyclic diisocyanate, Based hybrid composite resin composition having flexibility, conductivity, and fine patternability in combination with photoactive reactivity and heat resistance. In particular, in order to improve developability, it is preferable to use an acrylate-based composite resin having a functional group substituted with a dicarboxylic acid.

In one embodiment of the present invention, the electroconductive paste of the present invention comprises a first fluorene monomer capable of photo-curing and thermosetting, including an ester bond derived from a carboxylic acid and an acid anhydride and a (meth) acrylate group at the terminal thereof; A second fluorene monomer having an isocyanate group and a (meth) acrylate group at its terminals and capable of photo-curing and thermosetting; A multifunctional tertiary fluorene monomer having an aromatic dicarboxylic group and a (meth) acrylate group, thereby being excellent in interlaminar adhesive strength and being capable of photo-curing and thermosetting. In this embodiment, the order of the monomer units can be adjusted in the resulting copolymer by controlling the order and composition of the monomer feed. For example, a fluorene-epoxy urethane oligomer containing a long block of urethane bonds is first introduced into a short block of an oligomer obtained by polymerizing a fluorene-acrylate homopolymer and an aromatic acid anhydride in an appropriate ratio to prepare a copolymer And the tetracarboxylic dianhydride group containing a diphenyl group in the remaining fluorene-acrylate monomers as a whole.

In one embodiment of the present invention, the composition of the present invention comprises (A) 60 to 85% by weight of a conductive metal powder; (B) 10 to 25% by weight of a photosensitive resin composition; (C) 1 to 10% by weight of a solvent; And (D) 1 to 5% by weight of an additive, based on the total weight of the photocurable resin composition.

More specifically, the present invention aims to provide a photosensitive resin composition (B) having improved photoactivity and heat resistance and a fine pattern of a photosensitive silver paste for a touch panel using the same.

In one embodiment of the present invention, the present invention is a photopolymerizable oligomer resin having excellent photoreactivity, photoactivity and photo-crosslinkability by introducing an acrylate functional group and a photoreactive group in place of the conventional thermosetting urethane / epoxy / ester oligomer, is a hybrid type photosensitive resin composition applicable to a dual cure system including pre-UV curing and post-thermal curing processes.

In one embodiment of the present invention, the resin composition of the present invention imparts photoactivity and hardness to the light-giving portion of the main chain and the side chain of the molecule so as to be cured by a small amount of light, and the non- And a carboxylic acid group is introduced thereinto to give a developing property.

In one embodiment of the present invention, the main skeleton of the resin composition of the present invention is an acrylate oligomer resin containing fluorene, and such an acrylate resin is excellent in ease of viscosity control, conductivity, adhesiveness, solvent resistance and printability It has advantages.

In general, an epoxy resin is excellent in heat resistance and chemical resistance, a urethane resin is rich in flexibility and excellent in adhesiveness, whereas a general-purpose epoxy acrylate oligomer contains a large amount of chlorine ion, which is likely to cause electrical corrosion. In general, the epoxy acrylate has a hydroxyl group at a certain distance from the acryloyl group, which prevents some degree of oxygen inhibition upon UV curing. However, when the functional group is introduced, the absorption rate is increased due to the increase of the crosslinking density This increase in the absorption rate causes a fatal problem, particularly in the case of an electronic product, which degrades durability. On the other hand, the epoxy resin of the fluorene skeleton of the present invention is less susceptible to oxygen inhibition than the bisphenol skeleton, and has the advantage of exhibiting properties of high hardness and high heat resistance.

In one embodiment of the present invention, the urethane bonds of the present invention are designed to impart flexibility that is difficult to express in other materials because they show intermolecular interactions by hydrogen bonding of moderate strength. Specifically, by introducing ester and urethane bonds into the side chains of Fluorene-based acrylate oligomers and imparting a hydro clustering point (viscoelastic behavior and crosslinkability), it is possible to provide additional properties for fine patterning properties, adhesion, adhesion, So that they can contribute.

In one embodiment of the present invention, the epoxy-urethane composite type photo-formable acrylate oligomer resin having the fluorene structure as a basic unit of the present invention has low viscosity, excellent stability, excellent compatibility with other compositions and solubility , And is suitable for use in a photocurable (photosensitive) resin composition.

In one embodiment of the present invention, the fluorene-containing photocurable (photosensitive) composite resin of the present invention has a bulky molecular structure, a high degree of crystallinity, a high reactivity with a fluorene derivative comprising a large amount of aromatic rings and an aromatic acid anhydride Urethane-based acrylate composite resin, it has low thermal expansion / shrinkage characteristics while exhibiting low dielectric constant properties. Specifically, since the composite resin of the present invention is modified with a fluorene derivative, the content of the aromatic ring is increased and the electronic polarization phenomenon is reduced, so that the composite resin has a low dielectric property, which is advantageous for fine patterning. Also, due to the increase of the hydrophobic group, the hygroscopicity is low and the crosslinking property is also excellent, so that it has high heat resistance and chemical resistance, exhibits high photoreactivity and photoactivity, and can realize high sensitivity even at low exposure dose.

In one embodiment of the present invention, the paste prepared from the composition of the present invention can improve not only the photo-curability but also the developability, so that a fine electrode pattern can be formed on an electronic display panel such as a touch panel through a photo-curing process after printing.

In one embodiment of the present invention, the photosensitive resin composition (B) of the present invention may further comprise a photopolymerizable monomer, a photocuring initiator, and an additive, in addition to the photosensitive complex oligomer resin. For example, the photosensitive resin composition (B) of the present invention contains 80 to 95 wt% of the photosensitive oligomer (a), 5 to 15 wt% of the photopolymerizable monomer (b), 0.5 to 5 wt% of the photopolymerization initiator By weight, and 0.1 to 3% by weight of an additive (d).

If the content of the photosensitive oligomer (a) is less than 80% by weight as a constituent of the photosensitive resin composition (B), cracks due to photo-curing are generated, printing is poor, electrode formation is difficult, If it exceeds 95% by weight, the physical properties are lowered due to the occurrence of uncured components, and the adhesion between the conductive powder is lowered due to the increase of the residual amount, thereby lowering the resistivity characteristic. Can be reduced.

In one embodiment of the present invention, the photosensitive oligomer (a) of the present invention preferably has a weight average molecular weight (mw) in the range of 3,000 to 20,000 g / mol, and may be mixed with one or more acrylic oligomers or acrylic binders Do. The photosensitive oligomer prepared in the present invention has excellent compatibility with the structure of the cyclic molecule, thereby improving the solubility of the photosensitive resin composition and realizing the hybrid property of the thermosetting / photo-curing, so that the residual film ratio, mechanical strength, , Excellent chemical resistance and resistance to development, has an effect of improving conductivity and reducing resistivity, and can realize a fine patterning property.

In one embodiment, examples of the acrylic oligomer that can be mixed with the photosensitive oligomer (a) of the present invention include an epoxy acrylate oligomer (epoxy acrylate copolymer), a polyester acrylate oligomer, and a urethane acrylate oligomer One or more of these may be used in combination. The weight average molecular weight of the hybrid acrylic oligomer is preferably in the range of 500 to 1,500 g / mol.

Specifically, examples of the hybridizable acrylic oligomer of the present invention include polyfunctional dipentaerythritol hexaacrylate oligomer, glycidyl methacrylate, (meth) acrylic acid, alkyl (meth) acrylate, polyethylene glycol (meth) Glycol (meth) acrylate, and the like. Also, copolymers using pentaerythritol tri (meth) acrylate, pentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate may be used, but the present invention is not limited thereto. The content of the hybridizable acrylic oligomer may further be 0.1 to 30 parts by weight based on 100 parts by weight of the photosensitive oligomer (a) of the present invention. If the amount of the hybridizable oligomer is less than 0.1 part by weight, the curing reaction and the adhesion improving ability with the substrate may be lost. If the amount of the oligomer exceeds 30 parts by weight, the remaining oligomer The contact resistance is increased.

In one embodiment of the present invention, as the acrylic binder which can be mixed with the photosensitive oligomer (a) of the present invention, those generally used in the art can be used as an alkali soluble binder. Concretely, an acrylic binder resin containing a carboxyl group can be used, and more specifically, a copolymer formed by copolymerizing a monomer giving mechanical strength of a film with a monomer giving alkali solubility can be used.

Specifically, monomers usable for controlling the mechanical strength of the film include, for example, benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (Meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl Hydroxypropyl (meth) acrylate, ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, 2- (Meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (meth) Late, methoxy (Meth) acrylate, methoxytripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxypolyethylene glycol (Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, p-nonylphenoxypolypropylene glycol (Meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, oxyl (meth) acrylate, (Meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl methacrylate, methyl a-hydroxymethylacrylate, ethyl a-hydroxymethylacrylate And unsaturated carboxylic acid esters such as propyl [alpha] -hydroxymethyl acrylate, butyl [alpha] -hydroxymethyl acrylate, but are not limited thereto.

In one embodiment, the monomer that imparts alkali solubility includes, for example, (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethyl maleic acid, 5- (Meth) acryloyloxy) ethyl phthalate, mono-2 - ((meth) acryloyloxy) ethyl succinate and? -Carboxylic polycaprolactone mono But is not limited thereto.

For example, when an acrylic binder resin, which is a copolymer of the above-mentioned monomers, is used in combination, the viscosity can be controlled and the patterning ability using an alkali developer can be improved. Specifically, the binder resin for hybridization preferably has a weight average molecular weight of 3,000 to 50,000 g / mol. If the molecular weight is less than 3,000 g / mol, loss of the pattern may occur during the development process of the pattern, or pattern collapse may occur during the subsequent process. If the molecular weight is more than 50,000 g / mol, the viscosity becomes high and printing becomes difficult.

In one embodiment of the present invention, the content of the hybrid binder resin is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the photosensitive oligomer (a) of the present invention. When the content of the hybrid binder resin is less than 0.1 part by weight, the function as an effect of improving the patterning using the alkali aqueous solution is lost. When the amount is more than 20 parts by weight, the viscosity of the composition becomes too high,

In one embodiment of the present invention, the photosensitive oligomer (a) prepared with the photosensitive resin composition (B) of the present invention may be prepared using a thermal initiator if necessary. The thermal initiator may comprise a cation or radical initiator, which may lead to a chain polymerization of a fluorene- (meth) acrylate oligomer and a monomer containing a crosslinking functional group (such as a hydroxyl group, a carboxyl group and an acid anhydride, an isocyanate group or an epoxy group) have.

Specifically, the cationic initiator allows the oligomer to be thermally cured at a low temperature and at a high speed. Cationic initiators that can be used in the present invention include, for example, ammonium / antimony hexafluoride, triarylsulfonium hexafluoroantimonate salts, trianylsulfonium hexafluoroantimonate, Bis (dodecylphenyl) iodonium hexafluoroantimonate, iodonium (4-methylphenyl) (4- (2-methylpropyl) phenyl) hexafluoro N-benzylpyridinium salts, N-benzylpyridinium salts, N-benzylammonium salts, phosphorus compounds such as N-benzylpyridinium salts, N-benzylpiperazinium salts, N-benzylpyridinium salts, Ammonium borate salts, triphenylmethyl chloride, and mixtures thereof, preferably ammonium / antimony hexafluoride, trianyl sulfonium hexafluoroantimonate, triaryl sulfonium hexafluoroantimonate, tri Carbonyl chloride and the like, but is not limited to these.

Specific examples of the radical initiator that can be used in the present invention include benzoylperoxide, lauroylperoxide, diacetylperoxide, or di-tert-butylperoxide. peroxides such as butylperoxide; Hydroperoxide compounds such as cumyl hydroperoxide; Azobisisobutyronitrile (AIBN), 2,2'-azobis [2-methyl-N- (2- ( Azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis [N-butyl- Azo compounds such as 2,2'-azobis [N-cyclohexyl-2-methylpropionamide] and 2,2'-azobis (2-methylpropionate) But are not limited to these.

Particularly, in one embodiment of the present invention, the cyclohexane-carbonitrile-based compound decomposes at a temperature of 100 ° C or higher and reacts, so the curing reaction proceeds from the drying temperature (less than 100-200 ° C) Can be suppressed and consequently high resolution patterns can be realized. In addition, at room temperature, the curing reaction is inhibited and there is no viscosity change under the storage condition of 25-40 ° C.

In one embodiment of the present invention, the content of the cation and the radical initiator may be 0.01 to 10 parts by weight. When the content of the initiator is less than 0.01 part by weight, crosslinking with the oligomer is not sufficient and curing by the unreacted oligomer is lowered. When the content of the initiator exceeds 10 parts by weight, unnecessary initiator remains, Not only is it economical.

In one embodiment of the present invention, the photosensitive resin composition (B) of the present invention is a photopolymerizable monomer (b), and a (meth) acrylate-based monomer may be selectively used. Since the photosensitive resin composition (B) causes photo-curing in a short time using ultraviolet rays, a large amount of a solvent can not be used. However, when the viscosity is too high, the photopolymerizable monomer (b) having a lower viscosity than the photosensitive oligomer (a) is used for controlling the viscosity, because it adversely affects the film thickness and pattern forming conditions. The photopolymerizable monomer (b) has the effect of increasing the hardness of the cured film, facilitating the printing operation on the substrate, and enhancing the adhesion with the adherend. Bifunctional, and multifunctional monomers, depending on the number of (meth) acrylate groups present in a molecule. Increasing the content of multifunctional monomers increases the number of crosslinks. However, when the content of the monomer is increased to 6 or more, the cross-linking density is excessively increased, so that the shrinkage ratio is increased and cracks may be formed in the cured film.

Specifically, photopolymerizable monomers that can be used in the present invention include, for example, 2-hydroxypropyl acrylate (HPA), 4-hydroxybutyl acrylate (4-HBA) Monofunctional acrylate monomers such as octyl decyl acrylate (ODA) and isobonyl acrylate (IBOA); As the polyfunctional acrylate monomer having two or more functional groups, it is preferable to use an acrylic monomer such as ethylene glycol diacrylate (EGDA), neopentylglycol hydroxy pivalate diacrylate, neopentyl glycol hydroxy pivalate diacrylate But are not limited to, but are not limited to, neopentylglycol hydroxypivalate diacrylate modified caprolactone, bisphenol A diacrylate, hexanedioldiacrylate (HDDA), tetraethyleneglycol diacrylate (TTEGDA), trimethylol (TMP) or trimethylolpropane triacrylate (TMP (EO) 1-20TA) modified with 1-20 ethylene oxide groups, pentaerythritol triacrylate tr (DPTA), ditrimethylolpropane tetraacrylate (DTMPTA), dipentaerythritol hexaacrylate (DPHA), or 1- (4-hydroxyphenyl) propane triacrylate Ethoxylated dipentaerythritol hexaacrylate (EO) 1-20DPHA) modified with 20 ethylene oxide groups, dipentaerythritol hexaacrylate modified caprolactone, and the like. But the present invention is not limited thereto. By using the above-mentioned photopolymerizable monomer, the curing and developability of the binder composition can be improved at the same time.

In one embodiment of the present invention, the photopolymerizable monomer is preferably used in an amount of 20% by weight or less based on the total resin composition. More preferably 5 to 15% by weight. If the content is out of the above range, the monomer that does not participate in the reaction may remain as an impurity and the curing rate may be lowered, and the photo-curing may not be sufficient and the physical properties may be deteriorated.

In one embodiment of the present invention, the photopolymerizable monomer according to the present invention can be used by mixing a monofunctional acrylic monomer and a polyfunctional acrylic monomer. In one embodiment of the present invention, 5 to 50 parts by weight of the monofunctional acrylic monomer and 1 to 30 parts by weight of the polyfunctional acrylic monomer are preferably used, based on 100 parts by weight of the photosensitive oligomer (a) 7 to 20 parts by weight of monofunctional acrylic monomer and 1 to 13 parts by weight of polyfunctional acrylic monomer can be used.

In one embodiment of the present invention, the monofunctional acrylic monomer may be selected from the group consisting of acrylic morpholine (ACMO), tetrahydrofurfuryl acrylate (THFA), hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA) , Isobornyl acrylate (IBOA), and the like, but is not limited thereto. If the amount of the monofunctional acrylic monomer is less than 5 parts by weight, the viscosity may increase and the adhesiveness and conductivity may be poor. If the amount is more than 50 parts by weight, the ultraviolet curing property may be decreased and the productivity may be decreased.

In one embodiment of the present invention, the polyfunctional acrylic monomer is mainly used as a viscosity modifier, and conventional multifunctional acrylic monomers used in this application can be applied. For example, diethylene glycol diacrylate (Diethylene glycol diacrylate (DEGDA), dipropylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), hexanediol diacrylate (HDDA), polyethylene glycol 400 diacrylate (PEG 400DA), polyethylene glycol 600 diacrylate (PEG 600DA), and the like, but is not limited thereto. When the amount of the polyfunctional acrylic monomer is less than 1 part by weight, the viscosity may increase. When the amount is more than 30 parts by weight, the physical properties of the resin composition may be adversely affected.

In one embodiment of the present invention, the photoinitiator (c) is used for causing a polymerization reaction of the resin composition when ultraviolet rays are irradiated after forming a coating film, and any polymerization initiator for this purpose may be used. Specifically, it is preferable to use a conventional polymerization initiator which is activated by ultraviolet rays, more preferably a benzophenone type, benzoin, benzoin ether type, benzyl ketal type, acetophenone type, anthraquinone type, Oxo zantones and the like may be used. At this time, the compounds may be used singly or in combination of two or more.

Specifically, photoinitiators that can be used in the present invention include, for example, commercially available Irgacure 184 (1-hydroxycyclohexyl phenyl ketone) from Ciba Geigy, Cure 1173 (2-hydroxy 2-methyl 1-phenyl 1 -propanone), Darocur MBF (methylbenzoyl) methylenebromide formate), Agacure 752 (oxyphenylacetic acid 2- (2-oxo 2-phenylacetoxyethoxy) ethyl ester and oxyphenyl acetic acid 2- (2-oxo 2-phenyl acetoxy ethoxy) Hydroxyphenylacetic acid 2- (2-hydroxyethoxy) ethyl ester), IGACURE 651 (alpha, alpha-dimethoxy alpha-phenylacetophenone , alpha-dimethoxy alpha-phenylacetophenone), IGACURE 369 (2-benzyl 2 (dimethylamino) 1- (4- (4-morpholinyl) phenyl) yl 2- (dimethylamino) 1- (4- (4-morpholinyl) phenyl) 1-butanone), IGACURE 907 (4-methylthio) phenyl0 2- (4-morpholinyl) 1 -propanone), duralocyantipio (TPO) (diphenyl (2,4,6-trimethyl (2,4,6 trimethylbenzoyl) phosphine oxide), IGACURE 810 (phosphine oxide, phenyl bis (2,4,6 trimethylbenzoyl) (phosphine oxide, phenyl bis 6 trimethyl benzoyl), IGACURE 784 (bis (ita 5-2,4-cyclopentadiene 1-yl) bis (2,6-difluoro 3- (1H- bis (eta 5-2,4-cyclopentadien 1-yl) bis (2,6-difluoro 3- (1H-pyrrol 1-yl) phenyl) titani um), IGACURE 250 (4- (2-methylpropyl) phenyl) -, hexafluorophosphate (1-)), diarylphosphine Cure Bipy (BP) (benzophenone ), Daurocure CGI # 1800 (bisacyl phosphine oxide), and CGI # 1700 (bisacyl phosphine oxide and hydroxy ketone). But are not limited to these.

In one embodiment of the present invention, the photoinitiator is preferably contained in an amount of 0.01 to 10% by weight, more preferably 0.1 to 5.0% by weight of the total resin composition. If the content of the photoinitiator is less than 0.1 wt%, the photoreaction time may be prolonged or the photoreactivity may remarkably decrease, and the surface energy due to the unreacted monomer may increase, which may cause the adhesion strength to be weakened. Conversely, if the content of the photoinitiator exceeds 5.0% by weight, the unreacted photoinitiator may remain as an impurity. Surface unreacted part of the photoinitiator reacts with oxygen in the atmosphere to form a hydrogen donor, which leads to a decrease in the molecular weight, resulting in decreased adhesion and increased hygroscopicity. On the other hand, if the content exceeds 10% by weight, rapid photoreaction may be induced and bubbles may be generated.

In one embodiment of the present invention, the photocurable resin composition according to the present invention may contain various additives such as an antioxidant, a light stabilizer, an ultraviolet absorber, a thermal binder, a smoothing agent, a defoaming agent, a dispersant, A plasticizer, an organic filler, or a mixture thereof. Examples of the antioxidant that can be used in the present invention include Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1222 (Shiba Gagai, Japan), and light stabilizers Tinuvin 292, Tinuvin 144, Tinuvin 622 LD ), sanol LS-770, sanol LS-765, sanol LS-292, sanol LS-744 Examples of the thermal polymerization inhibitor include HQ, THQ, and HQMME. Examples of the smoothing agent, defoaming agent, and dispersing agent include BYK and the like. But it is not limited to these. At this time, the content of the additive may be varied in a range that does not change the physical properties required of the photocurable resin composition of the present invention, for example, in the range of 0.1 to 15 parts by weight based on the weight of the entire photocurable resin composition .

In one embodiment of the present invention, (A) the conductive metal powder is at least one selected from the group consisting of Ag, Au, Co, Ni, Cu, Pd, Pt, Is a metal powder selected from the group consisting of tin (Sn), zirconium oxide, tin oxide, antimony oxide, nickel oxide, aluminum oxide, indium tin oxide (ITO) and combinations thereof. The conductive powder can be used without any particular limitation as long as it is used as a conductive powder in the production of an electrode. Preferably, a silver powder can be used.

In one embodiment of the present invention, the conductive metal powder may be a powder having an average particle diameter of 0.05 to 10 mu m, preferably 0.1 to 5 mu m. The conductive metal powder may be used by mixing two or more kinds of powders having various particle sizes and shapes. In this case, the powders having an average particle diameter of 0.05-2 탆 and an average particle diameter of 2-10 탆 Can be mixed and used. The shape of the conductive metal powder may be spherical, non-spherical, dendrite, flake / plate, or a mixture of two or more thereof. It is advantageous to increase the precision of printing by mixing metal powders having various particle shapes and sizes. Such a conductive metal powder may be contained in an amount of 60 to 85% by weight in the paste composition. When the amount of the metal powder is less than 60 wt%, it is difficult to form a high-resolution electrode pattern by printing because the viscosity of the paste is too low. Even if an electrode is formed on the substrate, the spreading of the electrode is very serious and the aspect ratio of the pattern is extremely low. When the amount of the metal powder exceeds 85% by weight, the viscosity is so high that printing is not easy, so that it is difficult to form electrodes on the substrate. Also, since the content of the resin is relatively low, .

In one embodiment of the present invention, the solvent (C) constituting the photosensitive paste composition of the present invention is preferably an inert or non-aqueous solvent. At this time, it is preferable that the diluting solvent which is a liquid component of the resin has a boiling point in the range of 80 to 240 캜 so that the resin solid component can be cured within 20 seconds in an ultraviolet atmosphere. The solvent serves to plasticize the surface of the oligomer / polymer resin to increase the free volume and fluidity and to increase the mutual diffusion rate of molecular chains to form a uniform pattern. For example, terpineol, N-methylpyrrolidone (boiling point: 202 ° C), butyl cellosolve (boiling point: 171.2 ° C), and the like can be used in the present invention. Ethyl glycol monobutyl ether acetate with a boiling point of 192 ° C, Ethyl carbitol with a boiling point of 201.9 ° C, Ethyl citalol acetate with a boiling point of 217.4 ° C, Butyl carbitol, catechol and boiling point 230.6 ℃), ethoxyethyl acetate (boiling point 156.3 ℃), ethyl cellosolve (2-ethoxyethanol, boiling point 135 ℃), ethyl cellosolve acetate (ECA, Propylene glycol monomethyl ether (boiling point 121 ° C), propylene glycol monomethyl ether acetate (propylene glycol monoethyl ether acetate, boiling point: 156 ° C), butyl acetate (boiling point: 126 ° C), propylene glycol monomethyl ether l monomethyl ether acetate, boiling point 146 占 폚), gamma-butyrolactone (boiling point 204 占 폚), methyl ethyl ketone (MEK), boiling point 80 占 폚), and the like. But it is not limited thereto. (MEK), 2-ethoxyethanol (2EE), and ethylcellosolve acetate (ECA), in consideration of the adhesive strength of the print film to the substrate, It may be preferable to use any one substance alone or in combination of two or more substances.

A photocurable electrode paste having a weight ratio of the solid content: the organic solvent of 70:30 to 99: 1 to the solid content including the conductive metal powder (A), the photosensitive resin composition (B), and the photoinitiator (C) To form a composition. The photo-curable electrode paste composition of the present invention contains the above-mentioned solid content in a high content so that it can exhibit a high viscosity paste composition and can form a fine pattern by photo-curing. The viscosity of the paste composition is not particularly limited as long as it has appropriate fluidity and patternability. For example, the viscosity of the paste composition may be about 1,000 to 20,000 cps, about 2,000 to 15,000 cps, or about 3,000 to 10,000 cps (Brookfield viscometer; DV-II + pro viscometer, 25 캜, 3 rpm). The content of the solvent may be 1 to 30% by weight in the paste composition, preferably 1 to 10% by weight. When the content of the solvent is less than 1% by weight, the content of the solid is relatively high and printing can not be performed due to an increase in viscosity. Therefore, it is difficult to form an electrode pattern and the adhesion of the resin composition to the substrate is low And the electrode may fall off. When the content of the solvent is 30 wt% or more, it is difficult to form a high-resolution electrode pattern by printing because the viscosity of the paste is too low. Even if an electrode is formed on the substrate, spreading of the electrode is very serious and the aspect ratio of the pattern is extremely low.

In one embodiment of the present invention, the photo-curable paste according to the present invention may be prepared by adding additives, which are usually contained in a paste, if necessary in order to improve thermal and oxidative stability, storage stability, surface properties, flow characteristics, As shown in FIG. Examples of the additives include a thickener, a stabilizer, a dispersant, a defoamer, a surfactant, a leveling agent, a slip agent or a stabilizer, and a mixture thereof. These components are added to the photocurable electrode paste composition in an amount of 0.1-5 weight %. ≪ / RTI >

In one embodiment of the present invention, the electrode paste of the present invention having the above composition is prepared by blending the above-described essential components and optional components according to a predetermined ratio, and blending them in a blender or a 3-roll mill And can be obtained by uniformly dispersing.

In one embodiment of the present invention, the step of forming fine patterns of electrode paste using the photosensitive resin composition includes a step of applying a photosensitive resin composition on a substrate, and a step of exposing and developing the applied photosensitive resin composition .

In one embodiment of the present invention, the light irradiated in the exposing step has a wavelength of 200 to 500 nm, and the developer used in the developing step may be sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate Na ₂ CO ₃ ), sodium sulfite (Na ₂ SO ₃ ), sodium silicate, sodium silicate, ammonia, and combinations thereof.

In one embodiment of the present invention, the photosensitive resin composition (B) comprises a cardo-based acrylate oligomer resin containing a fluorene structure, and the thermosetting urethane-based, epoxy-based, ester-based monomer / oligomer / prepolymer Is a composite photocurable (photosensitive) resin composition which has been modified and polymerized.

In one embodiment of the present invention, the cargo-based acrylate oligomer resin containing the fluorene structure has the structure of the following formula (1)

Formula 1

R ₁ is each independently selected from the group consisting of -H, (meth) acryloyl, (meth) acryloyl C 1-10 alkyl, (meth) acryloyloxy C 1-10 alkyl, C 6-20 aryl, Wherein the C6-20 aryl, C1-20 alkyl, and C6-20 aryl C1-20 alkyl are substituted with a (meth) acryloyl group, and at least one carbon atom constituting the substituent is substituted with Lt; / RTI > may be substituted with one or more heteroatoms selected from N, O, S;

R ₂ is a substituted or unsubstituted C 1-10 alkylene, a substituted or unsubstituted C 4-14 cycloalkylene, a substituted or unsubstituted C 6-14 arylene, or a combination thereof;

R ₃ is selected from the group consisting of -H or a C1-10 alkyl group, a hydroxyl group, an epoxy group;

n is an integer of 1 to 6;

Here, suitable aliphatic and aromatic (meth) acryloyl groups for preparing R < ₁ > include the following compounds: 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate (2- hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl methacrylate, 2- 2-hydroxybutyl acrylate, grycerin dimethacrylate, 2-hydroxy-3-acryloyloxy propyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxy-3-phenoxy propyl acrylate, 2-acryloyloxy ethyl 2-hydroxy ethyl phthalate, Examples thereof include pentaerythritol triacrylate, trishydroxyethyl isocyanurate diacrylate, trishyroxyethyl isocyanurate dimethacrylate, pentaerythritol diacrylate, But are not limited to, acrylate monostearate, pentaerythritol diacrylate monostearate, pentaerythritol dimethacrylate monostearate, and the like.

As used herein, an alkylene group refers to a linear or branched divalent hydrocarbon moiety of 1 to 10, or 1 to 8, or 1 to 4 carbon atoms, and includes at least one unsaturated bond . But are not limited to, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, nonamethylene, decamethylene and the like, and one or more hydrogen atoms may be substituted with any substituent .

Also, the cycloalkylene groups used in the context of the present invention may have 4 to 14, or 4 to 10, or 4 to 6 ring carbon nonaromatic divalent monocyclic, bicyclic, or tricyclic hydrocarbon moieties And may include at least one unsaturated bond in the molecule. A divalent cyclopentane ring, a cyclohexane ring, and the like, but it is not limited thereto, and at least one hydrogen atom may be substituted with an arbitrary substituent.

The arylene group used in the specification of the present invention means a divalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety having 6 to 14, or 6 to 12 ring atoms, and includes a divalent benzene ring, Naphthalene ring, anthracene ring, biphenyl ring, and the like, but not limited thereto, at least one hydrogen atom may be substituted with any substituent.

In one embodiment of the present invention, the multifunctional composite photo-curable resin composition of the present invention is a photo-curable resin composition having a structure represented by the following formula (2)

(2)

here,

R ₁ is each independently selected from the group consisting of -H, (meth) acryloyl, (meth) acryloyl C 1-10 alkyl, (meth) acryloyloxy C 1-10 alkyl, C 6-20 aryl, Wherein the C6-20 aryl, C1-20 alkyl, and C6-20 aryl C1-20 alkyl are substituted with a (meth) acryloyl group, and at least one carbon atom constituting the substituent is substituted with Lt; / RTI > may be substituted with one or more heteroatoms selected from N, O, S;

L ₁ to L ₃ are each independently selected from the group consisting of -C (= O) -, -C (= O) NH- and -NHC (= O) -;

X and Y are C1-10 alkylene, saturated or unsaturated C4-14 cycloalkylene, C6-14 arylene or combinations thereof;

Z is a saturated or unsaturated C4-14 cycloalkylene having at least two -COOH groups, C6-14 arylene or a combination thereof,

l, m and n are each an integer of 1 to 6;

In one embodiment of the present invention, among the compounds of formula (2), R ₁ is preferably -H or (meth) acryloyl.

In one embodiment of the present invention, L ₁ and L ₃ are -C (═O) - and L ₂ -YL ₂ is -C (═O) NH-Y-NHC (═O) - Structure.

In one embodiment of the present invention, X is a C1-10 alkylene, a saturated or unsaturated C4-14 cycloalkylene, a C6-14 arylene, or a combination thereof, and the aromatic and alicyclic acid anhydride , And more preferably from an anhydride of a cycloalkane ring type containing at least one unsaturated bond. Specific examples thereof include, but are not limited to, cyclopentane rings, cyclopentene rings, cyclohexane rings, and cyclohexane ring anhydrides (acid anhydrides).

It is preferred that at least one carbon-carbon unsaturated double bond of the acid anhydride compound is conjugated with at least one carbonyl group of the acid anhydride group for better UV-induced radical curing. Due to the at least one carbon-carbon unsaturated double bond of the acid anhydride compound according to the present invention, the adhesion and heat resistance of the fluorene epoxy-modified acrylate derivative through the covalent bond resulting from the esterification reaction between the hydroxyl group of the side chain and the acid anhydride group Is secured.

In one embodiment of the present invention, in the case where at least one hydrogen atom has an ester bond formed by an acid anhydride substituted with a hydrophobic methyl group, it is possible to improve the resistance to water and oxidation, and to secure the heat resistance and the vulcanization resistance. Improvement can be expected.

In one embodiment of the present invention, the fluorene-type epoxy-modified acrylate ester oligomer is preferably 30 to 48 parts by weight, preferably 32 to 40 parts by weight, based on the entire photocurable resin composition. If the amount is less than 30 parts by weight, mechanical strength, heat resistance, and abrasion resistance may be poor. If the amount is more than 48 parts by weight, the viscosity of the resin may increase and the workability may decrease.

In one embodiment of the invention, the acid anhydrides for introducing X are preferably, but not limited to, the following compounds:

Here, R ₄ , R ₅ , and R ₆ are each independently hydrogen, a methyl group, or a halogen atom or a C1-10 alkyl group; a, b and c are integers of 0 to 2;

R ₇ to R ₁₂ are each independently a hydrogen, a methyl group, or a halogen atom, or a C1-10 alkyl group, a C4-14 cycloalkyl group, a C6-14 aryl group, or a combination thereof, ≪ RTI ID = 0.0 >S;< / RTI > d is an integer of 0 to 2;

R ₁₃ and R ₁₄ are each independently hydrogen, a methyl group, or a halogen atom or a C1-10 alkyl group; e and f are an integer of 0 to 2;

In one embodiment of the invention, the acid anhydrides for introducing X are preferably, but not limited to, the following compounds:

Y is a C1-10 alkylene, a saturated or unsaturated C4-14 cycloalkylene, a C6-14 arylene, or a combination thereof, and may be introduced by a compound selected from the following aromatic, aliphatic and alicyclic diisocyanate structures have. Preferred is an aromatic and alicyclic diisocyanate compound, more preferably an alicyclic cyclic diisocyanate compound containing a cyclohexane group free of double bonds or an aromatic cyclic diisocyanate compound containing an alkyl group between benzene and NCO Diisocyanate compound. The cyclohexane structure having no double bond or the alkyl group between benzene and NCO stops the resonance of the two due to the aromatic benzene structure and has a yellowing suppressing effect. At least one hydrogen atom of the diisocyanate compound may be substituted with a methyl group.

In one embodiment of the present invention, preferred diisocyanate compounds for introducing Y are, but are not limited to, those illustrated below:

Further, in one embodiment of the present invention, preferred diisocyanate compounds for introducing Y are exemplified by 4,4-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, 1,5'-naphthalene Diisocyanate, 1,4'-phenylenediisocyanate, 3,3'-dimethoxy-4,4'-biphenyllein diisocyanate, hexamethylene diisocyanate, 1,4'-cyclohexane diisocyanate, 4,4 ' -Dicyclohexyl methane diisocyanate, and isophorone diisocyanate, and these may be used alone or in combination of two or more. Particularly, a diisocyanate having a three-dimensional structure can be added, for example, 2,4-diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, xylylene diisocyanate, '-Dimethoxy-4,4'-biphenyllein diisocyanate, and the like, and the content thereof is suitably 2 to 25 mol% of the total diisocyanate content.

When these aromatic / alicyclic diisocyanates are added to the polymerization, an intermolecular hydrogen bond or an intramolecular hydrogen bond in a hard segment is loosely formed due to the steric hindrance of the diisocyanate, so that the soft segment, which is not substantially a hard segment, the same effect is obtained as the content of the soft segment increases. Accordingly, a resin composition having increased flexibility and elasticity can be obtained by forming a lot of soft domains, and cracking, shrinkage, and deterioration of physical properties of ester bonds in a molecular structure due to thermal hardening and photo-curing can be prevented and patterning can be improved. If the diisocyanate content is less than 2%, the effect of improving the flexibility and patternability is insufficient, and if it exceeds 25% by mole, the elasticity of the resin may be deteriorated rapidly. However, aromatic diisocyanates such as 4,4-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, 1,5'-naphthalene diisocyanate, 1,4'-phenylene diisocyanate and toluene diisocyanate can be used for polymerization When used, the yellowing due to the resonance double bond of the benzene ring structure can be exerted. Therefore, in the present invention, in order to realize heat resistance and fine patterning property to yellowing, alicyclic compounds having a cyclohexane group such as 1,4'-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate A diisocyanate compound and an aromatic cyclic diisocyanate compound containing an alkyl group between a benzene ring such as xylylene diisocyanate and 1,3-bis (1-isocyanato-1-methylethyl) benzene and NCO Most preferred. As a result, it is possible to realize excellent heat resistance and mechanical strength by polymerizing a large number of benzene structures and a selected cyclic acid anhydride due to the fluorene structure-containing, and it is possible to complement each other with low adhesiveness and patternability to high light transmittance.

In one embodiment of the present invention, the above-mentioned alicyclic and alkyl group-containing aromatic diisocyanate and the fluorene-type epoxy-modified acrylate containing a hydroxy group on the side chain are reacted to form a urethane bond securing heat resistance and vulcanization resistance, Adhesiveness and conductivity when the photocurable resin composition is formed into a coating film by copolymerization with a fluorene epoxy-modified acrylate ester. The fluorene-type epoxy acrylate oligomer modified with a urethane group is preferably 25 to 45 parts by weight, preferably 30 to 38 parts by weight, based on the entire photocurable resin composition. When the amount is less than 25 parts by weight, the abrasion resistance and the pattern forming ability may be poor. When the amount is more than 45 parts by weight, the viscosity of the resin increases and the workability may decrease.

In one embodiment of the present invention, Z may be formed by one compound selected from the following structures. Preferred as such compounds are aromatic and alicyclic tetracarboxylic acid anhydrides, more preferably dianhydrides having a diphenyl group.

In one embodiment of the invention, preferred compounds for introducing Z are as exemplified below, but are not limited thereto.

The tetracarboxylic dianhydride having a diphenyl group and the dicarboxylic acid resulting from the esterification reaction of the fluorene epoxy-modified acrylate having a hydroxy group in the side chain determine the acid value of the whole resin composition, It is preferable that developability for exposure and an aqueous alkali solution is ensured.

The patterning mechanism of the photosensitive paste by exposure and development using ultraviolet rays forms a salt by the neutralization reaction when the acid (-COOH) in the oligomer / polymer binder structure contained in the paste comes into contact with a developer which is an alkaline aqueous solution (R-COOH + Na ₂ CO ₃ → R-COO ^- Na ⁺ + NaHCO ₃ ), which is soluble in water and thus removes the paste in areas where it is not cured. On the other hand, the portion cured by ultraviolet rays is encapsulated by the cross-linked polymer network and is resistant to swelling, so that it is not washed away by the developer and remains as a pattern. It is the role of the monomer and the photoinitiator to form the part to be cured by exposure. When the photoinitiator is excited by ultraviolet rays, free radicals are formed, and these radicals react with monomers having carbon double bonds to form a photopolymerized chain rapidly and cure. The fluorene type epoxy-urethane acrylate composite resin according to the present invention is a multifunctional acrylate oligomer comprising a copolymer of fluorene type modified acrylate containing diacrylate and dicarboxylic acid. When the photopolymerization of the monomer proceeds It can have strong resistance to a developer because it forms a network by bonding with a monomer.

The fluorene-type acrylate oligomer containing a dicarboxylic acid is preferably 5 to 35 parts by weight, more preferably 15 to 30 parts by weight, of the total photocurable resin composition. When the amount is less than 5 parts by weight, the degree of curing of the coating film is decreased and alkalinity developability, surface hardness and heat resistance may be decreased. When the amount is more than 35 parts by weight, the hardness of the coating film may increase, resulting in poor flexibility, moldability, adhesion and conductivity.

In one embodiment of the present invention, the molar ratios of 1, m and n in formula (2) are preferably 1: m in the range of 0.8: 1 to 2.5: 1, and 1: n in the range of 0.6: 2 to 6.7: 2 . (meth) acrylate compound having a hydroxy group for forming an ester bond of (R) satisfying the condition of n < = (l + m) / 2 although the order of polymerization of l, m, , A range satisfying m / R &lt; 3 is preferable.

m is preferably not more than 60 mol%, more preferably not less than 25 mol% and not more than 50 mol%, based on (l + n). When the amount is more than 60 mol%, the viscosity increases and problems occur in the printing process. When the amount is less than 25%, the adhesiveness is deteriorated and the patternability is not fine or uneven. n is preferably not more than 50 mol%, more preferably not less than 0.5 and not more than 40 mol% based on (1 + m). If the amount is less than 0.5 mol%, the heat resistance effect will deteriorate after the crosslinking reaction.

In one embodiment of the present invention, the content of the ternary polymeric composite photosensitive oligomer resin (a) of Formula 2 is 80 to 95% by weight, based on the total weight of the photosensitive resin composition (B); The content of the photopolymerizable monomer (b) is 5 to 15% by weight; The content of the photopolymerization initiator (c) is 0.5 to 5% by weight; And the content of the other additives (d) is 0.1 to 3%. When the content of the oligomer is less than 80% by weight, cracks due to the photo-curing are generated. When the amount of the oligomer is more than 95% by weight, the property is deteriorated due to uncured.

Hereinafter, the present invention will be described in detail.

The present invention relates to a hybrid type composite photo-curable resin composition used for manufacturing an electrode paste for a touch screen panel, and provides a photo-curable resin composition having improved photoactivity and heat resistance.

1 is a photograph of cross-sectional profiles of patterns for Examples 1 to 4 and Comparative Examples 1 and 2 of the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples. It will be apparent to those skilled in the art that these embodiments are only for describing the present invention in more detail and that the scope of the present invention is not limited by these embodiments in accordance with the gist of the present invention .

Manufacturing example

Fluorene  Containing epoxy-urethane compound Photocurable Acrylate  Manufacture of resin

(1) Esterification and acrylation of fluorene-based epoxy oligomer: Preparation of prepolymer

For the purpose of imparting photoactive reactivity and crosslinkability, an acrylate functional group was introduced into a fluorene-based epoxy oligomer to prepare a bisphenol fluorene epoxyacylate oligomer. Ester linkages were formed by the addition reaction of the bisphenol fluorene epoxyacylate oligomer with the hydroxyl group and the cyclic carboxylic acid / anhydride to prepare photo-curable oligomers having flexibility together with heat resistance which is characteristic of epoxy.

(2) Isocyanation of prepolymer prepared: Preparation of urethane bond and polymer composite between prepolymers

A urethane bond was formed between the hydroxyl group and the diisocyanate group of the bisphenol fluorene epoxy acrylate oligomer using a bisphenol fluorene epoxy acrylate oligomer having photoactive reactivity and crosslinkability as a polyol to form an epoxy-urethane acrylate hybrid resin.

(3) Acid value of the prepared polymer and reactor application: Cross-linking of polymer and production of polyfunctional composite polymer

An epoxy-urethane acrylate complex polyfunctional resin was formed through the preparation of a copolymer of bisphenol fluorene epoxy acrylate oligomer and dianhydride (tetra-carboxylic acid anhydride). A phenolic / cyclic dianhydride or tetracarboxylic acid was added to the bisphenol fluorene epoxy acrylate oligomer to give a carboxyl group. The carboxyl group is most preferably from 0.5% to 30% of the total polymer, and the acid value is preferably in the range of from 40 to 200 mgKOH / g.

Concrete example

In the formula (1), examples of the compound to be introduced into the acrylating step of the fluorene-containing epoxy compound for the structure formation of R ₁ are as follows.

(Meth) acrylate, and reacts with an epoxy group (that is, a (meth) acrylate compound having a hydroxy group) to form a bisphenol fluorene epoxy acrylate unit structure.

Examples of the compound to be introduced into the crosslinking / polymerization step for the formation of the structure of R ₂ are as follows. To form an ester bond of the bisphenol fluorene epoxyacylate oligomer.

[Examples of dicarboxylic acid / anhydride-containing alkyl / cyclic compound]

Examples of the diisocyanate-containing alkyl / cyclic compound for the urethane bond of the bisphenol fluorene epoxy acrylate oligomer are as follows.

Examples of the acid value of the bisphenol fluorene epoxy acrylate oligomer and the cyclic and (di) phenylic dicarboxylic acid / anhydride compound for imparting the polyfunctional group are as follows.

Example

Fluorene  Containing ester / epoxy / urethane oligomer series hybrid  Composite photocurable resin

Example  One.

(1) Synthesis of bisphenol fluorene type epoxy [Scheme 1]

Epoxidation reaction was carried out using epichlorohydrin to fluorene type diphenol.

Epichlorohydrin was excessively used to introduce an epoxy group into the positive hydroxyl group of diphenol. After adding 25 g (0.071 mol) of 4,4 '- (9-fluorenylidene) -diphenol and 79 g (0.854 mol) of epichlorohydrin into a 250 mL round bottom flask, tetramethylammonium chloride Weight%) and dimethylsulfoxide (25 g, 100 weight% based on diphenol). The temperature of the reactor was raised to 100 DEG C with stirring using a magnetic stirrer. After the reaction was dissolved, sodium hydroxide (3.72 g, 0.093 mol) was added in portions over 1 hour. Thereafter, the mixture was stirred at a reaction temperature of 100 ° C for 6 hours. TLC was used to confirm the consumption of 4,4 '- (9-fluorenylidene) -diphenol and the introduction of an epoxy group. After confirming the reaction, the reaction mixture was decompressed to remove excess epichlorohydrin and dimethyl sulfoxide. Followed by a ring closing reaction. To this end, 4-methyl-2-pentanone (25 g, 100 weight% based on diphenol) was added to dissolve the reaction product and 30% aqueous solution of NaOH (0.5 eq) was added. Thereafter, the mixture was stirred at 100 占 폚 for 6 hours. TLC was used to confirm the ring closure of the epoxy group. After completion of the reaction, the mixture was washed with water to remove the salt, and the 4-methyl-2-pentanone layer was recovered, concentrated, and then precipitated using an excess amount of hexane. NMR was used to confirm the chemical structure of the product. 25.5 g of product in the form of a white powder were obtained, and the yield was 78%.

(2) Synthesis of bisphenol fluorene-type epoxy acrylate [Scheme 2]

Acrylic acid was reacted with bisphenol fluorene-type epoxy to introduce light-sensitive and photocurable properties at both ends.

(25.5 g, 0.055 mole) and acrylic acid (8.712 g, 0.121 mole) were placed in a 250 ml round-bottomed flask and propylene glycol monomethyl ether acetate (25.5 g, 100 weight%) was added and dissolved. Then, tetramethylammonium chloride (0.255 g, 1 wt%) and polymerization inhibitor 2,6-ditert-butyl-4-methylphenol (0.0255 g, 0.001 wt%) were added. Stirred using a magnetic stirrer, and reacted at 110 DEG C for 5 hours. TLC was used to confirm the exhaustion of the raw material. After completion of the reaction, the excess acrylic acid was removed by washing with water. After drying, it was dissolved in a small amount of methylene chloride and precipitated in hexane. NMR was used to confirm the chemical structure of the product. The product is in the form of a pale yellow powder and 25 g is obtained, yielding 84.1%.

(3) Polymerization of bisphenol fluorene-type epoxy acrylate and acid anhydride [Scheme 3]

(B-1) Polymerization of synthesized epoxy acrylate and acid anhydride: Preparation of epoxy acrylate ester

A bisphenol fluorene type epoxy acrylate (25 g, 0.041 mole) having acrylic groups attached to both ends thereof was reacted with bisphenol fluorene epoxy to obtain a 500-mL round-bottomed flask, and 120 g of propylene glycol monomethyl ether acetate was added. Benzyltriethylammonium bromide (0.75 g, 3 wt%) was added to the reactor, and the temperature of the reactor was raised to 130 ° C. To the reaction solution was added 1.37 g of maleic anhydride (0.014 mol) After stirring at 130 ° C for 5 hours, the ring opening of the acid anhydride and the reaction with the alcohol were confirmed by using FT-IR to determine the depletion of the anhydride group by the disappearance of the peak at 1700 to 1800 cm ^-1 Respectively.

(B-2) Polymerization of synthesized epoxy acrylate and diisocyanate: Preparation of epoxy acrylate ester-urethane polymer

To the urethane bond of the synthesized epoxy acrylate-ester polymer, m-xylylene isocyanate (3.5 g, 0.014 mol) was added to a flask at 50-55 ° C., and the mixture was thoroughly mixed. Then, 200 ppm of DBT (catalyst) Was refluxed and stirred for 10 hours to form a bond. Confirmation of urethane formation was confirmed by the disappearance of 2250 cm ^-1 peak of isocyanate using FT-IR.

(B-3) Polymerization of synthesized epoxy acrylate and acid dianhydride: Production of a polyester polymer having a structure in which two acrylate groups and two carboxylic acids are alternately contained

For imparting the acid value and developability of the synthesized epoxy acrylate ester-urethane polymer and for esterifying it, 4,4 '- (4,4'-isopropylidene diphenoxy) bis (phthalic anhydride ) (7.3 g, 0.014 mol). Benzyltriethylammonium bromide (0.75 g, 3 wt%) was charged and the reactor temperature was raised to 130 ° C. Thereafter, after stirring for 6 hours, the ring opening and exhaustion of the anhydride group were confirmed using FT-IR (decay of 1700-1800 cm ^-1 peak). The temperature of the reactor was lowered to room temperature, and propylene glycol monomethyl ether acetate (50 g, 200 wt%) was added to dilute the reaction product by filtration. Thereafter, the product was precipitated with hexane to give a pale yellow powdery product. NMR was used to confirm the chemical structure of the product. The molecular weight of the product was confirmed by GPC. The resulting mixture was reacted for 5 hours to obtain 89.91 g of a fluorene-based polymer having a dicarboxylic acid / diacrylate / urethane group.

Example  2.

Was carried out in the same manner as in (1) of Example 1. 2-carboxyethyl acrylate was used as a bisphenol fluorene-type epoxy compound in order to impart light sensitivity and photo-curability in (2). (3-bis (1-isocyanato-1-methylethyl) benzene as an isocyanate for urethane bonding and a phenyl group for imparting a dicarboxylic acid 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was used.

Example  3.

The epoxidation reaction was carried out in Example 1 (1) using 9,9-bis (4-hydroxy-3-methylphenyl) fluorene as the fluorene type diphenol. (Methacryloyloxy) ethyl succinate as a bisphenol fluorene-type epoxy compound was used in order to impart light sensitivity and photo-curability in the above-mentioned (2). (3), dimethylphthalic anhydride was used for the esterification, isophorone diisocyanate as the diisocyanate for the urethane bond, and oxydiphthalic anhydride as the anhydride containing the phenyl group for the dicarboxylic acid.

Example  4.

The epoxidation reaction was carried out by using 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene as the fluorene-type diphenol in Example 1 (1). 2-hydroxypropyl 2- (methacryloyloxy) ethylphthalate was used as a bisphenol fluorene-type epoxy compound in order to impart light sensitivity and photo-curability in (2). Methyl-5-norbornene-2,3-dicarboxylic acid anhydride for esterification in the step (3), 4,4'-diisocyanato-methylenedicyclohexane (HMDI) as a diisocyanate for a urethane bond, dicarboxylic acid Benzophenone-3,3'-4,4'-tetracarboxylic dianhydride was used as an anhydride containing a phenyl group.

Comparative Example  1 and 2. Epoxy-modified urethane Acrylate  Resins (1) and (2)

Acid value  Calculation

In order to measure the degree of introduction of the carboxylic acid groups of the polymerized binder resin, 0.1 g of each sample was taken and dissolved in 10 mL of acetone, and a small amount of phenolphthalein solution was added. A 0.1 N KOH aqueous solution was prepared and titrated while adding. The amount of 0.1 N aqueous NaOH consumed was measured to calculate the acid value.

Measurement formula: Acid value = 5.6108 x 0.1 x f x KOH consumption (mL) / S

f: factor of NaOH solution, S: amount of sample (g)

Photocurable hybrid  Preparation of composite resin composition

A resin composition was prepared by mixing 90% by weight of each of the synthesized photosensitive oligomers, 10% by weight of photo-curable monomer isobornyl acrylate, 4% by weight of photo-curable initiator Irgacure # 184 and 1% by weight of an antioxidant Irganox1010.

Photocurable (photosensitive) Paste  Manufacturing Example

An organic compound composed of a binder resin, a solvent and an additive were put together in a mixer and dissolved by stirring to prepare a vehicle. The metal powder was slowly added to the mixture while stirring the vehicle. The combined ingredients were mechanically mixed using a 3-roll mill. The impurities such as large particles and dust were removed through filtering.

Test Example

Property evaluation

The photosensitive electrode paste should have sensitivity so that the light receiving portion can be cured even with a small amount of ultraviolet light, and the cured coating film is required to have high heat resistance and low specific resistance.

The sensitivity, heat resistance and conductivity (resistivity) of the photosensitive resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were evaluated. The results are shown in Table 4 below. As can be seen from the results of Table 4, the resin composition of the present invention obtained in Examples 1 to 4 according to the present invention can form a pattern having a fine line width as compared with the composition obtained in Comparative Examples 1 and 2, And heat resistance. In particular, the sensitivity of Example 1 was increased by about 63% and 58%, respectively, when the film thickness was 2.5 μm and 3.0 μm, respectively, as compared with Comparative Example 1. In addition, the resin compositions of the present invention obtained in Examples 1 to 4 had a resistivity value reduced to about one-third of that of the compositions obtained in Comparative Examples 1 and 2.

(1) Sensitivity measurement

A film of 2.5 탆 and 3.0 탆 thick was formed by coating a photosensitive resin composition on a 6-inch wafer (track condition: Soft Bake 100 캜, 90 seconds) using track equipment (MARK 8, TEL) &Lt; / RTI &gt; Nanospec 6100). The photosensitive resin film was exposed with an aligner (MPA-600FA, Canon) equipped with a pattern mask, and developed using a track instrument (developing conditions: 1 wt% Na ₂ CO ₃ at 23 캜 for 65 seconds ), And the developed wafer was inspected by FE-SEM to confirm the sensitivity.

(2) Heat resistance measurement

The photosensitive resin composition prepared on a 6-inch wafer was coated on a 6-inch wafer using a track instrument (coating condition: soft bake at 110 DEG C for 90 seconds, film thickness of 2.5 mu m / 3.5 mu m) (Development condition: 1 wt% Na ₂ CO ₃ , 23 캜, 65 seconds). The developed wafer was subjected to a hard baking at 130 ° C for 120 seconds using a track equipment, and the cross-section of the pattern was observed by FE-SEM to determine the heat resistance. When there was no change in cross section, it was judged to be "O". When the pattern gradually changed after pattern formation, it was expressed as "Δ", and when a change in cross section immediately after pattern formation was observed, it was expressed as "X".

(3) Measurement of developing margin

The photosensitive layer is developed to form the desired pattern. The developing margin represents the time during which each pattern is retained in its original form before being peeled off. The change in pattern line width with development time (s) was measured as CD value. If the retention time of the pattern is relatively long, the development margin is determined to be 'O'. In the case where the retention time of the pattern is relatively short, 'Δ' and the pattern are expressed as 'X' when the pattern is separated immediately after pattern formation.

(4) Resistivity measurement

The resistivity of the pattern was measured with a milliohmmeter (Agilent, 4338B). The cross-sectional area of the pattern was calculated from the cross-sectional shape measured with Alpha-Step (KLA tensor, ASIQ). At this time, the average cross-sectional area was obtained by measuring the cross-section three to five times at different positions of each pattern. The resistivity of the pattern was calculated from the measured resistance and cross section.

[Evaluation Equipment]

1) Track: TEL's MARK8

2) Aligner: Canon's MPA-600FA

3) FE-SEM: Hitachi's S-4100

4) Thickness measuring instrument: Nanospec 6100 from Nanometrics

5) Resistance meter: Agilent's 4338B Milliohmmeter

6) Alpha-Step: ASIQ of KLA tensor

1 is a SEM image and CD (占 퐉) data (cross sectional profile photograph of a pattern) for Examples 1 to 4 and Comparative Examples 1 and 2 of the present invention (CD: critical dimension; minimum (critical) line width of pattern).

[Evaluation condition]

P / B (pre-bake): 100 占 폚 -90 seconds; UV exposure: 300 mJ / cm ² (365 nm)

Dev. (Development): 1wt% Na ₂ CO ₃ solution, 23 ° C, 65 sec

Dry: 140 ° C - 30 minutes

Specifically, Figure 1 is analyzed as follows:

Example 1. CD: 31.42 탆, aspect ratio (leading edge / line width): 0.289. Patterning of high aspect ratio and fine line width is possible.

Example 2. CD: 32.39 mu m, aspect ratio: 0.277. Patterning of high aspect ratio and fine line width is possible.

Example 3. CD: 33.38 탆, aspect ratio: 0.253. Patterning of high aspect ratio and fine line width is possible.

Example 4. CD: 35.35 mu m, aspect ratio: 0.249. Patterning of high aspect ratio and fine line width is possible.

Comparative Example 1 CD: 54.02 mu m, aspect ratio: 0.143. Low aspect ratio, and line width.

Comparative Example 2 CD: 53.01 mu m, aspect ratio: 0.111. Low aspect ratio, and line width.

The electrodes of the touch panel are printed in a pattern having a predetermined length, thickness (line height) and line width. At this time, if the aspect ratio (line height / line width) of the electrode pattern is low, the ratio of covering the electrode during ultraviolet irradiation becomes high, and consequently, the pattern forming ability and the electrode efficiency are deteriorated. On the other hand, as the aspect ratio increases, the area of the substrate absorbing the ultraviolet ray increases, so that the photoreactivity and the light absorptivity are increased, which is advantageous in forming fine patterns of the electrode and realizing high resolution and can lower the resistance value. High efficiency can be expected. That is, the electrode performance is determined by printing an electrode paste composition which gives an electrical function so that the aspect ratio of the fine pattern is high when printing.

As the aspect ratio of the fine patterns is increased by the resin compositions of Examples 1 to 4 due to the present incidence, the pattern is not broken or short-circuited, so that the durability and adhesion are excellent and the contamination of the substrate surface is minimized, It can be used advantageously not only as a touch panel, a flexible display electrode substrate, and an auxiliary electrode of a display transparent substrate but also as a negative electrode plate for a solar cell and a flexible printed circuit board (FPCB).

In contrast to Examples 1 to 4, in Comparative Examples 1 and 2, the viscosity of the electrode paste produced due to the low viscosity of the resin composition was low, leading to the spread of the printed pattern line width, which makes it difficult to realize a high resolution pattern, It is difficult to obtain an electrode pattern having an excellent aspect ratio.

Claims (16)

(A) Ag powder; (B) a photosensitive resin composition; (C) a solvent; And (D) an additive, wherein the photosensitive resin composition (B) comprises (a) a photosensitive oligomer / polymer; b) a photopolymerizable monomer; (c) a photopolymerization initiator, and (d) an additive. The method according to claim 1,
The photosensitive resin composition (B) comprises a cardo-based acrylate oligomer resin containing a fluorene structure, and is obtained by modifying a thermosetting urethane-based, epoxy-based, ester-based monomer / oligomer / prepolymer, Wherein the photo-curable resin composition is a multi-functional composite photo-curable resin composition. 3. The method of claim 2,
Wherein the cardo-based acrylate oligomer resin containing the fluorene structure has a structure represented by the following formula (1): &lt; EMI ID =
Formula 1

R ₁ is each independently selected from the group consisting of -H, (meth) acryloyl, (meth) acryloyl C 1-10 alkyl, (meth) acryloyloxy C 1-10 alkyl, C 6-20 aryl, Wherein the C6-20 aryl, C1-20 alkyl, and C6-20 aryl C1-20 alkyl are substituted with a (meth) acryloyl group, and one or more carbon atoms constituting the substituent May be substituted with one or more heteroatoms selected from N, O, S;
R ₂ is a substituted or unsubstituted C 1-10 alkylene, a substituted or unsubstituted C 4-14 cycloalkylene, a substituted or unsubstituted C 6-14 arylene, or a combination thereof;
R ₃ is selected from the group consisting of -H or a C1-10 alkyl group, a hydroxyl group, an epoxy group;
n is an integer of 1 to 6; 3. The method of claim 2,
Wherein the polyfunctional hybrid photo-curable resin composition has a structure represented by the following formula (2): &lt; EMI ID =
(2)

here,
R ₁ is each independently selected from the group consisting of -H, (meth) acryloyl, (meth) acryloyl C 1-10 alkyl, (meth) acryloyloxy C 1-10 alkyl, C 6-20 aryl, Wherein the C6-20 aryl, C1-20 alkyl, and C6-20 aryl C1-20 alkyl are substituted with a (meth) acryloyl group, and at least one carbon atom constituting the substituent is substituted with Lt; / RTI &gt; may be substituted with one or more heteroatoms selected from N, O, S;
L ₁ to L ₃ are each independently selected from the group consisting of -C (= O) -, -C (= O) NH- and -NHC (= O) -;
X and Y are C1-10 alkylene, saturated or unsaturated C4-14 cycloalkylene, C6-14 arylene or combinations thereof;
Z is a saturated or unsaturated C4-14 cycloalkylene having at least two -COOH groups, C6-14 arylene or a combination thereof,
l, m and n are each an integer of 1 to 6; 5. The method of claim 4,
R ₁ is -H or (meth) acryloyl. The method according to claim 4 or 5,
Wherein L ₁ and L ₃ are -C (═O) - and L ₂ -YL ₂ is -C (═O) NH-Y-NHC (═O) - structure. 5. The method of claim 4,
Wherein X is selected from the structures represented by the following formulas:

5. The method of claim 4,
Wherein Y is selected from a structure represented by the following formula:

5. The method of claim 4,
Wherein the Z is selected from the structures represented by the following formulas:

5. The method of claim 4,
l, m and n are from 1 to 6. &lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; 11. The method of claim 10,
1: m is from 0.8: 1 to 2.5: 1, and 1: n is from 0.6: 2 to 6.7: 2. 5. The method of claim 4,
Wherein the polymer has a weight average molecular weight (mw) in the range of 3,000 to 20,000 g / mol. 5. The method of claim 4,
The polymer had an acid value in the range of 60 to 150 mgKOH / g and a viscosity of 3,000 (measured by a Brookfield DV-II + pro viscometer using a spindle for 40 cP) To 10,000 cps (25 占 폚). 3. The method of claim 2,
Based on the total weight of the photosensitive resin composition (B), the content of the ternary polymeric photosensitive oligomer resin (a) of Formula 2 is 80 to 95% by weight; The content of the photopolymerizable monomer (b) is 5 to 15% by weight; The content of the photopolymerization initiator (c) is 0.5 to 5% by weight; And the other additives (d) is 0.1 to 3% by weight. The method according to claim 1,
(A) 60 to 85% by weight of a conductive metal powder; (B) 10 to 25% by weight of a photosensitive resin composition; (C) 1 to 5% by weight of an additive; And (D) 1 to 10% by weight of a solvent, based on the total weight of the composition. Applying the photosensitive resin composition according to claim 1 onto a substrate; And
And exposing and developing the applied photosensitive resin composition.

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